Textile Processing & Dyeing by AKR Chaudary

About the book
Since colour makes textiles attractive, coloration or dyeing has been

practised by mankind from ancient days. The dyes obtained from nature
were used as colorants for centuries. From the beginning of twentieth
century, synthetic dyes slowly replaced the natural ones. The materials
prepared from different textile fibres require dyes of different nature.
Thousands of dyes have been developed having varied properties and
hues.
Before dyeing, the materials are to be prepared thoroughly for better dye
pickup. Even white textile goods require proper preparation for better
usability and whiteness. Tremendous developments have been made in the
preparation and dyeing processes; the detailed discussions require several
volumes of book. The technicians and students prefer a single book, which
covers all aspects in a well-balanced manner. The theoretical and practical
aspects of conventional processes and recent developments are discussed
precisely in this book in order to enable the students and the technicians to
learn various processes in a better way from a single source. The book
contains the following eleven chapters:
♦ Chemistry of Textile Materials ♦ Water Requirements and Treatments
♦ Surface Active agents ♦ Preparatory Processes I (Cleaning)
♦ Preparatory Processes II (Whitening) ♦ Dyes and Dyeing
♦ Dyeing Machines ♦ Dyeing of Cellulosic Materials
♦ Dyeing of Animal Fibres ♦ Dyeing of Synthetic Fibres and Blends
♦ Eco-friendly Textiles
About the author

Asim Kumar Roy Choudhury is presently working as assistant professor at
the Govt. College of Engineering and Textile Technology, Serampore (India-
712201). He obtained M.Tech degree from I.I.T. Delhi and
Ph.D. degree from Calcutta University. He served several
textile and dye-manufacturing units. Since 1982 he is in
teaching profession and published several research papers
in journals like Color in Research and Application (USA),
Journal of Society of Dyers and Colourists (UK), Die Farbe
(Germany), and Colourage (India). He has authored a book
entitled Modern Concepts of Color and Application. He is a member of
AATCC Color Measurement (RA-36), Characterisation of Dyes (RA-87) and
Applied Dyeing Theory (RA-91) Research Committees.
Textile Preparation and Dyeing
Asim Kumar Roy Choudhury

Assistant Professor
Govt. College of Engg. & Textile Technology, Serampore,
West Bengal
India
Preface

Any aspiring technologist who sets out for a career in dyeing technology,
either in production, teaching or research, must have realised the non-
availability of a text-book which is comprehensive yet not too bulky. The
situation has become more difficult now as the present syllabus
encompasses several new subjects and each subject has become
voluminous with tremendous advancements in each field. The need for the
day is for a single comprehensive book which covers all aspects in a well-
balanced manner. Since I have a teaching experience of more than 20
years, I understand the necessity of a standard textbook which students can
use as the chief source of information on all aspects of dyeing. New
entrepreneurs or fresh technicians in the textile processing industry who are
desirous of having first hand knowledge of the subject also need similar
consolidated information.
The present book deals mainly with the classical processes for textile
dyeing as well as preparation of the material before dyeing and includes
recent technological developments. Both the theories and the practical
aspects are discussed precisely in order to enable the students and the
technicians to understand the processes clearly.
The first chapter deals with the chemical and physical structures and the
properties of various natural, regenerated and synthetic textile fibres.
Identification techniques of various textile fibres have been discussed
briefly, as satisfactory dyeing is possible only when the composition of
textile material is known.
Water quality is the single largest factor which decides the success of
dyeing processes. The second chapter broadly discusses the water
sources, qualities, requirements and treatments. Standard norms for water
quality required for various textile processes are mentioned. Today there is
a global concern about water and air pollution caused by effluents/
emissions from industries. Air pollution caused by textile industries is similar
to the pollution from other industries and is not specific to this industry
alone. However, water pollution is another story as this industry uses
iii
copious quantity of water, combines it with chemicals and the wastewater is

then discharged as effluent. The treatment of effluents before discharge is
discussed in detail.
The third chapter discusses various aspects of surface activity and
surface-active agents. Such compounds play a vital role at various stages
of textile processing. Special emphasis has been given while discussing
soaps and detergents, emulsifying agents and wetting agents which are
very important for textile dyeing and preparatory steps.
The fourth chapter spells out the preparatory processes for removal of
impurities from textile materials before dyeing and printing. Natural fibres
are broadly of two types. Cellulosic fibres such as cotton, jute etc. are
similar in properties and their preparatory processes are more or less
identical. However, the natural protein fibres, namely wool and silk, are very
different from cellulosic fibres and they require entirely diverse
pretreatments. Regenerated and synthetic fibres are factory-made, hence
the impurity content in these fibres is much lower. Their method of
preparation is much simpler than that of natural fibres.
The fifth chapter deals with whitening processes. Perfect whiteness is
required for the materials to be sold as white goods. This is achieved in two
ways. Firstly, the materials are bleached to remove colouring matters
present in the form of impurities. For further whitening, the materials are
treated with blue or violet colorants or optical whitening agents.
The sixth chapter clarifies the perception of colour and the chemistry
behind colour generation. Visual and instrumental colour measurement
methods are given in detail. Properties and classification of textile dyes are
also elaborated.
The seventh chapter deals with the dyeing machinery used for textile
dyeing operations.
The eighth chapter discusses various dyeing methods for the materials
composed of cellulosic fibres, namely the natural fibres like cotton, jute, etc.
and the regenerated fibres like viscose.
The ninth chapter describes dyeing methods of protein fibres like wool
and silk.
The tenth chapter comprises of dyeing methods for the synthetic fibres
namely polyester, nylon, acrylic etc. and their blends.
The eleventh chapter discusses eco-friendly textiles. A large number of
dye-intermediates used for the manufacturer of dyes and several
commercial dyes have been banned recently due to their adverse effects on
health. A comprehensive list of such products has been incorporated to
create awareness among users. German bans, the methodology of testing
and eco-auditing methods have been discussed. The use of eco-friendly
natural dyes as an alternative to synthetic dyes has been discussed in brief.
I wish to convey my sincere gratitude to Dr. Richard Aspland, Professor,
School of Textiles, Clemson Univerisity (USA) and Dr. M.L. Gulrajani,
Professor, Textile Dept., Indian Institute of Technology (New Delhi, India)
iv
for their valuable suggestions. I am thankful to my colleague, Dr. P.K.

Majumder for his suggestions.
I also wish to dedicate the book to my beloved mother, late Usha Roy
Choudhury, who sacrificed her life for our upbringing.
Asim Kumar Roy Choudhury

Contents
Preface ii
Chapter 1
CHEMISTRY OF TEXTILE MATERIALS 1
1.1 Introduction 1
1.2 Textile Fibres 1
1.3 Fibre Structure 2
1.4 Polymer System 3
1.5 Essential Properties of Fibre 3
1.6 Classification of Fibre Properties 5
1.7 Classification of Textile Fibres 6
1.8 Cellulosic Fibres 7
1.9 Protein Fibres 18
1.10 Synthetic Fibres 27
1.11 Important Fibre Properties 33
1.12 Fibre Identification 33
References 39
Chapter 2
WATER REQUIREMENTS AND TREATMENTS 40
2.1 Introduction 40
2.2 Sources of Water 40
2.3 Impurities and Their Effects 40
2.4 Methods of Water Softening 46
2.5 Sequestering Agents 49
2.6 Water Consumption 53
2.7 Water Quality for Process Water 54
2.8 Water Quality for Boiler Use 55
2.9 Effects of Effluent Characteristics 56
2.10 Degradability of Wastes 60
vi
2.11 Textile Effluents 62

2.12 Control of Effluent Quality 64
2.13 Effluent Treatment Methods 66
2.14 Effluent Treatment Plant 82
2.15 Recent Developments 84
References 87
Chapter 3
SURFACE ACTIVE AGENTS 88
3.1 Introduction 88
3.2 Surface Activity 89
3.3 Classification 91
3.4 Hydrophilic Groups 96
3.5 Hydrophobic Groups 97
3.6 HLB Values 99
3.7 Micelle Formation 102
3.8 Application Properties 103
3.9 Biodegradability 105
3.10 Emulsions 105
3.11 Soaps 110
3.12 Synthetic Detergents 112
3.13 Absorbency 122
3.14 Textile Auxiliaries 125
References 130
Chapter 4
PREPARATORY PROCESSES I (CLEANING) 131
4.1 Introduction 131

4.2 Aims of Preparatory processes 133
4.3 Preparatory Processes 134
4.4 Preparation of Cotton Materials 134
4.5 Preparation of Proteneous Materials 207
4.6 Preparation of Synthetic Materials 241
References 248
Chapter 5
PREPARATORY PROCESSES II (WHITENING) 250

vii
5.2 Reductive Bleaching Agents 252

5.3 Oxidative Bleaching Agents 255
5.4 Whiteness 310
5.5 Testing of Bleached Materials 323
References 323
Chapter 6
DYES AND DYEING 326
6.1 introduction 326

6.2 Properties of Dyes 328
6.3 Colour and chemical constitution 329
6.4 Colour Measurement 337
6.5 Instrumental Colour Specification 348
6.6 Visual Colour Specification 353
6.7 Solubility of Dyes 358
6.8 Substantivity and Reactivity 359
6.9 Fastness requirements 360
6.10 Classification of Dyes 371
6.11 Commercial Names of Dyes 378
6.12 Identification of Dyes 378
6.13 Theory of Dyeing 383
References 399
Chapter 7
DYEING MACHINES 402

7.2 Dyeing of Loose Stock and Tops 408
7.3 Yarn Dyeing Machines 413
7.4 Fabric Dyeing Machines 429
7.5 Garments and Footwear Dyeing 466
7.6 Foam Dyeing Machines 469
7.7 Space Dyeing Machines 473
7.8 Water Extraction or Drying 477
References 490
Chapter 8
DYEING OF CELLULOSIC MATERIALS 491
8.1 Fibre Structure 491

viii
8.2 Dye-classes 493

8.3 Direct Dyes 495
8.4 Reactive Dyes 514
8.5 Vat Dyes 555
8.6 Solubilised Vat Dyes 582
8.7 Sulphur Dyes 585
8.8 Oxidation Colours 597
8.9 Azoic Colours 600
8.10 Mineral Colours 619
8.11 Solubilised Pigment Colours 622
8.12 Resin-bonded Pigment Colours 623
References 625
Chapter 9
DYEING OF ANIMAL FIBRES 628

9.2 Acid Dyes 632
9.3 Chrome Dyes 655
9.4 Premetallised Dyes 666
9.5 Dyebath Bleaching 678
9.6 Aftertreatments 678
9.7 Stripping of Dyes 679
9.8 Low Temperature Dyeing 679
9.9 Reactive Dyes 682
9.10 Recent Advancements 685
9.11 Silk Dyeing 687
References 692
Chapter 10
DYEING OF SYNTHETIC FIBRES AND BLENDS 693

10.2 Mass Coloration 695
10.3 Disperse Dyes 701
10.4 Dyeing of Nylon Fibres 740
10.5 Dyeing of Acrylic Fibres 757
10.6 Dyeing of Blended Materials 776
References 803
ix
Chapter 11
ECO-FRIENDLY TEXTILES 805

11.2 Toxicity 810
11.3 German Ban 811
11.4 Testing Method 815
11.5 Eco-friendly Processing 815
11.6 Eco-auditing 817
11.7 Eco-labeling 819
11.8 Natural Dyes 821
References 825
Index 827
Chapter
Chemistry of Textile Materials 1
1.1 INTRODUCTION
The dyeing and printing processes are basically chemical processing of
textile materials. Textile materials called fabrics or cloths are prepared by
weaving (i.e. woven fabrics) or by knitting (i.e. knitted fabrics) with
continuous strands of textile materials called threads or yarns. Yarns are
prepared from short-length materials called staple fibres or continuous
materials called filaments. Fabrics called non-woven are prepared from
fibres directly (without making yarn) by special methods.
For successful chemical processing, thorough knowledge of the chemical
constitution, physiochemical structure and chemical properties of the textile
materials is extremely essential. One may wonder at the many and varied
properties of fibres, yarns and fabrics that have been produced, particularly
since the advent of man-made fibres. One may ask what makes a material
suitable for use as a textile fibre. Why fibre properties like strength,
elasticity, moisture absorbency, thermal properties, dyeability, resistance to
chemicals vary so widely. To answer all these questions, one must closely
examine the structure of textile fibres.
1.2 TEXTILE FIBRES

Textile fibres are defined as units of matter characterised by flexibility,
fineness and a high ratio of length to thickness. They should have sufficient
strength to resist breakage due to stress applied during manufacture and
use. They should also possess enough thermal and chemical stability to
withstand the environment to which the fibres are exposed. Moreover, an
extensibility of 5-50% is required, depending on the end-use of the final
product.
Until the introduction of man-made fibres, one had to rely on fibres from
natural sources. Not all of these fibres were suitable for use as textile fibres,
because they lacked certain characteristics, for example, many were not
2
long, flexible or strong enough. Soil, feed and other climatic and
environmental conditions affect natural fibres. These result in non-uniform
properties of natural fibres. Man-made fibres are not much influenced by
these factors and greater control can be exercised over their production.
However, even with greater control, slight variations in the production of
man-made fibres can give rise to significant variation in dyeability, strength
and some other properties.
Each individual fibre is made of millions of individual long molecular chains
of discrete chemical structure. The morphology, i.e. the arrangement and
orientation of these molecules within the individual fibre as well as the gross
cross-section and shape of the fibre influence the fibre properties. However,
the basic physical and chemical properties largely depend on the chemical
structure of the long molecular chains constituting the fibre. The total
number of units that repeat themselves in a chain vary from a few units to
several hundreds and is termed as the degree of polymerisation (DP) for
molecules within the fibre.
Cotton, for example, has a DP of about 10,000 and viscose rayon, a
regenerated fibre, about 300–350. The DP of man-made fibre is determined
by various factors during production of these fibres.
1.3 FIBRE STRUCTURE

With the exception of a few speciality fibres based on inorganic substances
like glass, asbestos etc., fibres are a class of solid organic polymers that are
distinguished from other polymers by their physical properties and by their
characteristic geometric dimensions. A fibre is readily identifiable as a
substance that is extremely long with respect to its width or diameter, is
flexible and has high anisotropic physical properties. However, fundamental
difference between fibres and other solid substances is in their molecular
structure, which in turn, decides the differences in their chemical and
physical properties.
For a complete description of fibre structure, it is useful to consider three
levels of molecular structure, each relating to certain aspects of fibre
behaviour and properties. The organochemical structure defines the
structure of the repeating unit in the base polymer and the nature of
polymeric link. This is directly related to chemical properties, dyeability,
moisture adsorption, swelling characteristics and indirectly to all physical
properties. The macromolecular structure describes the family of polymer
molecules in terms of chain length, chain length distribution, chain stiffness,
molecular size and molecular shape. A supermolecular structure provides a
description of the arrangement of the polymer chains, primarily in terms of
factors like orientation, crystallinity and fibrillar structure.
3
In general, all fibres that are useful in textile applications are

semicrystalline, irreversibly oriented polymers. This means that the fibres
have certain regions in which the molecular chains are highly oriented,
closely packed and near-perfectly arranged. These regions are usually
referred to as crystalline regions or crystallites. The degree of orientation
and the degree of crystallinity are important quantities that strongly influence
the physical properties of fibre. In other regions, the molecular chains are
not well ordered, tending to a random-coil configuration and these are
usually referred to as amorphous region. In the case of natural fibres, there
are various identifiable aggregates of polymer chains, which are very often
referred to as micelles, fibrils, microfibrils and also macrofibrils [1].
1.4 POLYMER SYSTEM

The basic unit of the textile fibre is a molecular segment called monomer
(mono = one, mer = unit) which is repeated a large number of times to form
a long chain or a molecule called polymer (poly = many). A polymer may
also be formed from two or more different monomers. Such polymers are
called copolymer. There is no definite regularity in the order of monomers,
which make up a copolymer. Some fibres may contain additional monomers,
which do not form part of the polymer chain and are incorporated to improve
certain properties of the fibre such as dye affinity (e.g., an acrylic fibre called
Zefran). Those are grafted onto the polymer chain as side group or branch.
In Figure 1.1, a rectangle, a circle and a triangle are symbolically
representing the chemical structure of three monomers. The homopolymers,
copolymers and grafted polymers, which can be prepared from the three
monomers, are symbolically shown in the figure [2].
1.5 ESSENTIAL PROPERTIES OF FIBRE

It was realised long back that the natural fibres consist of polymers held
together by various links or forces. The first step in the development of
man-made fibre was the manufacture of regenerated fibre using natural
fibrous raw materials. For example, cellulosic materials from plants or trees
are regenerated into viscose, which can be spun into yarn. The next step
was to produce chemicals, which have the ability to form links giving rise to
polymers called synthetic fibres. It must be realised that only a few of
organic chemicals can be used in the production of synthetic fibres. The
properties of the polymer necessary for fibre formation are as follows:
1. Molecular weight – a polymer should have high molecular weight, which
consequently results in considerably longer fibre. The length of polymer
4
Monomer 1 Monomer 2 Monomer 3
Symbolic structures of
homopolymers
Symbolic structures of
copolymers
Symbolic structure of grafted

polymer
Fig. 1.1 Symbolic Structures of Different Types of Polymers
contributes to the strength of the fibre by holding crystalline regions

together. To produce a fibre of adequate strength, the length of a
polymer molecule in the range of 100 nm (minimum) is required (1 nm =
10-9 metres). Many naturally available cellulosic materials can not be
used as textile fibres as they are much shorter in length.
2. Linearity – only predominantly linear polymers will form sufficient
crystalline regions, permitting an adequate number of inter-chain forces
of attraction to occur within the polymer system. The molecular chains,
which are bulky and/or branched, cannot pack closely enough together
to form a crystalline region resulting in a weak fibre.
3. Inter-fibre forces of attraction – there should be a sufficient degree of
inter-molecular links or bonds of one or more of the following types:
(i) Hydrogen bonds, which occur between positively charged
hydrogen atoms in one polymer molecule and negatively charged
oxygen, nitrogen or chlorine atoms in an adjacent polymer
molecule. Natural fibres are rich in hydrogen bonds.
(ii) Van der Waals’ forces are similar but weaker than hydrogen
bonds. They occur when polar groups are absent. The polymers
are to be closely packed so that attraction can occur between
slight charges of opposite character in the polymer chains. Both
the hydrogen bonds and Van der Waals’ forces of attraction are
weak, but the presence of these forces in large numbers in case
of closely packed polymers significantly contributes to its strength.
5
(iii) Strongest and chemically most stable covalent bonds or cross-

links are formed when any two atoms share a pair of electrons.
The greater the number of cross-links, the more rigid the fibre
becomes. However, a low degree of cross-links, as in case of
wool (disulphide bond) or elastomeric fibres, imparts a good to
excellent elasticity.
(iv) Ionic bonds are formed between oppositely charged polar groups
in polymers and are stronger than hydrogen bonds and Van der
Waals’ forces. They occur principally in protein fibres like wool
and silk, and polyamide fibres like nylons.
4. Orientation – a fibre consists of a large number of individual polymer
chains arranged in either highly ordered and highly oriented form called
crystalline region or randomly called amorphous region. In a fibre, the
extent and proportion of crystalline and amorphous regions may vary –
in natural fibres, the variation is created by nature and in case of man-
made fibres, the variation can be controlled during production. In some
polymers, the crystalline regions are formed during extrusion and
subsequent drawing process merely aligns the crystalline regions
parallel to the fibre axis; whereas in other systems, the polymers are first
formed in amorphous state and become crystalline during drawing.
There is a limitation on the extent to which drawing is carried out on
textile fibres. Highly crystalline fibres have harsh handle and poor
abrasion resistance, i.e. quickly damaged on rubbing.
5. Melting point – when a polymer is highly crystalline or when the
intermolecular attraction between the polymer molecules is strong, its
resistance to heat will be high. Most textile fibres are subjected to heat
treatment during production (e.g., during heat setting, dyeing or
finishing) or during use (e.g., during ironing, washing etc.). Hence, the
fibres should have high resistance to heat. Synthetic fibres have specific
ranges of temperature during which they melt, depending on the
chemical structure, molecular weight and the degree of crystallinity of
the polymer. Natural fibres do not melt as they have strong inter-chain
bonding and long chain-length. However, they turn yellow and are
damaged above certain temperature depending on the chemical
structure of the fibre.
1.6 CLASSIFICATION OF FIBRE PROPERTIES

Fibres have wide variations in chemical, electrical, mechanical, optical
and other properties, and the properties of a fibrous product naturally
depend on the properties of the fibres of which it is composed. Not only the
average values but also the range or statistical distribution is important. A
6
typical classification of such fibre properties with some examples is given

below [1]:
1. Geometric
(i) Length
(ii) Cross-section
(iii) Crimp
2. Physical
(i) Density – linear, bulk
(ii) Thermal – melting, transitions, conductivity
(iii) Optical – birefringence, refractive index, lustre and colour
(iv) Electrical – dielectric constant, resistivity
(v) Surface – roughness, friction
(vi) Mechanical – tension, compression, torsion, bending, shear
3. Chemical
(i) Response to acids, alkalis, oxidation, reduction and heat
(ii) Sorption – moisture, dyes
(iii) Swelling – anisotropy
1.7 CLASSIFICATION OF TEXTILE FIBRES

As the physical and chemical properties differ largely among fibres of
different origin, it is necessary to classify textile fibres based on the source
of origin. The types of textile fibres available globally are exceedingly large
and apparently, it is very difficult to categorise under a few classes.
Textile fibres are broadly divided into two classes – natural and man-
made. Nature provides us a large number of excellent fibrous materials that
can be used directly for yarn and fabric manufacture. Natural fibres may be
obtained from plant, animal or mineral sources. All plant fibres are
composed of primarily cellulose and secondarily other components like
hemicellulose, lignin, etc. Plant fibres can be further divided into various
sub-groups depending on the portion of the plant from where the fibre is
obtained e.g., seed (cotton), stem or bast (flax, jute etc.) or leaf (Sisal).
Fibres obtained from animals are mostly composed of amino acid residues
or protein. The most important animal fibres are silk and wool. In addition,
there are a large number of lesser-known hair fibres such as camel hairs,
goat hairs, rabbit hairs, etc.
The fibre obtained from mineral is asbestos.
Man-made fibres can be subdivided into three sub-classes:
1. Regenerated fibres are manufactured by dissolving natural fibre-

forming polymers and regenerating the polymer in the form of fibre
7
(truly continuous filament) by passing it through a fine orifice called

spinneret. Examples are various rayons namely viscose and acetate
fibres.
2. Synthetic fibres are made by chemical synthesis from simple
chemicals (i.e. monomers). After polymerisation, the melt or solution of
the polymer is passed through spinnerets and spun into filament. They
can be further classified as polyesters, polyamides (nylon),
polyurethenes (Spandex), polyvinyls, polymerised hydrocarbons or
polyolefins (polypropylene) and synthetic rubbers, depending on the
chemical composition of the fibres. Polyvinyls may have different
substitution (chloro, fluoro, cyano and hydroxyl) products, the most
important being mono-cyano substituted acrylics.
3. Refractory (ceramic) and industrial fibres like carbon, glass, metal,
etc.
Figure 1.2 shows classification of textile fibres [3].

Another method of classifying fibres would be according to chemical
structure, without regard to their origin. Fibres of similar chemical structure
can be grouped together as shown in Table 1.1.
The annual world-wide fibre used in 1996 [4] was 47 million tons with
fibre-wise break-up as follows:
Cellulosic - 44.7%
Polyester - 27.2%
Polyolefins - 9.6%
Polyamide - 8.6%
Acrylic - 5.7%
Wool - 3.1%
Others - 1.1%
This indicates the overall importance of cellulosic and polyester fibres
alone or in blends. These two fibres are accounted for 72% of world fibre
consumption. It is estimated that by the year 2010, the consumption of
polyester will be more than that of the cellulosic fibres.
1.8 CELLULOSIC FIBRES

Cellulose is the most abundant of all naturally occurring organic polymers,
thousands of millions of tons being produced by photosynthesis annually
throughout the world. Although exploited for several millennia in the form of
cotton, flax and other textile fibres and in the form of wood, it is only in the
1930s that its constitution as a linear high polymer of anhydroglucose units
was unequivocally established. Cellulosic fibres may be natural or man-
made. Again, natural cellulosic fibres may be obtained from different
8
Textile Fibre
Natural Man-made
Vegetable Animal Mineral Natural polymers Refractory and

or or or related fibres
Cellulosic Protein Inorganic
Cellulose esters
Regenerated Regenerated • Glass
• Silk cellulosic protein • Carbon
• Wool
• Acetate • Metal
• Minor • Asbestos • Rayons
hair fibres • Metal
(Viscose, oxide
• Casein
Cuprammonium) • Silica
Seed Skin or
Bast Fruit Miscellaneous
• Cotton
Leaf
• Kapok • Alginate
• Coir
• Jute • Natural rubber
• Flax • Sisal
• Hemp • Pineapple
• Ramie • Abaca, etc.
Synthetic
Polyamides Polyvinyl Polymerised Synthetic

hydrocarbons rubbers
Polyesters Polyurethenes
• Polyethylene
• Polypropylene
Substituted Substituted with Substituted with Substituted with

with chlorine fluorine cyano hydroxyl
• Teflon • Polyvinylalcohol
Mono-substituted Di-substituted Mono- Di-substituted

• Polyvinylchloride • Polyvinylidene substituted • Polyvinylidene
and derivatives chloride • Polyacrylics dinitrile
Fig. 1.2 Classification of Textile Fibres

portions of the plant. The most important is cotton fibre, which is obtained
from the seeds of cotton plant.
9
Table 1.1 Classification of Textile Fibres as per Chemical Constitution

Cellulosic Cotton, flax and other bast fibres, leaf fibres, rayons
Modified cellulosic Acetate (cellulose ester)
Protein (natural) Wool, silk, hair fibres, casein
Polyamide Nylon, aramid (aromatic nylon)
Polyester Terelene, Dacron, CD (cationic dyeable) polyester
Polyacrylic Acrylic fibres, modacrylics
Polyolefins Polyethylene, polypropylene
Vinyl Saran, Teflon (polytetrafluoroethylene)
Polyurethane Spandex
1.8.1 Cotton Fibre

Cotton is the most important natural fibre and it accounts for about 50% of
the total fibre production of the world. Cotton fibre is obtained from the seed
of the plant of the botanical family Gossypium. Cotton was being produced
and used in India from ancient times. At present cotton is cultivated in many
countries – the largest producers are the USA, India, Russia, Brazil, Egypt
and China. Some important varieties of cotton are Sea Island (51 mm,
0.017 mm), Egyptian (38–44 mm, 0.017 mm), American (23–32 mm,
0.21 mm), Indian (15–20 mm, varying) – the quantities in brackets are
average fibre length and diameter respectively, in each case.
Cellulose is a polymer of glucose. This is commonly known as pyranose
structure because of its similarity to pyran, having a ring structure consisting
of five carbons and an oxygen atom. It has been established, by measuring
the rotation of polarised light by glucose crystallised under varying
conditions, that there are two forms of dextrorotary glucose, known as the α-
glucose and β-glucose. The difference between them lies in the distribution
of the hydroxyl groups above and below the pyranose ring. In β-glucose, the
two hydroxyl groups at the extreme ends are at opposite location to each
other, whereas in α-glucose, the both hydroxyl groups are either at the top
or at the bottom of the pyranose ring. Polymers can be formed by
condensation of the two hydroxyl groups at the extreme ends of glucose
molecules forming an –O– link with liberation of water molecules (–OH +
–OH = –O– + H2O). Cotton is very nearly pure cellulose that is composed
of a long chain molecule having 10,000-16,000 β-anhydro-glucose units.
Starch and polysaccharide are polymers of α-glucose – they have no fibre-
forming attributes. The particular steric arrangement is, therefore,
responsible for the formation of cellulose in natural fibre. Two stereo-
isomeric methyl glucosides, derived from α-d-glucose and β-d-glucose, have
been isolated. It has been shown that cellobiose, (1-1), a disaccharide
10
present in cellulose, consists of two β-d-glucose molecules joined in the 1:4

positions. The structure of β-glucose indicates that if the linkage is between
hydroxyl groups in the 1:4 positions, each alternate unit must be turned
through an angle of 180°. Starch is a polymer of α-glucose molecules, in
which this alternate rotation of the molecule is not required for condensation
leading to linkages in the 1:4 positions. This difference is of high significance
because theoretical considerations demonstrate that it is only in case of the
β-linkage, it is possible for the polymer to be oriented in a straight line and,
therefore, to be potentially fibre forming.
CH2OH H OH
O
H H O H H
H OH H
O OH H H H H O
O
H OH CH2OH
(1–1) Cellobiose
Studies have also shown that the hydrogen atoms of all the hydroxyl
groups are hydrogen-bonded. These hydrogen bonds hold several adjacent
cellulose chains in close alignment to form crystalline areas called
microfibrils. Between the crystalline regions (about 70%) in cotton, disor-
dered amorphous regions are found. Penetration of dyes and chemicals
occur more readily in these amorphous regions. The cellulose polymer is
quite reactive because of the three free hydroxyl groups (one primary and
two secondary) on each β-anhydroglucose unit. The hydroxyl groups are
normally hydrogen bonded, but the bonds break quickly when immersed in
water.
Each cotton hair consists of a single elongated cell, one end of which
tapers to a point, whilst the other end is open where it has been removed
from the seed by the ginning process. Individual cotton fibres have ribbon
like structures of somewhat irregular diameter, with periodic twists or
convolutions (about 150–300 twists per inch) along the length of fibre. The
cross-section is kidney-shaped or similar to a collapsed tube. This particular
shape of cross-section is probably due to the asymmetry of the mechanical
strains during drying from a swollen cellular tube to the collapsed fibre form.
The central hollow channel is known as lumen.
The bulk of the fibre is contained in the innermost and matured secondary
wall. The secondary wall of the cotton fibre, which accounts for the bulk of
the fibre, is composed of uniformly sized fibrils in which the cellulose chains
are well aligned and closely packed in crystalline units. These fibrils,
11
oriented at a defined angle of 23° with respect to the fibre axis, are packed
in the fibre in concentric sheets or layers. These layers are referred to as
growth layers as they are formed in stages during the development of fibre.
In the secondary wall, the fibrillar deposition is in helical form with frequent
reversal of the helix along the length of the fibre. These points of reversal
provide the fibre with considerable extensibility. Such helical reversals are
unique for cotton.
The next outer layer, primary wall, is less crystalline. In primary wall, the
fibrils are overlapped and crossed, providing a tougher surface structure.
The outermost layer, called cuticle, contains pectin, fats and waxes, etc. It
acts as a barrier for the entry of water carrying dyes, etc.
The high crystallinity of cotton fibres makes it a moderately strong fibre.
Cotton is stronger (by about 20%) in wet condition. Cotton is one of the
densest fibres having specific gravity of 1.54. The heat conductivity of cotton
is moderate and its physical properties are unchanged by heating at 120ºC
for a moderate period.
Cotton is not soluble in common solvents. It is soluble in aqueous
cuprammonium hydroxide and cupriethylenediamine.
Cotton is hydrolysed by hot dilute or cold concentrated acids to form
hydrocellulose, but is not affected by dilute acids at room temperature.
Partial hydrolysis of the cellulose molecule causes rupture of the long chain
at several places without actually disintegrating the structure. The –C–O–C–
group in the β-anhydroglucose ring is broken into –CHO and –OH end
groups imparting reducing power to hydrocellulose due to subsequent
tautomeric change to an aldehyde by breaking the ring structure.
Cotton has excellent resistance to alkalis. Concentrated alkali solutions
swell cotton that is utilised in a finishing process called mercerisation, but
the fibre is not damaged. Mercerisation improves lustre, dyeability and
moisture uptake of cotton materials. During mercerisation, cotton is treated
for a short time (one minute or so) with about 20% caustic soda when alkali-
cellulose is formed. After subsequent neutralisation, it is converted into
cellulose hydrate, which after loss of water, left cellulose II having a slightly
different arrangement of the glucose units within the structural cell.
Oxidising agents such as hydrogen peroxide, sodium hypochlorite and
sodium chlorite are harmless in dilute conditions, but may damage cotton
considerably in higher concentrations, and under adverse conditions form
oxycellulose. Different oxidising agents act in different ways. Alkaline
solution of sodium hypochlorite yields a product with acidic properties but of
low reducing power (in glucose ring, –O–CH– + [O] → –COOH + –OH),
while converse is the case, when oxidation is caused by acids (in glucose
ring, –CH–CH– + [O] → –CHO + –CHO, or –CH2OH → –COOH). There is
in fact no loss in tensile strength in cotton containing oxycellulose until the
chains have been broken down by alkali.
12
1.8.2 Bast Fibres

Bast fibres namely flax, jute, ramie and hemp are obtained from the stem of
the respective plants. The fibres occur between the outer bark and the
woody portion at the central part of the stem. Since the bast fibres are an
integral part of the stem structure, they are not directly available for
spinning. They must be separated first from other tissues by a process
known as retting. The object of this operation is to break down the tissues so
that the useful fibres can be separated. There are various methods like
water, dew and chemical retting. In water-retting, the stalks are tied in
bundles and covered with water in a tank until fermentation caused by
bacteria sets in and softens the stem by destruction of the less resistant
tissues, rendering the intercellular adhesive substances soluble. If the
fermentation is allowed to proceed beyond this point, the fibres themselves
will be damaged. To avoid this, the progress of retting must be observed
carefully. The danger of the damage to the fibres, because of three-week
long operation, has serious objections, but the compensating advantage is
that the cost for carrying out the process is negligible. Dew-retting is similar
to the water process but slower. The stalks are spread out on grass and
allowed to ferment, the moisture being supplied either by dew, rain or
occasional watering. Sometimes the fermentation is started by water-retting
and the stalks are then laid out on the grass to complete the process. A
better colour of jute is claimed to be obtained by this process. Chemical-
retting consists of softening the tissues by the action of acetic acid or alkali,
either at normal temperature or at high temperature. After this treatment the
degradation products are washed away with water. Chemical-retting is
considerably quicker. After completion of retting, the excess liquor is
removed by hanging or by passing through a pair of rollers followed by
drying. The retted and dried stalks are subjected to a mechanical process
called breaking. They are crushed by passing through a pair of fluted rollers.
The pressure breaks up the woody tissue into small fragments, which readily
fall away. After breaking, the crude fibres are separated from the crushed
debris by scutching. This may be done by beating the broken stalks by hand
or in a beating machine, until the fragments of woody tissue are entirely
removed.
The bast fibres are multicellular – a number of fibre units or cells are held
together by natural adhesive materials. The molecular chains are extremely
long and bamboo-like cross-markings or nodes can be observed occurring
along their length.
Flax or linen is best among the bast fibres. It is stem fibre from the woody
stalk of Linum. Oldest textile fragments still comparatively intact are made of
linen. Its use is mentioned frequently in the Bible and in the histories of the
Egyptian, the Greek and the Romans. The fibre is mainly produced in
Europe – the largest producer being the Russia. In United States of
13
America, it is mainly cultivated for the seed oil called linseed oil, an excellent
drying oil used in paints and varnishes. Mercerisation, as in case of cotton,
is not necessary as the fibre is lustrous and natural brightness can be
improved by passing the fabric through heavy calendar rollers. It is smoother
than cotton and provides excellent summer suiting because of its good heat
conductivity. The fibre is very compact and dyeing is somewhat difficult. The
strength of flax makes it superior to cotton for certain applications.
Flax fibres vary in length from 25 to 76 mm. Each fibre is composed of a
number of fibrils consisting of several cells together. The fibre has the
appearance of a straight tube with thick walls and a narrow but distinct
lumen. The end of the fibre appears to be pointed and on the outer surface
longitudinal striations are visible. The absence of natural twist, the rough
surface and jointed structure probably assist spinning. The moisture regain
of flax is 13.75 and the yarn is about 5% stronger when wet than dry.
The chemical properties of flax are similar to those of cotton. Flax has
good resistance to acids, bases and chemical bleaches. Flax is resistant to
insects and micro-organisms except under severe moist, warm conditions.
The second important bast fibre is jute – a fibre obtained from various
species of Corchorus, native to India, Pakistan and Bangladesh. They are
retted by immersion in water during periods varying from 12 to 25 days. It is
similar in appearance to flax and hemp but are characterised by the
irregularity of the lumen. This is caused by variations of the cell walls, which
are thick in some places and extremely thin in others. Chemically, jute
differs from the other multicellular fibres in containing a considerable
proportion of lignin, which usually accompanies cellulose in woody tissues.
It is not as strong or as durable as flax or hemp. The individual fibres are
very short, being about 0.1 inch (0.25 cm) long. The fibres are stiff and
moisture regain is not very high. Shredding or falling of broken fibres during
handling is very common in jute fibre. Jute fibre has silk-like lustre, but it
tends to be brown in colour due to the presence of about 13% yellow-
coloured lignin in the fibre.
Jute’s low cost, moderate strength and easy availability makes it an
important fibre for use in sacks, bags and packing material.
Hemp plant is grown extensively in Russia, Italy, France, India and China.
It is a coarser fibre than flax, darker in colour and is difficult to bleach. The
fibre is strong and durable and the strand of hemp fibre may reach six feet
or longer. The fibre is very stiff and contains considerable amount of lignin. It
is mainly used for coarser fabrics including sack material, canvas, ropes and
twines.
Ramie is often referred to as China grass as it is native to many parts of
China and some Pacific Islands. Retting is quite difficult and the fibres are
separated not by dipping in water, but by manual or mechanised pulling
followed by degumming with plain or lime-water. Ramie is a white fibre with
14
excellent strength and lustre. In fact, it is the strongest and most durable
among the vegetable fibres. The fibre is stiff and fairly coarse. The cells of
the fibre are very long and the cross-section is irregular in shape. Ramie is
useful for industrial applications and for rough furnishing fabrics.
1.8.3 Impurities in Vegetable Fibres

Vegetable fibres contain various impurities in different quantities. A few
important impurities are discussed below.
Hemicellulose
Hemicellulose is a substance with the general properties of carbohydrates
and is a mixture of a variety of compounds, the proportions of which vary
according to the source of origin. It is soluble in 18% caustic soda solution
and this suggests that it may probably have a much lower degree of
polymerisation than cellulose.
Pectic Acid and Pectin
Pectic acid occurs in vegetables as calcium/magnesium salt or pectin (i.e.
methyl pectate). They are abundant in many fruits such as apples, pears
and sugar beet. Pectic acid is a long chain polymer similar to polysaccharide
having one carboxyl group (instead of CH2OH) for every sixth carbon atom.
It consists of a polygalacturonic acid backbone, which may be partially
methylated and often has rhamnose, arabinose, galactose and xylose and
other sugar bonded on as side chains. It is insoluble in water, but soluble in
alkaline solutions.
Lignin
This substance is absent in cotton, but occurs in considerable amounts in
bast fibres and is responsible for their yellowing. It is associated with woody
tissues in plants as cementing material. The constitution is not well
established, its low hydrogen content in relation to carbon suggests that it
may be composed of aromatic nuclei. 3,4 dihydroxyphenylpropane is a
degradation derivative and is probably one of its basic structural units. It is
soluble in sodium hypochlorite or sodium chlorite solution.
Fats and Waxes
The chemical nature of fats and waxes has never been investigated
exhaustively, because the actual amounts present in the fibres are very less.
Waxes are the product of monohydric alcohols, such as ceryl alcohol,
gossipyl alcohol, montanyl alcohol, etc. While the oils can be made water-
soluble by saponification, waxes are not saponifiable but can be removed by
15
emulsification with soap at high temperature. The melting point of cotton

waxes can vary between 68 and 80°C.
Nitrogenous Compounds
These impurities are degradation products of protoplasm, which are
contained in the cell when it was still living. They are basically protein and
polypeptides. Though they are present in small amounts, they can produce
undesirable effects in finished materials. They are readily soluble in boiling
alkali.
Mineral Matters
The quantity and composition of water-soluble mineral matters vary
according to the nature of soil on which cotton is cultivated. Silicon is always
present. The metallic salts commonly present are of iron, aluminium,
calcium and magnesium. All these salts are converted into respective
carbonates when burnt.
Natural Colouring Matters
The yellow or brown colour of cotton still remains even after scouring. These
natural colouring matters can be effectively destroyed or made colourless by
oxidising bleaching agents. They are present in traces and are probably
related to the flavone pigments of cotton flowers.
The tentative compositions of various vegetable fibres are shown in Table
1.2.
Table 1.2 Chemical Constituents of Vegetable Fibres (% on dry wt.)

Constituent Matured Cotton Flax Jute Ramie
α-Cellulose 88–96.5 70.3 69.7 79.1
Hemicellulose – 18.6 13.3 14.6
Pectin 0.4–1.2 2.0 0.2 2.1
Lignin – 2.2 13.1 0.66
Fat and wax 0.4–1.2 2.6 0.5 0.3
Nitrogenous compounds 1–1.9 2.8 1.6 2.1
Ash (inorganic salts) 0.7–1.6 1.5 1.6 1.1
Others 1.7 – – –
1.8.4 Rayon Fibres

Rayon and acetate fibres are not fibrillar in structure because the natural
cellulose morphology is eliminated during the manufacturing process of
these regenerated fibres. The regenerated fibres are much weaker and
more extensible than cotton, reflecting principally the lower degree of
structural regularity and perfection, and also lower degree of polymerisation
(molecular weight) of the cellulose chains.
16
Rayons are the first man-made fibres. Several types of rayons are being
produced currently. Rayons are regenerated cellulosic fibres. They are
produced by dissolving alkali-cellulose (obtained by reaction of wood pulp or
cotton waste with caustic soda) in carbon disulphide or cuprammonium
hydroxide, passing the solution through spinnerets and then solidified by
precipitation in mineral acid solution.
Viscose is normally dope dyed or mass coloured by adding pigments to
the viscose solution before spinning. This is preferred than conventional
dyeing due to better uniformity of shades, better fastness, lower coloration
costs, etc. However, the shade range is greatly limited as compared to
conventional dyeing processes. Delustrants like titanium dioxide, fire-
resistant chemicals etc. can also be incorporated to improve the appearance
and properties of the viscose yarn.
In the regenerated fibres prepared by the conventional method, the
cellulose molecules are not very highly oriented and the proportion of the
amorphous region is large. Consequently, the fibre has poor dry strength
and very poor wet strength.
High-wet-modulus rayons or polynosic rayons are produced from high-
grade cellulose and the precipitation is carried out under milder conditions to
prevent degradation of cellulose. Cellulose sodium xanthate is prepared
from unripened alkali-cellulose and dissolved in water instead of caustic
soda solution. It is then spun from a dilute sulphuric acid solution containing
no additives. The thread is stretched three times its original length during
coagulation. It has a microfibrillar structure not very different from that of
cotton. Polynosic fibres have very high tensile strength, less extension at
break and reduced swelling in water.
The majority of viscose rayon has a serrated surface and irregular cross-
sections due to skin (higher orientation) formation during precipitation. The
viscose fibre is long and straight unless the fibre has been crimped. The
fibre is much less crystalline (30%) than cotton (70%). High-tenacity rayons
are more crystalline.
Since rayons are essentially cellulose, the properties are very similar to
those of cotton. The differences in properties are due to differences in the
degree of polymerisation, crystallinity and orientation within the fibre. Unlike
cotton, the wet strength is less than the dry strength, and the reduction in
strength after wetting is less in case of polynosic fibres.
Rayons possess greater lustre than cotton and are often delustered by
adding suitable pigments before spinning.
The chemical properties are similar to those of cotton. However, these
fibres are less chemical-resistant than cotton. Prolonged exposure to
sunlight causes degradation and subsequent loss of strength. The fibre is
less expensive and hence is used as a substitute of cotton, especially for
17
blending with synthetic fibres. Rayons are resistant to common household

solvents and to light and heat, except under extreme conditions.
Both carbon disulphide and cuprammonium hydroxide cause
environmental problems, hence attempts have been made to develop an
alternate process. As a result, lyocell fibres have been developed which are
made by regeneration of cellulose from its solution with organic solvents,
e.g., N-methyl morpholine-N-oxide (NMMO) or from cellulose carbamate
solution – a reaction product of cellulose and urea. NMMO is recovered after
spinning. A number of lyocell fibres are available in the market such as
Tencel (Courtaulds, USA), LyoCell (Lenzig, Austria), NewCell (Akzo-Nobel,
Germany), etc. The viscose fibres have a folded or serrated cross-section,
whereas lyocell fibres have a round or oval cross-section. The fibre is
homogeneous and skin-core morphology is as in viscose. The crystallinity
and orientation are higher than those of viscose. The dyeing behaviour is, in
general, like other cellulosic fibres. The dye yield for selected dyes are
higher than that of viscose, but less than that of mercerised cotton. The
substantivity towards dyes is similar to viscose.
1.8.5 Cellulose Acetate Fibres

Cellulose acetate is the first man-made thermoplastic fibre – the fibre
softens rather than decomposes or ignites when exposed to sufficient heat.
Thus, it resembles most synthetic fibres. During World War I, the solution of
the fibre in acetone was used as a protective finish for the wings of
warplanes to make them more resistant to fire and sub-zero weather.
The fibre is prepared by substituting hydroxyl groups of cellulose with
acetate groups. Acetylation with acetic acid is a very slow process. Hence,
acetic anhydride is used for the purpose along with an acid catalyst (mostly
sulphuric acid). The reaction takes about 8 hours when all three hydroxyl
groups are converted into acetate groups to form cellulose triacetate. On
partial hydrolysis by adding water to bring the acetic acid concentration to
95% and standing for about 20 hours, some of the hydroxyl groups are
regenerated and secondary acetate fibre with a ratio of 2.4 acetyl groups per
glucose residue is obtained. It is precipitated by adding excess water,
washed and dried. The mass is dissolved with three times its weight of
acetone or methylene chloride. Stirring is carried out for 24 hours for
complete dissolution and may be stored for necessary time to complete
ageing. Delustrants and pigments may be added at this stage. The mass is
then filtered and exposed to vacuum to remove air bubbles. The viscous
solution is forced through spinnerets into an enclosed chamber through
which a stream of hot air passes in the direction opposite to that in which the
yarn is moving. The solvent is evaporated and can be reused.
18
When examined under a microscope, acetate fibres show no longitudinal

striations. The cross-sections are irregular but in the shape of lobes and the
indentations are not so deep as in the case of viscose.
Both acetate and triacetate are weak fibres having low tenacity. However,
they are relatively inexpensive. High elongation at break tends to
compensate its low strength to some extent. Abrasion resistance is poor.
However, the resistance to pilling is excellent. Fabrics made from both the
fibres have excellent draping characteristics and high lustre that can be
reduced by adding delusterants. Both fibres are susceptible to attack by a
number of household chemicals. They are damaged by strong acids, bases
and oxidising bleaching agents, but are resistant to their dilute solutions.
Heat resistance is good below melting point. They can be safely ironed
below 175ºC, but direct contact with the iron should be avoided. Acetate is
used in dresses, blouses, foundation garments, garment linings, household
furnishing and speciality fabrics. Triacetate is used for sportswear and for
garments with high pleat retention.
1.9 PROTEIN FIBRES

Natural protein fibres are formed by animal sources through condensation of
α-amino acids to produce repeating polyamide units with various
substituents on the α-carbon atom. The sequence and type of amino acids
making up individual protein chains contribute to the overall properties of the
resultant fibre. Two major classes of natural protein fibres are keratin (hair or
fur) and secreted (insect) fibres. The most important members of the two
groups respectively are wool (derived from sheep) and silk (excreted by
various moth larvae such as Bombyx mori ). Wool is composed of an
extremely complicated protein called keratin, which is highly crosslinked, by
disulphide bonds from cystine amino acid residues. However, the silk fibre is
composed of much simpler secreted protein chains, which are arranged in a
linear pleated structure with hydrogen bonds between amide groups on
adjacent protein chains. In general, protein fibres are fibres of moderate
strength, resiliency and elasticity. They have excellent moisture absorbency
and static charge is not built up on them. They are fairly resistant to acids,
but are readily attacked by bases and oxidising agents. The fibres have a
tendency of yellowing in sunlight. They are comfortable under most
environmental conditions and they possess excellent aesthetic qualities.
1.9.1 Wool
Wool is a natural highly crimped protein hair fibre derived from sheep. Major
varieties of wool come from Merino, Lincoln, Sussex and other varieties of
19
sheep. Worsted fabrics are made from highly twisted yarns of long and finer
wool fibres usually blended with polyester fibre, whereas woollen fabrics are
made from less twisted yarns of coarser wool fibres.
Under a microscope, the fibre appears as a solid rod with its surface
covered with horny scales resembling fish scales. The scales project slightly
from the stem of the fibre and point slightly outwards toward the tip – the
coarser the wool, larger the scales. The wool fibre is complex in structure
and consists of three tissues arranged in successive layers from the surface
inwards – the cuticle, the cortex and the medulla. Each of these is further
subdivided by tissue differentiation.
The cuticle is formed of thin scales of hard and horny consistency. These
overlap and protrude for about one-third of their length, the end being
directed towards the tip of the fibre. The outermost layer of these scales is a
tough membrane known as epicuticle. Beneath this is exocuticle and the
innermost layer is endocuticle. The epi and exocuticles contain a large
proportion of sulphur with many cystine cross-linkages giving them high
biological and chemical resistance. The endocuticle is somewhat less
resistant.
The cellular portion just below the scales is known as cortex. About 90%
of the fibre is composed of cortical cells. Two distinct tissues can be
discerned in the cortex and they are the ortho-cortex and the para-cortex.
The electron microscope shows that the ortho-cortex has a macrofibrillar
structure, whereas in the para-cortex there are no clearly defined macro-
fibrillar boundaries, and in addition, the microfibrils seem to be packed in a
more regular pattern than those of the ortho-cortex. The central portion is
called medulla.
Wool fibre is composed of extremely complex, highly cross-linked keratin
proteins made up of over 19 different amino acids. The most important
amino acid is sulphur-containing amino acid, Cystine, which forms cross-
links through disulphide bonds (–CH2–S–S–CH2–) between adjacent chains.
Keratin differs from most other proteins because it contains about 3–4% of
sulphur.
A wool polymer is about 140 nm long and about 1 nm thick. In the normal
relaxed state, the wool polymer has a helical or spiral configuration, known
as α-keratin. Stretching the wool fibre will tend to stretch, straighten or
unfold its polymer. The unfolded configuration of the wool polymer is known
as β-keratin. The β-form will always attempt to return to α-form.
The keratin in natural wool is heavily contaminated with impurities to the
extent of 30–70%. The average composition of Australian Merino and
crossbred fleeces is as shown in Table 1.3 [5,6].
The compositions vary with the fineness of wool fibre. Table 1.4 illustrates
composition of typical wool fibres of different fibre diameters. The lower yield
20
Table 1.3 Average Composition (%) of Raw Wool Fibres [5]

Ingredient Merino Cross-bred
Fibre 49 61
*
Dirt 19 (6.3-43.8) 8 (7.9 )
Suint 6 (2-12) 8 (2.2-12.1)
Grease 16 (10-25.4) 11 (1.6-8.5)
Water 10 12
*
Bracketed values are minimum-maximum ( average) values for different
lots from ref. [6]
Table 1.4 Illustrative Compositions of Wool Fibres with Varying Diameter [7]
Diameter (µm) Æ 23 23 28 35 45
Yield (%) 63 54 72 75 87
Clean dry fibre (%) 54 45 63 66 76
Water (%) 10 10 11 12 12
Grease (%) 15 8 9 5 5
Suint (%) 5 4 12 10 7
Dirt (%) 15 30 4 7 -
V.M. (%) 1 3 1 - -
obtained from other varieties of wool with the same diameter may arise from
the presence of extra dirt or vegetable matters (V.M.) [7].
Adventitious dirt is inherently adhered with wool fibre. This is held by the
adhesive action of the grease and falls away when the latter is removed
during scouring. Fragments of vegetable substance picked up from various
sources are often collected when sheep rub their bodies against bushes.
Those may be particles of straw, seed, burr or bast fibre.
Suint is a complex mixture derived from sweat of the animal. It contains
potassium salts of fatty acids, such as oleic and stearic acids. The simple
organic acids such as acetic, lactic, butyric and valeric acids, are also found
in the free state as well as potassium salts. Amino acids like leucine, glycine
and tyrocine are also detected. These are soluble in water and can be
isolated from the raw wool by aqueous extraction.
Wool fat is derived from fatty acids and a complex monohydric alcohol,
cholesterol (C27H45OH) or its isomer, isocholesterol. The number of wool
wax acids may be as high as 138, predominantly consisting of alkanoic, α-
hydroxy- and ω-hydroxy-acids. Each group contains normal, iso (having a
terminal isopropyl residue) and anteiso (having a terminal iso-butyl residue)
series of varying chain length, with practically all the acids being saturated.
As with the wool wax acids, the number of alcohols identified has also
21
increased as analytical techniques have been improved. Thus, the number

of components of the aliphatic alcohols reported between 1955 and 1974
rose from 17 to 69. The unsaponifiable portion of wool wax consists of
aliphatic alcohols and alkane 1,2 diols, cholesterol, triterpene alcohols and a
small amount of hydrocarbons. The monoalcohols and diols consist of
normal, iso and anteiso series. Further studies showed that cholesterol and
the triterpene alcohols are the major components of wool wax alcohols.
They are present in equal amounts and together they represent about 72%
of total unsaponifiable material. The total aliphatic alcohol represents about
22% of the composition [8].
Wool fat is not truly fat, but wax, since all true fats are derivatives of
glycerol. Wool fat is a yellowish wax-like substance soluble in organic
solvent. It is difficult to saponify. When heated for a long time with alcoholic
potassium hydroxide or solution of potassium hydroxide in glycerol, it splits
up into cholesterol and the potassium salt of the fatty acid. It retains its
creamy consistency even when mixed with an approximately equal quantity
of water. Lanoline, widely used in cosmetic preparation, is a mixture of
purified wool wax with 20% water.
Dirt, water-soluble suint or dried perspiration and wool wax are removed
by scouring with soap and alkali before dyeing and printing. After separation
during scouring, wool wax is contaminated with detergent and suint and is,
therefore called wool grease, as distinct from wool wax. Wool wax melts at
37-38ºC and is soluble in chloroform, carbon disulphide, trichloroethylene,
benzene and many other organic solvents. Triglycerides of natural fats and
oils are absent.
Burrs or vegetable matters such as thorns or seed coats, which sheep
picks up during grazing, may also present. These impurities are removed by
a strong sulphuric acid treatment called carbonisation.
When all the impurities are removed, only keratin remains. It is constituted
of 19 different amino acids, the important ones being:
Glutamic acid ≅ 16.0%
Cystine ≅ 13.1%
Arginine ≅ 10.4%
Serine ≅ 9.5%
Proline ≅ 8.1%
Leucine ≅ 8.1%
It must be remembered that all these amino acids are α-amino acids and
can be represented as HN-CHR-CO-OH, the group –R, in wool may be
aliphatic, aromatic, hydrophilic, acidic, basic, heterocyclic or sulphur
containing groups.
X-ray analysis shows that the long-chain keratin molecules are organised
in orientated and amorphous regions. Unstreached and stretched wool
22
fibres show different X-ray diffraction diagrams, corresponding to two forms

known as α- and β-keratin respectively. The longitudinal repeat spacings are
0.334 and 0.514 nm respectively for the above two forms. The elasticity of
wool, together with the alterations in the X-ray diagrams, shows the
existence of a fold in the peptide chain in the unstretched state.
In the helical structure, hydrogen bonds are formed between carbonyl and
secondary amino groups in adjacent turns of the coil. In the stretched
β-form, the hydrogen bonds become intermolecular instead of
intramolecular. Mechanical tension causes the rupture of the hydrogen
bonds in the alpha helix and this may be assisted by the action of chemicals
as well as by the application of heat. The rupture of these hydrogen bonds is
the necessary preliminary to the uncoiling of the molecule for transformation.
Apart from the hydrogen bond, ionic bonds may also be present. When
carboxyl and amino groups in the branched chains are situated opposite to
each other, there is a possibility of salt linkages being formed. Salt-links
exist between pH 4 and pH 8, but are ruptured by excess of acid and alkali.
Isoelectric point is the pH at which all the acid and basic groups in keratin
are electrostatically in equilibrium. When excess hydrogen ions are present,
they will be attracted by the electronegative carboxyl ions leaving a net
positive charge on wool. At higher pH, the excess of hydroxyl group will
result in a negative charge on the fibre neutralising -NH3+ groups. The
isoelectric region of wool is between pH 4.8 and 7.
A unique feature of keratin is the existence of cystine linkage
(–CH2–S–S–CH2–) between adjacent peptide chains. The cross-links tend to
make the α form rigid and increase the amount of work needed to stretch
the fibres to the β configuration. The cystine link also has a profound effect
upon the mechanical properties of the fibre. The disulphide bond is covalent
and not very sensitive to pH, but there are a number of reagents, including
water especially in the form of steam, which can break it down.
Wool is a fibre of moderate lustre. Wool fibres possess low to moderate
strength and very high elongation at break. They have excellent resiliency
and recover readily from deformation, except under high humidity. The fibre
is highly moisture absorbent.
Wool is insoluble in all solvents except those capable of breaking
disulphide cross-links. It does not swell in polar solvents. It is stable while
heated up to 150ºC and is a good heat insulator. Wool is a self-
extinguishing fibre and burns slowly even in contact with flame.
Wool is resistant to attack by acids, but is very sensitive to weak bases
even at low concentration. Strong alkalis like sodium or potassium hydroxide
hydrolyse keratin into alkaline salts of amino acids. It dissolves in 5% boiling
caustic soda solution. Weak alkalis like ammonia, sodium carbonate, etc.,
may cause slight damage and can render the fibre less resistant to
23
subsequent processes. Initially epithelial scales are loosened giving access

to less resistant cortex, which is rapidly broken into soluble products.
The oxidising agents attack the cystine linkage, although the reaction is
unknown. It is irreversibly damaged and discoloured by dilute oxidising
bleaches such as sodium hypochlorite. Chlorine, and to some extent other
halogens break down cystine bonds. Chlorine and its compounds are
applied under controlled conditions to make wool shrink-resistant. Hydrogen
peroxide, under certain conditions, oxidises all the sulphur, with the
formation of sulphuric acid or sulphates. Reducing agents cause reductive
scission of disulphide bonds within the wool, eventually causing wool to
dissolve. Reducing agents like sodium bisulphite, are used to break
disulphide bonds and under controlled conditions, new bonds are formed.
Hence, these can be used for setting of wool fibres. Wool is resistant to
attack by biological agents such as mildew, but is susceptible to attack by
various species of moths, which are able to digest the fibre.
Wool and other keratin fibres can be set for better dimensional stability.
The setting is a process of rearrangement of various intermolecular links.
When moist wool is dried whilst under tension it will not return to its original
length. However, the stretch is not permanent. The fibres will contract again
on prolonged standing or when immersed in water. Permanent setting of
wool occurs when immersed in water at 100°C.
1.9.2 Speciality Hair Fibres

There are many important speciality hair fibres having wool-like
characteristics, which are commercially valuable, because in combination
with wool they produce fabrics with interesting property [9]. Figure 1.3 shows
the sources of such speciality fibres.
Although the speciality hair fibres have properties similar to wool, they
have some distinctive features too. For Mohair or Angora goat fibres, the
epidermal scales are only faintly visible. Consequently, the fibre is more
lustrous and more resistant to abrasion and wear. It is widely used in men’s
clothing, often in combination with wool and silk.
Cashmere wool is native to Tibet, India, Iran, Iraq, southern China and is
finer in texture than wool and is difficult to distinguish physically as well as
chemically from finer quality of sheep’s wool. Extremely fine sweaters,
infant’s wear and luxury coats may be prepared from cashmere wool.
Camel hair is mostly obtained from eastern Asia. Fibres chiefly come from
two-hump Bactrian camel rather than one-hump camel. The fibres from
different parts of the camel have different fineness. Finer grade camel hairs
are finer than Cashmere wool. For both the fibres, the epidermal scales are
more visible than wool and Mohair fibres.
24
Speciality Hair Fibres
High Grade Low Grade Fur
Goat Musk ox Camel Cow Horse Angora Common

family family rabbit rabbit
Fur hairs
Angora Cashmere Camel, Llama

goat goat Common Bactrian
goat
Mohair Camel hair Llama Alpaca Vicuña
Cashmere
Huanzo
Fig. 1.3 Sources of Speciality Hair Fibres

Llamas are camel-like in appearance, but are smaller in size and are
native to the mountains of western South America. They have coarse,
straight outer hair. The fibres are usually brown, but some are white. Alpaca,
an animal smaller than the Llama, provides very fine, silky and strong fibres.
The finest fibre producer is Vicuña, which exists in the high mountains of
Peru. The animal must be killed to obtain the fleece. Hence, the supply is
very limited.
1.9.3 Silk
Silk possesses nearly all the desirable properties of a textile fibre – strength,
elasticity, softness and substantivity for dyes. Silk has been cultivated in
China since about 2600 BC and it is probable that the uncultivated variety
was collected and used long before this date. Silk is protein-containing
secretions which are secreted as filaments by the glands of the larvae of
different species of moths [10, 11]. Mulberry silk or cultivated silk is obtained
from the moth larva, Bombyx Mori, which is commonly known as silkworm. It
shares about 80% of the worldwide silk market. Only long and considerable
experience, along with enormous patience, has lead to the success in the
cultivation of the silkworm known as sericulture. There are four stages in the
life circle of silkworm namely egg, larva, pupa in the cocoon and adult moth.
Depending on the climate and the species of the silkworm, several
generations of silkworms can be produced in a year.
The female moth lays about 400 eggs of the size of the head of a pin at a
time. After 10–14 days, the shells break and caterpillars creep forth. As the
25
caterpillar voraciously eats mulberry leaves, it grows very quickly and its
length increases about 30 times within a month. When it reaches maturity,
the caterpillar stops eating and begins to spin the silk filament forming the
cocoon. The two silk glands contain the fibroin in dissolved form, which on
emerging in the air becomes insoluble in water. The silk gum (sericin)
envelopes and binds together the two glands. About 3 days are required for
the spinning of cocoon or the elliptical enclosure around the caterpillar, and
a further 3 days for the transformation of larva. Emergence of the moth
takes about 14 days more. During this period, the insect is to be killed by
putting the cocoon into hot water.
Cocoon colour may vary from white to very bright golden-yellow, the
variation in the colour of the cocoon can also be observed in the same lot.
For better quality silk, the cocoons are to be sorted according to colour.
Similarly, cocoon shape may vary from spherical to egg shape.
From cocoon, silk is separated by reeling process. The cocoons are
soaked in hot water and then placed in water in a steam-heated basin. By
being turned regularly with brushes, the cocoons are kept submerged so
that silk gum softens. Five to ten filaments are then drawn together and are
reeled as a single thread.
The filaments of the cocoons pierced by moths as well as those of
defective cocoons cannot be reeled. Spun silks are made from such
cocoons by the methods similar to spinning of cotton fibre.
The other type called wild silk is obtained from silkworms that mostly live
in the wild on bushes and trees. The most important representative of this
type of silk spinning moth belongs to the family Antheraea or wild silkworm.
There are several such species, but only a few are used for producing silk.
In India, there are three popular wild silk varieties in use namely Tasar or
Tussah (Antheraea mylitta), Eri (philosamia ricini) and Muga (Antheraea
assamensis) silks. Cocoon of Tussar moth is about four times as large and
much harder and browner in colour than those of Mulberry silkworm. Eri silk
is similar to Tussah silk, but has a lighter natural colour. It is harder and less
lustrous than cultivated silk. It is difficult to reel the filament from their
cocoons and waste-spinning method is used. Muga silk is native to Assam
state of India. It is either white or light brown in colour.
Wild silk cocoons are produced by three different kinds of breeding
methods:
• Wild silkworms living on trees

• Wild silkworms cultivated like Bombyx Mori, but outdoors
• Partly outdoor and partly indoor
Silk is a very fine regular, translucent mono-filament fibre of high lustre,

softness and strength, and is a highly valued fibre. The filament may be up
26
to 600 metres (m) long, but averages about 300 m in length. The diameter
may vary from about 12-30 microns. The beauty and softness of silk’s lustre
is due to the triangular cross-section of the silk filament. As silk filament is
usually twisted about itself, the angle of reflection changes continuously.
Consequently, the beam of reflected light is broken, resulting in a softer,
more subdued lustre [2].
Natural silk is secreted by silkworms in the form of Bave consisting of two
separate continuous filaments of the true silk fibre. Each filament is
composed of fibroin, embedded in a surrounding sheath of sericin, also
known as silk gum. The gum amounts to about 20–30% in case of Mulberry
silk, and 5–15% in case of wild silk, the percentage is on the weight of the
bave. The gum content and quality (namely solubility) vary according to the
quality and origin of the silk. It contains fats and oils around 0.5–1% and
natural pigments 1.0-1.4%. The sericine is responsible for harsher feel of
raw silk. It is dispersed and removed by hot soap solutions to which a mild
alkali such as sodium carbonate may be added, if required. The fibroin is
much simpler in structure than wool keratin and composed of simple amino
acids like glycine (about 40%), alanine (about 30%), tyrosine (about 10%)
and serine (about 15%). No sulphur-containing amino acid like cystine (as in
case of wool) is present in fibroin. In the absence of cross-links and with
limited bulky side-groups present in amino acids, fibroin molecules align
themselves parallel to each other and hydrogen bonds are formed resulting
in a highly crystalline and oriented pleated-sheet structure. Silk fibres are
smooth surfaced and triangular in cross-section with rounded corners. To
imitate silk-like lustre, synthetic fibres with trilobal cross-section are
developed.
Except for the presence of phenylalanine and valine, sericin yields the
same amino acids as fibroin on hydrolysis. The proportions, however, are
different - about double quantity of Serine and much smaller amount of
glycine, alanine and tyrosine. Silk gum does not contain crystalline region.
Sericin dissolves in acids below pH 2.5 and in alkalis above pH 9.5. In the
raw state the silk filament looks matty. On removing sericin, silk receives its
well-known soft, elegant lustre. Raw silk comes in many shades ranging
from white to yellow, greenish to brownish. After degumming, the fibroin may
be white, off-white or creamy, depending on the variety and the extent of
degumming. The gum is not completely removed in every case. Silk yarn
may be partially degummed for certain effects. For Mulberry silk such
varieties are:
• Ecru silk where fat, waxes and about 2–5% gum are removed.
• Souple (supple) silk where 6–15% gum is removed.
• Cuite or boiled off silk which is completely degummed.
27
Fineness of silk yarn varies considerably depending on origin and number

of filaments. Silk fibres are strong with a moderate degree of recovery from
deformation.
Silk is soluble in hydrogen bond-breaking solvents such as aqueous
lithium bromide, phosphoric acid and cuprammonium hydroxide solutions.
It exhibits good heat insulating properties and can be heated up to 150ºC.
Silk exhibits relatively good resistance to organic acids, the dilute solutions
of which enhance lustre and improve scroopy handle. However it is not as
resistant as wool. In the presence of strong acids, its peptide (–CHR–
CONH–) chains break down resulting in rapid loss in tensile strength.
Silk is damaged readily by alkali solution. The degradation depends not
only on the pH, but also on the type of the alkali cation. Alkali resistance of
fibroin is greater than wool keratin. Nevertheless, it dissolves in 5% caustic
soda solution even at cold, while wool requires boiling temperature to
dissolve.
Strong oxidising agents such as hypochlorite rapidly discolour and
dissolve silk, whereas reducing agents have little effect except under
extreme conditions. Silk is resistant to attack by biological agents, but is
yellowed and rapidly looses its strength on exposure to sunlight.
Silk has the capacity to form chemical bonds with certain metal salts such
as tin chloride, which is used for weighting (increase in weight) of silk,
mostly for yarn-dyed necktie fabrics [12].
Scroop is the peculiar cracking sound produced when silk fabric is folded
together or squeezed by hand. However, this is a property acquired after
treating the material in dilute acetic or tartaric acid and drying without
washing. Silk is also easy to clean from dust and dirt as the fibre surface is
smooth and devoid of short protruding fibres. However, extreme care is to
be taken in handling the fibre during aqueous treatments, especially at high
temperature.
1.10 SYNTHETIC FIBRES

The term synthetic fibres refers to textile fibres formed by chemical
synthesis to create giant molecules. Several thousand units of simple
chemical compounds of low molecular weight add to one another to form a
long continuous chain. Such giant molecules are known as polymer and the
simple chemical constituent is known as monomer. When a variety of
monomers participate in polymerisation reaction, they are known as
comonomers. Polymerisation is the process of manufacturing polymers
through heat and pressure. Some prefer to call them as manufactured fibres
to differentiate them from natural polymeric fibres such as cotton and wool.
All synthetic fibres have some common properties such as:
28
1. All of them are thermo-plastic, i.e. the fibres soften instead of

decomposing or igniting when exposed to sufficient heat. Unless
the material is heat-set, it will shrink and creases will be formed
while ironing or during hot aqueous treatment such as dyeing.
Heat-set material is dimensionally stable. Thermoplastic fibres can
be permanently heat-set after drawing and orientation. The heat-
set fibres possess structural integrity and do not shrink up to the
setting temperature. The thermoplastic fibres or yarns can also be
texturised to give dimensional loft and bulkiness in three ways:
(i) Fibre deformation and setting at or near their softening
temperature,
(ii) Entanglement of fibres by air, or
(iii) Differential setting within the fibres or yarns.
2. Increasing temperature has two discernible effects on synthetic
fibres. At first, there is a loss of rigidity in the molecular structure,
due to breaking of hydrogen bonds in the disorganised regions
caused by thermal vibration. This is known as second-order or
glass-rubber transition. The temperature at which the transition
occurs is known as glass transition temperature or Tg. At higher
temperature, a further change occurs when the crystalline structure
breaks down and the polymer melts. Owing to lack of uniformity in
the distribution of the organised and disorganised regions, and also
variations in the degree of polymerisation, neither change is at a
clearly defined temperature. For nylon 6,6 (section 1.10.1) the
glass transition temperature varies between 50° and 80°C, and for
polyester it is between 50° and 130°C, but averages at about 80°C.
For acrylic fibres containing no comonomer, Tg is 100–110°C, but a
copolymer containing 5–10% of vinyl acetate or methyl acrylate
could have a Tg of 75°–80°C. Dye uptake by a polymer is very low
at temperature below its Tg.
3. These fibres are hydrophobic – they do not absorb moisture. The
lack of moisture absorbency results in formation of static charges
on the fibres due to abrasion and is also responsible for their poor
dyeability. Generally, they can be more quickly washed and more
rapidly dried.
4. Synthetic fibres are resistant to natural deterioration through
bacteria, mildew and insects like beetles and moths.
5. Synthetic fibres are lighter in weight, i.e. they have lower specific
gravity than natural fibres, and lighter fabrics are produced by
them.
6. Due to poor moisture absorption, the cloths made from synthetic
fibres have in general poor wearing comfort.
29
7. Due to smooth surface, the fibres are slippery causing difficulty in

sewing.
8. Many such polymers have the ability to absorb oils and greases of
both vegetable and animal origin. Unless the stains are removed
quickly, they may become permanent showing grey coloration.
9. Synthetic fibres are less flammable than natural fibres. They melt
and drip and tend to form beads instead of ashes.
10. As these fibres are manufactured under controlled conditions, they
are much purer and whiter. Only some impurities, which are added
for better spinnability or weavability, are present. Some accidental
impurities may also exist. As such, very little preparatory processes
are required before dyeing or printing of these materials.
11. Depending on the spinneret cross-section, synthetic fibres may
have different cross-sections such as round, trilobal, pentalobal,
dog-bone, hollow or crescent. There are also bicomponent fibres,
in which two polymers may be arranged in a matrix, side-by-side or
sheath-core configuration.
Synthetic or manufactured fibres, important for textile applications, belong

to three chemical groups, namely polyamide, polyester and polyacrylic
fibres.
1.10.1 Polyamide Fibre

The polyamide fibres include nylon and aramid fibres. Both fibre types are
polymers of long-chain polyamides. Less than and more than 85% of the
amide groups are attached to the aromatic rings respectively for the nylon
and aramid fibres. Nylon fibres are generally tough and durable and they
find a wide range textile applications, while fully aromatic aramid fibres are
resistant to high temperature, exceptionally strong and durable.
Aliphatic polyamides, now generally referred to as nylons, were the first
truly synthetic fibres introduced into the market in the 1940’s primarily as
replacements for silk filaments. The two most common nylons are nylon 6
and nylon 6,6, the numerals designating the nature of monomer from which
the condensation polymer is derived. In nylon 6,6 the monomer units are
hexamethylene diamine and adipic acid, the numbers indicating the number
of carbon atoms in the diamine and dibasic acid respectively. In nylon 6, the
monomer is caprolactum, which is made from the six-carbon ε-aminocaproic
acid.
In nylon 6, the amide groups are located in a continuous head-to-head
arrangement, whereas in nylon 6,6 the amide groups reverse direction each
time in a head-to-tail arrangement [13].
30
Nylon 6: [-(CH2)5CONH-]n
Nylon 6,6: [CO(CH2)4CONH(CH2)6NH-]n
Nylon 6,6 was developed in the United States, whereas nylon 6 was
developed in Europe, Japan and developing countries like India.
Nylon 6 is produced by ring-opening chain growth polymerisation of
caprolactum in the presence of water vapour and acid catalyst. It is then
melt spun at 250–260ºC. Nylon 6,6 is prepared by step-growth
polymerisation of hexamethylene diamine and adipic acid and melt spun at
280–290ºC. Both the fibres are drawn mechanically to orient the fibres
following spinning. The degree of polymerisation (DP) of nylon 6 and nylon
6,6 molecules varies from 100 to 250 units. The degree of crystallinity
depends on the degree of orientation given to the fibre during drawing.
Nylon fibres are usually rod-like with a smooth surface or trilobal in cross-
section. Multilobal or star and other complex cross-section and side-by-side
bicomponent fibres are also manufactured.
The two nylons are very similar in structure and properties. The amide
group serves as the site for moisture absorption in these fibres which makes
them reasonably hydrophilic. They also provide ionic sites for the dyes.
Nylon 6,6 has higher melting point, lesser dyeability and little harsher feel
than nylon 6. Nylon 6,6 melts at 262ºC, while nylon 6 melts at 215ºC. Nylons
are strong fibres. Recovery from stretch deformation is very good. Nylons
are stiff fibres with excellent resiliency and recovery from bending
deformation. They are of low density and are moderately hydrophilic with
moisture regain of 4–5%. Nylons are soluble in hydrogen bond breaking
solvents such as phenols, formic acid and benzyl alcohol. They have very
high abrasion resistance and find use in rope manufacturing and similar
applications, which are regularly subjected to friction.
Nylons are fairly resistant to chemical attack. They are attacked by acids,
bases, reducing agents and oxidising agents only under extreme conditions.
At elevated temperature and under sunlight, they undergo oxidative
degradation with yellowing and loss of strength.
Aramid or aromatic polyamide fibres are formed by polymerisation of
aromatic diacid chlorides with aromatic diamine in a polar aprotic solvent
such as N,N-dimethyl formamide. The meta and para-substituted benzene
dicarboxylic acid chlorides are used for Nomex (1-2) and Kevlar (1-3) aramid
fibres respectively to react with diamine. Because of the linear para
structure, the molecular chains in Kevlar are extremely stiff and can be fully
aligned in drawing operations. The resulting highly crystalline fibre is
correspondingly strong and stiff. The meta structure of Nomex does not
allow such orientation and crystallinity and the important characteristics of
this fibre are its thermal stability and flame resistance. The aromatic units
confer stiffness to the polymeric chains and limit their flexibility. Hydrogen
31
bonding between amide groups on adjacent chains and strong Van der
Waals’ interactions between aromatic rings provide a tightly packed, strongly
held molecular structure and account for the strength and thermal stability of
aramid fibres. The aramids are the strongest of the man-made fibres. The
fibres are stiff with excellent resiliency and recovery from bending
deformation. The fibres are swollen and dissolved in aprotic polar solvents
or strong acids. The aramids have very high heat and electrical resistivities,
have excellent insulating capabilities and are unaffected by heat up to
250ºC.
O O O O
C CN NH C CN NH
n n
(1-2) Nomex (1-3) Kevlar
The aramids are extremely resistant to chemical or biological attack.

Under extreme conditions and at elevated temperatures, concentrated acids
and oxidising agents may attack aramid fibres. Aramid fibres are used in
fabric applications where high strength and low flammability are important.
1.10.2 Polyester Fibre

It is the leading man-made fibre in production volume and owes its popu-
larity due to its versatility alone or as a blended fibre in textile materials. It is
extensively used in woven and knitted apparels, home furnishings and in-
dustrial applications.
Polyesters are those fibres containing at least 85% of a polymeric ester of
a substituted aromatic carboxylic acid, including but not restricted to
terephthalic acid and p-hydroxybenzoic acid. The major polyester in
commerce is polyethylene terephthalate (1-4), an ester formed by step-
growth polymerisation of terephthalic acid and ethylene glycol or ester ex-
change reaction between dimethyl terephthalate and ethylene glycol at
250–300ºC in the presence of a catalyst to a DP of 100–250. The resultant
polymer is isolated by cooling, solidified and dried. Polyester fibres are melt
spun at 250–300ºC followed by fibre orientation and stretching. The
polyester molecular chains are stiff due to the presence of periodical
phenolic groups. The molecules tend to pack tightly resulting in Van der
Waals’ forces to play, causing a highly crystalline fibre. Polyester fibres can
be highly drawn to produce a fully oriented and highly crystalline structure.
The degree of orientation can be varied over a wide range to achieve fibres
with various combinations of physical properties.
Polyester fibres are usually smooth and rod-like with round or trilobal
cross-sections. The fibre is extremely strong, relatively stiff and possesses
32
excellent resiliency and recovery from bending deformation. The fibre is

quite hydrophobic.
It is swollen or dissolved by phenols, chloro-acetic acid or certain
chlorinated hydrocarbons at elevated temperatures. The fibre exhibits
moderate heat conductivity and has high resistivity, leading to static charge
build-up. On heating, the fibre softens in the temperature range of 210-
250ºC and melts at 250–255ºC.
O O
C COCH2CH2O
(1–4) Polyethylene Terephthalate
The fibre is highly resistant to acids (both organic and mineral), bases,
oxidising and reducing agents and is only attacked by hot concentrated
acids and alkalis. It is not attacked by biological agents.
Poor dyeability and moderate flammability of polyester have resulted in
formulation of modified terephthalate esters. Introduction of sulphonic acid
group on the benzene ring of terephthalate (e.g., sodium benzene 1,3 di-
sulphonate or sodium dicarbomethoxybenzene sulphonate) leads to cationic
dyeable polyester. Halogens (e.g. bromine), phosphonate groups
substituted within the structure provide flame-retardant characteristic to the
fibre, especially if antimony oxide is present in fibre matrix.
Surface modification of polyester with hot alkali is also done in certain
commercial varieties in order to achieve silk-like softness.
1.10.3 Acrylic Fibres

The acrylic fibres include acrylic, modacrylic and other vinyl fibres containing
cyanide groups as side chains. The fibres containing more than 85% and
less than 85% acrylonitrile are known as acrylic (1–5), and modacrylic (1–6)
fibres, respectively. The remaining components or the comonomers used in
the polymerisation are methyl methacrylate, vinyl acetate or vinyl pyridine. In
general, these fibres possess a warm bulky handle, good resiliency and
wrinkle resistance. The copolymer of DP of about 150–200 is formed
through free radical emulsion polymerisation. After precipitation, it is dried
and dissolved in an appropriate organic solvent and either wet-spun by
passing through a precipitating solution, or dry-spun by passing through a
hot air chamber.
Acrylic fibres are usually smooth with round or dog-bone cross-section.
Many bicomponent acrylic fibres (i.e. two different polymers extruded
33
through the same spinneret simultaneously) are produced to provide a bulky

texturised structure on drawing.
Acrylic fibres are fibres of moderate strength and elongation at break. The
fibre is moderately stiff and possesses excellent resiliency and recovery
from bending deformation. Moisture regain is low, but higher than polyester.
Where
R
R = H, -CH3
CH2CH CH2C O O
x y
/ /
CN R n R = -COCH3, -OCCH3,
N
(1–5) Acrylics: x > 85%, y < 15%, (1–6) Modacrylics: x < 85%, y > 15%
Acrylic fibres exhibit good chemical resistance to mineral acids and
common solvents. The fibres are only attacked by concentrated acids and
are slowly hydrolysed by weak alkalis. Acrylic fibres are unaffected by
oxidising and reducing agents except for sodium hypochlorite solution at
elevated temperatures. Acrylic fibres are unaffected by biological agents and
sunlight. On heating above 200ºC, acrylic fibres soften and undergo
oxidative attack by complex mechanism with the formation of condensed
unsaturated chromophoric (coloured) groups in the fibre.
Acrylic fibres have found a wide spectrum of use where soft, wool-like
characteristics are desired. Such uses include sweaters, skirts, dresses,
suits, knitted wear, blankets, socks, carpets, upholstery, etc.
1.11 IMPORTANT FIBRE PROPERTIES

Estimates of some important fibre properties are summarised in Table 1.5
[14].
These estimates are approximate and valid in general. Significant
differences may be observed especially for synthetic fibres depending on
the manufacturing conditions.
1.12 FIBRE IDENTIFICATION

Different fibres vary in dyeing properties. Before dyeing of an unknown
material, the fibre is to be identified correctly to ensure perfect dyeing. For
correcting dyeing faults, sometimes it is also necessary to check whether
any unwanted fibre is present. The most common methods include
34
microscopic examination, solubility tests, burning characteristics, density or

specific gravity test and staining tests.
Table 1.5 Important Physical Properties of Textile Fibres

Fibre Specific Fibre Moisture Initial Tenacity Elongation
-1
Gravity Diameter Regain Modulus (gf tex ) at break (%)
-1
(mm) (%) (gf tex )
Cotton 1.5-1.58 0.014-0.024 7-8 400-740 19-46 5.6-7.1
Flax 1.5 0.016 10-12 – 19-54 3
Jute 1.48-1.5 0.02 10 – 31.5-40.5 1-1.2
Wool 1.28-1.34 0.17-0.4 14-16 210-310 11-14 29-43
Silk 1.25-1.3 0.009-0.024 10-11 750 39 23-24
Viscose 1.46-1.54 Varies 11-13 500-800 20-51 8-20
Polyester 1.34-1.38 Varies 0.4 600-1200 25-54 12-55
Polyamide 1.14 Varies 2.8-5.0 200-300 32-65 16-65
Modacrylic 1.16-1.18 Varies 1.2-2.5 600-700 18-30 20-50
1.12.1 Microscopic Identification

Longitudinal and cross-sectional views of fibres of 100–500 magnifications
may provide information about surface characteristics facilitating fibre
identification [15]. The longitudinal and cross-sectional views of different
fibres are briefly described in Table 1.6.
Figures 1.4 and 1.5 show longitudinal and cross-sectional views of various
natural and man-made textile fibres as seen under a microscope.
1. For cotton, more or less pronounced convolutions can be seen in

longitudinal view and a large variation in shape and size of cross-section
and large lumen can be seen in cross-sectional view.
2. For jute, nodes and variation in lumen diameter can be seen in
longitudinal view. Cross-sections show bundles of naturally occurring
fibres. The outlines of the ultimates are polygonal and lumens are
circular or elliptical.
3. For viscose, fibres of normal tenacity type are shown. Numerous
striations can be seen under longitudinal view and serrated outline of
the filaments can be seen under cross-sectional view.
4. For acetate rayon, bright tricel filaments or primary cellulose acetate
fibres are shown. Heavy striations can be seen in longitudinal view.
Irregularly lobed cross-sections can also be seen.
5. For nylon, two types of filaments are shown. (1) Featureless normal
nylon shows specks of delustring agents. (2) Trilobal or profiled nylon,
35
for which the cross-sections have been purposefully modified.

Longitudinal view shows broad shadow lines due to the indentation
between the lobes.
6. For acrylic fibres (Orlon type 42), the ribbon-like twist, which is the
characteristic of the fibres with a peanut-like or elongated cross-
sectional shape, can be seen in longitudinal view.
Table 1.6 Microscopical View of Various Textile Fibres

Fibre Longitudinal Cross-sectional
Cotton Ribbon shaped with periodic Collapsed tube or bean shaped,
twists called convolutions. After central channel or lumen may be
mercerisation, the fibres visible. For mercerised cotton, the
become cylindrical. cross-section is approximately
circular.
Flax, Jute Multiple fibres cemented Bundles of polygons with large
together, bamboo-like with lumen in the centre.
cross-markings called nodes.
Wool Crimped solid rod with fish-like Circular or elliptical, variable in
scales on the surface. diameter.
Raw Silk Rough filaments cemented in Triangular with rounded corners, in
pairs, separated in places. pairs.
Degummed Structure-less, like a hollow Separated fibres, triangular, rounded
Silk glass rod. corners.
Viscose Rod-like with striations Commonly serrated.
Polyester, Featureless rod-like, depends Circular or other shape depending
polyamide, on spinneret shape and on spinneret shape and spinning
and acrylic spinning conditions. conditions.
1.12.2 Solubility Tests

The chemical structure of the fibre determines its solubility in various
solvents and provides a simple but accurate identification of the fibres. The
fibres and the corresponding solvents are listed in Table 1.7.
1.12.3 Burning Test

The reaction of fibre to open flame is a useful guide in identification of fibre.
Natural fibres and regenerated fibres will burn to ashes with a characteristic
smell. Thermoplastic synthetic fibres will melt, fuse and shrink, forming hard
beads.
Cotton and regenerated cellulosic fibres like viscose will burn quickly with
the smell of burning paper, leaving little or no ash.
Protein fibres (e.g. wool, silk) burn slowly with the smell of burning hair,
leaving easily crushable black beads.
Acetate fibres burn and melt with the smell of vinegar or acetic acid,
leaving hard black beads.
36
Longitudinal View Cross-sectional View
Cotton
Jute
(bundles)
Wool
Degummed
Mulberry Silk
Fig. 1.4 Microscopic Longitudinal and Cross-sectional Views of

Various Natural Textile Fibres
Polyamide fibres form glassy beads with the smell of amine.

Polyester fibres produce irregular beads with an aromatic smell.
Polyacrylic fibres leave small hard black beads.
37
Longitudinal View Cross-sectional View
Viscose
Rayon
Acetate
Rayon
(1) (2) (1) (2)
Nylon
Polyester
Acrylic
(Orlon
Type 42)
Fig. 1.5 Microscopic Longitudinal and Cross-sectional Views of

Various Man-made Textile Fibres. Nylon: (1) Normal (2) Trilobal.
38
1.12.4 Specific Gravity Test

Fibre density or specific gravity test may be used as an aid to fibre
identification. A series of solvent mixtures of varying density may be
prepared. If the specific gravity of the fibre is greater than that of a particular
solvent mixture, it will sink and if less, it will float.
1.12.5 Staining Tests

Fibres have varying dyeing affinity for different classes of dyes. Dye
mixtures of different classes may be used to check the fibre type. Two or
more stains may be used to confirm the fibre content.
Table 1.7 Solubility of Textile Fibres in Various Solvents
Fibre Solvent
Cotton Cuprammonium hydroxide solution, 70% sulphuric acid
Flax, jute Dissolves with brown colour in 70% sulphuric acid
Wool 5% caustic soda at boil, the vapour blackens lead acetate paper
Silk 5% caustic soda solution at cold
Viscose Cuprammonium hydroxide solution, 60% sulphuric acid
Acetate Acetone
Polyester Hot m-cresol, hot o-chlorophenol
Polyamide Hot m-cresol, 90% formic/hydrochloric acid, 60% sulphuric acid
Acrylic Boiling dimethyl formamide
1.12.6 Other Analytical Tests

In addition to the above simple tests, a number of sophisticated analytical
methods are in use for the thorough characterisation of structural, physical
and chemical properties of the fibres, such as:
1. Optical and electron microscopy
2. X-ray diffraction
3. Infra-red spectroscopy
4. Ultraviolet-Visible spectroscopy
5. Thermal analysis
6. Elemental and end-group analysis, etc.
Textile materials are manufactured from fibres either obtained from nature,
or are manufactured synthetically or regenerated from naturally occurring
substances. They belong to various chemical classes and vary widely in
physical and chemical properties. For perfect coloration of textile materials
39
without hampering their physical properties, a thorough knowledge of the

fibre is absolutely essential. If the fibre is unknown, it is to be correctly identi-
fied.
There are a number of simple tests for identifying textile fibres. Besides
there are a number of sophisticated analytical methods, which may be
necessary to know finer details of textile materials.
REFERENCES
1. P.K. Chatterjee. 1988, Absorbency, In: Textile Science and Technology, Vol. 7, 2nd
Edn. (Amsterdam, Netherlands: Elsevier).
2. E.P.G Gohl and L.D. Vilensky. 1980, Textile Science (Melbourne, Australia:
Longman).
3. B.C. Goswami, J.G. Martindale and F.L. Scardino. 1977, Textile Yarns –
Technology, Structure and Application (New York, USA: John Wiley).
4. J. Park, and J. Shore. 2000, TCC & ADR 32 (1), 46-50.
5. E.R. Trotman. 1968,Textile Scouring and Bleaching (London, UK: Charles Griffin).
6. W.S. Simpson and G.H. Crawshaw (Eds.). 2002, Wool: Science and technology
(Cambridge, UK: Woodhead).
7. M. Lewin and S.B. Sello (Eds). 1983. Fundamentals and Preparation, Part A In:
Chemical Processing of Fibres and Fabrics, Vol. 1. (New York and Basel. Marcel
Dekker).
8. S. Collins and R.S. Davidson. 1997, Rev. Prog. Coloration 27, 42-58.
9. Jules Labarthe. 1975, Elements of Textiles (New York, USA: Macmillan).
10. Text Book of Tropical Sericulture, 2nd Printing. 1980. (Tokyo, Japan: Japan
Overseas Corporation Volunteers).
11. Manual of Sericulture, Reprint of FAO Agricultural Services Bulletin Series. 1987
(Bangalore, India: Central Silk Board).
12. Silk and Colour, Brochure No. 9307.00.88. 1985 (Bastle, Switzerland: Sandoz Ltd.).
13. H.L. Needles. 1986, Textile Fibres, Dyes, Finishes and Processes, A Concise
Guide (New Jersey, USA: Noyes).
14. V.B. Gupta and V.K.. Kothari (Eds.). 1997. Manufactured Fibre Technology (London,
UK: Chapman & Hall).
15. Identification of Textile Materials, 5th Edn. 1965, (Manchester, UK: Textile institute)
Chapter
Water Requirements and Treatments 2
2.1 INTRODUCTION
In a textile processing plant, water is a vital raw material not only for the
boilers supplying steam for heating and drying purposes, but also for all the
wet processes such as scouring, bleaching, dyeing, printing and finishing.
The success of these processes largely depends on the quality of the water
being used. Generally, two qualities of water are to be maintained
separately – very pure quality for feeding to the boiler, and moderately pure
quality for processing purpose.
2.2 SOURCES OF WATER

Water with a high degree of purity, is rarely obtainable from natural sources.
The mineral constituents differ in quantity and relative proportions,
depending on the source. Supplies of water may be broadly classified into
three groups [1]:
2.2.1 Surface water

It is mainly accumulation of rainwater in streams, rivers and lakes. As it
passes over the surface of the earth, it carries organic matters of varying
stages of decomposition, a part of which is converted into nitrates by
nitrifying bacteria. It also dissolves various mineral matters, depending on
the nature of the soil or rock coming in contact, or may be turbid due to their
suspensions. Generally, it contains sulphates and chlorides as well as
bicarbonates of calcium and magnesium. Decaying vegetables may
distinctly discolour surface water.
2.2.2 Subsoil water

Water, collected from shallow wells or surface springs, is actually surface
water percolated a small distance through the soil or rock. It is generally free
41
from suspension, as water is being filtered by the passage through soil. It,
however, contains dissolved organic matters. Subsoil water is often rich in
carbon dioxide arising from metabolism of vegetable life. It converts
insoluble calcium carbonates of rocks into water-soluble bicarbonates. The
impurity content of subsoil waters may vary significantly.
2.2.3 Deep well water

Water from deep wells or deep tube-wells is collected from a considerable
depth below the ground, and such water has percolated through several
layers of ground. Such water is generally free from organic matters due to
filtration and bacterial action. The mineral content, however, may be very
high because of prolonged contact with several layers of rocks and soil. It
may contain sodium bicarbonate in addition to the bicarbonates and other
salts of calcium, magnesium and iron.
2.3 IMPURITIES AND THEIR EFFECTS

Different impurities commonly present in water are grouped as [2]:
1. Suspended solids
2. Dissolved mineral salts
3. Organic and colouring matters
4. Dissolved gases
5. Bacteria and other micro-organisms
The impurities affect the following characteristics of water and are,

therefore, assessed regularly for the feed water in textile industries.
2.3.1 Turbidity and Colour

Turbidity, an optical property of water, is a measure of the extent to which
light is either absorbed or scattered by suspended materials in water. Both
the size and surface characteristics of suspended materials influence the
absorption and scattering of light through a water sample. The erosion of
soil and the presence of excessive vegetable fibres and micro-organisms
may cause turbidity. Usually, domestic and industrial wastewater contains
soap, detergent and other emulsifying agents which produce stable colloids,
and thus cause turbidity. Turbidity of water is not only aesthetically
displeasing, but also not acceptable to environmental engineers because of
the fact that the colloidal materials associated with turbidity provide
absorption sites for chemicals as well as micro-organisms that may be
harmful. Turbidity reduces the efficiency of chlorination in water treatment
42
plants and may interfere with the light penetration and photosynthesis in
natural water bodies.
For use in textile processing, water must be clear. Turbidity may be due to
large or small particles suspended in the water. The suspended matters are
undesirable as they can adversely affect the quality of dyeing and finishing
in wet processing. In boilers and cooling systems, they promote deposition
of objectionable scale and increased carry over of solids in steam.
Natural water is normally colourless. However, occasionally it possesses
objectionable colour due to dissolved or finely dispersed organic matters,
and rarely due to mineral salts. Organic matters like algae, fungi and
bacteria may build up during long storage. A tintometer may be used to
measure colour in Hazen units. Generally little is known about the
composition of such colouring matters and these may create various
problems in wet processing. Colour can also be measured in terms of
absorbance values (optical density) at several wavelengths across the
visible spectrum (at 50 to 100 nm intervals). The samples are to be filtered
through a 0.45 mm filter before measurement. A peak at 500 nm denotes a
red coloration, which usually causes public complaint.
2.3.2 Dissolved Mineral Salts

In surface and underground water, sodium chloride and sodium sulphate are
commonly present. In addition, carbonates, bicarbonates, sulphates and
chlorides of calcium and magnesium may also be present in varying
quantities. Iron salts may be present in considerable quantities, especially in
underground water. Zinc and copper salts are occasionally present in trace
quantities. Due to dissolved solids, especially calcium carbonate and
calcium sulphate, scales are formed on metal surface. Scale formation
reduces heat transfer rate as well as the thermal efficiency of the boiler
plant. More serious problems, like failure of water tube, may occur due to
overheating. Corrosion may occur due to the presence of dissolved alkalis,
acids, salts and dissolved gases like oxygen.
Iron salts are detrimental in textile processing in many ways. In scouring
and bleaching, they impart yellow tints to white goods and may cause
catalytic decomposition of bleaching agents and consequently degradation
of the textile materials. In dyeing, iron may form complex with some dyes
causing dulling of shades.
Estimation of solid content (ppm = parts per million) may be measured in
terms of Total Solids, Total Dissolved Solids (TDS) and Suspended Solids.
A known volume (100 ml) of water sample is taken in a dry weighed
evaporating disc and evaporated to about dryness preferably on a sand
bath. It is then transferred to an oven maintained at 105±5ºC and kept for
one hour. It is then cooled and weighed (g = grams).
43
6
Weight of solid (g) x 10
Total Solids (ppm) =  (2.1)
Volume of sample (ml)
The same method and formula may be used for the estimation of Total
Dissolved Solids using water after filtration.
Suspended Solid (ppm) is the difference in value of total solids and total
dissolved solids. TDS can be quickly measured by measuring conductivity of
the solution.
2.3.3 Dissolved Gases

Gases like carbon dioxide, oxygen, nitrogen, ammonia and hydrogen
sulphide are found present in varying quantities as dissolved in water.
2.3.4 Alkalinity
The bicarbonate and carbonate salts, present in water, are responsible for
the alkalinity of water. The amount of mineral acid consumed for
neutralisation of a known volume of water is denoted as index of alkalinity.
Excessive alkalinity may interfere into dyeing or finishing processes and
may corrode metallic surfaces. It may also cause foaming in boiler followed
by carry over of solid particles with steam.
A known volume (50 ml) is taken in a conical flask and phenolphthalein
indicator (4–5 drops) is added. The solution is titrated against standard
hydrochloric acid (preferably 0.1N) until the end point (pH 8.3) is reached.
The acid consumed at this stage is known as P alkalinity and is a measure
of carbonate present. If end point is reached before titration, it may be
concluded that carbonate is absent and alkalinity is due to bicarbonate
present. The sample after titration with phenolphthalein is titrated with
methyl orange until the end point (pH 3.8) is reached. The total acid
consumed is an index of total alkalinity, M, expressed as CaCO3.
ml of acid consumed x N x 50 x 103
Total alkalinity, M (as CaCO3, ppm) =  (2.2)
volume of sample (ml)
where N = normality of acid.
2.3.5 Hardness
The presence of salts of calcium or magnesium in water is responsible for
hardness of water and leads to the formation of insoluble precipitates with
soap. These may be deposited on the goods, thereby assisting soiling and
even impairing handle of the cloth. Usually they are not deposited evenly
and are one of the causes of poor levelling in subsequent dyeing. Moreover,
44
these salts may precipitate some dyes during dyeing, or form complexes
resulting in dulling of shades. Other metal salts, such as iron and strontium,
may also contribute to hardness, but they are generally present in smaller
amounts as compared to calcium and magnesium. Iron salts are, however,
very harmful in textile dyeing and are responsible for dulling of shades.
Two types of hardness may be distinguished – temporary and permanent.
Temporary hardness arises from bicarbonates, and can be removed simply
by boiling when the bicarbonates precipitate as carbonates.
Ca(HCO3)2 → CaCO3 + H2O + CO2 (2.3)
It is a contributory factor in the formation of scales in boilers, which is a
deposit, amongst other things, of calcium carbonate and magnesium
hydroxide, the latter is a decomposition product of magnesium carbonate.
MgCO3 → Mg(OH)2 + CO2 (2.4)
Permanent hardness is associated with sulphates and chlorides of calcium
and magnesium. These are highly soluble in water and expulsion of
dissolved gases makes no difference in their solubility. These require
chemical treatment for their removal. Most waters contain both temporary
and permanent hardness, but the proportion of the two varies.
Expression of Hardness
Irrespective of the salts present, hardness is expressed in terms of CaCO3.
Hardness may be expressed in degrees or in parts per million. Units of
hardness vary from country to country and some of them are listed in Table
2.1. In British usage, water of 0°–4° is soft, 4°–7° moderately hard, 7°–20°
hard and >20° very hard.
Table 2.1 Units of Water Hardness [3]

Unit(º) Definition Quantity in parts per million
American 1 grain CaCO3/U.S. gallon water 17.1 as CaCO3
British/Clark 1 grain CaCO3/U.K. gallon water 14.3 as CaCO3
5
French 1 part CaCO3/10 parts water 10 as CaCO3
5
German 1 part CaO/10 parts water 10 as CaO, 17.9 as CaCO3
6
Russian 1 part Ca/10 parts water 2.5 as CaCO3
Estimation of Hardness
The simplest method is based on titration with a standard soap solution,
which depends upon the following reaction:
2C17H33COOK + CaCO3 → (C17H33COO)2Ca + K2CO3 (2.5)
45
It follows that 2 x 282 g of oleic acid is equivalent to 100 g of calcium

carbonate.
Standard soap solution is prepared by dissolving pure oleic acid in alcohol
and made neutral to phenolphthalein by stirring into concentrated potassium
hydroxide solution until a pink colour appears, which is finally discharged
with just enough oleic acid. The solution is then diluted with a mixture of
alcohol and water (2:1). The solution is standardised against calcium
chloride. Soap solution is used, generally, to determine total hardness only.
The test method is very simple but the accuracy is limited [1].
More accurately, hardness is estimated by titration with standard EDTA
(ethylenediaminetetraacetic acid) solution (disodium salt). Buffer is prepared
by dissolving 6.75 g pure ammonium chloride in 57 ml of ammonia and
remaining water to make 100 ml. Buffer tablets may be used. Indicator is
prepared by mixing 0.5 g Solochrome Black WDFA (ICI) or Eriochrome
black T (Geigy) (C.I. Mordant Black 11, 14645) with 4.5 g hydroxylamine
hydrochloride and the mixture is dissolved in 100 ml water. The dye, blue in
alkaline solution (pH 10), forms a red complex with Ca or Mg ion. During
titration, these metals combine with EDTA in preference to forming the dye-
complex (red). Consequently, the blue colour of the dye reappears (see
section 2.5). A known volume (50 ml) of the water sample is taken in a
conical flask. Two ml of buffer and four to six drops of the indicator are
added and titrated until red or pink colour of the solution turns blue.
ml of EDTA solution used x 106
Total Hardness (as CaCO3, ppm) =  (2.6)
Sometimes it may be necessary to estimate total chlorides and sulphates.
Chloride is estimated by titration with standard silver nitrate solution (0.1 N)
using potassium chromate as indicator. The end point is judged by
appearance of an orange precipitate of silver chromate.
ml of silver nitrate x N x 35.5 x 103
–
Total chlorides (as C l , ppm) =  (2.7)
where N = normality of silver nitrate.
For sulphate determination, the water sample is evaporated to dryness
and the solid is treated with concentrated hydrochloric acid to convert it into
chlorides. The solution is again evaporated to dryness and re-dissolved with
dilute hydrochloric acid. Ammonium chloride and ammonium hydroxide are
added to precipitate metallic ions of iron, aluminium, etc. Ammonia is boiled
off and the solution is filtered. To the hot filtrate, concentrated hydrochloric
acid and barium chloride are added and kept overnight, to precipitate
46
sulphates as BaSO4. The precipitate is filtered, washed, refiltered and

ignited with the filter paper and the residue is weighed as BaSO4.
96.06 x weight of BaSO4 (g) x 106
Total Sulphates (as SO4–, ppm) =  (2.8)
233.43 x Volume of sample (ml)
2.4 METHODS OF WATER SOFTENING

There are three ways in which hardness is removed on an industrial scale –
lime-soda process, base exchange process, and demineralisation process
(i.e. removal of all dissolved salts).
In the primitive lime-soda process, hydrated lime and sodium carbonate
are added to precipitate calcium and magnesium ions as compounds of low
solubility. The method is less effective and produces a large amount of
sludge. The pH of water also changes during treatment. The method is not
useful particularly for the dyeing industry.
Both base-exchange and demineralisation processes are based on
exchange of ions by natural product, zeolites or with synthetic ion-exchange
complexes. For many uses, it is suffice to reduce hardness by exchange of
calcium and magnesium cations with sodium cation keeping anions intact.
The process, known as base-exchange process, provides soft water, but an
equivalent quantity of sodium salt will be present in the treated water. In
demineralisation process, two subsequent exchange processes are used,
one for the anions and another for the cations. The content of mineral salts
may be reduced to that present in distilled water. Four types of ion-
exchange resins are available, namely
1. Cation Exchanger
(a) Strong acid (b) Weak acid
2. Anion Exchanger
(a) Strong base(b) Weak base
The strength of the acid or basic groups is important since this will
determine the pH range over which the resin will act as a useful ion-
exchanger. Undissociated groups are effectively out of action for this
purpose. Ion-exchange materials may be regarded as insoluble
polyelectrolytes consisting of an enormous non-diffusible anion or cation and
a simple diffusible counter-ion.
Most of the naturally occurring ion-exchange minerals are crystalline
alumino-silicates. The well known naturally-occurring cation exchanger,
zeolites are hydrated silicates of sodium and aluminium with a general
formula, (Na2O)x(Al2O3)y(SiO2)z (H2O)n. Ion-exchangers are now synthesised
47
in large quantities. One of the most successful synthetic cation exchange

resins, because of its chemical stability, is cross-linked polystyrene. It is
obtained by polymerisation of a suspension of styrene in water, together
with a cross-linking agent such as divinylbenzene. The polymer is produced
in the form of spherical beads that are convenient for packing in softener
plant. It is further treated with sulphuric acid to make a product that will react
with calcium salts (Figure 2.1). This product does not allow silica built up as
in case of zeolite.
—CH—CH2 —CH—CH2 — CH—CH2 —CH—CH2 —CH—CH2 — CH—CH2
H2SO4
SO3H
—CH—CH2 —CH—CH2 — CH—CH2 —CH—CH2 —CH—CH2 — CH—CH2
SO3H SO3H
Fig. 2.1 Cation-exchange Resins from Polystyrene Cross-linked with

Divinylbenzene and Subsequently Sulphonated
The base-exchange reaction with hard water may be represented as

follows:
Ca(HCO3)2 + Na2 Z → CaZ + 2NaHCO3 (2.9)
CaSO4 + Na2Z → CaZ + Na2SO4 (2.10)
MgCl2 + Na2Z → MgZ + 2NaCl (2.11)
These reactions virtually go to completion and after hard water has
percolated through a bed of base-exchange substance, generally present in
granular form (sieved to a particle size around 1–2 mm in diameter in case
of zeolite), the water emerges with a hardness of 0.2º or even less.
However, the base-exchange capacity is limited and will eventually
become exhausted. Fortunately the process is reversible and the bed can
be regenerated by passage of a concentrated salt solution.
CaZ + 2NaCl → CaCl2 + Na2 Z (2.12)
The calcium (or magnesium) chloride and residual sodium chloride are
washed away, and the regenerated sodium zeolite compound can be used
again. The regeneration can be repeated for a large number of times until
the granules break down into powder. The regeneration is necessary after
treatment of a specific volume of water by the plant and is controlled by
frequent measurement of hardness of treated water. A cyclic procedure is
48
set up, namely softening, regeneration, water wash (to remove excess salt),
softening and so on. Between softening and regeneration, it is sometimes
desirable to backwash by passing water upwards through the bed for a short
time to remove any matter that has been filtered out by the bed. The
advantages of the base-exchange process are:
1. It yields water of zero hardness.
2. The process is very convenient and raw water can be pumped directly
through the base exchange bed to service.
3. It occupies very little space.
4. There is no sludge to be disposed off.
However, water having temporary hardness will cause sodium bicarbonate
in the softened water. If it is in excess quantity, it may interfere with the
dyeing process or lead to boiler corrosion. When the source water is
extremely hard, the base-exchange process may be costlier than the lime-
soda process.
In demineralisation process, we need an anion exchange resin too. All
soluble salts are removed. This process is useful for the treatment of feed
water used in high-pressure boilers. This is rarely done in the textile
industry, since the boilers in textile mills work at low or medium pressures.
The raw water is first passed through a bed of strongly acidic cation
exchange resin, capable of replacing cations with hydrogen ions that are
converted into respective acids.
Ca(HCO3)2 + H2Z → CaZ + H2CO3 (2.13)
CaSO4 + H2Z → CaZ + H2SO4 (2.14)
MgCl2 + H2Z → MgZ + 2HCl (2.15)
In the second stage of demineralisation, water is passed through a bed of
strong anion exchange resin, that is a hydroxyl resin capable of replacing
anions of acids converting them into water.
HCl + ROH → RCl + H2O (2.16)
H2SO4 + 2ROH → R2SO4 + 2H2O (2.17)
H2CO3 + 2ROH → R2CO3 + 2H2O (2.18)
H2SiO3 + 2ROH → R2SiO3 + 2H2O (2.19)
Weakly basic anion-exchange resins cannot remove weak acids like
carbonic and silicic acids. However, carbonic acids are unstable. A suitable
degasifier may remove carbon dioxide, evolved during its decomposition.
Groups capable of exchanging anions may, in an analogous way to the
cation exchangers, contain groups which are strong bases, e.g. -N+(CH3)3,
or weak bases, e.g., -NH3+. This may be achieved via condensation or
addition reactions. The most important anion-exchange resins are those
prepared from cross-linked polystyrene. Basic groups may be introduced in
49
a variety of ways. One method is nitration and to reduce the nitro-resin to an

amine, the basic strength of such material is, however, very weak.
Polystyrene beads can be chlormethylated by Fridel-Craft reaction using a
catalyst such as aluminium chloride and subsequently reacted with
ammonia, primary, secondary or tartiary amines (Figure 2.2). The two
amines most commonly used are trimethylamine and dimethylethanolamine.
—CH2 —CH—CH2 — —CH—CH2 — —CH—CH2 —
NH3
NR3 +
—
CH2 Cl CH2 NH3Cl
+
—
CH2 NR3Cl
Fig. 2-2 Anion-exchange Resins from Chloromethylated Polystyrene

and Subsequently Treated with Ammonia or Amines
Other vinyl polymers may also be used. Alternatively, a monomer carrying

vinyl group may be used. Vinyl pyridine and p-dimethylaminostyrene may be
polymerised with a suitable polyfunctional cross-linking agent. Such
products are weak bases, but they become strong by quarternisation.
Hydrogen-exchange (cation) resin is regenerated with the help of strong
acids such as hydrochloric acid or dilute sulphuric acid (<2%). The anion-
exchange resin is regenerated by a solution of sodium hydroxide or sodium
carbonate. Strongly basic anion-exchange resin is to be regenerated by
warm (40oC) caustic soda solution. The effluents of regeneration in the
above two cases are strongly acidic and strongly alkaline in nature and are
to be neutralised before discharge.
2.5 SEQUESTERING AGENTS

In the absence of a water softening plant in an industry, it is also possible to
reduce the unwanted interference of heavy metal ions during soaping or
dyeing by using a sequestering agent. A sequestering agent is a substance
50
that suppresses a property or reaction of metal ions without removal of that

metal from the system. The suppression of the properties of a metal relies
on the formation of a co-ordination compound of the metal with suitable
agents, generally giving rise to a chelate structure. Compounds in which the
metal is joined to two or more donor groups of a single ion or molecule are
referred to as chelate compounds. The donor molecule or legend may be
unidentate, bidentate, tridentate, etc. according to whether it forms one, two
or three covalent linkages with the metal atom.
The earliest uses of sequestering agents go back many years. Various
compounds like hydroxycarboxylic acids (e.g. citric, tartaric, etc.),
polyphosphates and aminocarboxylic acids are in use for many years.
Graham discovered polyphosphates in 1833, but commercial production
started in UK in 1932. Aminotriacetic acid was first found useful in
preventing precipitation of the insoluble salts and soaps of calcium and
magnesium in Munz (Germany) in 1935.
Nowadays three types of sequestering agents are in use, namely
1. Polyphosphates
2. Aminopolycarboxylates
3. Hydroxycarboxylates
Various polyphosphates are effective sequestering agents under

appropriate conditions. The most important polyphosphate used as a
sequestering agent is sodium hexametaphosphate, commercially known as
Calgon. The chemical structure is complex and is tentatively assigned as
Na6P6O18. It reacts with calcium or magnesium in the following way:
Na4[Na2(PO3)6] + Ca++ → Na4[Ca(PO3)6] + 2Na+ (2.20)
The calcium compound formed does not precipitate soap nor does it
confer any other properties of hard water. Others polyphosphates in use are
sodium polyphosphate, sodium tripolyphosphate, sodium trimetaphosphate
and sodium pyrophosphate.
The aminopolycarboxylates are powerful chelating agents. These are
derivatives of iminodiacetic acid, NH(CH2COOH)2, mostly sold as free acids
or as sodium salt. The most common is ethylenediaminetetraacetic acid,
known as EDTA, (HOOC−CH2)2−NCH2CH2N–(CH2–COOH)2, sold as di- or
tetra-sodium salt. EDTA forms 1:1 complexes with most cations thereby
making it a simple reagent compared with many others in which 2:1 or 3:1
complexes may be formed. The nature of complex formation during
chelation with calcium ion is shown in Figure 2.3.
It forms colourless complexes with colourless cation but, with coloured
cations, the colour is deepened, e.g. the complex with Ni2+ is blue, with Cr3+,
Co3+ and Mn3+ violet to ruby red. Complexes with divalent cations are very
51
NaOOCCH2 CH2COONa
NCH2CH2N
NaOOCCH2 CH2COONa
++
+ Ca
NaOOCCH2 CH2CH2 CH2COONa
N N
CH2 CH2 +
+ 2Na
Ca
CO CO
O O
Fig. 2-3 Chelation of EDTA with Calcium Ion

stable in slightly acidic or basic solutions, but those of trivalent metals are
stable in high acidity (pH 1-2) and some tetravalent complexes even at
pH<1. The formation of the complexes occurs almost instantaneously with
the notable exceptions of chromic, ferric and aluminium ions.
The disodium salt of EDTA crystallises as a dihydrate but the tetrasodium
salt is too hygroscopic to be prepared in pure form. EDTA can be used to
soften hard water in small quantities. It can be used during scouring of
textile materials especially for wool where huge quantities of soap are used.
It may be used in bleaching and dyeing where traces of iron or other metallic
contamination might cause damage of materials and dulling of shades
respectively.
Other useful members of this group are diethylenetriaminepentaacetic
acid (DTPA) and nitrilotriacetic acid (NTA), N(CH2COOH)3 .
NTA has very low solubility and the complexes formed with metals are not
very strong.
Also useful in certain circumstances are derivatives of these
aminocarboxylic acids, in which one or more of the carboxymethyl groups
has been replaced by a hydroxyethyl group to give a
hydroxyaminocarboxylic acid. The examples are:
(a) N-(hydroxyethyl)ethylenediaminetriacetic acid (HEDTA)
(b) N,N-bis(hydroxyethyl)glycine (DEG)
In the former compound, one such group of EDTA, and in the latter two
such groups of NTA have been substituted.
The stability of the chelated complex is generally expressed in terms of
chelating constant, which is the logarithm of the equilibrium constant of the
52
chelating reaction. A high stability constant indicates a high sequestering

effect. Among the aminopolycarboxylates, the stability constant for a
particular metal ion generally increases in the order:
NTA < HEDTA < EDTA < DTPA
Metals can also be listed in order of increasing stability constant:
Mg2+ < Ca2+ < Mn2+ < Al3+ < Zn2+, Co3+ < Pb2+ < Cu2+, Ni3+ < Fe3+
Thus Mg2+-NTA complex has the lowest, and Fe3+-DTPA the highest
stability.
The inorganic polyphosphates tend to be most efficient under slightly
acidic conditions, whilst the amino-polycarboxylates generally work best
under neutral or alkaline conditions. One disadvantage of the
polyphosphates is that at a high temperature of 100ºC or above, they
hydrolyse into simpler phosphates in aqueous solution that cannot retain the
metal atom in sequestered form and may even precipitate any sequestered
metals as orthophosphates. The rates of hydrolysis mainly depend on pH
and temperature. This is why they are used less extensively than more
versatile and stable aminocarboxylates. A structural compromise between
these two types of compounds can also give products with sequestering
property, although they are phosphonates rather than phosphates since they
contain -C-P-, rather than –C-O-P- linkages. Examples of such
phosphonated amino polycarboxylates are:
(a) Ethylenediaminetetramethylphosphonic acid (EDTMP)
(b) Diethylenetriaminepentamethylphosphonic acid (DETMP)
(c) Aminotrimethylphosphonic acid (ATMP)
These are mostly used in detergent formulations as sodium, potassium,
ammonium or alkanolamine salts.
The hydroxycarboxylic acids provide a range of sequestering agents, of
which best-known are citric acid, tartaric acid and gluconic acid, the
poisonous oxalic acid is now rarely used. They are, however, much less
important as a sequestering agent. Most di- and tri-valent ions are effectively
chelated by tartaric and citric acid in the presence of ammonia. Gluconic
acid is especially useful in caustic soda solution and as a general-purpose
sequestering agent.
In recent years, the trend is to replace EDTA and DTPA with heptonate
and gluconate.
The use of certain sequestering agents may remove metal from a dye,
which subsequently change in shade and/ or fastness properties. Metal-
complex acid and mordant dyes are obviously vulnerable, but many direct
and reactive dyes also contain such metals.
The method of estimation of hardness has been discussed in section
2.3.5. The mechanism behind the technique is that the dye, Eriochrome (or
53
Solochrome) black T is an azo dye containing two hydroxyl groups in O-O/

position. The colour of the dye changes when the two phenolic groups are
ionised. If the anion is represented by H2I n-, the dissociation of the phenolic
group may be as follows:
H2I n- (wine red) ↔ H2I n2- (blue) ↔ H2I n3- (orange) (2.21)
The pK values are 6.3 and 11.5 respectively. The solution is, therefore,
wine red below pH 6, blue between 8 and 12 and orange above 13. In dilute
solutions, the concentration of hydrogen ion is often very small. Hence,
hydrogen ion concentration in moles/litre is often expressed as negative
power of 10, i.e. - log (hydrogen ion concentration in moles/litre). This is
termed as pK value.
With calcium or magnesium, chelation occurs as follows:
M 2+ + I n3- (orange) ↔ MI n- (wine red) (2.22)
M 2+ + HI n2- (orange) ↔ MI n- + H+ (wine red) (2.23)
In the latter, the reaction is almost completed, provided the pH range is 8-
10 so that the hydrogen ion is completely removed. The above reaction is
based on 1:1 complex and is valid up to pH 8.5. At pH 9.5, it becomes 1:2
and even 1:3 at pH 12.4.
In order to determine calcium and magnesium ions in hard water, the
water is brought to about pH 10 with ammonium hydroxide. After the
indicator (dye) is added, it is titrated with EDTA. As EDTA is run, chelation
occurs until finally the metal is removed from the metal-indicator chelate due
to superior chelating power of EDTA. When this happens, the wine red
colour of the dye metal chelate disappears and the blue colour of the
hydrogen form of the indicator appears. This technique is accurate, but the
results are affected by Cu2+ and Mn2+ ions. Traces of Cu2+ will prevent
colour change, possibly due to either the chelate with copper being very
stable, or ionising so slowly that the end point is over-run. Mn2+ causes the
colour to fade. These difficulties may be overcome by the use of new
indicators, which are not affected by copper or manganese ions.
2.6 WATER CONSUMPTION

Numerous studies in ATIRA [2] show that the daily water consumption of an
average sized textile mill in India having cloth production of about
8,000 kg/day is about 1.6 million litres.
The pattern of water consumption for the various processes/plants is
illustrated in the pie chart (Figure 2.4), which shows that the highest water
consumption is in the bleaching department.
54
ATIRA norms for water consumption in various stages of textile wet

processing are shown in Table 2.2.
Others
9%
Weaving
9%
Spinning Bleaching
6% 38%
Boilers
14%
Printing Dyeing
8% 16%
Fig. 2.4 Water Consumption in a Textile Mill
Table 2.2 Water Consumption in Wet Processing [4]

Process Litres/kg of Material
Conventional Bleaching 90
Continuous Bleaching 70
Mercerising 25
Cloth Dyeing (Jigger) 45
Cloth Dyeing (Continuous) 35
Yarn Dyeing (Package) 60
Printing 100
Finishing 15
2.7 WATER QUALITY FOR PROCESS WATER

In a composite mill, ATIRA estimated that about 62% of total water
consumed is utilised by the wet processing machines, mainly the washing
machines, kiers, jiggers, soaping machines and mercerising machines. An
average sized mill requires a million litres of water per day for the wet
processing section.
The impurities like iron, calcium and magnesium salts are undesirable
since they create problem in dyeing and finishing. By using water free from
the above metallic ions, the damages in dyeing and finishing can be reduced.
Since the volume of water utilised in the wet processing of a mill is very high,
the mills generally cannot afford very sophisticated treatments like partial or
full demineralisation. The precipitation process, like soda-lime process, is
unacceptable, due to the fact the soft water available from the process
55
contains a large amount of suspended solids and occasionally the pH is very

high. Hence, the mills use simple sodium ion-exchangers for the treatment of
water.
Desirable water quality recommended by Bureau of Indian Standards [IS:
201-1964] for textile wet processing is shown in Table 2.3. An American
recommendation [5] is shown in Table 2.4.
Table 2.3 Recommended Water Quality for Textile Wet Processing [2]
Characteristics Tolerance
Colour (Hazen, max.) 5-20
Turbidity (Silica scale, max.) 5
pH 6-7.5
Total Hardness (as CaCO3, ppm) 50
Iron as Fe, ppm 0.25
Manganese as Mn, ppm 0.10
Table 2.4 American Recommendation of Water Quality for Textile Wet

Processing [5]
Characteristics Tolerance
Silica, ppm 0.5-3
Total Hardness (as CaCO3, ppm) 0-25
Total Dissolved Solid, ppm 65-150
Iron as Fe, ppm 0.02- 0.1
Manganese as Mn, ppm 0.02
Alkalinity to Methyl Orange (as CaCO3 ,ppm) 35-64
2.8 WATER QUALITY FOR BOILER USE

In majority of the textile mills, steam is generated at a pressure of about 10
kg/cm2g or less. The steam generation rate varies from about 5,000 to
30,000 kg/h depending upon the size and requirement of the processing
departments. About 80% of the mills are working with Lancashire boilers,
while the rest use either water-tube boilers or package boilers.
The impurity leads to scale formation and/ or corrosion depending on
composition of the impurity, the former, in turn, leads to overheating of water
tubes. These result in lower heat transfer rates from the metal surfaces and
also at times failure and breakdown in steam generation systems. Other
consequences of impurities are carry over of solids in steam, priming and
56
foaming. The recommended quality of boiler feed water by Bureau of Indian

Standards [IS: 1680-1976] is given in Table 2.5.
Table 2.5 Recommended Tolerance for Boiler Feed Water

2
Characteristics Pressure (kg/cm )
Below 18 18-42
Total Hardness (as CaCO3, ppm) Below 25 Below 25
Total Alkalinity (as CaCO3, ppm) (of TDS) 15-20% 15-20%
pH ≥ 8.5 8.5-9
Dissolved Oxygen, ppm - 0.02-0.05
1
Na2SO4: NaOH > 2.5 > 2.5
2
NaNO3: NaOH > 0.4 > 0.4
1 2
(Either of combination or is added to remove dissolved oxygen)
2.9 EFFECTS OF EFFLUENT CHARACTERISTICS

The effect of sewerage pollution of the water may be physical, chemical and
biological. The colour, turbidity, taste and odour are heavily affected by
contamination and the water becomes unfit for domestic consumption. The
change in pH and salt content makes the water corrosive for industrial and
boiler uses.
A variety of substances, majority of which are organic, are oxidised bio-
chemically in the receiving water bodies and thereby, reduce the amount of
dissolved oxygen (DO) available. Biodegradable organic matters are utilised
by natural micro-organisms during metabolic process as their source of food
and energy. Municipal wastewater, industrial effluents and agricultural
(irrigation) return waters are some of the sources of oxygen demanding sub-
stances. These biodegradable substances include starch, fat, protein, acid,
alcohol, aldehyde, ester, etc. The aerobic metabolism of aquatic micro-
organisms predominates when oxygen is available. The end products of
such metabolism are more or less non-objectionable. But as soon as the DO
drops, fish and other aquatic lives are threatened and in extreme cases,
killed. Subsequently in an oxygen-depleted environment, very quickly
anaerobic metabolism commences utilising the remaining food or substrate.
The end product of such anaerobic metabolism is undesirable and the
resulting odour, taste and colour reduce the acceptability and attractiveness
of water.
Non-biodegradable or refractory substances are resistant to biochemical
degradation, some of them being even hazardous. Such refractory
substances include tannic acid, lignic acid, cellulose, phenols, etc. Some
polysaccharides and benzene are non-biodegradable. Alkyl benzene
sulphonate (ABS), widely used in the manufacture of detergents, is non-
57
biodegradable, while its substitute linear alkyl sulphonate is biodegradable

and thus eco-friendly.
Nutrients include all inorganic substances required by the aquatic life
forms for their growth in macro or micro quantities. The nutrients of major
concern are nitrogen and phosphorous, while others like calcium, iron,
manganese, boron, etc., are also added to the aquatic environment. In
terms of water quality, these may be considered as pollutants when they
encourage excessive growth of aquatic plants, particularly algae. The
process of nutrient enrichment is known as eutrophication. Any uncontrolled
discharge of phosphates is likely to cause eutrophication.
Only a few natural organic substances contain halogens in their molecules
and chlorinated organic compounds are usually synthetically produced.
Because of their manifold favourable qualities, they have found widespread
acceptance in households and industry throughout the world. Unfortunately,
their environmental risk is also considerable. Most of them are resistant to
biodegradation, they are lipophilic and concentrate in fatty tissues. In
addition to being acutely toxic to human beings, many organohalides are
proven or suspected carcinogens.
The abbreviation AOX stands for adsorbable organic halogens. In the
strictest sense of the term, AOX is a measured value for organically bound
chlorine, bromine and iodine in a given substance. It cannot be ruled out that
in future fluorine compounds will also be included in the list of AOX donors.
When selecting products, textile finishers insist on being informed of the
theoretical AOX value of a product, which indicates nothing else than its
theoretically calculated halogen content.
In the early 1970s, Kuhn and Sontheimer in Germany developed the AOX
method for the analysis of organohalogens, consisting of adsorption on
activated carbon, rinsing off inorganic chlorides, pyrolysis of the
organohalogens and microcoulometry. The result is expressed in milligrams
of chlorine per litre, regardless of the actual composition (chlorine, bromine
or iodine). The AOX method was standardised first in Germany (DIN
38409H14) having the highest recovery rates and being most practicable,
this method of determination has meanwhile come into world-wide use.
Federal effluent law sets a threshold value of 100 µg/l AOX for discharge
into surface water and permits a discharge of 0.5 mg/l AOX into sewage
plants. A criticism often raised is that the AOX method does not differentiate
between hazardous and non-hazardous substances, as there is no quick
screening test for such differentiation. Bleaching is the main source for AOX
in cotton processing. Pretreatments such as alkaline boiling significantly
reduce the AOX level. AOX concentrations after bleaching are higher if the
cotton contains greater amounts of impurities. In chlorine-Hercosett
(Hercules) process of wool shrink-proofing, the AOX concentration may be
58
as high as 39 mg/l in the effluent, representing an average AOX load of

350 g/ton of wool processed. In Dichloroisocyanuric acid (DCCA) method of
shrink-proofing, the continuous process yields high AOX values due to
excess reagent and discontinuous batch processes give lower AOX
concentrations, i.e. below 10 mg/l [6].
In dyeing, reactive dyes and other dyes containing halogens in the
chromophore and/ or reactive group may increase the AOX level. In dyes,
the halogens are deliberately introduced to achieve desirable properties.
The presence of halogen atoms may affect shade, light-fastness, other end-
use fastness properties and application characteristics of dyes. It is virtually
impossible to attain the present state-of-the-art in every case exclusively
with halogen-free products. Among the reactive dyes, certain reactive
groups are based on halogenated heterocycles. A halogen atom which is
split off during covalent bond formation cannot be considered an AOX-active
halogen. The AOX value (mg Cl/l) of a residual dyebath may be calculated
as follows:
C x (100 – E) x H x 35.5
AOX = ———————————— (2.24)
10 x V x M
where C = concentration of dye in g/l
E = % exhaustion of dye
H = theoretical halogen content %
V = bath volume in litres
M = molecular weight of halogen
For a 2% dyeing in a dyebath with M:L ratio of 1:10 and 95% exhaustion
of a dye of theoretical halogen content of 5%, the AOX concentration in the
residual bath is estimated to be 5 mg/l from the above Equation. Based on
experience published in the literature, it must be assumed that discoloration
is necessary whenever the dye concentration in the wastewater released to
the treatment plant exceeds 5 mg/l.
Simple filtration reduces AOX significantly. Microfiltration yielded a
reduction up to 40%. Flocculation reduces AOX by about 50%, but large
amount of flocculating agents are required and the AOX-containing floc
would have to be disposed of or incinerated. Adsorption on charcoal is
effective but expensive [7].
According to an estimate in 1977 [8], about 40,000 to 80,000 tons of dyes
and 1,500 to 1,800 tons of pigments are discharged in a year by the textile
processing units due to incomplete exhaustion, washing operation, etc.
About 15% of total world production of colorants is lost in the synthesis and
processing of colorants. About 10–20% of dyes is lost in residual liquor due
to incomplete exhaustion. For water-insoluble pigments, the loss is only
59
1–2%. One of the major factors determining the release of a dye to the
environment is its degree of fixation on the substrate. The fixation, on the
other hand, is clearly dependent on individual circumstances and governed
by several factors including depth of shade, application method and liquor
ratio. It is, therefore, impossible to give a definite set of figures. A tentative
summary, given by Easton [9] is shown in Table 2.6.
Table 2.6 Estimated Degree of Fixation of Various Dyes on Fibres [9]

Dye Class Fibre % Fixation %Loss in Effluent
Acid Polyamide 80–95 5–20
Basic Acrylic 95–100 0–5
Direct Cellulose 70–95 5–30
Reactive Cellulose 50–90 10–50
Sulphur Cellulose 60–90 10–40
Vat Cellulose 80–95 5–20
Metal-complex Wool 90–98 2–10
Disperse Polyester 90–100 0–10
The problem of coloured effluent is mainly encountered while dyeing
cellulosic fibres, which account for almost 50% of the total fibre consumed
by the textile industry. The table shows that as much as 50% of reactive
dyes used may be lost to the effluent.
The dyes are not truly water pollutants since the biological effects are
negligible. However, some azo dyes, e.g. benzidine-based direct dyes, are
easily reduced to colourless primary organic amines, which are more toxic
than the original dyes.
The environmental problems posed by the dyes are rather moderate in
their impact, but great complexities arise due to the variation in chemical
structures and properties of a few thousand dyes in use. The problem is
enhanced by the fact that many auxiliaries used during dyeing, such as
cationic fatty acid polymers, quaternary mono-, di- and tri-alkyl ammonium
salts, are not biodegradable and are difficult to remove.
Extensive tests indicate that the dyes are generally absorbed to the extent
of 40–50% by the bio-mass and are thus partially eliminated in sewerage
plants; practically no biodegradation takes place. The large dye molecules
have high affinity for various materials and some are only sparingly water-
soluble. Porter and Snider [10] showed that most of the textile dyes are non-
biodegradable. Dyes are required to show a high degree of chemical and
photolytic stability in order to fulfil the fastness requirements of textile
materials. Due to such stability, they are not readily degraded under the
aerobic conditions prevailing in the biological treatment plant. Unless colour
is removed by chemical or physical means, it may pass with discharge water
and lead to public complaint even if the concentration of dye is as low as
60
1 mg/l. Unnatural colours like red and purple usually cause most concern –
blue, green or brown colours are less objectionable.
While coloured organic substances generally impart only a small fraction
of the total organic load in wastewater, their high degree of colour is easily
detectable and detracts the aesthetic value of streams, rivers, etc. As far as
public is concerned, the removal of colour is often much more demanded
than the removal of soluble colourless organic substances which usually
contribute more to increase BOD (Biochemical Oxygen Demand) of the
wastewater. Small quantities of dyes (less than 1 ppm for some dyes) are
visible in water and so give rise to concern. Most dyestuffs have a
mammalian toxicity low enough so that they do not cause problems.
Dyestuff manufacturing units are more polluting. Many of the dyestuff
intermediates are toxic and some are even carcinogenic. Dyestuff
manufacture involves sulphonation, nitration, reduction, aminolysis, diazo
coupling, etc., which accounts for large organic and inorganic chemical inputs.
The combination of these processes generates diverse liquid, gaseous and
solid pollutants that eventually migrate to our ecosystem.
The injurious biological effects of the wastes as listed by Ellis [11] are as
follows:
1. The suspended matters slowly settle at the bottom of rivers
destroying various plants under the sea and thereby killing fishes,
which consume these plants as food.
2. Materials having an oxygen demand reduce the dissolved oxygen
content of the stream to a point where fish cannot survive.
3. Acidity or alkalinity of the discharge water affect fish life, most of those
require a pH value of 6.4 to 8.4.
4. Fresh water fishes cannot tolerate a sudden change in osmotic
pressure due to increase in salinity. About 7,000 ppm of sodium
chloride is usually lethal to fresh water fishes.
5. Constant accumulation of toxic substances may kill the fishes. High
carbon dioxide concentration in water is also fatal to fishes.
2.10 DEGRADABILITY OF WASTES

There may be three cases of biodegradability, namely:
1. A substance may be readily biodegradable, which is easily degraded
in natural watercourses.
2. Inherently degradable substances show very good biodegradation in
wastewater treatment plant.
3. Bio-eliminable substances show good eliminability in the simulated
conditions of a wastewater treatment plant.
61
The degradability of the waste chemicals can be measured by two

parameters measuring the oxygen demanded or consumed during
degradation, namely Biochemical Oxygen Demand (BOD) and Chemical
Oxygen Demand (COD), also known as Dichromate value (DV) [1].
Under normal conditions, the oxygen absorbed by bacteria is replaced by
freshly dissolved oxygen derived from the air. The total amount of oxygen
absorbed over a period of five days at a temperature at which bacteria can
breed is a very good pragmatic measure of the objectionable nature of the
effluent. This is measured by estimating Biochemical Oxygen Demand or
BOD.
BOD is determined by estimating the dissolved oxygen in water both
before and after incubation at 20ºC for 5 days. The difference between the
two values multiplied by the dilution factor gives the BOD. A measured
quantity of the sample under investigation is diluted with well-oxygenated
water so that not more 50% of oxygen present will be absorbed at the end of
5 days. The mixture is taken in a 250 ml stoppered bottle in such a way that
no air bubble is trapped at the top. The dissolved oxygen is measured by
adding 1 ml of a saturated solution of manganese chloride, introduced by a
pipette reaching nearly to the bottom of the bottle, and similarly 1 ml of a
33% solution of sodium hydroxide containing 10% of potassium iodide is
added. Finally, the mixture is acidified with hydrochloric acid. Iodine is
liberated in equivalent quantity to that of dissolved oxygen and is titrated
with centi-normal sodium thiosulphate (0.248 M) solution, 1 ml of which is
equivalent to 0.00008 g of oxygen.
Dichromate test to measure COD is based on the amount of potassium
dichromate used in oxidising the organic matters in water. 10 ml of water
sample is taken in a flask. To avoid interference from chlorine, mercuric
chloride is added which forms complex with chlorine. Silver sulphate is also
added as catalyst to promote oxidation of low molecular weight fatty acids.
5 ml of 0.020833 M dichromate solution is added and the mixture is boiled
gently under a reflex condenser for 2 hours. After cooling, the residual
dichromate is determined by titration with standard ferrous ammonium
sulphate solution, using ferron indicator. A blank test using pure water as
sample is also to be carried out. COD can be measured much faster than
BOD. Biodegradability is the ratio of BOD and COD expressed as
percentage.
Essentially BOD is the indirect measure of total bio-degradable organic
matters in water. In spite of low precision, the test is widely used for
measuring organic matters in water because of the direct conceptual
relationship between BOD and oxygen depletion potential of the waste.
COD tests are used to quantify the total organic substances in water. In fact,
COD is the oxygen equivalent of the amount of potassium dichromate
62
required to oxidise the organic fraction of the wastes, under acidic

conditions.
If biodegradability of waste water is greater than 0.6, the waste can be
treated biologically. When the ratio is less than 0.3, other methods are
suggested for treatment. But when the ratio varies between 0.3 and 0.6,
acclimatisation of seed micro-organisms are needed for an effective
biological treatment. The acclimatisation involves the gradual exposure of
the waste in increasing concentrations to the seed or initial microbiological
population, under controlled conditions.
2.11 TEXTILE EFFLUENTS

Textile mills discharge large quantities of effluent water into public sewerage
or surface water on the open land that is to be treated up to certain
tolerance limits. An average sized mill having cloth production of about
8,000 Kg/day discharges about one million litres of effluent water per day.
The characteristics of effluent water vary widely among various wet-
processing sections. Desizing process consumes less amount of water, but
the effluents of this process is characterised by high BOD value, high TDS,
significant amount of suspended solid (mostly in colloidal form). Scouring
effluents have high BOD and COD values, high temperature (70-80ºC), pH
as high as 10-12, high cation in the form of sodium and high TDS. The
effluents from dyeing section have high temperature, high solids, high COD,
pH normally above 7 and high amount of sodium ion content.
A composite waste from an integrated cotton textile mill may contain
several chemicals, predominantly starches, dextrins, gums, glucose,
carboxymethyl cellulose, gelatine, waxes, pectins, alcohols, fatty acids,
mineral and organic acids, soaps, detergents, sodium hydroxide,
carbonates, sulphides, chlorides, sulphates, bleaching agents (peroxide and
chlorine compounds), dyes, pigments, etc. The pH varies between 4 and 12
and also the colour varies due to presence of various dyes. The actual
quantities of the various effluent parameters vary widely from unit to unit, but
tentative ranges for a few parameters reported [12] are BOD – 200-1,800
mg/l, total solids – 1,000-1,600 mg/l, suspended solids – 30-300 mg/l,
alkalinity – 300-900 mg/l, chromium – 0-25 mg/l
The characteristics of composite effluents from various textile mills have
been estimated by ATIRA [2]. The approximate range of values is shown in
Table 2.7. Another study [13] reported pollution loads of various sectors of
textile industry as shown in Table 2.8. The quantities are in mg/l. The
bracketed quantities are for wool dyeing units.
63
Table 2.7 The Characteristics of Composite Effluents Estimated by

ATIRA
Characteristics Estimated Range
pH value 6.7–9.5
Total alkalinity, mg/l 500–796
TDS, mg/l 2,180–3,600
Suspended solids, mg/l 80–720
BOD, 20ºC, 5 days mg/l 60–540
COD, mg/l 592–800
Chlorides (as Cl) mg/l 488–1,390
Sulphates (as SO4) mg/l 47–500
Calcium (as Ca) mg/l 8–76
Magnesium (as M) mg/l 7–53
Sodium (as Na) mg/l 610–2,175
Table 2.8 The Characteristics of Effluents from Different Sectors of

Textile Industry [13]
Cotton Synthetic Wool Scouring (Dyeing)
pH 8–12 7–9 3–10 (5–10)
BOD 150–750 150–200 5,000–8,000 (500–600)
4 4
COD 200–2,400 400–650 10 –2x10 (1,700–2,400)
Alkalinity 180–7,300 550–630 80–100 (240–300)
Phenol 0.03–1 – –
Oils & grease 4.5–30 – 2,000–2,500 (400–500)
SS 35–1,750 50–150 5,000–6,000 (500–700)
4 4
TDS 2,100–7,700 1,060–1,080 10 –1.3x10 (800–1,000)
Sizing agents are used to strengthen the warp yarns before weaving,
which are subsequently removed before dyeing by a process known as
desizing. Sizing units significantly increase pollution load. The fungicide,
pentachlorophenol, is used to prevent mildew formation. However, it is
prohibited in the effluent and to be largely eliminated at source. The BOD/
COD data of various sizing agents are given in Table 2.9.
Table 2.9 Pollution Load of Sizing Agents

Agents COD (mg O2/g) BOD (mg O2/g)
Starch 900–1,000 500–600
CMC 800–1,000 50–90
PVA 1,700 30–80
Polyacrylates 350–1,650 50
Galactomanans (Guar gum) 1,000–1,150 400
PET dispersions 1,600–1,700 50
Protein-based 1,200 700-800
64
While discharging into inland surface water, public sewerage and on the
land for irrigation purpose, the tolerance limits for various substances (in
mg/l, maximum permissible) and parameters commonly encountered in
textile mill effluents are specified by Bureau of Indian Standards as given in
Table 2.10.
Table 2.10 Tolerance Limits of Various Substances (mg/l, max)/

Parameters for Industrial Effluents Discharged to Various Destinations
Characteristics ISW PS AL
pH 5.5–9 5.5–9 5.5–9
Temperature, ºC 40 45 –
Suspended solids 100 600 200
Dissolved solids (inorganic) 2,100 2,100 2,100
Chloride (as Cl) 1,000 1,000 600
Sulphate (as SO4) 1,000 1,000 1,000
Sulphide (as S) 2 – –
BOD, 20°C, 5 days 30 350 500
COD 250 – –
Oil and grease 10 20 10
Lead (as Pb) 0.1 1 –
Copper (as Cu) 3 3 –
Zinc (as Zn) 5 15 –
6+
Chromium (as Cr ) 0.1 2 –
Total chromium (as Cr) 2 2 –
Residual chlorine 1 – –
Dissolved phosphates (as P) 5 – –
Phenolic compounds 1 5 –
Free ammonia (as NH3) 5 – –
Total Kjeldahl Nitrogen 100 – –
ISW – Inland surface water, PS – Public sewerage, AL – Agricultural land.
(IS: 2490, part I, 1974, amended in 1985, Bureau of Indian Standards)
2.12 CONTROL OF EFFLUENT QUALITY

Before the treatment of effluent, certain steps or precautions are to be taken
to minimise the pollution load. Some are discussed below.
2.12.1 Equalisation
Effluent characteristics like pH, temperature, BOD, alkalinity, etc. vary widely
from time to time depending on the textile wet-processes carried out at
different times. In order to even out such dynamic characteristics, the
effluents are held for duration as long as several hours (8-16 hrs) or a few
days, depending on the capacity of the treatment plant and the quantity of
65
effluent generated. Equalisation also brings about self-neutralisation of

different alkaline and acidic streams. Pollution may also be diluted when
concentrated and dilute streams are mixed together. The effluent may be
optionally screened to remove floating matters like fibres and linters before
taking into an equalisation tank.
2.12.2 Recovery of By-products

The effluent load can be reduced considerably if some of the polluting
chemicals present in the effluents can be recovered e.g., recovery of caustic
soda from mercerisation waste. Costly dyes can be recovered from the dye-
house waste by dialysis, reverse osmosis and other techniques. Heat from
the wastewater can be used for preheating, thereby reducing the
temperature of discharge water.
2.12.3 Process Modification

By suitable modification of the processes and by using more eco-friendly
chemicals, the quality of wastewater can be improved.
Using carboxymethylcellulose and polyvinyl alcohol instead of starch in
sizing, mineral acids instead of enzymes in desizing, mineral acids and
ammonium sulphate instead of acetic acid, synthetic detergents instead of
soap, emulsions instead of gums in printing, durable finishes instead of
temporary finishes, the BOD load can be reduced considerably. Dyes
having high exhaustion power minimise residual dye in the effluent.
2.12.4 Loss of Chemicals

Many a time, spillage and leakage may cause several raw materials to
spread into the drain. Reduction of such wastage will reduce the pollution
load significantly.
2.12.5 Segregation
Sometimes it is beneficial to segregate waste streams containing highly
toxic or specific chemicals that can be treated separately and more
efficiently. For example, dye-liquors from the dyeing section can be
separately treated with coagulants and/ or absorbents before they are
diluted on mixing with the main stream of discharge water.
66
2.13 EFFLUENT TREATMENT METHODS

Effluent treatment methods, also known as end of pipe treatment, can be
classified into three broad types [2], namely
1. Physical methods such as dilution, equalisation, gravity separation,

floatation, filtration, screening, sedimentation, centrifugation,
adsorption, membrane separation, etc. These treatments mostly
remove suspended, precipitated or flocculated solid particles.
2. Chemical methods like neutralisation with acid or alkali, coagulation
with alum, iron salts, etc. followed by flocculation and
sedimentation, lime treatment to reduce sodium ion in the effluent,
ion-exchange, oxidation with sodium hypochlorite or hydrogen
peroxide, reduction.
3. Biological methods consist of aerobic and anaerobic digestion,
plant absorption, percolating filters, bioscrubbers, biofiltration, etc.
to reduce BOD of the effluent within the stipulated limit.
The textile effluent treatment processes may be carried out in several
stages.
Preliminary treatment processes of dye waste include equalisation,
neutralisation and possibly disinfection.
Primary stages are mainly physical and include screening, sedimentation,
floatation and flocculation. The objective is to remove debris, undissolved
chemicals and particulate matters.
Secondary stages are used to reduce the organic load. It consists of a
combination of physical, chemical and biological methods.
Tertiary stages serve as polishing treatments such as adsorption, ion-
exchange, chemical oxidation, reverse osmosis, etc.
The most important methods followed for effluent treatments are [9]:
1. Coagulation, flocculation and precipitation methods

2. Oxidation methods
3. Adsorption methods
4. Biological methods
5. Membrane separation methods.
2.13.1 Coagulation, Flocculation and Precipitation

This should be considered as the first stage of the effluent treatment plant.
The coagulation is a process, which involves precipitation of impurities to
produce microflocs. This can be achieved by pH adjustment or by addition of
inorganic or organic coagulating chemicals. A subsequent process,
flocculation, entails aggregation of microflocs into larger agglomerates. The
67
precipitate is then removed by either floatation, settling, filtration or other

physical technique to generate a sludge that is normally further treated to
reduce its water content.
The advantages of these methods are:
• Relatively simple equipment with low capital cost.
• Rapid removal of colour.
• Significant reduction of COD and, if filtration is used, of suspended
solids.
The disadvantages are:
• Considerable volume of sludge is generated which may contain
hazardous chemicals and, therefore, enough disposal facility will be
required.
• The chemicals are to be added on a continuous basis.
• Running costs are high.
• Carry-over of synthetic polyelectrolyte, if used, can have detrimental
effects on the sewerage treatment.
The common coagulants are alum, iron salts, lime and organic polymers.
Lime is partially effective in removing polyacrylic sizes. The pH, temperature
and total dissolved solids affect the precipitation process. However, these
are difficult to control with the constantly changing composition of the waste.
Sufficient time is to be allowed for stabilisation of the precipitates.
The ancient water purification method of precipitating impurities with alum
is still successfully used on a large number of pollutants. Alum treatment
operates best when pH of the effluent is around 7.5. Therefore, for alkaline
mill effluents, alum treatment should be preceded by treatment with
sulphuric acid. A dosage of 400–500 mg of alum per litre is generally
recommended. The alum dose is generally given by addition of alum
solution from an overhead tank. Alum is unsatisfactory for the removal of
azoic, reactive, acid and basic dyes, but is good for treating disperse, vat
and sulphur dyes.
In another method, ferrous sulphate (FeSO4, 7H2O) is used. The
recommended dose is 300–400 mg per litre. If hydroxide alkalinity is
insufficient, lime is to be added. Flocs of ferrous hydroxide, Fe(OH)2 react
with dyes and other solid impurities and the mixed solid particles settle
easily in the subsequent sedimentation unit. Sometimes a mixing tank
precedes the sedimentation tank where the effluent is given intense
agitation by means of rotary agitators to mix the coagulants with the
effluents.
The additional advantage of these coagulation methods is that the BOD of
the waste is reduced considerably by removal of organic solids. However,
TDS of the effluent increases by an amount, varying from 2 to 18%.
68
There are also other types of coagulation techniques in use. A popular

treatment of wool scouring waste liquor is by treating it with concentrated
sulphuric acid. Wool fats and waxes are recovered from the coagulated
mass.
Some dyes as vat and sulphur dyes can be precipitated by oxidation and
pH adjustments. These dyes in the effluent water are present in water-
soluble reduced form. By aerial oxidation with or without catalysts such as
manganese salts, hydroquinone, etc. the dyes can be precipitated. The pH
may fall from 12 to 10 during oxidation. Often pH correction may be
required. Aeration of sulphur dyes should not be made below pH 9, to avoid
the risk of hydrogen sulphide evolution.
Recently organic polymers or polyelectrolytes have been developed for
colour removal treatments and in general, they offer advantages over
inorganics as coagulators – sludge production is much less and colour
removal is significantly improved. They are mostly cationic polymers, which
are toxic to freshwater fish in spite of low mammalian toxicity. Care must be
taken to ensure that the flocculation conditions ensure low residual polymer.
Certain polymers inhibit nitrification process, giving rise to increased levels
of ammonia in the river. The polyelectrolytes, e.g. ZETAG-MAGNAFLOC
(Allied Colloids (UK), are high molecular weight, water-soluble polymers
based on acrylamide and its coploymer. Most of the products in this range
are cationic while a few are anionic in nature. Organic substances normally
require cationic polyelectrolytes for optimum flocculation. However, prior
treatment of such substrates with inorganic coagulants such as aluminium or
ferric salts or lime, may radically alter this situation. Highly biological sludges
usually react most favourably to highly cationic polyelectrolytes. Inorganic
substrates normally require anionic polyelectrolytes for optimum flocculation.
The use of organic polymers offers a potentially attractive short-term
improvement of problem relating colour. However, serious problems of
nitration inhibition and fish toxicity may arise, adequate data are not yet
available.
2.13.2 Oxidation Techniques

Oxidative processes are currently being used in the industry for discoloration
treatments of wastewater, for sterilisation of water and for biological
treatments. A variety of oxidation techniques can be used to decolourise dye
wastes. These oxidative processes for wastewater treatment comprise
biological, UV (ultraviolet) irradiation, incineration and wet oxidation (low
pressure/ high pressure) and oxidation with sodium hypochlorite, hydrogen
peroxide, ozone and nitric acid.
In wet-air oxidation, the aqueous mixture is heated under pressure in the
presence of air, which oxidises organic materials. The oxidation products
69
are generally less complex and can be treated by conventional biological

methods. The efficiency depends on reaction time and temperature. The
reactors usually operate at 180–320°C under pressure of 350–3,000 psi.
Complete oxidation may not be necessary for discoloration. The oxidation
may be partial in which the conjugated bonding system in the chromophore
is destroyed forming colourless compounds. The total oxidation of the
organic materials may also be carried out to form carbon dioxide and
inorganic ions. However, a huge quantity of oxidising agent is required in the
latter method and is, therefore, uneconomical in most cases. Nearly all
oxidation processes take place via free radical mechanisms and as such, it
is difficult to have control on the reaction once it is started. Partial oxidation
may result in unknown products, which are more harmful to the
environment.
Chlorine, in the form of sodium hypochlorite, can decolourise many
dyebaths efficiently, but not all. It is a high redox potential oxidant with a foul
odour and corrosive effect and is stable only at high pH. Water-soluble dyes
such as direct, acid and reactive dyes are decolourised, but not water-
insoluble disperse dyes. It is a low cost technique. However, excess chlorine
may react with organic materials in the effluent forming absorbable
organohalides (AOX), which are objectionable above certain limits. Further
dechlorination of wastewater may be necessary in order to prevent toxic
effects in the ensuing biological processes.
Chlorine dioxide is less reactive than chlorine and gives rise to fewer side
reactions. It is highly effective against reactive, direct, disperse and
premetallised dyes and can be used as a polishing (or secondary) treatment
(treatment time: 30 minutes). However, it has no effect on some dye classes
such as vat dyes.
Hydrogen peroxide is a stable product, which does not require any special
storing equipment. As it is totally soluble in water, less care is required for
application as compared to other oxidative chemicals. Unlike hypochlorite, it
has no biological toxicity. However, it is costly and due to slower reaction, a
large amount of space is required. It alone cannot decolourise dye waste at
normal temperature and pH. In acid solution with Fe (II) (Fenton’s reagent)
as a catalyst, the peroxide forms vigorous hydroxyl radicals, which have
higher oxidation potential than both that of ozone and hydrogen peroxide.
H2O2 + Fe++ Æ Fe+++ + OH¯ + •OH (2.25)
It may be used to discolour dye wastes. The process is more environment-
friendly and produces very little sludge.
Fenton’s reagent can be used for soluble dyes like reactive dyes and
insoluble dyes, such as vat and disperse dyes, for both concentrated and
dilute wastes. However, many disperse dyes (such as blue dyes) cannot be
70
decolourised by Fenton’s reagent and most disperse dyes require higher

amounts of hydrogen peroxide and iron salt. This is most successful for
treating concentrated colour waste such as pad liquors and has potential as
a first-stage treatment. The vigorous oxidation also reduces the COD of the
effluent. Neutralisation after treatment precipitates iron oxide and hydroxide
along with residual insoluble dyes, which are adsorbed and/ or flocculated.
The disadvantage of the process is that it forms greater iron/ lime sludge.
In photochemical oxidation process, hydrogen peroxide is added to the
effluent followed by irradiation by ultraviolet light in a photochemical reactor.
The ultraviolet light reacts with peroxide forming hydroxyl radicals, which
oxidise organic compounds. Part of the ultraviolet light can directly break
bonds in those compounds. The oxidation is complete – the process does
not produce any harmful compounds.
Ozone is a very powerful oxidising agent, which decolourises dye wastes.
Ozone is to be generated on site and its toxicity to the operating personnel
must be taken into consideration.
In ozone discoloration, the COD decreases while AOX remains
unchanged. However, there is a risk that the inorganic chloride ions could
lead to halogenation reactions and thus increased AOX concentration. A
high COD reduces effectiveness. Ozone reaction is highly selective.
Nitrogen bound in the azo dyes is oxidised to elemental nitrogen, which will
escape from the system in that form. No toxic aromatic amine is formed from
the azo dyes. Water-soluble direct, acid, reactive dyes and water-insoluble
disperse dyes are decolourised by ozone as are the dyes containing azo,
anthraquinone and phthalocyanine chemical groups.
In the presence of catalysts (e.g. titanium dioxide), UV irradiation may be
used for discoloration of textile waste. UV irradiation may be combined with
ozone and hydrogen peroxide. The latter combination can degrade disperse,
direct, vat, reactive and metal-complex dyes in approximately 3-10 min. The
technique is both environmentally friendly and easy to apply. However, its
high costs make it prohibitive.
Oxidative and more recent photooxidative techniques of discoloration of
textile wastewater are both promising but both need further improving. The
techniques should be applied before biological treatments since the reaction
products are biodegradable. Photooxidative techniques are advisable for the
removal of noxious and recalcitrant chemicals as these techniques detoxify
all chemicals besides dyes, especially toxic chemicals such as surfactants,
carriers, pesticides etc. which may be present in textile wastewater.
However, the method is costly and has several drawbacks such as radiation
hazards [14].
71
The advantages of oxidation techniques are:
• Low sludge generation and consequently lower cost for sludge

removal and disposal.
• Partial oxidation is economical and involves low capital and running
costs.
• Total oxidation generates only carbon dioxide and inorganic salts.
• The process is extremely rapid, resulting in lower equipment size
and costs.
• Total oxidation with hydrogen peroxide and ozone is highly
expensive.
• Oxidation reduces carbon loading only and increases inorganic
materials in the effluent.
• All such techniques require a sludge-producing pre-treatment (e.g.
coagulation or biological) for efficient performance.
• Partial oxidation may produce by-products, which are more harmful
than those present in the original effluent.
2.13.3 Adsorption Methods

Various adsorbents such as activated carbon, inorganic substances with
high surface area, synthetic ion-exchangers, natural and synthetic
bioadsorbents, can be used for treatment of dye effluents. For maximum
efficiency, the concentration of impurities in the feed stream should be as
constant as possible to avoid the release of adsorbed material back into the
stream if the concentration falls. For multicomponent mixtures, the strongly
bound species may displace more weakly bound components.
Activated Carbon
Activated carbon is the original absorbent used to absorb dye molecules.
This is available in granulated and powdered form. The former is used in
columns through which effluent is passed. The powdered form is dosed as
slurry into effluent stream for subsequent removal and disposal. Most of the
dyes are adsorbed by activated carbon, but the required contact time varies
from a few minutes to an hour.
Activated carbon has the capacity to remove organic chemicals and dyes
from wastewater. Limited success has been achieved with highly soluble
compounds like salts, alcohols, acids, etc. and also with poorly soluble
compounds like pigments. Medium weight organic compounds like dyes,
detergents, etc. are best absorbed by the carbon particles. 5 g/l of activated
carbon is claimed to convert a coloured mill wastewater into colourless
72
water. Suspended solids should not be more than 50 ppm. Carbon is

reactivated by heating at 170ºC. High-temperature regeneration process
may be uneconomical for small users. On the other hand, disposal, if done,
is to be made in a protected site to avoid further pollution in other
watercourses. Activated carbon does not remove inorganic components
from the effluent stream. Hence, the treated water cannot be used for
recycling. Considering cost and merits-demerits of the treatment, the
process is not very attractive for large-scale application. However, it may be
used economically as final polish to a multistage effluent plant.
Carbon adsorption method reduces about 80% of the organic load.
Combination with biological method is mutually beneficial. Simple organic
compounds like acids and alcohols have low affinity for carbon in aqueous
medium, but are effectively eliminated by the biological method. On the
other hand, dyes and other poor biodegradable products can be efficiently
adsorbed by carbon. Similarly, adsorption and coagulation methods can be
combined. When removal of surface-active agent was attempted in a
particular case, 200 ppm of aluminium sulphate was required to give a good
floc. However, after carbon treatment, only 30–50 ppm was required. The
sludge volume was reduced by 75–85%, facilitating sludge handling. This
combined process helps removal of disperse dyes, pigments and vat dyes
from a dye-house wastewater, as they are not effectively removed by
carbon.
Inorganic Absorbents
Inorganic absorbents like high-surface-area silica, cinder ash, clays, etc. can
be used for treatment of dyes in the effluent and their efficiency depends on
the ionic charge of the dye. Silica is reasonably effective for positively
charged basic dyes, but inactive for negatively charged reactive dyes.
Cinder ash is also inactive for reactive dyes, but is very cost-effective, if
available locally. These absorbents are mostly ineffective for inorganic
substances in the effluent.
Clays are hydrous alumina silicates. Bentonite is abundantly available and
is inert in nature. For clays, the pH of the incoming effluent is to be adjusted
to 6.5–7 and after treatment with clay, the pH is further adjusted to 10.
Regeneration of inorganic absorbents is simple and can be carried out by
several techniques. Biomass may be allowed to grow in the bed using
organic pollution load as a food supply.
Synthetic Ion Exchangers
Hundreds of ion-exchange resins are marketed throughout the world. As
discussed earlier, those are broadly classified as cation and anion exchange
materials, which contain fixed anionic and cationic groups respectively.
73
Deionisation is achieved by a combination of cation and anion exchange

resins. The method removes most of the mineral constituents more
completely than distillation. The degree of purification is generally measured
by determining the conductivity of the deionised effluents. Production of
effluent conductivity, as low as in pure water, requires a mixed bed
containing a strong acid cation exchange resin and a strong base anion
exchange resin. Water having mineral constituents above 1,000 ppm seems
to be uneconomical. Partial deionisation is a probable alternative.
Since most dyes are ionic in nature, they could in theory be removed by
ion-exchange resins. However, conventional resins are selective for small
anions and cations. Macroporous resins are reported [9] to be effective for
removal of larger organic ions rather than the smaller inorganic ions. The
regeneration may be carried out with organic solvents like methanol, which
may be subsequently recovered and recycled leaving behind a solid, mostly
organic mass.
Bioabsorbents
Among the oldest methods for treatment of wastewater is the use of
adsorbents derived from biological matters or biomass. Because of its low
costs and widespread availability, biomass has often been tried for effluent
treatment. The term biomass includes a wide range of materials, dead plant
and animal matters, agricultural, forest, fermentation and shellfish by-
products.
Bioabsorbents are naturally occurring polymers (or their synthetic
derivatives) which are biodegradable and can adsorb substances or can act
as ion-exchangers. One such product is chitin, poly 2-acetamido-2-deoxy-d-
glucose (C5H13NO5)3, a complex organic substance, very similar to cellulose
but contains nitrogen. It is a white flaky material, which is insoluble in water,
dilute acids, cold alkalis and organic solvents. It forms an essential part of
the shells of shellfish like prawns, crabs, etc. and insects. It is also found in
some fungi. Chitosan is a derivative of chitin, obtained by deacetylation. It
also remains in small quantities as impurity in chitin. Several studies have
been made [9] and chemical instability and long time required for equilibrium
are reported. The material is suited only for anionic or weakly anionic dyes.
A direct relation exists between chitosan concentration and quantity of dye
removed, hence it is the principal component for dye removal. Low pH is
required, suggesting that chitosan acts as a weak-base anion-exchanger.
However, at pH 3–4, chitin is chemically unstable and produces carboxylic
acids and significant quantities of nitrites and dissolved total organic carbon
(TOC). Therefore, the bed life will be limited. Moreover, at low pH, there is a
risk of emission of toxic or harmful gases due to interaction of the acid with
other effluent components such as sulphides or chlorinating agents. With
74
increase in temperature, adsorption of small-molecule dyes decreases while

that of bulky dyes increases.
The adsorbent can be regenerated by an alkaline wash. The concentrated
dye solution thus obtained is to be coagulated and settled into sludge.
Other than chitin/chitosan, biomasses for colour removal include fungal
and microbial biomass, rice hull, unmodified lignocellulose, etc.
Fibre-based Synthetic Bioabsorbents
Cellulose-based ion-exchange materials have been developed which have
the following advantages:
• They have higher chemical resistance and do not produce nitrite
under operating conditions.
• Their exchange capacity is higher than natural bioadsorbent chitin
and need not to be loaded under acidic condition.
• Both anion and cation-exchangers have been made, hence, the
whole range of dissolved dyes can be treated.
• They can be regenerated a significant number of times.
• Tailor-made product can be made to suit a given application.
• Synthetic cellulose-based adsorbents are extremely useful in
removing colour for those sites having insufficient space, but there is
a requirement for off-site regeneration and treatment of colour
concentrate produced.
2.13.4 Biological Treatments

The method is based on the fact that certain varieties of bacteria degrade
selected organic compounds into simpler compounds through metabolism.
This may occur under aerobic (presence of free oxygen) or anaerobic
(absence of free oxygen, reduction process) conditions. It is important that
the type and concentration of metallic substances (e.g. Zn, Cu, Cr) and
conditions such as pH (preferably below 7), temperature (preferably below
35°C), and so on, that kill off the organism population are carefully
controlled.
Conventional biological treatment systems are based on activated sludge
approach for reducing BOD and COD within textile effluent. In aerobic
treatment processes, liquid wastes are fed into a reactor containing a
microbial population. Air is supplied to provide oxygen to enable the
microbes to respire, metabolise the organic molecules and grow. Various
reactor configurations are used which at maintaining a high concentration of
microbes to maximise the digestion rate. Options include using immobilised
microbes as trickling filter beds or recycling a portion of the microbes
produced as in activated sludge processes. The organic components of
75
wastewater are metabolised essentially into carbon dioxide, water and

biomass. The biomass is removed from water as sludge. Some non-
metabolised components are also removed by adsorption on the sludge.
The decomposition and bacterial growth are high. The rate of digestion can
be improved by deep shaft technology, where compressed air is effectively
used to increase oxygen concentration and biomass respiration efficiently.
One major disadvantage of aerobic digester is that it generates a
considerable amount of sludge. The treated water may still contain a
significant amount of colour and require further polishing treatments. Dyes
are poorly degradable by this process. However, their adsorption on the
micro-organisms is possible so that they can be removed from the water
with the sludge. The sorptive removal of dyes is often referred to as
bioelimination. It varies widely from dye to dye, with no clear structural
correlation to explain their behaviour. Highly water-soluble acids and
reactive dyes are poorly adsorbed, while direct, basic and disperse dyes are
adsorbed in the high to medium range.
In the anaerobic process, which widely occurs in nature, organic
substances are degraded mainly into gaseous substances (principally
methane or carbon dioxide) and smaller amounts of solid end products than
in the case of aerobic digestion. Microbial population, which exists in
anaerobic digestion systems, is different from those of aerobic systems and
are sensitive to oxygen. A series of metabolic reactions occur in the
absence of oxygen by at least three different groups of bacteria. Since not
all bacteria grow at the same rate, the rate of incoming flow to the digester is
to be carefully controlled. The process has the following advantages:
• Low energy requirement, since no oxygen is to be introduced.
• Less sludge is formed.
• The resulting biogas can be used for heating purposes.
• Under anaerobic conditions, even difficult-to-degrade substances,
such as synthetic dyes, can be biodegraded.
It does not, however, reduce BOD to the low levels achieved by aerobic
digestion.
However, the main disadvantage is that anaerobic degradation is much
more sensitive to disturbances than the aerobic type and is very expensive
to install. The treatment may be restricted where energy recovery is
attractive or to remove critical wastes as pretreatment prior to aerobic
treatment. Anaerobic digestion has been tried for the treatment of wool
scouring effluents with pesticide removal greater than 80% and COD/BOD
removal between 70% and 90%. Nutrient requirements are minimal but the
performance suffers as steady conditions are difficult to achieve [12].
A large number of intermediate products, like various organic acids and
lower alcohols, are formed by biodegradation from carbohydrates, fats and
76
proteins. Nitrogenous materials degrade into amino acids and ammonia.

The gases formed are primarily methane, hydrogen, carbon dioxide and
hydrogen sulphide [8].
Dyes usually have a synthetic origin and complex aromatic molecular
structures that make them more stable and more difficult to biodegrade. A
wide range of micro-organisms including bacteria, fungi, and algae are
capable of efficiently decolourising a wide range of dyes. Among these
micro-organisms, fungal biomass can be produced cheaply using relatively
simple fermentation techniques and inexpensive growth media. Fungal
biomass, which would otherwise be a nonessential product of various
industrial fermentation processes, can also be used to remove dyes from
dyehouse wastewater. Most research work to date has concentrated on
living fungi for biodegradation and biosorption of the dyes. A study [15]
showed that dead fungal biomass of Aspergillus niger is effective in
removing Acid Blue 29 from aqueous solution. The biomass was pretreated
with sulphuric acid at pH 4.0 for 24 hours. It was then washed thoroughly to
bring pH to 6.0.
Several enzyme preparations from various fungi have been observed [16]
to decolourise triarylmethane, azo, anthraquinone, indigo and metal chelate
dyes. In all preparations, laccase was a predominant enzyme, but lignin
peroxidase and/ or manganese peroxidase was also present. All were most
active at 50°C and pH 5.0. The discoloration efficiency depended on the
source of enzyme and the substrate (dye). The absence of unsubstituted
hydroxyl or amino group on the aromatic rings in C.I. Acid Violet 17 and C.I.
Basic Red 9, were beneficial for initial attack by phenol oxidases. This is in
agreement with the general catalytic mechanism of laccases, which catalyse
the abstraction of a hydrogen atom from the hydroxyl group of mono- and
poly-phenolic substrates and from aromatic amines. Similarly, the azo dye,
C.I. Acid Orange 5 degraded to a lesser extent than C.I. Direct Blue 71 and
C.I. Reactive Black 5. The nature of substituents on the aromatic ring has
been shown to influence enzymatic degradation. Methyl and methoxy
substituents enhance while electron withdrawing chloro, fluoro and nitro
substituents inhibited oxidation by a laccase. With anthraquinone dyes, no
such general trend was observed. Some anionic and cationic auxiliaries
tend to denature enzymes.
Some white rot fungi (lignin peroxidase, manganese peroxidase, and
laccase) have the ability to decolourise textile dyes and the composition of
the media affects the result. Fungi can decolourise dyes faster in nitrogen-
limit medium than in nitrogen-sufficient medium [17].
Azo dyes, even with several azo groups in their structure, are readily
decolourised by anaerobic biomass. The removal was not affected by the
type of dye used, even at high concentrations. The dispersing agents did not
77
seem to affect the removal of the organic load in any significant way.
Anaerobic digestion should be implemented to remove anionic azo dyes and
the subsequent colour produced by them. The compounds are reduced to
aromatic amines, which can be later degraded by an aerobic treatment.
Anthraquinone dyes can be removed in 2 or 3 days at a very low
concentration (35 mg/l) in order to avoid inhibition of the biomass or else to
be removed previously by coagulation or flocculation [18].
Two biological treatments are most common − activated sludge process
and biological filtration.
In activated sludge process, the effluent is mixed and aerated with a
flocculent suspension of micro-organisms, called activated sludge, which
predominantly consists of a variety of bacteria. Activated sludge is produced
in sewerage works by continuously recirculating sewage through aeration
tanks. The mixed liquor then flows to a settling tank where the activated
sludge is separated before being recycled to mix again within the incoming
waste. The bacteria feed on the impurities in the wastewater and in a
properly working plant, the overflow from the settling plant is clear and is
suitable for being discharged. Activated sludge plants are of two types:
1. Plants with single aeration compartment, in which the incoming
waste rapidly and completely mixes with the full volume of mixed,
recycled liquor.
2. Plants with a number of aeration compartments in series, or those
with a long channel through which the incoming waste flows with
only a small part of the total volume mixed, undergoing aeration.
In biological filtration or tricking filter process, the wastewater is evenly
distributed over the surface of a bed of suitably graded inert medium, such
as coke, hard clinker broken rock or gravel. As the liquor percolates through
the bed, bacteria and other micro-organisms develop as a thin coating on
the inert medium, feeding on the organic impurity of the waste, oxidising
some to carbon dioxide and other products and some to new bacterial cells.
The coating thickness is to be kept thin to avoid choking by controlling waste
concentration through proper dilution and load on the filter. A good filter
medium should be uniform in size and similar in dimension in all three
directions.
The PACT system (Zimpro Environmental Inc.) is an example of the
combination of a physico-chemical method of colour removal combined with
a conventional activated sludge process. Powdered activated carbon is
added to the waste stream before treatment, to the recycle sludge, or to the
aeration tank itself. A carbon dose of 400 ppm is reported to increase the
removal of BOD, COD and colour significantly.
Most of the industrial wastewater does not contain sufficient amount of
nutrients for good microbial growth. For these types of waste, nutrients are
78
added to the reactors in the form of urea, super-phosphates or any other

compound containing nitrogen and phosphorous. For a balanced growth of
micro-organisms in a biological reactor, the BOD:N:P ratio of 100:5:1 and
100:2.5:0.5 are to be maintained respectively in aerobic and anaerobic
systems.
Special care should be taken in regard to toxic wastes. Some of the toxic
substances like phenols, cyanides, formaldehydes, etc. yield to acclimatised
micro-organisms in the reactors. But most of the toxic substances, like
copper, zinc, chromium and several synthetic organic compounds interfere
with biological oxidation. As such, these must not be subjected to biological
treatment or may be pretreated chemically before biological treatment.
2.13.5 Membrane Separation

For better economy, some efforts have been made to recycle the water as
well as chemicals instead of removing wastes before draining [19]. Chemical
and biological methods can be used to treat water for recycling, but waste
chemicals cannot be recovered by these treatments - those are either
destroyed or contaminated during the treatments. Reverse osmosis process,
on the other hand, can separate 80-95% of the chemicals present in the
original waste stream.
Membrane separation processes cover a wide range of separation using
different types of membranes. Membrane technologies operate at ambient
temperature and thus consume low energy compared to other processes.
There are five types of membrane separation processes for water
purification, namely [12]:
1. Microfiltration (MF)
2. Ultrafiltration (UF)
3. Nanofiltration (NF)
4. Hyperfiltration (HF) or Reverse Osmosis (RO)
5. Electrodialysis (ED)
All of them separate solutes from a solution, based on their molecular
size. In all the processes, except reverse osmosis, the separation is based
on the membrane pore size and the difference in the size between solute
and solvent. The membrane pore size in reverse osmosis is so small that it
may not actually exist in a discrete physical stage. The mechanism in this
case is believed to be a solution diffusion type mechanism. The solvent
dissolves in the membrane material and then diffuses across the matrix
leaving the solute on the upstream side.
Microfiltration (MF)
Microporous membranes enable liquids to flow through them normally. Pore
size is around 100 Angstrom. Microfiltration separates materials in suspension
79
(particles of 0.1 micron and above) from those in solution. It copes with the
effluents containing detergents and dispersing agents. Microfiltration is not a
satisfactory end-treatment, but may be used for the partial removal of colour
and organic materials before sewage or before reverse osmosis or activated
carbon treatment.
Ultrafiltration (UF)
This is a pressure driven membrane separation process, having pore size in
the range of 7 to 50 Angstrom. In Ultrafilter-type membrane, transport is
partially by a porous mechanism, but membrane-penetrant interactions are
also important. Regenerated cellulose, ion-exchange membranes,
polyelectrolyte complexes fall into this category. Ultrafiltration membrane
systems are used to filter out colloids and polymers of molecular weights
ranging from 500 to 5,000,000. This is more suitable and economical for
polymeric wastes, which are held back by a membrane while the salt
impurities pass through it. Synthetic textile sizes (PVA, CMC and
polyacrylates) are claimed to be recovered efficiently by ultrafiltration
technology. Starch-based sizes are normally not recoverable by this process,
as those are to be degraded during desizing process.
Different available configurations of UF membrane are [12]:
• Flat membrane in plate and frame structure
• Tubular
• Hollow fibre type
• Most common, spirally wound modules
Ultrafitration and microfiltration are applied to the treatment of textile
effluents to reduce suspended solids and organic materials of high
molecular weight to form sludge for disposal. Neither of these techniques
can reduce inorganic salts or the colour, unless they are adsorbed on to
other material that is removed. As stand-alone techniques, they are suitable
only for the reduction of COD and suspended solids, but are very useful as
part of a multi-stage treatment unit.
Nanofiltration (NF)
The pores of this type of membranes are smaller in size compared to those
of UF membranes, such that most of the organic compounds bearing very
low molecular weight linear chain structure are rejected while monovalent
cations combined with monovalent anions or salts pass through the
membrane. Cations and anions of higher valency such as Ca++, Mg++ or
-- --
SO4 , CO3 do not pass through the permeate. Hence they can be used for
softening of water. The membranes are not so tight as Reverse Osmosis
membranes, hence pressure drop and driving pressures are of a much
lower order (10–15 kg/cm2 as against 10–65 kg/cm2 for RO). The molecular
80
weight cut off for this type of membrane is lower that of UF membrane.
Using a combination of UF and NF membranes, separation and selective
recovery of process chemicals or products can be achieved at a higher
efficiency compared to conventional processes, particularly surfactants and
finishing agents.
This technique requires the effluent to be circulated significantly more
rapidly than for reverse osmosis, but can achieve concentration factors in
excess of ten. The concentrate contains virtually all the organic impurities
and some of the inorganic impurities from the effluent, and requires
treatments by alternate techniques. As with reverse osmosis, the
membranes require frequent cleaning as dyes, etc. may permanently attach
to or react with the plastic membrane. At present, both ceramic and
stainless steel nanofiltration membranes are too costly to use. They are
available in different configurations, but the tubular or spirally wound
modules are most common. Pressures required for separation using
nanofiltration membranes are always much lower than those required in
Reverse Osmosis membranes, but slightly higher than those required in UF
membranes.
Dyehouse water, given a treatment with nanofiltration unit can be used
directly for washing after dyeing. The permeate, from dark reactive dyeing,
which contains salt and alkali, can be used for setting up new baths [20].
The best way is to use nanofiltration for the total wastewater and reuse
water, energy, as well as the concentrates, wherever possible. It is also
possible to use nanofiltration for treating wastewater of deep dyeing as a
supplement to usual treatments. The higher capital and running costs of the
nanofiltration system, as against reverse osmosis and the arrangement of
wastewater piping, seem to be the main problems. It generates lesser
volume of concentrate, but higher concentration of inorganic salts than
reverse osmosis. The major disadvantages of nanofiltration are very similar
to those of reverse osmosis.
Hyperfiltration (HF)/ Reverse Osmosis (RO)
When a solution of higher concentration is separated by a semi-permeable
membrane, the solution of lower concentration flows towards the more
concentrated side due to difference in osmotic pressures of the two solutions.
When sufficient external pressure is applied on the more concentrated
solution, water flows in the opposite direction, i.e. towards the less
concentrated side. By selecting proper matrix of membrane, the separation of
water and solutes (e.g. salts, organic compounds, etc.) is achieved.
Hyperfiltration or reverse osmosis systems are based on molecular
diffusion membranes made from extruded plastic film, metal foil, etc. Here
the effluent is forced under moderate pressure across a semipermeable
81
membrane to form a purified permeate and a concentrate. The whole mass

of solid is removed by this method. Low molecular weight salts, such as
sodium chloride, can be recovered to an efficiency of 30-98%. Most reverse
osmosis membranes are manufactured for seawater desalination. The
method has the following disadvantages:
(a) High capital costs.
(b) At least 20% of the total effluent is not treated.
(c) The concentrate contains virtually all the impurities from the factory
effluent.
(d) The concentrate is to be further treated by some other technology
before disposal.
(e) The permeate may still contain too high a level of impurities for
recycling.
Table 2.11 shows the properties of the above four membrane filtration
systems. The membranes are classified according to their molecular weight
cut off, which is defined as the smallest molecular weight species for which
membranes have more than 90% rejection [12].
Table 2.11 Separation Characteristics of Membranes

Membrane Pressure, Pore size, nm MW* Application
System bar
MF 0.1–1 100 10
5 Microsuspensions, emulsions
4
UF 0.5–5 10 10 Microemulsions,
micromolecules, micelles
NF 5–30 1 200 Larger molecules, oligomers,
multivalent ions, dyes
RO 20–100 0.1 100 Salts
* molecular weight cut off of separable materials
Electrodialysis (ED)
Electrodialysis is an electrochemical separation process with charged
membranes and an electrical potential difference is used to separate ionic
species from water and uncharged components. A series of anion and cation
exchange membranes are arranged in an alternating pattern between an
anode and a cathode. While passing effluent through the system, ion
concentration increases in alternate components and the solution is depleted
of ions. The membranes are composed of a polymer matrix containing fixed
negatively charged groups, which are counterbalanced by labile positively
charged cations. HDPE, styrene-DVB, PVC, PTEE, etc. are some of the
materials used for preparation of these membranes. ED is widely used for
desalination of brackish water. By the development of new membranes with
better selectivity, the use of ED is gaining interest for removal of pollutants in
the food, chemical and textile process industries.
82
No simple technique will remove colour from a complex dye waste

mixture. The process chosen must be matched to the dye waste of the
particular factory at which it is installed. Biological or coagulation and
flocculation techniques result in large quantities of sludge, the site and cost
of disposal for the sludge are to be considered when choosing a system.
Before deciding about treatment, the total water usage is to be studied and
to be reduced as far as possible. These days water is costly and the
treatment of effluent is expensive. A number of effluent treatment techniques
provide opportunity for recycling over 70% of water. However, the relevant
technologies are very costly and the advantages of such action will vary
from site to site.
2.14 EFFLUENT TREATMENT PLANT

The demand for variety in textile materials and colours has propagated the
utilisation of a large number of dyes and chemicals. The majority of dyes are
retained in the final textile material, but most of the chemicals and residual
dyestuffs are discharged in the effluents. The toxic chemicals may be
present as auxiliaries (surfactants) in the detergent or soap, dyeing
auxiliaries (surfactants), dye, dyeing carriers and bacterial finishes used in
the textile industries [21]. A combination of more than one treatment
process is usually necessary to achieve adequate removal of all
contaminants. Because of the wide range of dyes in use, each plant will
have to establish the most economical treatment for the effluent. Each waste
seems to demand a tailored solution requiring a combination of methods.
Textile wastes are generally coloured, high in BOD and total dissolved
solids, highly alkaline and hot [21]. Effluent treatment unit operations are
usually combined in a site-specific scheme after evaluation of effluent
characteristics. Unit operations are typically drawn from the following
categories:
1. Primary treatment
(a) Physical – equalisation, screening, settling.
(b) Chemical – neutralisation, lime addition, alum addition, iron salt
addition.
2. Secondary treatment
(a) Biological – activated sludge, extended aeration, lagoons.
(b) Physical/ chemical – powdered activated carbon addition to
biological process.
3. Tartiary treatment
(a) Physical – secondary clarification, mixed media filtration,
ultrafiltration, granular activated carbon, powdered activated carbon.
(b) Chemical – ozonation, chlorination.
83
The various stages of a typical textile effluent treatment plant are shown in
Figure 2.5. The effluent is first passed through a bar screen to remove
floating matters and oil. The screened raw effluent enters first at the
equalisation-cum-neutralisation tank, which is open, semi-underground
rectangular RCC tank. PVC perforated pipe-grids are fitted at the bottom
through which air is blown at an angle of 45° towards the bottom of the tank
to prevent settling of the suspended solids. The effluent is detained for
4–8 hours in the tank, during which an automatic balanced dose of dilute
hydrochloric acid is given from an overhead tank by gravity to maintain
neutral pH of the effluent. Hydrochloric acid or sulphuric acid is generally
used for neutralisation, as the textile effluent is mostly alkaline.
Equalisation-
cum- Flash
Screening neutralisation Clariflocculator Aerator
mixer
tank
Aerator
Sludge Clarifier
bed
Outlet
Fig. 2.5 Flow Sheet for Textile Effluent Plant

The equalised and neutralised effluent is then pumped by means of open
impeller pumps to the flash mixer. In the flash mixer, alum and/ or any other
coagulant solution is mixed with the effluent and vigorously stirred by means
of mechanical stirrers. Alum dosing produces flocculation due to chemical
reaction.
The effluent is then sent to the clariflocculator, which is similar to an
equalisation tank, but circular in construction. Here the effluent is retained
for 8 hours during which period most of the suspended solids (mostly
inorganic) settle down at the bottom of the tank. Alum flocs settle slowly
along with smaller suspended solids. The sludge from the bottom is swept
by a mechanical rake arm and is sent to sludge beds. The scum layer
containing oil, grease, etc. floating on the surface is removed by a slow
moving mechanical skimmer arm and is dumped into a scum chamber.
The chemically treated effluent is then sent to the aerator for biological
treatment. In two successive circular, open, semi-underground RCC tanks
84
fitted with surface aerator units, the effluent is vigorously churned and
thereby the BOD is reduced due to intimate contact with atmospheric
oxygen. Optimum value of suspended solids is maintained by recycling
some organic sludge from the succeeding clarifier using sludge pumps.
Clarifier, the final unit in the effluent treatment plant, is also an open, semi-
underground, circular RCC tank. The effluent is held in the unit for about 8
hours. A portion of the settled sludge is sent back to the aeration tank and
the excess sludge is sent to sludge-bed. Clear treated effluent flows by
gravity into the drain, which is a small earthen channel.
Sludge-bed consists of graded metal layers with a thick layer of sand at
the top. The excess of water passes through the layers into the drain. The
solid sludge is allowed to dry and is removed from time to time. Before final
disposal of the sludge containing hazardous materials like pesticides,
chlorinated hydrocarbons, etc. it may have to be incinerated at a
temperature of about 990-1,480°C.
2.15 RECENT DEVELOPMENTS

Various developments in the effluent treatment processes have been
reported in the literature. Excess of caustic alkalinity can be removed by
using carbon dioxide in the flue gas from the boiler. By this means, the
alkalinity can be reduced to pH 9 at virtually no cost. The colour of the dye-
house effluent can be eliminated by treatment with hydrogen peroxide in the
presence of iron salts – the process is more environment-friendly and
produces very little sludge.
Wastewater containing azo dyes is discoloured by γ ray irradiation in the
presence of N2O or H2O2. Aqueous organic waste effluents containing dyes
are discoloured, degraded and rendered more biodegradable by subjecting
them to penetrating ionising radiation from Co60 or any other source of
penetrating rays in the presence of oxygen and a multivalent cation such as
Fe++ or Fe+++ [22].
A recent study [23] shows that the standard sewage treatment by aerobic
digestion of textile effluent removes most of the biodegradable portion of the
effluent. However, toxicity reduction is negligible by the process. A
significant portion remains undegraded after aerobic digestion. The
biodegradable portion of the effluent (mostly starch, sugars, waxes, etc.)
plays little or no part in the toxic action of textile effluent. Therefore, the
remaining, non-degradable portion of the effluent, such as metals, salts,
complex organic compounds and dyestuffs, must be responsible for the
toxicity assessed in the study.
85
Previous studies have shown that the most widely used aerobic digestion
process using activated sludge does not fully degrade textile effluent, neither
does it substantially reduce its toxicity as tested for aquatic life [24]. The
effluents will require further treatments to eradicate the harmful components.
The additional treatments include oxidation (e.g. ozonation), adsorption (e.g.
on activated charcoal) or fine filtration. Hydrogen peroxide alone does not
sufficiently decolourise dye waste but it is successful when combined with
UV light or ferric iron (Fe+++). Chlorine dioxide has been tried, but is not as
successful as peroxygens. The problem with such treatments is that
although they are necessary for a cleaner and healthier environment, they
are invariably expensive. They also tend to shuffle the waste around,
concentrating it for disposal by incineration or landfill rather than disposing it.
Degradation products after oxidation are sometimes more harmful than the
original waste component, as in case of ozonation.
The possibility of producing highly toxic chlorinated products (AOX) has
curbed the use of chlorine and hypochlorite.
The studies were made to monitor aerobic digestion process to
accommodate textile effluent more effectively. There are two possible routes to
tailor activated sludge to suit a particular type of waste – sludge seeding and
sludge conditioning. Sludge seeding involves adding particular micro-
organisms to the sludge which are capable of digesting the waste and then
culturing the sludge to maintain a high proportion of these organisms. Sludge-
conditioning involves repeatedly exposing the community of micro-organisms
in activated sludge to a specific type of waste, with the aim that organisms,
which are capable of digesting this will thrive and replicate, so that eventually
there are a large proportion of them in the community. Both methods aim to
produce a based community, dominated by the species that are more suited to
digesting a specific waste type. Initial trials showed promising result [24].
Biotechnology encompasses a range of scientific and engineering
techniques for applying biological systems in order to remove problematic,
often poisonous, liquid, solid or gaseous wastes. Several waste treatment
systems based on aerobic and anaerobic bacterial action have been
developed to treat textile industry wastewater. One of the serious
environmental problems the textile industry has been facing is the removal
of colour from dyebath. Highly water-soluble reactive and acid dyes are
particularly problematic, passing unaffected through conventional treatment
systems at the sewage works. Only biological treatments can offer complete
destruction of the dyestuff, with a simultaneous reduction in BOD and COD
[25]. Researches carried out by National River Authority (UK) suggested that
absorbence (section 6.4) measurements are the most suitable approach for
determining colour in wastewater. Colour standards are expressed as fixed
absorbance values over a range of wavelengths at 50 nm intervals in the
86
visible spectrum. The samples are passed through a 0.45 µm filter to

analyse and the absorbance is measured in 1 cm path length cell.
The colour and the chemical composition of textile effluents are usually
subjected to both daily and seasonal variations dictated by production
routines and fashion cycles. A single, universally applicable end-of-pipe
solution is, therefore, unlikely. Many synthetic dyes, such as azo dyes, are
resistant to microbiological degradation under aerobic conditions maintained
in common treatment plants. Many dyestuffs, in particular disperse, direct
and basic dyes, are removed from wastewater via adsorption on to activated
sludge. However, highly water-soluble reactive and acid dyes are poorly
adsorbed on activated sludge.
In Europe, 60% of sewage sludge is anaerobically digested prior to landfill
or incineration. However, anaerobic digestion is often slow and does not
generate an oxidised wastewater suitable for discharge to inland waters.
Azo dyes are susceptible to anaerobic biodegradation but reduction of azo
compounds can result in odour problems. Biofilters and bioscrubbers are
now available for the removal of odour and other volatile compounds.
The Deep Shaft process, developed by ICI, is a variation on the activated
sludge system with a deep hole below the ground. The hydrostatic pressure
at the bottom of the column improves oxygen transfer to a mixture of raw
sewage and activated sludge. However, the process does not remove
reactive dyes.
Biological aerated filters (BAF) or biofilters comprise of a submerged
packed bed with a fixed biofilm, which is continually aerated. The reactor is
periodically backwashed to remove biomass and trapped solids. BAF
systems occupy less space and treat greater load of BOD – up to 8 kg/m3
BOD per day, compared with 0.6 kg/m3 BOD per day for activated sludge
process, and 0.4 kg/m3 BOD per day for trickling filters [25].
In many cases, sequential aerobic-anaerobic degradation treatments are
considered. Sometimes the systems are enriched with specifically isolated
bacterial species to aid degradation of a particular dyestuff or dye class. The
degradation of reactive azo dyes under anaerobic conditions is believed to
be due to the action of azo reductase enzymes as follows:
R1—N=N—R2 + 4e— + 4H+ → R1—NH2 + R2—NH2 (2.26)
Many gut organisms produce extracellular flavonoid compounds, which
reduce azo bonds in food dyes. Recently this mechanism is proposed to
utilise in textile dyestuff discoloration. The gram-negative bacteria,
Shewanella sp. isolated from an industrial effluent stream has shown to
degrade a range of reactive dyes successfully [25].
87
REFERENCES
1. E.R. Trotman. 1984, Dyeing and Chemical Technology of Textile Fibres, 6th Edn.
(London, UK: Charles Griffin).
2. P.B. Jhala, M.M. Vyas and K. Subrahmanyam. 1981, Water and Effluents in Textile Mills
(Ahmedabad, India: ATIRA).
3. R.H. Peters. 1967, Textile Chemistry, Volume II (Amsterdam, Netherlands: Elsevier).
4. Norms for Textile Industry, Part 3. 1982, (Ahmedabad, India: ATIRA).
5. H.C. Spiel, and W.K. Schwarte. 1957, Textile Chemicals and Auxiliaries (New York, USA:
Reinhold)
6. B.M. Müller. 1992, Rev. Prog. Coloration (SDC, UK), 22, 14-21.
7. Anonymous. 1993, The Textile Industry and Wastewater In: Colour Chronicle (Sandoz,
India), Jan -March issue.
8. R. Anliker. 1977, Rev. Prog. Coloration (SDC, UK), 8, 60.
9. P. Cooper. 1995, Colorants in Dyehouse Effluent (Bradford, USA: SDC)
10. J.J. Porter and E.H. Snider, 1976. WPCF Journal, 9, 2198.
11. A .K. Roy Choudhury. 1984, Colourage (India), November, 13-18.
12. P. Vankar. 2002, Textile effluent (I.I.T. Delhi, India: NCUTE).
13. Y. Asolekar (co-ordinator). 2000, Environmental Problems in Chemical Processing of
Textiles (I.I.T. Delhi, India: NCUTE).
14. Uygur. 1997, JSDC (UK), 113, 211-217.
15. Y. Fu and T. Viraraghavan. 2001, AATCC Review (USA), January issue, 36-40.
16. E. Abadulla and others. 2000, Text. Res. J. (USA), 70, 409-414.
17. I.R. Hardin, H. Cao, and S.S. Wilson. 2000, TCC & ADR (USA), 32 (11), 38-42.
18. I.M.C. Goncalves, R.S. Porter and others. 2000, JSDC (UK), 116, 393-397.
19. G.A. Goodman, and J.J. Porter. 1980, Am. Dyestuff Rep. (USA), 69 (10), 33-39.
20. W.B. Achwal. 1998, Colourage (India), May, 39-42.
21. IEC International Environmental Consultant Ltd., Ontario, Canada. 1989, Survey of Textile
Wet Processing And Pollution Abatement Technology (Jodhpur, India: Divyajyoti
Prakashan).
22. J. Thampi, and R. Paul. 1997, Colourage (India), October, 47-49.
23. C.Moran, M.E. Hall, and R. Howell. 1997, JSDC (UK), 113, 272-274.
24. Moran. 1998, JSDC (UK), 114, 117-118.
25. N. Willmott, J. Guthrie and N. Gordon. 1998, JSDC (UK), 114, 38-41.
Chapter
Surface Active agents 3
3.1 INTRODUCTION
No dyeing or printing process can be done with dyes and water alone. Every
colorant-fibre system requires the use of additional products called
auxiliaries to ensure its reliable functioning and control. Even during
preparatory steps before dyeing or printing, several auxiliaries are needed
for quick and proper preparation. However, proper evaluation of the product
is very much necessary to check whether the auxiliary has been promoted
purely for commercial reasons or it serves a definite technical need.
An auxiliary has been defined as a chemical or formulated chemical
product which enables a processing operation in preparation, dyeing,
printing or finishing to be carried out more efficiently, or which is essential if
a given effect is to be obtained.
The services rendered by auxiliaries are enormous. A single auxiliary may
fulfil multiple functions. A few primary functions of auxiliaries [1] are:
(a) To prepare the material perfectly for coloration or to enhance
whiteness of white goods.
(b) To improve sorption characteristics of the colorants by acceleration,
retardation, blocking or migration.
(c) To stabilise colorant in the application media by improving solubility,
dispersion, emulsification, preventing or promoting oxidation or
reduction, etc.
(d) To protect or modify the dyeability of the substrate at varying
temperatures and other processing conditions.
(e) To improve fastness of dyes.
It is difficult enough to put together a comprehensive yet manageable list
of the general application types of auxiliaries. It becomes even more difficult
to classify them chemically, especially as many of them are more or less
complex mixtures, of imprecisely known structures or even unknown as
trade secret. A useful trade publication first appeared in 1967, the eleventh
89
edition (1988) of which lists over 6,000 currently available products [2]. The
publication classified auxiliaries by trade name, manufacturer and according
to use. No classification has been made by chemical type.
The auxiliaries can be broadly classified as surfactants and non-
surfactants. The latter include simple electrolytes, acids and bases of both
organic and inorganic types. Examples are sodium salts (chloride, sulphate,
acetate, carbonate, etc.), sulphuric, hydrochloric and acetic acids,
complexing salts (potassium dichromate, copper sulphate, EDTA, sodium
hexametaphosphate), oxidising agents (e.g. hydrogen peroxide), reducing
agents (e.g. sodium hydrosulphite, sodium sulphide), simple organic
chemicals (e.g. o-phenyl phenol, formaldehyde), fluorescent brightening
agents (FBAs), polyelectrolytes (e.g. sodium alginate or
carboxymethylcellulose).
Surfactants are, in general, substantially organic in nature and much more
complex in structure than non-surfactants.
3.2 SURFACE ACTIVITY

A surface or interface is the boundary between two phases and is of
fundamental importance to the behaviour of the system as a whole. For
example, adhesion is an effect of the surface or interface between two solid
phases, or in some instances, between a liquid and a solid phase. Similarly,
emulsification, wetting, spreading, foaming, detergency, adsorption are
phenomena involving interfaces between two phases. Only a single surface
can exist between two phases. Three phases or more can have only a line
in common, but not a surface [3].
Five types of phase interfaces are possible: solid-gas, solid-liquid, solid-
solid, liquid-gas and liquid-liquid. The three phases involving at least one
liquid phase are susceptible to the influence of surface active agents.
Three fundamental characteristics of phase interfaces are:
1. The transition from one phase to the other is a sharp one and the
boundary itself is statistically not more than one or two molecules
thick.
2. A definite quantity of free energy is associated with every unit of
interfacial area. Interfacial energy, expressed in ergs per square
centimetre, is equivalent to an interfacial tension expressed in dynes
per linear centimetre. For liquid-gas interface, it is an usual practice
to use the term surface tension, which arises from the geometrical
unbalance of the force fields acting on the molecules in the interface.
Low interfacial tension is associated with high adhesion, as in case
of water and clean glass. On the other hand, mercury can be easily
90
separated from a glass plate due to high surface tension between

them. Low surface tension of the soap solution causes extensive
soap solution-air interface in the form of foam.
3. An electrical potential exists across the phase interfaces. The drop in
electrical potential across a phase interface is very important in case
of emulsions and suspensions. Charge characteristics may often be
modified profoundly by the addition of simple soluble ionic
components to the system.
The addition of any solute will generally alter the surface energy of the
liquid phase in which it is dissolved. The alteration may be positive or
negative i.e. surface tension may be raised or lowered. The surface tension
of water changes from 72.7 to 73 and 77.5 ergs/cm2 on dissolution of 1%
and 10% caustic soda respectively. For significant change in surface
tension, a large quantity of caustic soda is necessary.
However, certain solutes, even when present in very low concentration,
have the startling property of altering (mostly lowering) the surface energy of
their solvents to an extreme degree. Such solutes are known as surface
active agents or surfactants and the said property is known as surface
activity. The oldest and most widely used surface active agent is soap.
Surface activity is best known in aqueous systems. However, surface
activity may also be exhibited in non-aqueous systems. Oleic acid is
distinctly surface active in hydrocarbon oils. Many extreme-pressure
lubricants, drawing lubricants and cutting oil additives are also oil-soluble
surface active agents for oils.
Surface active agents are characterised by a linear long-chain molecular
structure, a portion of which is compatible with oils while the other portion is
compatible with water. Usually, one end comprises a hydrocarbon radical of
hydrophobic nature (called hydrophobe) characterised by weak valence
forces, whereas the other end is of a hydrophilic nature (called hydrophile)
with strong residual or secondary valence forces. The term hydro has been
used because in most of the cases water is the solvent medium. However,
the more general terms lyophilic and lyophobic may be used to describe
attraction and repulsion to the bulk solvent medium.
The above definition is somewhat arbitrary and there are many
substances outside the scope of this definition, though those are responsible
for various effects associated with surface activity. Such effects include
lubrication, wetting, detergency, foaming, etc. Some of these materials act
as third phase in the true microscopic sense. For example, water-repellent
agents applied on textiles deposit hydrophobic films constituting a separate
phase on the fabric surface.
Many water-soluble macromolecular substances such as starches, gums,
cellulose derivatives, proteins, polyvinyl esters, etc. have pronounced
91
activity in emulsification, detergency and other surface phenomena. In

general, they do not have an unbalanced hydrophilic structure; neither do
they have any pronounced effects on surface tension as with soap.
Solubility is a necessary characteristic for surface active agents. However,
a large class of insoluble materials is capable of spreading in the form of a
monomolecular layer on the surface of base liquid, as in case of true surface
active agents. They do not constitute a third phase in any macroscopic
sense and their presence is detected largely by measurement of the energy
and electrical characteristics of the treated surface. Many finishing agents
like permanent water repellent called Zelan (Du Pont) are surface active
agents, but those are mainly deposited as hydrophobic film and their surface
activity is not operative.
Certain substances such as spreading oils prevent foaming when added in
small amounts. Actually, some anti-foaming agents are surface active,
whereas others are merely mechanical coverings.
The term, surface active agent, therefore, loosely used to designate any
substance whose presence in small amounts markedly alters the surface
behaviour of a given system. In a more restricted sense, surface active
agents are soluble substances whose presence makes the surface
properties of a solution markedly different from those of the pure solvent.
Almost all solutes are surface active to a certain extent and, therefore, the
distinction between a surface active and a non-surface active solute is
quantitative rather than qualitative in nature [3].
Though a large number of synthetic surface active agents are in use, soap
is still the most widely used of all surface active agents. The main
disadvantage of soap is its instability to hard water or acids, which has been
largely overcome by synthetic products.
3.3 CLASSIFICATION
The surfactants used as textile auxiliaries can be divided into four major
groups, depending on the type and distribution of the polar forces as shown
in Table 3.1.
Table 3.1 Classification of Surfactants

Class Hydrophobe Hydrophile (associated ion)
Anionic Weakly negative Strongly positive
Cationic Weakly positive Strongly negative
Nonionic Uncharged Uncharged
Amphoteric Possessing both positive and negative charges, one or other
dominates in solution depending on pH
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3.3.1 Anionic Surfactants

This class still accounts for the largest number of surfactants used in
coloration process despite active development of nonionic types in recent
years. The essential feature of this class is a long-chain molecule linked
through anionic groups, usually carboxylate (–COOX), sulphate (sulphuric
ester, –OSO3X) or sulphonate (–SO3X), occasionally phosphate,
carboxymethyl or other groups to a relatively small cation (X), generally
sodium, although ammonium, potassium and other cations are also used.
– +
Carboxylates (R–COO X ) are the oldest types of surfactants known long
before the advent of petrochemical industry. They could be obtained from
naturally occurring fats and oils (glycerides), R1–COO–H2C–(CH–COO–R2)–
CH2–COO–R3, by alkaline saponification. The three carboxylic ester groups
(RCOO–) may carry the same or different hydrophobes, generally containing
8 to 22 carbon atoms, the most common being laurate, palmitate and
stearate among saturated types, and oleate and linoleate among the
unsaturated. Sodium stearate is an anionic substance as it ionises in
+ –
solution to form Na and the long-chain stearate anion, C17H35COO , which
is responsible for the surface activity.
Alkylaryl compounds are also used. Among wetting agents, the most
– + –
important is disodium alkenylsuccinates, R-CH=CH-CH(COO Na )CH2COO
+
Na in which the saturated R group may contain 3 to 14 carbon atoms.
The surfactant properties of the carboxylates, as with other types of
surfactants, are dependent on the number of carbon atoms in the
hydrophobe. Surface active properties start at C8 compounds, C8–C12
carboxylates are wetting agents while detergency and emulsifying properties
become evident with C12–C18 alkyl groups. The solubility decreases with
increasing length of the alkyl group and reaches useful limit with the C22
compounds.
The major disadvantage of the carboxylates is that they tend to be
precipitated by acids and hard water, since the free acids and the calcium
and magnesium salts of the carboxylates are insoluble.
Recently introduced modified carboxymethylates are prepared by reacting
selected nonionic surfactants with chloroacetic acid. The members of this
hybrid range are insensitive to calcium and magnesium and are excellent
detergents. As compared to nonionics, these compounds are more stable to
electrolyte and high temperature (no cloud point problem).
Sulphates or sulphuric esters of the long-chain fatty acids were the first
alternative to the carboxylates. They are essentially half esters of sulphuric
– +
acid (R-OSO3 Na ). Like mono-, di- and tri-carboxalate, sulphates can be
prepared from mono-, di- and tri-hydrophobe-bearing products. Many oils
(olive, castor, tallow, cottonseed, rapeseed, etc.) are used as starting
93
materials. The first member of the group, sulphated olive oil, was used as a
mordant in dyeing as long back as 1834. Sulphation occurs at the double
bond of the unsaturated fatty acid in the glycerides.
– +
–CH=CH– + H2SO4 Æ –CH2–C(OSO3 H )H– (3.1)
Another very popular product, Turkey Red Oil or sulphated (wrongly called
sulphonated) castor oil possesses useful wetting, emulsifying and dye-
levelling properties. The sulphation mostly occurs at the hydroxyl group
rather than at the double bond.
– +
–CH(OH)–CH2–CH=CH– + H2SO4 Æ –CH(OSO3 H )CH2–CH=CH– (3.2)
At present, however, long-chain fatty alcohol sulphates (e.g. with cetyl
– +
hydrophobe, C16H33OSO3 Na ) and particularly the sulphated ethers are of
greater importance. The stability of the sulphates to mild acidic conditions
and to hard water is much better than that of the carboxylates and is efficient
for most purposes. Under more stringent acidic conditions, however, they
may hydrolyse.
Another type of sulphated product, the ester sulphates, can be prepared
by esterifying a fatty acid with a short-chain alcohol and then sulphating.
Such products (e.g. sulphated butyl ricinoleate) are particularly useful as
foaming, emulsifying and wetting agents.
An important class of anionic surfactants developed recently is sulphated
–
polyethers or alcohol polyoxyethylene sulphates, C16H33–(OCH2CH2)XOSO3
+
Na . It is prepared by ethoxylating fatty alcohol to give a polyether
containing a terminal hydroxy group, which is then sulphated. They are often
referred to as lightly ethoxylated alcohol sulphates. Actual structures may be
quite complex. These can be viewed partly anionic and partly nonionic
surfactant, although the degree of ethoxylation is much lower than that of
purely nonionic surfactant.
Among sulphonated anionic surfactants, the most important surfactant is
– +
sodium dodecylbenzene sulphonate (H25C12RSO3 Na , R = benzene group),
most widely used in domestic washing powders. Naphthalene and other
aromatic hydrophobes are also used to produce sulphonates. Of greater
importance, however, are the more complex condensation products that
form the basis of many excellent dispersing, resist and aftertreating (syntan)
agents. Typical examples are the condensation products of naphthalene
sulphonates with formaldehyde and the lignosulphonates derived from paper
pulping processes.
Sulphosuccinates can combine two hydrophiles, sulphonates and
carboxylate moieties in a single molecule. The most important is sodium
– +
dioctylsulphosuccinate, H17C8OOC–CH2–CH(SO3 Na )–COOC8H17. As
usual, a wide choice of hydrophobes is available and includes alcohols,
lightly ethoxylated alcohols, alkanolamides.
94
Anionic surfactants based on phosphate esters, are currently of growing

commercial and technical importance. Mono- or di-esters (R-O-
P(OH)(OH)=O or R-O-P(OH)(OR)=O) can be formed. Most phosphate
esters are based on alcohols and especially their ethoxylates, including
aliphatic and alkylaryl types.
3.3.2 Cationic Surfactants

The cation active or cationic surface active agents form a cation containing
the elongated low-affinity portion of the molecule. In the cationic class, the
most prevalent ionic groups are primary, secondary and tertiary amino
+ –
groups and especially the quaternary ammonium groups, (NR4) X where
one R group is long chain hydrophobe and other R groups are lower alkyl
groups. All four R groups can be varied to alter the balance of properties of
the products. By far the most important types of cationic surfactants used in
textile processing are the quaternary ammonium salts. Aromatic
components may be used as in case of alkyldimethylbenzylammonium
chlorides. Like quaternary ammonium surfactant, the pyridinium salts, such
as cetylpyridinium chloride are also very important. The said surfactant
ionises as follows:
+ –
C16H33C5H5NCl ↔ C16H33C5H5N + Cl (3.3)
Less important ionic groups in this class are phosphonium and
sulphonium groups. Imidazoles can be quaternised to yield cationic
surfactants. The range of products available as cationic surfactants is
enormous.
The common anions are chloride and bromide. Generally, cationic
surfactants are not very stable under alkaline conditions, when water-
insoluble free bases of the quaternary compounds are formed.
Many of the cationic products including the quaternary amines and
+ –
imidazoles, can be ethoxylated (RCH3N[(CH2CH2O)xH]2 Cl ), forming
cationic analogues of the ethoxysulphates and ethoxyphosphates as in the
anionic series. They are essentially cationic/nonionic hybrid surfactants,
often referred to as modified cationic, weakly cationic or even modified
nonionic. Their cationic nature can be controlled not only by changing alkyl
substituents, but also by changing the degree of ethoxylation. Besides the
ethoxylate moiety confers useful emulsifying properties.
3.3.3 Nonionic Surfactants

Nearly all nonionic surfactants contain the same type of hydrophobes as in
the case of anionic and cationic surfactants, with solubilisation and
surfactant properties arising from the addition of ethylene oxide to give a
product having the general formula R-(OCH2CH2)XOH. The properties
95
become evident when x = 6, but in theory the degree of ethoxylation can be

continued almost indefinitely. Optimum surfactant properties are generally
found when x = 10-15, although higher homologues (e.g. x = 50) are known.
A typical nonionic surfactant may have the value of x = 12 and R = C16H33.
The great majorities are adducts of ethylene oxide with hydrophobes
derived from three sources, namely:
1. Fatty alcohols and alkylphenols

2. Fatty acids
3. Fatty amines and amides
The common adducts are with p-nonyl and p-octyl phenol and to a lesser
extent 2,4 dinonylphenol, p-dodecylphenol and 1-alkyl naphthols. Since the
hydrophobe may have secondary products and the degree of ethoxylation is
an average value, the product with the same chemical name may vary in
detailed composition and properties.
An alkylphenol adduct is essentially similar to that as above with a
benzene ring incorporated in the group R. Polyfunctional alcohols of varying
complexity, such as glycols and polypropylene glycols of varying chain
lengths, also provide useful nonionic agents.
Whereas alcohol and phenol derivatives are characterised by ether
linkages, adducts of ethylene oxide with fatty acids give rise to monoesters
(H33C16CO [OCH2CH2]XOH) and diesters. These are less stable than ethers
in strongly acidic or alkaline media, hydrolysing to the original fatty acid and
polyethylene glycol.
Adducts of ethylene oxide with fatty amines can yield to mono (H23C11NH
[OCH2CH2]XH) and disubstituted products, as can the adducts with fatty
amides. These structures are far complex as the ethylene oxide addition
takes place randomly.
Not all nonionic surfactants are ethoxylates. Analogous propylene oxide
adducts are known. Quite different products include sucrose and sorbital
esters, alkanolamides and fatty amine oxides. Sorbital fatty esters are water-
insoluble and are used as emulsifiers in oil-based systems or can be
ethoxylated to render them water-soluble.
Nonionic surfactants have the advantages that they are available in liquid
form and can be diluted easily. Their lack of affinity for textile fibres makes
them easily rinsable from textile materials.
3.3.4 Amphoteric Surfactants

Amphoteric surfactants contain both an anionic and a cationic group, such
that in acidic media they tend to behave as cationic agents, and in alkaline
media as anionic agents. The pH (not necessarily pH 7) at which the anionic
96
and cationic properties are counterbalanced, is known as isoelectric point.

At this point the molecule is said to be zwitterionic and its surfactant
properties and solubility tend to be at its lowest. This class is of lesser
importance, as only a few of them have yet attained widespread use.
However, they are theoretically important, since the charge on the molecule
as a whole varies with the pH of the medium.
Recently a few amphoteric surfactants have gained importance. The
+ –
simplest type is higher alkylaminoacids (C16H33N H2CH2COO ).
Disubstituted amines and ethoxylated products are also synthesised.
Cetylaminoacetic acid, for example, ionises in water as follows:
+ –
C16H33NH-CH2COOH ↔ C16H33N H2CH2COO (3.4)
Sulphates and sulphonate analogues of carboxylates, such as the
+ –
sulphobetaine (R- N(CH3)2-(CH2)3SO3 ), can also be used as amphoteric
agents.
Classification based on hydrophobic group is not very useful as the
number of sources of hydrophobic groups is limited and many substances
greatly differing in properties will be grouped together under this system. It is
important to note that a single hydrophobic group can often be used to
synthesise a wide range of surface active agents.
The surface active agents are often loosely classified according to the
purpose for which they are used, such as wetting agents, detergents,
emulsifiers, hydrotropic substances, dyeing assistants, etc. However, a
single substance may serve several functions quite efficiently.
Surface active agents may be classified based on their uses, physical
properties (water-soluble or solvent-soluble) or on the basis of chemical
structure. However, none is entirely satisfactory. Schwartz and Perry [3]
classified surface active agents primarily according to the nature of
solubilising group, secondarily according to the way the hydrophilic and
hydrophobic groups are joined, and tertiarily on the basis of the nature of
hydrophobic group.
3.4 HYDROPHILIC GROUPS

The basic purpose of the hydrophile is to confer solubility, mostly aqueous.
The simple moieties most often employed are as follows:
(a) In anionic surfactants, sodium, potassium or ammonium cations,
associated with negatively charged groups on the hydrophobe such
as carboxylate, sulphonate, sulphate or phosphate.
(b) In cationic surfactants, chloride, bromide or methosulphate ions,
juxtaposed with, for example, positively quaternary nitrogen atoms.
97
(c) In nonionic surfactants, ethylene oxide or propylene oxide moieties.
More complex hydrophilic moieties like mono-, di- and tri-ethanolamine

and the corresponding isopropanolamines are often employed.
3.5 HYDROPHOBIC GROUPS

There is a much wider choice of hydrophobes. Most are based on
substantially linear long-chain alkanes, either saturated or unsaturated. They
were originally obtained from naturally occurring fats and oils, but these
sources were later superseded by petroleum products, which were cheaper.
Quite recently, with escalation of the price of crude oil, there is an increasing
return to the natural sources.
Commercial products rarely contain single pure hydrophobe. Most of them
are mixtures containing a range of hydrophobes, since the raw materials
from which they are made are generally mixtures of homologues. For
example, a batch of coconut oil, a rich source of the lauric hydrophobe
(49%), contains various other hydrophobes like myristate, palmitate, oleate,
stearate, caprylate, etc. Clearly, a surfactant produced from such a mixture
will contain a very large and variable number of homologues and isomers.
Hence two products with the same nominal constitution, but from different
manufacturers, often differ in details of composition and properties. As a
general rule, only even-numbered carbon compounds are present in
naturally occurring fats and waxes – odd numbered ones are generally
made by synthesis. There has been a trend in recent years to produce more
homogeneous fractions of the raw materials in surfactant manufacture.
The most common hydrophobes used as the basis for surfactants are
those containing 8 to 18 carbon atoms.
The carboxylates of saturated hydrophobes may be represented by the
formula, CH3(CH2)XCOO. Depending on the value of X, the hydrophobes are
named (chemical names and trivial names in brackets) as follows:
X= 6, octanoate (caprylate)
8, decanoate (caprate)
10, dodecanoate (laurate)
12, tetradecanoate (myristate)
13, pentadecanoate (isocetate)
14, hexadecanoate (palmitate)
15, heptadecanoate (margarate)
16, octadecanoate (stearate)
98
Carboxylates of unsaturated hydrophobes may be represented as:

CH3(CH2)XCH=CH(CH2)YCOO, depending on the value of X and Y, the
names are:
X = 1, Y = 7, 9-dodecenoate (lauroleate)
X = 5, Y = 7, 9-hexadecenoate (palmitoleate)
X = 7, Y = 7, 9-octadecenoate (oleate)
Any hydrophobe can yield each of the main (i.e. anionic, cationic, nonionic
and amphoteric) types of surfactants in much the same way as the same
chromophore can be used in anionic, basic or nonionic dyes.
Some of the usual types of hydrophobic groups are as follows:
1. The naturally occurring fats and oils such as castor, fish, olive,
sperm, coconut and tallow oils, are the most important raw materials
for hydrophobic groups. The straight alkyl chains of 8 to 18 or more
carbon atoms are derived from them. A wider range of detergents is
manufactured from them directly or after suitable chemical
modification.
2. The lower alkyl groups of 3 to 8 carbon atoms, usually derived from
alcohols, are frequently attached to aromatic nuclei such as benzene
or naphthalene to form hydrophobic groups. A number of important
wetting agents belong to this group. The octyl group, C8H17 is widely
used in the manufacture of surface active agents.
3. Propane, isobutane, and some of the isomers of pentene and
hexane can be readily polymerised to branched-chain mono-olefins
of 8 to 20 or more carbon atoms. In alkyl benzene sulphonate, widely
used in detergents, the alkyl group may be a tetramer of propane.
This is further condensed with benzene and the product is
subsequently sulphonated.
4. Petroleum hydrocarbons in the range of 8 to 20 or more carbon
atoms are very important raw materials for hydrophobic groups.
Kerosene, light oil and paraffin wax fractions are commonly used.
5. In the refining of petroleum oils by washing with sulphuric acid, the
surface active petroleum sulphonates are obtained.
6. The higher alcohols and hydrocarbons, obtained by reaction of
carbon monoxide or dioxide with hydrogen, or as by-product in the
methanol synthesis, are widely used as sources of hydrophobic
groups.
7. The terpenes and terpene alcohols are largely used as alkylating
agents for aromatic nuclei. Such alkyl aromatic compounds are
excellent hydrophobic groups.
99
3.6 HLB VALUES

Surface active agents have varying properties depending on the nature and
ratio of hydrophilic and hydrophobic groups. For example, among the
anionic surfactants C8-C12 alkyl hydrophobes tends to be predominantly
wetting agents, whilst the C12-C18 analogues exhibit better detergency and
emulsifying properties. Clearly as the hydrophobic character of the
surfactant is increased, the aqueous solubility decreases and oil solubility
increases. Thus, the balance between the hydrophobic and hydrophilic
moieties of a surfactant is a critical factor in determining its major
characteristics. To dictate the properties of surface active agents, Griffin [4]
developed a system called hydrophilic-lipophilic balance or HLB. In this
system, each surface active agent is given a number, called HLB value, that
numerically represents the hydrophilic and hydrophobic tendencies of the
material. Such scale covers a range of values from 0 (the lipophilic or
hydrophobic extreme) to a hydrophilic extreme of 20. In HLB system, a
theoretical compound that could be considered 100% hydrophilic is
arbitrarily assigned an HLB value of 20. A value of 10 approximately
represents the point at which the hydrophilic and hydrophobic portions are in
balance. This scale is especially useful in describing the properties of the
nonionic ethoxylates and is of particular value in describing the formation of
emulsions. Each material to be emulsified is also rated as to the HLB value
of the emulsifier required to form an emulsion.
All surface active agents are amphiphilic or amphipatic compounds, i.e.
each molecule contains an oleophilic or hydrophobic and a hydrophilic
moieties. The former is a hydrocarbon tail and consists of material readily
soluble in oil or solvents of low polarity. The second moiety is chemically
similar to compounds, which are hydrated and extensively soluble in water.
It consists of a negatively or positively charged ionic head-group in case of
anionic or cationic surfactants plus the counter-ions for electro-neutrality.
The HLB value depends on the ratio of the hydrophilic and hydrophobic
properties. Thus, in general, the molecules that are soluble or dispersible in
oil have low HLB values, whereas those, which are dispersible or soluble in
water, have high HLB values.
In effect, the HLB value is determined by the chemical composition and
the degree of ionisation or hydration of the emulsifier molecule. Nonionic
compounds like glyceryl monostearate are strongly lipophilic and poorly
hydrophilic and have low HLB values. Polyoxyethylene esters and ethers
with long polyoxyethylene chains are strongly hydrophilic and have high
HLB values. In general, the emulsifiers with low HLB values will tend to
promote the formation of water-in-oil emulsions and those with high HLB
values will form oil-in-water emulsions. However, the exact HLB values
100
required for a specific oil phase must be determined experimentally, since

each type of oil will probably require a different HLB system.
As a rough guide, emulsifiers with HLB value of 6 or less are useful in
forming water-in-oil (W/O) emulsions and those with the HLB values ranging
from 8 to about 18 are useful in forming oil-in-water (O/W) emulsions. For
solubilisation of oils, surfactants with HLB values of over 15 should be
considered. The relation between the HLB values and the behaviour of the
surface active agents is listed in Table 3.2.
Table 3.2 Relation between HLB value and Properties of Surfactants

HLB Values Properties
1.5-3.0 Antifoaming
3.5-6.0 Emulsifying (W/O)
7.8-9.0 Wetting
8.0-18.0 Emulsifying (O/W)
13.0-15.0 Detergency
15.0-18.0 Solubilising
The approximate HLB values required for preparing emulsions with

different hydrophobic compounds are shown in Table 3.3.
While preparing an emulsion, emulsification tends to be most efficient
when the HLB value of the agent matches that of the oil phase. Often a
mixture of surfactants makes a more efficient emulsifying agent than a
single product having the same HLB value of the mixture. Similarly, if the oil
phase to be emulsified is itself a mixture, each of its components will
contribute to the effective HLB value, which can be determined by carrying
out preliminary emulsification tests with agents of known HLB values.
3.6.1 Calculation of HLB Value

The HLB values of various types of nonionic compounds can be calculated
as follows:
1. For polyoxyethylene-fatty alcohol condensates,
HLB = E/5 (3.5)
Where E is the percentage by weight of the hydrophilic portion of the
molecule. In the case of a polyoxyethylated fatty alcohol containing
75% (by weight) of ethylene oxide adduct the HLB value would be
75/5 = 15.
2. For polyol and polyoxyethylene esters of fatty acids,
HLB = 20 (1 - S/A) (3.6)
Where S is the saponification number of the ester and A is the acid
number of the fatty acid portion of the ester. Thus a given sample of
101
sorbitan monolaurate with a saponification number of 164 and with an

acid number of 290 would have an HLB value of 20*(1 - 164/290) = 8.7.
Table 3.3 Required HLB Values for Different Emulsions

Ingredient Type of Emulsion
Water in oil Oil in water
Cresylic acid – 10
Oleic acid – 11
Stearic acid 6 15
Cetyl alcohol – 15
Lauryl alcohol – 13
Butyl stearate – 11
Carbon tetrachloride – 9
Dimethyl phthalate – 15
Kerosene – 12
Lanolin, anhydrous 8 10
Mineral spirit – 10
Xylene – 10
Castor oil – 12
Cotton seed 5 12
Palm (synthetic) oil – 13
Pine oil – 13
Silicone – 11
Sucrose acetate isobutyrate – 14
O-dichlorobenzene – 12
O-phenylphenol – 16
Petrolatum 5 12
Bees wax 4 12
Ester (synthetic) 4 14
Paraffin 4 11
Polyethylene (oxidised) – 9
Tallow, hydrogenated – 11
These equations do not appear to give proper HLB values for nonionic
compounds containing polypropylene oxide or polybutylene oxide adducts or
for compounds containing nitrogen or sulphur. The actual constitution of a
surfactant rarely conforms to its nominal structure. Consequently, the
102
theoretical method of calculation is of limited utility, the practical methods

are more reliable. The HLB value may be determined directly by analysis or
by comparison, with a range of surfactants of known HLB values. The HLB
value of a mixture of surfactants is calculated by adding HLB values (B) of
the individual surfactants weighted by respective fractional quantities (F).
BM = F1B1 + F2B2 + F3B3 + ······· (3.7)
3.7 MICELLE FORMATION

All surfactants in solution tend to form more or less ordered agglomerates of
molecules called micelles. A micelle is a group of molecules associated in a
cluster as spherical aggregates, from which the more mobile ions have
migrated, leaving a net negative charge on the cluster and a smaller number
of detached cations (gegenions) in adjacent positions. In water, the
surfactant molecules orient themselves with their hydrophobes at the centre
of the cluster.
As surfactant is added gradually to water, the surface tension falls quite
rapidly until at a certain concentration of surfactant is reached. Then it
begins to level off more or less sharply. At higher concentration, lamellar or
sheet-like uncharged micelles replace the globular structure. They are
formed of oriented uncharged soap molecules arranged with all the
–COONa or –CH2 groups occupying adjacent planes. There is an abrupt
change in all the properties of detergent solutions in the region of 0.2%, due
to transition from ionised solution to the micellar state. The concentration
corresponding to the formation of such aggregates is termed the critical
micelle concentration (CMC) and it can be determined experimentally in a
number of ways. In general, the CMC decreases with increasing size of
hydrophobe and the CMCs of nonionic agents tend to be lower than those of
ionic types, since with the nonionics, micelles can form more easily in the
absence of polar charges.
The critical micelle concentration (CMC) is an important benchmark in
describing the adsorption of a surfactant at either the liquid-solid or liquid-
gas interface and that in the latter case, the maximum surface tension
reduction achievable (usually occurring at CMC) is also an important
parameter in describing the compound’s surface activity in the particular
system [5].
Fully ionised surfactants, either anionic or cationic, typically exhibit CMC
between 0.1 and 0.001 moles/litre. The exact value for a particular
hydrophilic group depends on the size of the hydrophobic portion. For
straight-chain aliphatics, the CMC is approximately halved for each
additional CH2 group up to about 18 carbons. Beyond this, there is little
103
change. The CMC also depends strongly on the counter-ion concentration in

the solution due to screening effect, which tends to counteract the lateral
electrostatic repulsion encountered in the formation of micelle. The CMC of
a given surfactant is divided roughly by three for each unit increase in the
molarity of univalent counter-ion. The dependence on polyvalent counter-ion
concentration is much steeper. The effect of temperature on the CMC of
ionic surfactants is changeable and usually fairly straight over modest
temperature ranges. The CMC for a nonionic surfactant is usually two to
three orders of magnitude lower than that of an ionic of corresponding
molecular weight, since there is no lateral electrostatic repulsion
encountered in the formation of micelles. The dependence on the size of
hydrophobic portion is also greater than for ionics, being decreased roughly
by a factor of three for each additional methylene group. For
polyoxyethylenated compounds of a given hydrophobic portion, the CMC
increases with increasing number of ethylene oxide (EO) units, since this
increases hydrophillicity. Typically, the increase is of the order of 5-10% for
each EO unit. The CMC decreases on addition of electrolyte, but the
decrease is less for nonionics as compared to that in case of ionics. The
CMC of nonionics decreases sharply with increase in temperature until a
temperature well below 100°C for most of them when they precipitate out as
giant micelles. This temperature is termed as the cloud point. It is higher for
high EO/hydrophobe ratio in the molecule. Organic additives may have a
strong depressing effect on the CMC for either type of surfactant. Not all
surfactants are capable of forming micelles.
3.8 APPLICATION PROPERTIES

Anionic and cationic products generally tend to react with each other,
usually diminishing the surfactant properties of both and often resulting in
precipitation of the complex formed. This interaction can sometimes be
prevented by the addition of a nonionic agent or using ethoxylated sulphate
or phosphate as an anionic agent. The oxyethylene chains act as dispersant
for any complex that may be formed. Amphoteric compounds are
incompatible with anionics in acid solution, but are generally compatible with
cationic and nonionic agents.
Though the carboxylate surfactants have good wetting and detergent
properties, their main disadvantage is that they react with calcium and
magnesium ions causing instability in hard water. They are also insoluble in
acidic medium. Carboxymethyl surfactants are unaffected.
The sulphates are specially developed to overcome the drawback of the
carboxylates, but they are hydrolysed by acids. The sulphonates are
excellent detergents and are unaffected by strongly acidic and alkaline
104
conditions. The higher alkyl sulphonates have useful lubricating properties.

The sulphates are poorer wetting agents than the sulphonates, but are
valuable emulsifying agents, especially in combination with nonionic agents.
The sulphosuccinates have a high propensity to foaming and their solubility
is not generally good, but the monoesters have good detergency properties
and the diesters are particularly rapid wetting agents.
The more recently developed phosphates are also stable towards calcium
and magnesium ions. The phosphates are biodegradable, low foaming
detergents and are stable to acids and alkalis. They are soluble in organic
solvents, hence are suitable for dry-cleaning. The recently developed
perfluoroalkyl anionic surfactants are currently very expensive, but are
powerful surfactants at very low concentrations and are stable in hostile
chemical environments, they also exhibit surface activity in organic solvents.
Cationic agents are generally less useful as detergents but they have
useful properties as softeners, germicides and emulsifiers.
Nonionic agents are compatible for both anionic and cationic agents. They
are stable to calcium and magnesium ions. Fatty acid esters are readily
hydrolysed by acid and alkali. Others are stable and effective over a wide
range of pH. The solubility has inverse relation with temperature for the
nonionic agents. As the temperature rises, the solubility decreases until a
temperature is reached, when it becomes insoluble and precipitates out
causing cloudiness of the solution. The temperature, called cloud point,
depends on the ratio of oxyethylene units and the length of hydrophobe. For
example, dodecanol heptaoxyethylene, C12H25(OCH2CH2)7OH has a cloud
point of 59ºC. For any given hydrophobe, the cloud point increases with
increasing degree of ethoxylation. Conversely, for a fixed number of
oxyethylene units, the cloud point decreases with increasing size of
hydrophobe. The cloud points are also lowered by the presence of
electrolytes, the effects varying with the electrolyte and its concentration.
The inverse solubility arises from the solubilisation of the nonionic
molecules by hydrogen bonding of water with the ether oxygen atoms. As
the temperature rises, the energy within the bonds becomes insufficient to
maintain their cohesion and dehydration takes place with consequent
decrease in solubility. The surface activity tends to be optimal just below the
cloud point.
Foaming properties of nonionics vary and some block copolymers can
even be used as defoamers.
The amphoteric agents exhibit excellent compatibility with inorganic
electrolytes, alkalis and strong acids. Their stability in strongly acidic solution
is so high that they are even used in cleaning compositions based on
hydrofluoric acid.
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3.9 BIODEGRADABILITY
The wide spread attention on environmental properties of surfactants has
been focussed due to their persistent foam-creating tendency when
discharged. The surfactants may or may not be biodegradable. Straight-
chain products are adequately biodegradable, while the branched-chain
products are not. There appears to be some uncertainty regarding the
biological effects of nonionic surfactants. Moore et al. [6] have summarised
the biodegradability behaviour of surfactants as follows:
1. Biodegradability as well as solubility decreases with increasing

hydrophobicity of surfactants, irrespective of their ionic type.
2. Toxicity decreases with the increase in ethoxylation.
3. Because of lesser hydrophobicity, anionic surfactants are in general
less toxic than the nonionic agents.
4. Even small quantities of surfactants can damage certain food chains
in aquatic systems.
5. Due to decrease of hydrophobicity, nonionic surfactants become less
toxic when sulphated.
6. The complex formed by the reaction of anionic and cationic
surfactants is readily biodegradable and much less toxic than the
reactants themselves.
Some of the surfactants are reported to cause skin irritation, while the
others are mild to skin. The following types are recognised as being mild to
the skin: sulphosuccinate mono-esters, alkylsethionates, acylsarcosides,
acyltaurides and amphoteric agents at their isoelectric points. Alkanolamides
and fatty amine oxides are claimed to act as skin protectors and are used to
counter the skin de-fatting tendency of other surfactants in some domestic
products.
3.10 EMULSIONS
An emulsion [7, 8] is a two-phase system consisting of two incompletely
miscible liquids, the one being dispersed as finite globules in the other. The
dispersed, discontinuous internal phase is the liquid that is broken up into
globules. The surrounding liquid is known as the continuous or external
phase. Industry usually broadens this description to include colloidal
dispersions, as well as dispersions of solids such as wax-emulsions or
emulsion paints, considering them as an emulsified polymerised vehicle and
a pigment system respectively. In addition to emulsions, there are similar
systems based on other than liquid-liquid phases as shown in Table 3.4.
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Table 3.4 Emulsions and Similar systems

Type Internal Phase External Phase
Emulsion Liquid Liquid
Foam Gas Liquid
Aerosol Liquid Gas
Suspension Solid Liquid
Industry is most concerned with the emulsification of oil and water and the
designations, O/W for oil-in-water and W/O for water in oil, are widely used.
Unquestionably, emulsion formation is aided and guided by the
emulsifying agent, the usual function of which is to reduce interfacial tension
and allow the formation of the greatly enlarged interfacial area with a much
reduced energy input via mechanical agitation.
3.10.1 Emulsion Theory

When oil and water are mixed with stirring, a temporary emulsion may form,
but because of high interfacial tension, the two phases will separate quickly
unless a single or multiple emulsifying agents are added to stabilise the
system. Even so, most emulsions are thermodynamically unstable and will
eventually separate.
Emulsifiers are a subdivision of the general class of surface active agents.
Wetting agents, solubilisers, detergents and suspending agents all belong to
the same class surface active agents and sometimes the uses of many tend
to overlap. However, the term emulsifier means a product, which increases
the ease of formation of the emulsion and/or to promote the stability of the
emulsion. They are large amphiphatic molecules and promote emulsion
stability by reducing the surface tension between the oil and water phases.
When an emulsifier is added to a mixture of oil and water, it is absorbed
on the surface of the oil or water particles depending on the type of
emulsion. This phenomenon reduces interfacial tension, promotes the
stabilisation of finely dispersed particles and controls the type of emulsion
that is produced. The absorbed emulsifier forms a physical and electrostatic
barrier delaying coalescence of the dispersed particles.
At low concentration of an anionic emulsifier, a monolayer of surfactant is
absorbed and an electrical double layer built up around the droplets. The
double layer consists of the charged portion of the emulsifier at the water
interface and in case of an anionic emulsifier, the cations surround it. If the
cation concentration is low, the thickness of the electrical double layer will
be great and the long-range repulsive force will be active in causing the
droplets to repel one another when they approach. There must be sufficient
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emulsifiers to give a tightly packed film around each oil droplet. On ageing,
additional emulsifier is withdrawn from the solution and goes into the film.
Nonionic emulsifiers may also have a zigzag or convoluted helix form and
probably functions by hindering the close approach of emulsion droplets,
thus preventing coalescence.
3.10.2 Selection of Emulsifier

In selecting an emulsifier for the end product, one must consider the type of
emulsion desired, chemical compatibility with the other components in the
system, the consistency (i.e. liquid or cream), the type of equipment
available, stability under a variety of conditions, etc. For example, acidic
preparations like antiperspirant utilising aluminium salts cannot use soap
emulsifier as the latter will precipitate as aluminium salts. Similarly, an ester
type emulsifier will be hydrolysed in a strongly alkaline emulsion.
Although Griffin proposed that the emulsifiers with HLB value of 3.5-6 form
water in oil emulsions, others found that HLB value does not show good
correlation with emulsion behaviour. Stable emulsions may be obtained with
emulsifier with lower HLB values, probably because of higher emulsifier
concentration resulting in viscous emulsion and thereby, the rate of
creaming is retarded. The other important factor is the degree of emulsifier
solubility in the oil phase. Poor solubility in oil will make an emulsion
unstable.
If the required HLB number of the oil phase is known, a blend of emulsifier
the fitting required HLB may be used. If the required HLB value is not
known, it must be determined by experimentation. A pair of emulsifiers –
one of low HLB value and other of high HLB are chosen. The former is
dissolved in oil phase and the latter in water phase. A dozen of emulsions
are prepared using different mixtures of the two emulsifiers. The range of
HLB value of the mixtures that give the smoothest emulsion with least
coarseness is used. The mid-point is considered as the required HLB value.
If an emulsion having 37% oil phase consisting of mineral oil (HLB 12),
lanolin (HLB 10) and cetyl alcohol (HLB 15) in the ratio of 35:1:1, the
required HLB value can be calculated as follows:
Required HLB = Sum of oil phase of individual hydrophobic component
multiplied by respective HLB value = 35/37x12+1/37x10+1/37x15 = 12.1.
The composition (%) of a blend of two emulsifiers having HLB values 4.3
and 15 to meet the required HLB value of 12.1 may be calculated as follows:
If X is the quantity of first emulsifier as ratio, 4.3X + 15 (1-X) = 12.1 or X =
0.27 (or 27%). The required quantity of the second emulsifier = 1- 0.27 =
0.73 (or 73%).
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3.10.3 Characteristics of Emulsion

Emulsification allows a formulator to produce a product that will exhibit most,
if not all, of the physical characteristics that are desired. This is one of the
unique advantages of emulsions. For example, to apply a small percent of
an oil, wax, or film-former to a surface, the active ingredient may be
emulsified or solubilised. However, when solubilised, the solution will have
relatively fixed properties of appearance, viscosity, flammability, etc.
However, when emulsified, the emulsion can be formulated over a wide
range of appearances, viscosity, flammability and many other
characteristics.
3.10.4 Appearance of Emulsions

Emulsions may vary in appearance. The appearance is governed essentially
by the particle size and by the difference in refractive indices of the external
and internal phases. Transparency may be gained either by having both
phases of the same refractive index, or by virtue of the internal phase being
dispersed as such small particles that refraction does not occur, because
the particle size of the emulsion is several times smaller than the
wavelength of light. This is shown in the Table 3.5.
Table 3.5 Effect of Particle Size on Appearance

Particle Size Appearance
Macroglobules Two phases may be distinguished
>1 micron Milky-white emulsion
1-0.1 micron Bluish-white emulsion
0.1-0.05 micron Grey semi-transparent
< 0.05 micron Transparent
The opalescence and semi-transparency of an emulsion is explained by

Raleigh's law of light scattering, which states that the intensity of scattering
is inversely proportional to the fourth power of the wavelength. Thus, the
blue light of shorter wavelength is much more scattered and results in the
bluish colour observed, as shown in Table 3.5.
3.10.5 Viscosity of Emulsions

Emulsions can be thin or thick fluids, pastes or gels. Their viscosity is close
to that of the external phase so long as the external phase represents more
than half of the volume of the emulsion. The viscosity of the continuous
phase may be increased by adding thickeners or gelling agents that are
compatible with the emulsifier. Many thickeners, such as
carboxymethylcellulose, methylcellulose and natural gums or clays, may
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often be added with little or no change in the basic emulsifier. If the

thickener or gelling agent is itself a surfactant, adjustment of the overall
balance of the emulsifier may be necessary. Emulsion viscosity can often be
reduced by increasing the proportion of the continuous phase, usually water.
However, the addition of polar solvents such as alcohol or acetone usually
cause a marked reduction of viscosity and emulsion stability. This is
presumably because the emulsifier, being more soluble in the alcohol, is
extracted from the interface and the interface is weakened. Thickening or
thinning of the dispersed phase usually has little or no effect on the viscosity
of the emulsion. As the proportion of the internal phase is increased beyond
50% by volume, the viscosity of an emulsion increases to a point where the
emulsion is no longer fluid. When the volume of the internal phase exceeds
the volume of the external phase, the emulsion becomes crowded and the
apparent viscosity is partially structured viscosity.
Viscosity of an emulsion can be lowered by:
1. Increasing the proportion of the continuous phase.

2. Decreasing the viscosity of the continuous phase.
3. Addition of surface active agents as suspensions causing flocculation
or deflocculation.
Viscosity of an emulsion can be raised by:
1. Adding thickeners as soap gels, lipophillic fatty acids, esters, gums and
alumina gel to the continuous phase.
2. Increasing the proportion of the internal phase.
3. Reducing the particle size of the emulsion or by reducing clumping of
the existing particles.
4. Incorporating finely divided air as a third phase.
The particle size of liquid-liquid emulsion is related to the method of

preparation, the energy input, the viscosity difference between the phases
and the amount and type of surfactant used.
A simplified counting tool has been described by Becher [9]. The particle
size may be roughly estimated by noting the appearance of a thin layer as it
drains from the side-wall of a jar. Larger is the particle size, higher is the
coalescence and lower is the stability.
The particle size of an emulsion may be reduced by increasing the amount
of emulsifier, by improving the HLB value of the emulsifier, by preparing the
emulsion via phase inversion to provide an extended internal phase at the
time of phase inversion to the final emulsion type and by improved agitation.
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3.10.6 Stability of Emulsion

An emulsion may break in two ways – by creaming or by phase separation.
Since the particles of an emulsion are freely suspended in a liquid, they
obey Stokes law, unless electrically charged. The settling or rising of the
particles is apparent by a difference in colour shading of the layers formed.
These actions are termed sedimentation and creaming or sometimes
referred to as downward and upward creaming respectively, the direction
depending on the specific gravity of the two phases. The greater is the
difference of the specific gravity, the more rapid and complete is the
separation. Lower the size or greater the electrical charge of the particles
and higher the viscosity of the continuous phase, the slower will be the
separation. Creaming is not called phase separation until the continuous
phase is clear.
Phase separation is a result of agglomeration and coalescence of the
dispersed phase. It is usually reversible if a relatively large proportion of
emulsifier is employed. Most emulsions that are prepared using
considerable mechanical effort are not reversible.
True emulsion stability is achieved when the particles of the dispersed
phase do not agglomerate and increase in size. Many commercial
emulsions have added requirements like no creaming and stability to
vibration, high shear, elevated temperature, dilution, addition of salts,
solvents, etc. The dispersability or solubility of emulsion is determined by the
continuous phase. Thus, if the continuous or external phase is water
soluble, the emulsion may be diluted with water.
3.11 SOAPS
Soap is a metallic salt of a saturated/unsaturated higher fatty acid. There
may be various metallic salts, but only sodium and potassium salts are used
as detergents. Commercially soap is manufactured by boiling natural oils or
fats with aqueous solutions of sodium or potassium hydroxide, the reaction,
known as saponification, takes place as shown in Eqn. 3.8.
CR H2R+1O·OC-CH2 CH2OH
CR H2R+1O·OC-CH + 3NaOH Æ 3 CRH2R+1COONa + CHOH (3.8)
CR H2R+1O·OC-CH2 CH2OH
The three carboxylic ester groups may carry the same (as shown in the
equation) or different hydrophobes, generally containing 8 to 22 carbon
atoms, the most common being laurate, palmitate and stearate among the
saturated types, and oleate and linoleate among the unsaturated. At
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ambient temperatures, the unsaturated fats tends to be liquids and the

saturated ones solids. Natural oils and fats are triglycerides, i.e. esters of
fatty acids with glycerol. The above reaction gives out glycerol as a by-
product. The mixture of soap and glycerol, thus obtained, is then saturated
with common salt. Soap, being sparingly soluble, separates and rises to the
surface, where from it is skimmed off. It is washed with water and dried. Oils
used in soap manufacture are coconut oil, tallow, olive oil, cotton seed oil,
palm oil, groundnut oil, soya bean oil, bone fats, etc. The above oils are
triglycerides of one or more of the following fatty acids – caprylic (R=7),
capric (R = 9), lauric (R = 11), myristic (R = 13), palmitic (R = 15), stearic
acid (R = 17), oleic (R = 17, double branched chain), linoleic (R = 17, triple
branched chain) acids.
In a more recent process, fat-splitting compound called Twichell’s reagent
is used. It is prepared from oleic acid, benzene and sulphuric acid. Oils or
fats are boiled with equal quantity of water and then 1% (on the weight of
the fat) of the above reagent is added with stirring. The hydrolysis is
complete after a period of 30 hours. Soaps are manufactured by neutralising
the separated fatty acid with sodium carbonate or hydroxide. The process
permits recovery of glycerol in much purer form [10].
Soap dissolves sparingly in cold water but dissolves readily in hot water.
In dilute solutions the molecules are ionised as follows:
- +
CRH2R+1COONa ↔ CRH2R+1COO + Na (3.9)
Soap and free fatty acids may combine to form what is called acid soap.
The relative proportions of various ions and molecules, which are in
equilibrium, will depend upon the dilution of the solution and the nature of
the fatty acids combined with the alkali metal. The solutions are colloidal.
When a concentrated solution of soap is cooled, the latter does not
crystallise out as an inorganic salt, but forms a gel, which melts on cooling.
Relatively high electrical conductivity of soap solution can be observed, a
feature not a characteristic of normal colloidal dispersions. It is suggested
that this is due to the presence of ionic micelles at above 0.03%
concentration, which are formed because they brought about a reduction in
the surface free energy of the long-chain molecules by aggregation.
3.11.1 Properties of Soap

The number of carbon atoms in the aliphatic chain mainly determines the
properties of soap. No detergency power can be expected if number of -CH2
groups is less than 9. One of the highest naturally occurring fatty acids,
sodium stearate with 17 carbon atoms attached to the carboxyl group, is an
extremely good detergent. However, due to high molecular weight, the
solubility in water is poor, especially at low temperature. Oleic acid has the
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same number of carbon atoms as stearic acid, it has similar detergency, but
its solubility is higher due to the presence of a double bond at the 9:10
position dividing the chain into two segments.
Sodium laurate with 11 -CH2 groups is much more soluble, but it
possesses moderate detergency. The properties of soap are greatly
governed by its molecular weight, which also determines its melting point.
However, the fatty acids are generally mixtures and their melting points are
not clearly defined. Hence, an alternate property called titre is more widely
used. The titre is the setting point – the temperature at which the molten
fatty acids solidify. This is easier to measure than melting point. The molten
fatty acid is placed in a glass tube and is allowed to cool. A thermometer is
used to stir the molten mass vigorously and the temperature at which
crystallisation accompanied by cloudiness starts is noted. A slight rise in
temperature at this time is noted. The peak of the temporary rise in
temperature is the titre of the fatty acid. The titre of castor oil, olive oil,
coconut oil, cotton-seed oil and tallow are 3°C, 25°C, 30°C, 35°C and
40-45°C respectively.
A good soap should have the following properties:
1. At least 62% of combined fatty acids and between 6.5 and 8.5% of
combined alkali. The actual percentage of combined alkali depends
upon the mean molecular weight of the fatty acids. High molecular
weight fatty acids provide better detergency and have comparatively
low combined alkali content.
2. Free fat or fatty acid, unsaponifiable matter and free alkali should be
absent. Sodium carbonate or sodium silicate is often added to make
the soap harder or to improve its detergent power. However, it is
preferable to use pure soap and a predetermined amount of alkali
should be added, if required.
3. Salts such as common salt or Glauber’s salt should be present in
small quantities – any excess should be considered as adulterant.
3.12 SYNTHETIC DETERGENTS

Soaps of all types are inactivated in acid solution and are rendered
ineffective by water hardness and high concentration of dissolved salts such
as seawater. For such uses, detergents or alkaline cleaner must be
employed. The starting materials for soaps are natural products like oils and
fats, while synthetic detergents or simply known as detergent are
synthesised from various chemicals.
The term detergent is reserved for those agents capable of removing,
dispersing and suspending solid soils from the surface being cleaned.
Detergents are considered to be surface active agents, which lower the
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surface tension of their solutions and promote wetting out of soil particles.
They also have the property of deflocculating soil clumps and keeping in
suspension so that rinsing action can be carried out without redepositing the
soil on the substrate.
Detergents may be anionic or nonionic in nature. Anionic detergents are
most powerful and popular. Chemically they belong to sulphates of fatty
alcohols, olefins, oils (e.g. sulphated castor oil or Turkey red oil),
monoglycerides, amide condensates, alkyl aryl polyether and sulphonates of
alkyl amides, ethers, olefins (α-olefin sulphonate), etc. A very popular
ingredient in detergent manufacture is dodecylbenzene sulphonate,
commonly known as acid slurry. It is neutralised with sodium carbonate
(product known as STPP) or caustic soda to prepare soluble sodium salt.
Nonionic detergents are unaffected by any ionic reaction and are not
precipitated in the presence of cationic agents as in case of anionic
detergents. Foaming is generally less for nonionics and detergency for oily
soil is good. The properties of almost any class of nonionic agents can be
altered in gradual steps from emulsifier to powerful cleaner, from wetting
agent to penetrant, by varying the ratio of hydrophobic to hydrophilic groups.
Important chemical classes belonging to this group are condensates of fatty
acids with amines (e.g. diethanolamine) and ethylene oxide, condensates of
ethylene oxide with alkyl phenols, polypropylene glycol and fatty alcohols.
3.12.1 Detergent auxiliaries

Detergents are formulated products and most often contain, in addition to
surfactants, several auxiliaries like builders, soil-suspending or anti-
redeposition agents, anticorrosion agents, suds-controlling agents, fabric
whiteners, bluing agents, bleaches, fabric softeners, antibacterial agents,
enzymes, perfumes and others. These are added into detergents to improve
their efficiency.
The function of protective colloids, thickeners or suspending agents is to
keep soil particles suspended and dispersed, thus preventing agglomeration
into clumps of soil with consequent redeposition onto the surface of the
material being cleaned. Typical agents are bentonite, carboxymethyl
cellulose (CMC), polyvinyl alcohol, gelatine, glue, starch, etc. Bentonite and
CMC are most important.
Builders are sequestering agents or water softening agents, which
combine with calcium or magnesium to form soluble complexes instead of
insoluble precipitates. Among other functions performed by builders, is
maintenance of alkalinity in the wash solution. Soap itself is decomposed by
acid and is hydrolysed to a certain extent even by pure water. Builders also
neutralise fatty acid components in soil forming soap. In addition, they
increase the negative zeta potentials of soil and fabric, and thus aid in
114
preventing soil from redepositioning during washing process. Builders or

sequestering agents are of two types – polyphosphates and organic amine
derivatives. Both function by chelating or complexing hardness ions to form
undissociated soluble compounds. Polyphosphates include sodium
tetrapyrophosphate, sodium hexametaphosphate, pentasodium
tripolyphosphate, tetrasodium and tetrapotassium pyrophosphate, trisodium
orthophosphate. The phosphates cannot be used at pH 12 and above. The
pH of effectiveness is limited to 7 to 10.5.
Organic chelating agents are much more effective in sequestering
hardness than polyphosphates, but are costlier. Most of them are related to
ethylenediaminetetracetic acid (EDTA). They are stable in solution and the
effectiveness increases as pH increases. The relative sequestering power of
sodium salts of EDTA, hexametaphosphate and tripolyphosphate are 201,
74 and 36 mg/CaCO3 sequestration per gram [11]. The less effective but
cheaper substitute for EDTA is nitrilotriacetic acid (NTA). Both are used as
sodium salt. Less popular builders are sodium carbonate, borax, silicates,
citrates, organic polymers and polyelectrolytes, oxidised starches and
sodium oxydiacetate (ODA). In recent years, the trend is to replace EDTA
and DTPA with heptonate and gluconate.
Polyphosphates and phosphonates have low bioeliminability and may
cause eutrophication (excessive growth of aquatic plants) and have been
banned in many countries. The recent trend in developed countries is to
use acrylic copolymers (e.g. sodium acrylate, sodium maleate) as detergent
builders instead of phosphates. The use of carbonates is also gaining favour
as a replacement of phosphates.
One of the most noticeable properties of many surface active agents is
their ability to produce foam. The importance of foaming power is sometimes
overemphasised, because it is being falsely linked with detergent efficiency.
For some purposes, however, such as ore floatation, fire-fighting
compositions, certain cosmetic preparations, etc. it is of primary importance.
In many applications, foam is a secondary phenomenon and purely
incidental to the desired working of the detergent. Sometimes, as in
distillations and evaporations, it is actually a serious disadvantage. Foam or
lather may be defined as a measurably stable honeycomb structure of air
cells whose walls consist of thin liquid films. Foams are formed by
introducing air or other gas under the surface of a mass of liquid or by
agitating the surface so that it breaks and encloses air. Foams are
destroyed as the liquid drains out from between the two parallel surfaces of
the individual film, thereby causing the film to become progressively thinner.
At a certain thickness, the film collapses.
Pure liquids do not foam. Nevertheless, various solutions (e.g. certain
inorganic salt solutions) besides those containing surface active agents,
115
have marked foaming power. Surface tension destroys any individual film.
Hence, solutions of low surface tension are best foamers.
Solvents find many uses in cleaning operations. Degreasing by the use of
solvents alone is an important operation. However, it is not uncommon to
use solvents and surface active agents together. Naphtha soaps have long
been popular, and industrially compounded detergents, such as Merpentine,
comprising a synthetic detergent and turpentine, are used for special
purposes. Water-immiscible solvents are added to detergent solutions when
the soil is extraordinarily heavy and is greasy in nature, for example, in
removing paint or tar from raw wool. The solvent is usually added to a
concentrated stock solution of the soap or detergent, in which it forms a
stable emulsion. The solvent remains emulsified in the diluted, ready-to-use
bath. It probably functions by dissolving the soil, thus rendering it fluid and
easy to remove by emulsification in the aqueous phase of the bath. Among
commonly used solvents are pine oil, terpene solvents, aromatic solvents
and particularly hydroaromatic solvents such as hexalin and tetralin.
Dry-cleaning, of course, uses solvents as the bath liquor and employs
solvent-soluble detergents. The solvents, both synthetics and petroleum
types, are used in dry-cleaning of textile materials. Perchloroethylene
dominates the field of synthetic solvents, although some trichloroethylene
and carbon tetrachloride are still used. Considerable quantities of both
Stoddard solvent and 140°F (60°C) solvent are used in petroleum systems.
Some of these solvents are now incorporated in liquid detergents, specially
used for textile scouring purpose. A small amount of solvent is emulsified
into liquid detergents, which promotes quick removal of oily and waxy
materials. However, incorporation of solvents enhances water pollution
problem.
3.12.2 Theory of detergency

In textile scouring and in most detergency jobs, a film of oil (and wax in case
of scouring) accompanied by dirt is to be removed from the fibre or fabric
surface. The job can be divided into four steps:
1. At first, the material surface is to be wetted by the aqueous phase.

2. The oil, the wax and the dirt must be detached from the material.
3. The oil/soil is to be dispersed in the deterging medium.
4. A stable emulsion/dispersion of the oil should be formed to prevent
redeposition on the cleaned surface.
To accomplish each of the basic sub-processes of detergency, three types

of means are available − mechanical, physical and chemical. The agitator in
a washing machine is a mechanical means. The solution action of a solvent
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and the wetting action of a surface active agent are examples of physical
action. The chemical conversion of an insoluble soil to a soluble material
employs the chemical means for effecting cleaning.
The first step in detergency is the penetration of the wash liquor into the
fabric, replacing the fibre-air interface with the fibre-aqueous solution
interface. This takes place in two successive stages: first wetting of the
surface, and then of the bulk of the fabric.
The physicochemical basis for wetting of a solid surface by a liquid may
be explained as follows (Fig. 3.1). A drop of liquid (W) placed on a fibre
surface (F) in air (A) will spread out until it makes a contact angle θ, defined
by the plane of the solid surface and the tangent to the liquid-air interface, θ
is measured in liquid. The contact angle is a measure of the degree to which
a solid body is wetted by a liquid. This angle is a characteristic equilibrium of
a solid-liquid system and that its magnitude is inversely related to the
attraction between the two phases.
To establish a contact angle, the most common procedure has been to
place drop of liquid on the horizontal surface of the solid and measure the
angle directly by some optically enhanced means. If the liquid drop spreads
completely, the contact angle is considered to be zero. For this to happen, it
is obvious that the attraction between solid and liquid must be at least as
great as the liquid-liquid attraction. At the other extreme, the liquid may form
a sphere so that the contact angle would be 180°. In most real situations,
the influence of gravity will distort the liquid solubility that an actual 180°
angle would not be formed.
γWA A
θ W
γFA γFW
F
Fig. 3.1 Vectors Representing Forces at Fibre/Water/Air Interface
The formation of water droplets can be explained by considering forces

operating at water, fibre and air interfaces. The shape of the water layer on
the fibre, at equilibrium, will be resultant of the following three forces:
1. The surface tension between water drop and surrounding air, γWA
2. The surface tension between fibre and water, γFW
3. The surface tension between fibre and air, γFA
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The forces acting at one of the junctions between the three phases are
represented in Figure 3.1. The direction of γWA is that of a tangent to the
surface of the water drop at the point of contact.
The measurement of interfacial tension is difficult, but the determination of
the value of θ is comparatively easy. Useful information can be derived from
the contact angle because when the forces are in equilibrium, their
relationship is expressed by Young-Dupré equation, neglecting gravity
effects, shown in Eqn. 3.10.
γFA = γFW + γWA cos θ, 0º ≤ θ < 180º
γFA - γFW
or cos θ =  (3.10)
γWA
As mentioned γ represents surface or interfacial tensions in dynes per
centimetre which, for liquids, are numerically equal to surface free energies
in ergs per square centimetre. It must be remembered that in practice, the
air phase (A) contains vapour of the liquid W. Young-Dupré relationship has
never been confirmed because an independent method of measuring either
γFA or γFW has not yet been achieved.
At equilibrium, the surface free energy should be at a minimum.
Accordingly, the solid should be covered preferentially with the phase having
lowest surface tension. A cosine can vary from +1 (θ = 0°) through 0 (θ = 90°)
to –1 (θ = 180°).
1. When (γFA - γFW) ≥ γWA , θ = 0° and the drop spreads out completely.
2. For γWA > (γFA - γFW) > - γWA , the drop makes a finite contact angle.
3. If (γFA - γFW) ≤ - γWA , θ = 180° and the drop will be completely
spherical.
A situation never encountered in practice is for θ to reach 180°, meaning
no adhesion between liquid and solid. On smooth surfaces, the contact
angle rarely exceeds 120°. In practice, a contact-angle greater than 90°
indicates poor wetting of the solid by the liquid. There is a tradition to label
solid surfaces that form advancing contact angles less than 90° as
hydrophilic or wetting, and those for θ > 90° as hydrophobic or non-wetting.
However, it has been claimed [5] to be illogical and misleading when applied
to systems where there are no capillary effects. 90° contact-angle as
boundary condition is valid only for capillaries with parallel walls. In most
cases dealing with fibrous systems, capillary walls are curved and an
advancing angle greater than 90° may still permits some spontaneous
uptake. While geometrical factors (surface roughness and porosity) have a
profound effect on contact angles and wettability, the chemical nature and
physicochemical characteristics of the solid surface are also important. The
work of Zisman and co-workers, summarised in [12], has reported a linear
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relationship between the cosine of the contact angles formed on a smooth

surface by different liquids and the surface tension of these liquids:
cos θ = a - bγWA (3.11)
The linear relationship was found to hold good for several organic
polymers and low molecular weight compounds despite the variety of
spreading liquids used. These solids, like most organic substances, have
free surface energies below 100 ergs/cm2 and they are, therefore, said to
have low-energy surfaces.
The equilibrium contact angles can be measured for thoroughly purified
liquids and very clean and glossy smooth surfaces. Frequently a liquid
makes a greater contact angle when advancing over a dry surface than
when receding form a previously wetted surface. However, in this case, the
advancing and receding contact angles can be made identical by letting the
liquid drops to advance or recede very slowly to approach equilibrium
conditions. By plotting cos θ against surface tension, γWA of various liquids
for a particular solid, we get a straight line. The surface tension at which the
straight line reaches unit value for cos θ is called critical surface tension for
spreading, γc. The liquids of surface tension equal to or smaller than the γc of
a solid will spread out indefinitely on its surface. As a cosine cannot exceed
unity, the above linear wetting curve becomes horizontal once they reach γc.
The critical surface tension is a characteristic property of a solid. The most
inert and least polar solids such as polytetrafluroethylenes have lowest γc
values and very few liquids spread freely on their surfaces.
Wetting out of fabrics is not a serious problem in detergency. The
polymers commonly used for textile fibres have critical surface tensions for
spreading of 40 dyne/cm or higher and many surfactants lower the surface
tension of water to about 30 dyne/cm at critical micellar concentration.
Furthermore, fabrics have higher critical surface tension than smooth film of
the same material. The difference was found to be about 20 dynes/cm for
flurocarbon and silicon finishes [13]. These soil-repellent finishes probably
render the fabric difficult to wet by detergent solutions.
It is reported [14] that the contact angle will be even smaller for a rough
surface, if the contact angle on a smooth surface of the same material is
less than 90°. However, if the contact angle on the smooth surface is higher
than 90°, on the rough surface it will be still higher. In other words, a
complete or partially wettable surface will be more wettable if rough. A
nonwettable surface will be even less wettable if rough.
When a textile material covered with a layer of oil or wax, is immersed in a
warm aqueous solution of soap and observed under a microscope, it can be
seen that the film bunches up and ultimately forms spherical globules which
are easily detached.
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The pioneering work of Adams [15] has shown that the removal of oily soil
from fibre surfaces consists of its displacement by the wash water through a
mechanism of preferential wetting, also termed as exchange wetting.
Formally, there is an analogy between the displacement of air by water
discussed earlier and the displacement of oil by water. When a fibre soiled
with oil is immersed in pure water, usually very little happens. θ of oil phase
remains close to zero and θ of aqueous phase is nearly 180°. Addition of a
very small amount of surfactant to the water lowers θ and increases cos θ of
the aqueous phase.
In Figure 3.1, we may now consider, an oil drop (instead of water drop)
surrounded by aqueous phase (instead of air). The value of θ will decide
which liquid phase will stick to the solid surface and which one will be
displaced. Without modifying the Eqn. 3.10, we may consider equivalent
surface tensions with phases A = aqueous (instead of air) and W = oil
(instead of water). Now, in Eqn. 3.10, if γFA > γFW, cos θ must be positive and
contact angle should be less than 90°. In this case, the oil will tend to cover
the fibre, in preference to the aqueous phase. When, however, θ is greater
than 90°, the value of cos θ will be negative and, therefore, γFW must be
greater than γFA, with the result that the aqueous phase will displace the oil.
With increasing amount of surface active agent in solution, γFA will be much
lower as compared to γFW. Consequently, θ will be much greater than 90°
and the oil drops will be displaced much quickly and much efficiently. In
presence of a detergent, the oil will assemble as spherical drops, which will
be easily detached, from the fibre by agitation. The oil globules acquire a
sheath of detergent molecules oriented with their hydrophobic tails
immersed in the oil and their hydrophilic heads projecting into the aqueous
phase. The surface active molecules will also align themselves on the fibre,
again with the hydrophilic groups directed outwards towards the detergent
solution. The two hydrophilic layers will attract water molecules, which will
be pushed in between the oil drop and the fibre surface, and this will assist
in detachment of the oil drop.
The dispersed oil globules will carry negative charge due to migration of
sodium ions. The oil globules will mutually repel each other making emulsion
stable and thus, redeposition will be prevented.
The particles of dirt will also attract surface active molecules. Dirt may be
of two types. In one case, the hydrophobic tail is being attracted with
hydrophilic group directed outward as in case of oil drop. In other case,
hydrophobic tails are projected outward. This layer will behave like a drop of
grease and will further attract the hydrophobic tail of surface active
molecules. The second layer will direct hydrophilic heads outward. In either
case, the result is a particle surrounded by a hydrophilic sheath with
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negative charge, as in the case of dispersed oil drop. The dispersion will be
stabilised due to this negative charge.
The significance of stabilisation of the emulsion or dispersion varies
considerably between different cleaning operations and probably is of
greatest importance in laundering where tatte-tale grey is the result of
redeposited soil.
Redeposition of soil can be avoided or minimised by several means [11]
such as:
1. Maintenance of the soil in such finely dispersed condition that it will
not get entrapped again on the cleaned surface.
2. Establishment of a repulsion, soil to soil, and between soil and
cleaned surface.
3. Removal of contaminated detergent solution from contact with the
surface being cleaned.
4. Continued agitation of the contaminated solution while still in contact
with the surface, to prevent settlement of the soil.
5. Flushing of the cleaned surface to rinse off not only residual
detergent solution, but also any soil that may have collected back on
the surface.
When the cleaning action of surfactants is considered, their adsorption on
the substrate and on the soil is important. The degree of adsorption depends
on the type and concentration of the surfactant, on the temperature and
particularly on the type of adsorbent i.e. the substrate or soil. The
mechanical, electrical and chemical properties of the substrate-liquid and
soil-liquid interfaces are altered, which consequently affect the cleaning
efficiency of the surfactant.
An important consideration in detergency is the critical micellar
concentration. In case of sodium lauryl sulphate, the surface tension
decreases with increase in detergent concentration up to 0.15% and then
surface tension increases with further increase in concentration. Detergency
increases significantly with increase in concentration up to 0.25% and then
changes marginally. Hence, the concentration above 0.25% is wastage of
detergent. The discontinuity in the property with increase in concentration is
due to micelle formation. Individual molecule participates in surface activity
and micelle formation keeps the concentration of the molecules constant in
the solution. The length of the hydrophobic tails has considerable influence
on the value of critical micellar concentration, the nature of the hydrophilic
head seems to be comparatively less important.
The soils encountered in different industries vary, both in chemical nature
and in the manner in which they are attached to the object to be cleaned.
Thus, in laundering, the soil on a particular garment might be a combination
of any number of soiling agents with which the garment comes in contact
during use. In the textile industry, the soil may be a naturally occurring raw
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fibre constituent that must be removed in processing or it may be an agent

that has been added to temporarily assist some steps in the yarn or fabric
manufacturing process. The soils may be classified as:
1. Those which are soluble in the liquid phase of the deterging system.
2. Those which are rendered soluble or otherwise dispersible by the
chemical action of some component of the deterging system.
3. Those which are inert to solution and chemical action and which are
only removable by properly applied mechanical energy, perhaps
assisted by the physical effects of some surface active agent.
3.12.3 Evaluation of Detergency

It is difficult to study an effect such as detergency that involves numerous
factors on which full control cannot be attained. More often, however, the
study is limited to a few more easily controlled factors.
There are two categories of tests for determining detersive efficiency of a
given bath. The most accurate is a field trial under conditions of actual use.
Many wool-scouring plants test new detergents by scouring wool with them
under their usual operating conditions. In tests of this nature, the soiled
substrates are not truly standard, but they fall within a definite range and are
standard from practical point of view. In the laundry-work, soil removal is
usually estimated visually. In wool scouring, on the other hand, the degree
of cleaning is measured very accurately by extracting and weighing the
residual wool grease on fibres.
However, these field trials are in large scale and require huge material and
time. Moreover, the operating conditions are usually fixed, either by customs
or by limitation of the equipment. A new detergent may require somewhat
different conditions to deliver its best performance. To overcome these
defects, a number of laboratory tests are carried out using artificial washing
conditions, but the sample to be cleaned is taken from a full-scale plant lot of
soiled goods. These tests are particularly important in the textile industry.
Detergents for wool scouring may be tested by taking a small weighed
quantity of wool, thoroughly opened by hand and treated in two or three
successive detergent baths containing 0.05% detergent and 0.3% soda ash
at about 120°F (49°C). After treatment in the final bath, the wool is rinsed,
squeezed out and air-dried. The residual wool wax, measured by extraction
with petroleum ether, should be less than 1% on the weight of wool.
Detergents for scouring of cotton and rayon piece goods should be tested
under conditions similar to those encountered in actual plant operation.
Temperature, time of treatment, bath concentration, degree of agitation and
liquor ratio are carefully controlled. After being washed, rinsed and dried, the
fabric test strips are partially immersed in water. The height to which the
water rises by capillary or wicking action, and the rate of rise, indicate the
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extent to which hydrophobic impurities are removed i.e. the efficiency of

cleaning. Other wetting tests such as sinking time, etc. may also be
employed.
The method, which is most widely used, for determining detergency
involves use of a mechanical washing device called launderometer. This
consists of a thermostatic bath fitted with rotating clamps for holding a series
of stainless-steel pots. The standard soiled cloths are placed inside the pots
together with a measured amount of the detergent bath to be tested and a
number of small stainless-steel balls. The balls provide mechanical agitation
and a light beating action as the pots rotate. The washing is carried out for a
fixed length of time at a fixed temperature. After washing, the samples are
removed and rinsed with water. The degree of soil removal is measured
directly, or more effectively by measuring whiteness visually or
instrumentally by a spectrophotometer, in terms of whiteness indices.
Standard soils may be prepared in various ways such as:
1. For cotton, 6 g. oildag (a commercial graphite-mineral oil

suspension) or finely dispersed carbon black, 1.7 g an edible
vegetable oil and 3,000 ml carbon tetrachloride.
2. For worsted 0.5 g lamp black, 7.5 g edible tallow, 25 g Nujol
(medicinal mineral oil) and 4,000 ml carbon tetrachloride.
Carbon tetrachloride acts merely as a solvent or carrier for soil. The goods
are impregnated in the solution, squeezed and dried before putting into the
detergent bath.
3.13 ABSORBENCY
Absorbency refers to the ability of a porous solid material to take up and
retain, under various conditions, significant amount of water or other liquids
by several distinct spontaneous processes, namely:
1. The condensation of liquid into the pores or crevices of a solid matrix

from the vapour phase (capillary condensation).
2. The penetration of liquid into a solid matrix when one side of the
porous solid is in contact with a large liquid reservoir (penetration
absorption).
3. The movement of small liquid masses (also called threads) into the
interior of a porous matrix.
4. The uptake of liquid into a porous solid, which is totally immersed
(immersion absorption) in a large liquid reservoir expelling trapped
air from the solid.
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5. The motion of either large or small liquid masses along the

macroscopically rough surface of a porous matrix.
Absorbency depends on the bulk properties such as resistance to

compression-expansion, shear and torsional distortion, etc. of the solid, the
structure of solid matrix, namely pore size, size distribution, shape, texture
and roughness of the solid surfaces, and liquid properties like viscosity. It
also critically depends upon the specific chemical makeup of the three
interfaces involved. The surfactants play an important role in determining the
properties of the interfaces involved.
3.13.1 Wetting and Rewetting Agents

There are two principal modes by which surfactants are used to promote
absorbency. As wetting agent, the surfactant is added to the liquor prior to
its contact with the solid porous mass. Wetting agents are used as aids in a
variety of processes including cleaning of impurities from textile materials
made of natural fibres. They are used in many processes whose object is
the impregnation of porous solids such as textiles or papers with various
materials such as sizing, wet and dry strength additives, antistatic agents,
dyes, fillers, softeners, water-proofing agents, soil release additives, etc. In
every case, the object of the wetting step is the rapid and thorough
displacement of air from the surface of the solid so that a uniform and
complete deposition upon it of various chemicals may be effected. The
wetting agent is usually just a vehicle for the accomplishment of the
necessary liquid-solid contact. In some cases it is desired to deposit a
chemical on the solid surface, the chemical itself be a wetting agent.
In the second major mode as rewetting agent, surfactant is used to
promote absorbency as pre-treatments of the solid surface with an
absorbent, which promote subsequent wetting by a liquid. It acts by yielding
a minimum value for the solid-liquid interfacial tension keeping gas-liquid
interfacial tension almost unaffected. The surface tension of the liquid is not
significantly changed unless the rewetting agent is rapidly desorbed. Such
products are used to manufacture various absorbent products like baby
diapers, surgical dressings, sanitary napkins, absorbent cotton, blotting
paper, etc. These are used mostly in the manufacturing textiles, which are
hydrophobic in the absence of such treatment. Good wetting agents may be
good rewetting agents too, the usual case is, however, just reverse.
For nonionic surfactants, optimum wetting behaviour at 25°C appears to
be attained for compounds with 6-8 oxyethylene units and an effective
hydrophobic chain length of 10-11 carbon atoms. Highest wetting power is
generally achieved by surfactants whose cloud points are just above the
temperature at which the test is conducted. For nonionic block copolymer
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surfactants, optimum wetting is achieved by materials with just enough

polyoxyethylene units to confer a minimal solubility.
For both ionic and nonionic surfactants, a considerable improvement in
wetting behaviour can be achieved by employing branched chain
hydrophobic groups rather than straight chain compounds [16]. This has
been confirmed by studying wettability of a series of branched C14
compound (sodium hexadecylsulphate) for cotton material [17]. The
diffusibity of the C7-C7 sulphate is more than twice that of the C14 straight
sulphate. Optimum wetting is achieved when the hydrophilic group is
centrally located in the molecule. Wetting may not be affected much by the
reduction of liquid surface tension. Only strong reduction may be helpful.
Though wetting is the first step in cleaning process, good wetting agents
are often poor candidates for detergency. Paraffin chain salts of 16-carbon
atoms give good detergency but are poor wetting agents, whereas the C12
compounds are good wetting agents but poor detergents. Good detergent
action depends on the highest possible equilibrium adsorption, while wetting
is more strongly dependent on kinetics. In choosing a wetting agent for use
in conjunction with an overall process (such as detergency) involving several
steps, other considerations must be taken into account. Powerful detergent
action, for example, may be achieved by using mixtures of strongly
absorbing nonionics in mixture with branched-chain anionics [17].
Rewetting agents are used in a variety of hydrophobic solid substrates
such as various synthetic fibres and a few natural fibres. Poor hydrophilicity
of such products also affects some of their properties like antistatic and soil
release properties. The use of rewetting agents does not improve
absorbency of pure cellulosic materials. In fact, good anionic wetting agents
for other materials show little tendency to adsorb on pure cellulose.
However, natural cellulosic fibres carry a number of hydrophobic impurities,
which significantly reduce its wettability in natural state. Localised
hydrophobicity may be caused by incomplete removal of such impurities or
purposeful/accidental addition of lubricants and sizes at various stages of
processing. A rewetting agent may be used to provide good initial
absorbency. They provide good wetting only for the initial contact of the
material but do not provide a permanent enhancement of hydrophilicity. If a
high degree of permanence or substantivity is required, the surfactant must
generally be covalent bonded to the surface, or polymerised in situ, cross-
linked, etc. In the early 1970s a new class of materials called
superabsorbent were developed, which could retain a substantial quantity of
fluid in its polymer network, significantly more than what could be held in
conventional absorbent fibres.
The role of rewetting agents is to either cover an entire hydrophobic
surface or selectively cover hydrophobic patches of otherwise hydrophilic
surfaces. For good performance, they must be adsorbed strongly and evenly
125
on the hydrophobic surface from an aqueous solution exposing its

hydrophilic moiety to the solution phase. This usually implies amphipathic
adsorption. The kinetics of adsorption may be unimportant as sufficient time
may be provided for the equilibrium to be achieved with anionic or nonionic
surfactants, with the latter generally preferred due to the greater density of
their equilibrium adsorption.
A second general criterion for rewetting surfactants is that the anchorage
to the solid surface be at least sufficiently strong so that they resist
reorientation and desorption over the period of the time of storage of the
treated product or during the wetting period. Thermodynamics favour such
reorientation since it results in lowering of surface free energy. Lower energy
hydrocarbon groups, for example, are exposed, rendering the surface
hydrophobic. Strong amphipathic anchoring is favoured by relatively large
hydrophobic groups and hydrophilic groups of just sufficient size to confer
necessary solubility for the purpose of its application and be sufficient to
impart the necessary wetting characteristics of the surface.
A third general criterion for choosing rewetting agents concerns the ability
of the material to adsorb evenly over the solid. It is observed that
surfactants, which are liquids or amorphous solids when dry, make better
rewetting agents than those which are crystalline.
In textile finishing, resiliency, dimensional stability and wrinkle resistance
are associated with hydrophobicity, while soil release, moisture absorbency
and antistatic properties are associated with hydrophilicity. Finishes using
surfactants often rendered durable through in situ bonding to the fibre or
lateral polymerisation, must provide acceptable compromises with respect to
these properties. This often requires the use of fairly complex mixtures of
surfactants, each having a different function.
Surfactants provide a powerful means for promoting absorbency, acting as
either wetting or rewetting agents. In either case, the adsorption of the
surfactant to the solid surface exposing lyophilic functional groups is
essential. Substances as wetting agents must diffuse quickly to the interface
and, therefore, branched chain, medium weight materials are preferred. As
rewetting agents, strong equilibrium adsorption and the strength of
monolayer overturning and desorption.
3.14 TEXTILE AUXILIARIES

As mentioned at the beginning, every colorant-substrate system requires the
use of additional products, known as auxiliaries, to ensure its reliable
functioning and control. Soaps, detergents and wetting agents are the most
important auxiliaries, which have been discussed in detail. Unlimited types
and numbers of textile auxiliaries are in use, a few of which are discussed
126
below:
3.14.1 Dispersing Agents

Dispersing agents are substances, which promote uniform and stable
suspension of relative small particles in a given matrix. The commercial
significance of dispersing agents in the textile field is readily apparent when
we consider that 20-60% of every commercial disperse and vat dyes
consists of dispersing agent.
Three types of such agents are in use:
1. Surfactants, mainly anionic and nonionic

2. Water-soluble, polyelectrolytes, mostly anionic, such as
condensation products of formaldehyde with arylsulphonic acids (e.g.
β-naphthalene sulphonic acid) and the lignin sulphonates
3. Polymers such as acrylic acid copolymers, sulphonated polyvinyl
compounds, alginates and carboxymethylcellulose
Out of the three groups, the polyelectrolytes form the major group of
dispersing agents. They are generally incorporated in dyes during finishing
stage. The surface active agents play a subsidiary role in dispersions
involved in textile coloration.
3.14.2 Solubilising agents

The term solubilisation refers to the homogeneous mixing of an otherwise
insoluble agent into a liquid medium by addition of a solubilising agent,
invariably a surfactant. This agent acts as an amphiphilic bridge between the
insoluble agent and the medium. For example, methyl naphthalene
dissolves sparingly in water, but on addition of a surfactant such as
nonylphenol poly(oxyethylene)sulphate, its aqueous mixture changes from
colloidal to an apparently clear solution state. Solubilisation may be viewed
as changes through a reversible colloidal form that begins with wetting and
proceeds through dispersion or emulsification to solubilisation. Solubilisation
may be considered as an extension of emulsification or dispersion in which
the proportion of surfactant has been increased to the level where the
discrete droplets (or particles) that characterised the emulsion have been
completely absorbed into surfactant-medium phase.
In some cases, solubilisation is aided by the addition of a small amount of
a water-miscible solvent such as an alcohol or glycol, whereas the presence
of electrolytes can have a deleterious effect. Temperature too can be
important. A system that is emulsion (or dispersion) at one temperature may
become solubilised at a different (usually higher) temperature and vice
versa.
127
3.14.3 Levelling and Retarding agents

Unevenness in a dyed material may be caused by rapid uptake of dyes
during dyeing from aqueous solution. This can be minimised by using
levelling or retarding agents. These are invariably surfactants – anionic,
cationic, nonionic, amphoteric or their mixtures. The main mechanisms by
which levelling agents operate are:
1. Nonionic agents usually form water-soluble complexes with the dye,

some degree of solubilisation being involved.
2. Ionic agents are primarily dye or fibre substantive. Dye-substantive
agents may form complexes with the dye and there is a competition
between the levelling agent and the fibre for the dye. In case of fibre-
substantive agents, the competition is between levelling agent and
the dye for the fibre.
As the temperature of the dyebath, increases the complex gradually

breaks down, or the attraction between the agent and dye/fibre is
superseded by dye-fibre interaction so that more dye is adsorbed by the
fibre. The complex therefore should have optimum, rather than maximum,
stability relative to the conditions of application. This is achieved by
adjusting the HLB of the surfactant. However, dye-agent interaction is so
specific that each member of a range of dyes may require a different
balance. Commercial levelling agents, therefore, may contain more than one
surfactant.
Many, but not all, levelling agents promote migration of dye in addition to
retarding the dyeing process and such agents will be a further aid to level
dyeing. Levelling agents are also widely used as stripping agents, either
alone for non-destructive stripping or together with, for example reducing
agents for destructive stripping.
3.14.4 Foaming Agents

Foams are necessary for water and heat saving low-liquor processes. In
theory, any surfactant that causes foam, can be used. In practice, the choice
is between anionic and nonionic agents or their mixtures considering overall
compatibility. Long chain alcohol sulphonates and ethoxylates as well as
sulphates and sulphosuccinates are used. Among anionic agents
sodium/ammonium lauryl sulphate and sodium dioctylsulphosuccinate, and
among nonionic agents lauryl/ decyl/tridecyl alcohol polyoxyethylene may be
used. Foams are stabilised by increasing viscosity with the help of
thickening agents like polysaccharides, carboxymethylcellulose, polyvinyl
alcohol, polyacrylic acid as well as compounds like sodium tripolyphosphate,
sodium hexametaphosphate, etc.
128
3.14.5 Defoaming agents

Sometimes the presence of foam may create problems in processing, hence
they are destroyed by adding defoaming agents or antifoam. Foams are
stabilised by decreasing the rate of liquid drainage from the film walls.
Conversely, foam destabilisation can be made by increasing the liquid
drainage and thereby thinning and eventual rupture of the film. An effective
defoamer should be insoluble in the foaming system and should have a high
rate of spreading, generally due to lower surface tension than that of
foaming system.
Defoamers are generally of anionic or nonionic nature and fall into two
groups. The first group consists of water-soluble surfactants with
polar/nonpolar moiety. They simply act as spreading agents and are more
frequently used as vehicles or carriers of the second group of defoamers,
which are emulsions of water-insoluble silicones or organic based
compounds of low volatility and high spreading power. The active organic
based defoamers include:
1. Fatty acids, their glycerides and other esters, including fats, waxes,
mineral and vegetable oils, fatty alkyl-amines and amides
2. Higher alcohols such as 2-octanol, 2-ethylhexanol, cyclohexanol,
lauryl and cetyl alcohol
3. Polyglycols, especially polypropylene-1,2 or –1-3-glycol
4. Insoluble alkyl esters of phosphoric acid, especially tributyl
phosphate
The active silicon-based defoamers have traditionally been

polyalkylsiloxanes. Silica (SiO2) is chemically bonded to the polysiloxane to
render its surface hydrophobic.
3.14.6 Fibre Lubricants

Lubricants are used in wet processing to minimise the formation of durable
creases during high-temperature processing. The lubricant should form a
thin protective coating around the fibre to lower the surface tension and
flexural rigidity. Relatively hydrophobic surfactants containing a proportion of
solubilised or emulsified oil or wax are suitable for the purpose. However,
their compatibility with dyes and auxiliaries used in dyeing is to be carefully
checked. Nonionic surfactant or anionic polyoxyethylene sulphates and
phosphates are suitable. Anionic agents perform better than nonionic agents
at high temperature conditions, as no cloud point is associated with them.
Oils and wax may interfere into coloration process. Hence, ethoxylated
surfactants without them are presently in use. Such products are hydrotropic
and thus impart a temporary anti-static effect.
129
3.14.7 Softeners
It is difficult to define in scientific terms the quality of fabric softness and
handle or feel, since it involves several factors. Cationic softeners are
undoubtedly the most important as they have strong affinity for cellulosic
materials. The most common are quaternary alkylammonium compounds.
The preferred anions are methosulphate or ethosulphate, since they are less
corrosive than chlorides. Sometimes cationic softeners are mixed with a
nonionic surfactant which act as a lubricant.
3.14.8 Dye-fixing agents

Some dyes, mostly anionic in nature, are not very fast to washing when
applied on cotton. The dyed cloth may be after-treated with a cationic dye-
fixing agent to improve the fastness by the formation of a complex inside the
textile material. Previously dye-fixing agents were based on alkyl pyridinium
halides. The literatures show that many amines, quaternary ammonium,
phosphonium and tertiary sulphonium compound can be used as dye-fixing
agents. A popular product is a condensate of formaldehyde and
dicyandiamide as shown in Figure 3.2.
+ –
-[NH2–CH2–NH-C=N-CH2 -]n nCl
NH
CN
Fig. 3.2 Dye-fixing Agent

Many similar compounds such as condensates of formaldehyde and
melamine, polyamines and cyanuric chloride, chloroalkanes and
polyethylene imine have been developed as dye-fixing agents.
Formaldehyde-based compounds are not eco-friendly and are now
substituted by other products. Interaction of the dye-fixing agents relies on
the weak electrostatic bonding. Hence, the complex may not be very stable
while washing with soap/anionic detergents. Quaternary ammonium
compounds are also very effective germicides and may be used for rot-
proofing finish.
Surface active agents are, therefore, versatile in properties and uses, their
main use is as detergent. As textile auxiliaries, they have an important role
to play. The behaviour of anionic, cationic and nonionic surface active
agents largely depends on their HLB values. Other than surfactants, a large
number of organic and inorganic chemicals including various types of
polymers are also used as textile auxiliaries.
130
REFERENCES
1. J. Shore (Eds.). 1990, Colorants and auxiliaries, Volume 2 - Auxiliaries (Bradford, UK:
SDC).
th
2. Index to Textile Auxiliaries. 11 Edn. 1988, (Bradford, UK: World Textile Publications).
3. A.M. Schwartz and J.W. Perry. 1949, Surface Active Agents, Their Chemistry and
Technology (New York,USA: Interscience).
4. Griffin. 1949, J. Soc. Cosmet. Chem., 1, 311.
nd
5. P.K. Chatterjee. 1988, Absorbency, Textile Science and Technology, Vol. 7, 2 Edn,
(Amsterdam, Netherlands: Elsevier).
6. S. B. Moore et al., Text. Chem. Colorists, 19, (1987) 29.
7. J.L. Kenneth (Eds.). 1975, Emulsions and Emulsion Technology, Surfactant Science
Series (part I and II), Vol. 6 (New York: Mercel Dekker).
8. Kirk-Othmer Enclyclopedia of Chemical Technology, Vol. 8. 1985 (New York, USA:
John Wiley & Sons)
9. P. Becher. 1964, J. Colloid Sci., 19, 468-472.
10. E.R. Trotman. 1968, Textile Scouring and Bleaching (London, UK: Charles Griffin).
11. W.W. Niven (Jr.). 1955, Industrial Detergency (New York, USA: Reinhold).
12. F.M. Fowkes (Eds). 1964, Contact Angle, Wettability and Adhesion, Adv. Chem.
Series 43, American Chemical Society, Washington, USA)
13. W.G. Cutler and R.C. David. 1972, Detergency – Theory and Test Methods, Part 1
(New York, USA: Marcel Dekker).
14. H. Mark, N.S. Wooding and S M Atlas. 1971, Chemical Aftertreatment of Textiles
(New York, USA: Wiley-interscience).
15. N.K. Adam. 1937, JSDC, 53, 121.
16. M.H. Schick. 1977, Text. Chem. Colourist, 9, 31-37.
17. M.J. Schwuger. 1981, Anionic Surfactants, Chap.7, Surfactant Series, Vol. 11 (New
York, Dekker).
Preparatory Processes I Chapter
(Cleaning) 4
4.1 INTRODUCTION
For perfect coloration of a substrate, it is necessary that all the impurities be
removed from the surface so that the colorants can perfectly sit on the
surface or penetrate inside the substrate as required by the particular
system. The colorants should also be clearly visible without interference by
the colour of the impurities.
Textile materials possess a variety of impurities. Some are natural or
inheriting as discussed in chapter 1, or they may be added purposefully for
better spinnability (in yarn manufacturing) or weavability (in fabric
manufacturing). Such materials are also occasionally contaminated by
accidental impurities acquired while handling of the materials. All such
impurities are to be removed before actual dyeing or printing processes. The
steps by which the impurities are removed are called preparatory processes.
As the impurities present vary from fibre to fibre, the preparatory processes
will differ and the conditions of treatments are to be decided by considering
fibre properties too. Preparatory processes may be broadly classified into
two groups, namely:
1. Cleaning processes, where bulk of the foreign matters or impurities
are removed by physical or chemical means.
2. Whitening processes, in which trace colouring matters are destroyed
chemically or the whiteness of the materials is improved optically.
The present chapter is devoted to cleaning processes, while the next
chapter discusses whitening methods.
Cotton fibre is a single biological cell. It is built up in four parts – lumen,
secondary wall, primary wall and cuticle (inside to outside). Lumen is the
nutrient transportation tube for the cotton cell. It still contains small amounts
of bioorganic materials, which add a yellowish shade to the fibre. The
secondary wall is built up of cellulose layers – it adds about 91.5% of fibre
and has a crystallinity index of 70%. The primary cell wall, which mainly
132
consists of protein, pectic substances and glucans, is about 2.5% of fibre

weight. It has a crystallinity index of about 30%. The protective cuticle is
made of wax compounds, mineral matters, pectins, fatty acids, high
molecular weight alcohols and their esters. The outer layer was originally
thought to be made of two layers. However, later it was found that waxes do
not constitute separate layer. It is probably distributed in the primary cell
wall, but highest concentration is at the surface and seen to be closely
connected with the pectic substances. Calcium plays an important role in
binding the structure.
The composition of combined primary cell wall and cuticle is as follows [1]:
Cellulose/(xylo-)glucan - 54%,
++
Pectic substances (ca salt) - 9%,
Waxes - 14%,
Protein - 8%,
Ash - 3%,
Others - 12%.
The pectic substances act as adhesive binding wax to the fibre. When it is
removed, wax can be subsequently emulsified. Among all non-cellulosic
materials, only part of calcium pectate/wax complex has to be removed in
order to obtain a fully wettable and dyeable fibre. The natural waxes bestow
a soft touch on the fibre, but are undesirable for the subsequent dyeing and
finishing operations. These products provide lubrication during spinning, but
are to be removed subsequently to impart water absorbency.
The scouring process, while purifying the α-cellulose, imparts the
hydrophilic character and permeability necessary for the subsequent
processes (bleaching, mercerising, dyeing or printing). Good scouring is the
foundation of successful finishing.
In scouring, wax removal is not the only factor to be considered. In other
words, there is no correlation between the water absorbency and its natural
wax content. Absorbency, as indicated by the time required for wetting to
take place when the fabric is immersed in water, varies with scouring
treatment and may have markedly different values even though the wax
content is similar. An explanation to these results is that the distribution of
the wax alters absorbency. This has been confirmed by the fact that wax
extraction by solvent may yield a non-absorbent cotton, whereas a mild
scour may yield an absorbent cotton with a higher wax content. Lack of
absorbency may be observed even if the wax content is low – there is
sufficient area still covered with wax to present a hydrophobic surface. A
fibre immersed in boiling water for sometime, followed by air-drying, may be
wettable as the molten wax forms droplets which remain as such after
drying. By contrast, when drying at high temperature, the melted wax may
133
spread back over the fibre and forms a hydrophobic surface. The main
barrier to the penetration of water is the primary wall of cotton. The study
with an electron microscope shows that scouring causes numerous pits in
the primary wall. The primary wall is modified when boiled with 1.5% caustic
soda and is destroyed completely when boiled with 3% caustic soda at 40
psi pressure.
Mineral salts constitute another impurity, which must be removed during
pre-treatment. These may not affect exhaustion in batch dyeing, but in
continuous dyeing with material to liquor ratio (M:L) less than 1:1, render
some dyes to precipitate on the material. They also catalytically decompose
bleaching chemicals. Heavily coloured lignified substances like residues of
seeds, husks and leaves are also objectionable in the finished material.
4.2 AIMS OF PREPARATORY PROCESSES

The aim of preparatory wet processing is to treat the goods by standard
procedures so that they are brought to a state in which they can be dyed,
printed or finished without showing any fault or damage on the material. The
prepared materials should have the following properties:
1. Uniform power of absorption for dyes and chemicals in subsequent

processes.
2. An even water imbibition value.
3. Removal of all types of impurities including broken seeds etc.
4. Minimum damage of the material.
5. Absence of creases and wrinkles.
6. High whiteness value.
Preparation, however, is non-added-value stage of the coloration process

and for this reason, the preparation stage of the process is often not
optimised. Frequently preparation process is excessive, and high quantities
of chemicals, auxiliaries and utilities (water, steam, electricity and time) are
unnecessarily used. This can result in a high carry-over of preparation
residues (cotton impurities and preparation auxiliaries) that will have
negative influence on both dyeability and the dyeing system, or will require
long multi-stage intermediate wash-off procedures. The pretreatment
process must balance the requirements of the dyeing and finishing stages
and the intended end use of the textile material.
134
4.3 PREPARATORY PROCESSES

Different textile materials possess different inherent impurities. The
preparatory processes, therefore, vary for textile substrates. However, they
can be generalised into a few types as follows:
1. Removal of loose fibres or yarns projecting on the surface. In
singeing process, the removal is done by burning, while in shearing
and cropping process, the removal is by cutting (mostly projecting
threads, which hamper uniform printing) with the help of extruder
type of blade.
2. Removal of starch or other sizing materials, which are applied on
yarn before weaving, for better weavability. The process is known as
desizing.
3. The most important preparatory step is known as scouring, by which
most of the water-soluble and water insoluble impurities are
removed.
4. Bleaching is the last preparatory step in which colouring matters
present in the textile materials are removed. The material becomes
whiter in appearance, consequently the dyed or printed materials
become more bright and pure in colour. If the final product is to be
sold as white, the bleached material may be subsequently treated
with a blue pigment or an optical whitening agent to make the
appearance dazzling white.
5. For synthetic textile materials, an additional preparatory step called
heat-setting is done before or after scouring, to achieve dimensional
stability of the material during subsequent treatments at high
temperature.
4.4 PREPARATION OF COTTON MATERIALS

Cotton is mostly processed in fabric form and rarely in fibre form. Some
quantities of cotton material are prepared and dyed in yarn form. The
different stages for processing of cotton fabrics are shown in Figure 4.1.
Grey inspection Mending and rectification Singeing
Dyeing/Printing Bleaching Scouring Desizing
Packaging Finishing Mercerising (optional)
Fig. 4.1 Sequence of Operations in Cotton Fabric Processing

135
4.4.1 Inspection and Mending

Grey fabrics are first inspected to check whether they are in conformity with
the standard. They are sorted into lots. Fabrics in each lot should be of
same width and similar weight per unit length so that they can be processed
in the same manner. All the pieces of the lot are sewed end to end with
loops, which can be easily removed after finishing. The seams should be 10
mm wide and for certain processing e.g. chain mercerising and continuous
drying, the seams should be wider (15 mm) and stronger. In some textile
units, gluing or bonding of fabric is used instead of sewing in order to reduce
the amount of rags. A polymer coat is applied to the ends of the fabrics to
be bonded, which are then placed between heated metal surfaces. The
polymer melts and binds the ends of the pieces.
The fabric after sewing end to end is passed slowly over an inspection
table with inclined glass top. The table is illuminated with a fluorescent lamp
fitted below. The illuminated fabric is visually inspected for various weaving
faults, damages, etc., which are suitably marked with coloured pencils. The
marked fabric is then repaired for missing end (warp) or pick (weft) by
mending, or the damaged portion is cut off which may otherwise be
entangled with machine parts causing excessive damage.
Until recently, this important step was considered to be a routine one.
However, with the enforcement of stringent quality control regulations,
scientific practices or electronic devices soon overcome bad practices such
as nominal checking or no checking. The use of electronic instruments has
enabled precise inspection of a piece, leaving no scope for unnecessary
cutting. Stains, holes, thick and thin places and warp/weft thread breaks can
now be detected by laser beams as in Sick-scan-system Ko-Re-Tra of E.
Sick, GmbH [2]. The apparatus operates on three different principles –
coaxial (emitter and receiver at the same place), remission (receiver at a
freely adjustable angle) and transmission (receiver on the opposite side of
the fabric). The light source is helium-neon laser or a xenon high-pressure
lamp.
An unmended hole or an oily stain can give rise to either tearing or hole-
formation in bleaching or to patchy dyeing. If a physical damage is already
present, that portion is best cut off and the pieces are re-stitched. Similar is
the case for intensively oil-stained portions.
In addition to the naturally occurring impurities, a number of impurities are
embedded on the textile materials accidentally. The most common
accidental impurities are stains caused by various agents, which are easily
visible in the embedded portions. Most of the stains should be removed by
local spotting with an efficient stain remover followed by thorough rinsing
and soaping.
The stain removers are generally a solvent (e.g. acetone, methylated
spirit, petrol), solubilising agent (e.g. acetic or oxalic acid), oxidising agent
136
(e.g. sodium hypochlorite solution, potassium permanganate and oxalic acid

or hydrogen peroxide) or reducing agent (e.g. sodium hydrosulphite) for the
material present in the stain. Some stain removers are available in the
market, which are capable of removing varieties of stains.
Non-scourable oils are difficult to remove from cotton giving rise to uneven
dyeing. The oil, grease and tar stains are generally removed by spotting on
the stained portion with a stain remover comprising emulsified solvents in
liquid forms. The solvents may be carbon tetrachloride, tri- and tetra-
chloroethylene, isopropyl alcohol, etc. The emulsifier may be anionic (such
as sulphated oils or alkyl aryl sulphonates) or nonionic (ethylene oxide
condensates). The stains are spotted with the stain remover, rubbed, left for
a short time, and then washed. The treated area should not be dried before
washing.
4.4.2 Shearing and Cropping

After inspection and mending, small projected yarns may remain on the
surface of the fabric, which obstruct penetration of dyes during dyeing and
printing processes. They may also be entangled with machine parts causing
damage of the materials. These projected yarns are removed by a process
called shearing and cropping, during which the projected fibres or yarns are
cut from the fabric surface.
In shearing operation, dry or occasionally slightly dampened fabric is
drawn between a shearing bed or table and the shearing device, which
consists of a shearing cylinder and a ledger blade. The action is similar to
that of a lawn mower.
Figure 4.2 [3] shows a simplified diagram of shearing machine. The
shearing cylinder (1) generally consists of a thick-walled hollow cylinder with
a bearing journal firmly inserted at both ends. The cylinder should not be
unbalanced or eccentric in running. The speed of the cylinder during
shearing is between 500--2000 rpm depending on the fabric to be sheared.
Depending on the particular design, the cylinder has 10-24 or, in the case of
carpet shearing machine 40 spiral blades (2) mounted securely around its
circumference. In conventional shearing cylinder the shearing spirals are
fitted onto the cylinder in equal distances regardless of the number of spirals
used. In modern shearing machines as in Multicut MC-5, the spirals are
arranged asymmetrically to avoid periodic variation of pile length. The
angled foots or support limbs of spirals are bent in such a way that it
matches the curvature of the cylinder and always point in the opposite
direction to the rotation of the cylinder in order to absorb pressure developed
during shearing. To prevent heating up during running, felt saturated with oil
is placed against the shearing cylinder.
137
1 2 2 1
3 3
4
6
4
5 5
6
(a) (b)
Fig. 4-2 Shearing Machines with (a) Hollow Table and (b) Pointed Table [3]
The spirals are made with different profiles having names like knee,
concave, cleaning, breaking, mortice, etc. They have different cutting or
wedge angles. Cutting edges running parallel to the cylinder axle have
obtuse (>90°) cutting angles, while those running in a straight line diagonally
to the cylinder axle have acute (<90°) cutting angles. Most of them have
sizes around 1.1-2.0 mm except for mortice spirals (4 mm) used for shearing
of carpets.
The ledger blade (3) is a 10-12 cm wide knife blade, 3-6 mm thick,
corresponding in length to the width of the shearing machine. This is ground
on its underside for approx. 3 cm towards the cutting edge. An absolutely
uniform contact surface between the cutting edge of the ledger blade and
the fabric (4) is ensured. The opposite side of the blade is screwed or
clamped to the support beam. The cutting angle of the blade should be
small in order to obtain the cleanest possible shear. The cutting edge of the
ledger blade generally has lower hardness than that of the spirals.
Consequently the wear of ledger blade is more. This is advantageous, as
grinding of ledger blade is less expensive than that of shearing cylinder.
The shearing table (5) may be hollow 4.2(a) or pointed 4.2(b). Seams
must not be allowed to pass under the shearing device, otherwise they will
be cut open. Seam joint sensors (6) lift the shearing rolls away from the
fabric surface or the shearing bed is lowered, whenever a seam-joint
reaches the shearing point.
Rotating brushes are installed both in front of, as well as behind the
shearing device to align the fibres correctly for shearing and to remove cut
ends after shearing respectively.
The modern shearing machines are generally computer-controlled and
have the following features or components:
138
1. Fabric feeding device ensuring the entry of crease-free fabric

(electronically controlled).
2. Pair of two or more revolving shearing or cutter rolls with left and
right hand spiral blades. A 4-cutter machine has four cutting points,
two for face and two for reverse side of the fabric.
3. Shearing machine fitted with serrated blades have been found
satisfactory for the cutting of polyester materials.
4. Before leaving the machine, the fabric is brushed by a spiral
revolving brush.
5. Fibre fluff collection by vacuum suction devices.
6. Fluff exhaust.
7. Ferrous and non ferrous metal detectors (electronic),
8. Seam joint sensors, which lift the shearing rolls away from the fabric
surface, whenever a seam-joint comes in contact.
9. Width and thickness sensing devices. The thickness (of fabric)
measuring device provides automatic shear height (the distance
between the shearing device and the shearing bed) adjustment.
10. Length measurement.
11. Modern shearing machine can operate at a speed of 100 m/min.
Shearing has assumed great importance recently, in view of its potential
for improving fabric quality. In case of polyester blended fabrics, in
particular, shearing has proved to be of great value in reducing the
incidence of micro beads for dyed fabrics. In case of cotton fabrics, in
particular, care should be taken to see that the shearing blades do not
scratch the surface of the fabric, which otherwise may cause dyeing defects
during subsequent dyeing.
4.4.3 Singeing Process

When yarn is made from short staple fibres, the two ends of the fibre may
not be embedded inside the yarn and are projected due to the twist imparted
during spinning. For multi-filament yarns, some filaments may break or cut in
places and are projected from the surface. Singeing is a very effective
method for removal of projected fibres. Singeing of textile fabrics is
necessary for several reasons as follows:
1. Many cotton materials are valued for their smooth appearance e.g.
lustrous sateen and satin weaves, poplins for shirting, handkerchief
fabric, etc. When yarn or fabric is made, the surface appears fuzzy or
hairy due to the presence of projected fibres or yarns. The smooth
lustrous appearance of fabric is thus affected. Similarly, sewing and
embroidery threads should have a smooth surface devoid of
projected fibres.
139
2. Unsinged fabrics are also soiled easily.

3. The protruding fibres obstruct subsequent dyeing and printing
process in an uncertain manner. It is almost essential with goods
intended for printing.
4. The goods to be mercerised are singed to develop maximum lustre
in the fabric.
5. In case of polyester/cellulosic blended fabrics, singeing is the best
method for controlling pilling. Pills or beads are formed on the
surface of these fabrics during use. Sometimes double singeing is
done to minimise pilling.
However, the process is not essential for all types of fabrics.

The object of singeing is to burn off projecting hairs without scorching or
otherwise damaging the body of the fabric. Improper singeing may cause
irreparable faults. Some singeing faults and recommended precautions are:
1. Before singeing, the fabric should be perfectly dry, as wet fabric is

scorched much more readily than dry fabric. The fabric may be dried
by passing over a heated cylinder.
2. Uneven singeing can cause streaks when the fabric is dyed, or
bubbles when the fabric is finished.
3. Improper singeing may lead to as much as 75% tensile strength loss
in warp direction.
4. The fabric to be singed should not contain any acid-releasing salt
(e.g. zinc chloride normally used as anti-mildew agent), which may
liberate acid on heating and thus tender the fabric.
5. Stopping of machine may cause heat bars on fabric.
6. Creases produce streaks, which are magnified when dyed.
7. Singeing may cause hardening of size and can lead to difficulties in
desizing.
8. There is a possibility of thermal damage to temperature sensitive
fabrics.
9. During singeing of synthetic fabrics, the protruding fibres melt and
recede from the flame and form beads. The beads are disoriented in
morphological structure and they absorb more dyes, causing specky
dyeing. In order to avoid this problem, these fabrics are singed after
dyeing. However, when dyeing is carried out by thermosol method,
singeing before dyeing does not create much problems.
The types of singeing machines commonly employed are:
1. Plate singeing machine

2. Rotary cylinder or roller singeing machine
140
3. Gas singeing machine

The first two methods are based on passing the fabric over internally
heated (750°C) red-hot metallic parts, curved copper plates (2.5-5.0 cm
thick) in plate singeing and rotating copper cylinder in roller singeing at a
very high speed. Special traversing arrangements for the fabric are provided
to prevent local cooling and wear and tear of the metallic parts. Plate and
roller singeing are obsolete nowadays, because of insufficient singeing and
a typical hardness on the fabric produced by them. Although gas plants are
known for long time, the type and size did not suit the processing houses.
With the advent of suitable gas units, the old contact singeing methods soon
became outdated and the gas-fired singeing machines achieved universal
approval. Contact singeing (roller singeing) is still used to singe velvets.
In a gas singeing machine, the fibre ends should be loosened from the
body of the sized yarn by pre-brushing and subsequently burnt by the flame.
When the flame with a temperature of about 1,300ºC touches the cold and
moist material, an air/steam buffer zone is created between the flame and
fabric. This may hinder singeing operation. The flame should have sufficient
and controlled thermal and mechanical energy to reach to the base of
material. The situation is further complicated by the fact that the pyrolysis of
cotton is an exothermic process while that of polyester is endothermic.
Polyester ignites at 480º-500ºC, while it melts at much lower temperature
(250º-270ºC). In order to avoid melting of polyester before burning, the
energy is to be supplied in a shock form and pyrolysis should be like an
explosion igniting the whole length of the projected fibre instantly [2].
In a gas singeing machine (Figure 4.3), the fabric in open-width passes
with a speed of 50-180 m/min with the help of a guide roller (1) through a
pair of hot metallic drying cylinders (2) to dry as well to warm up the fabric to
be singed. The fabric is then passed through a number of weft straighteners
or curved rollers (3) to remove weftwise creases from the fabric. The fabric,
after passing through a braking device (4), is subjected to cleaning by
1 7
2 3
6
6 8
Fig. 4.3 Schematic Diagram of Gas Singeing Machine

141
means of brushes, which rotate in a direction opposite to fabric motion. The

brushes are placed inside a chamber (5) and an exhaust fan removes the
fluff and dust collected by the brushes. Then the fabric passes over gas
burners with ceramic nozzles (6) where singeing is carried out. Dust and
gaseous combustion products released at the burners are exhausted
through a ventilation hood (7). Two or more gas burners are used and the
passage of the fabric is so arranged with the help of a large number of guide
rollers that the both sides of fabric can be singed in a single passage. The
same set or two different sets of burners may be used for singeing both
sides of the fabric by threading the fabric suitably. After singeing, the fabric
is still hot and may carry some sparks along with it. It is, therefore, drawn by
the roller of a mangle through a trough of water called quench box (8), in
which all sparks are extinguished. To avoid wetting of the fabric, quenching
by passage through steam is also possible. An additional desizing
compartment may be incorporated so that the materials may be
impregnated with the desizing solution followed by squeezing.
The main operating elements of a gas singeing machine are gas burners
which may be of three types: (a) with open flame (b) with closed combustion
chamber, and (c) radiation type. In burners with open flame, a major part of
the heat is lost which limits the machine efficiency. In the second type, a
complete combustion of gas takes place in a small chamber so that the
ceramic nozzle covering the flame is heated to the temperature close to that
of flame. Direct singeing systems as above require more attention on the
part of the operatives. In indirect system, there is no direct contact between
the fabric surface and the flame. In radiation burners, fire-proof ceramic
blocks are heated to a high temperature, which release the heat as infrared
radiant energy. The infrared rays (and not the flame) surround the protruding
fibre-ends, which have only a moderate heat retaining capacity. However,
this heat is sufficient to raise them to burning temperature without affecting
the whole fabric. The process, however, cannot remove fibres from the
interior of the fabric; to avoid pilling an in-depth action is necessary.
In gas singeing machines, automatic feeding of a suitable mixture of gas
and air under pressure is provided to the burners in order to ensure
complete gas combustion. Coal gas, petrol gas or butane gas may be
utilised. In recent years, there is a trend to use fully combustible flue instead
of gas-air mixture. It is possible to adjust the width of the burner to suit that
of the fabric. It is also possible to adjust the flame height and consequently
the heat intensity, by altering the pressure of the gas or air-gas mixture, and
is expressed in terms of the height of the manometer in cm.
In modern singeing machines, the gas/air mixture has to be thoroughly
mixed and metered at constant pressure and in the stoichiometric ratio for
burning. Osthoff-80 singeing machine utilises a patented double burner
flame system with a Singmatic card control, which automatically controls
142
flame height, width and temperature. The singeing effect is maintained by

controlling the fabric temperature after singeing to a preset value. On the
compact Parex 5000 Series Mark VI singer of Ernest Turner, there is
pneumatic control of the angle of the flame to the fabric, while ultraviolet
flame scanners, rapid start-up and automatic cleaning of the burners
combined with rapid shutdown are valuable features of the machine.
The speed for protein fibre combustion is much lower than that of
cellulosic fibres; hence, woollen fabrics are singed at a speed of about
45-70 m/min. A couple of felt-covered rollers are used instead of a
quenching device or any other spark extinguisher.
A modern singeing machine should be versatile and should be capable of
singeing all types of fabrics e.g. blends, synthetic filament and spun fabrics.
Depending on the type of fabric, singeing positions may required to be
varied (Figure 4.4) such as [4]:
1. Tangential singeing
2. Singeing on water-cooled rollers or with counter-acting cool air
3. Singeing onto free- moving fabric
(a) Tangential (b) Water-cooled Roller (c) Onto Fabric
Fig. 4.4 Different Burner Positions in Modern Gas Singeing Machine
In tangential singeing, the flame impinges on the fabric at an angle.

Consequently, only protruding fibres are burnt and the fabric surface is not
directly affected. This is ideally suited for lightweight and sensitive fabrics.
This is also suitable for synthetic filament fabrics, as they require mild
singeing just to remove tiny broken filament-ends only.
In another variation, the flame impinges directly on the fabric and it is
reflected back to the surface by the water-cooled roller situated at the back
of the fabric. An elastic steam-air cushion formed inside the fabric, resists
deeper penetration of the flame and singeing occurs only at the surface. The
fabric also remains cooler and heat-sensitive fabrics are protected from
singeing heat. Thus, this singeing position is most suitable for synthetic,
blended and open-structured fabrics.
In the third variation, the flame passes through the fabric and both sides
are accessible to the flame. The flame enters the interstices of the fabric
143
and, therefore, imparts good singeing. This position is very suitable for
fabrics made from natural and man-made cellulosic fibres, and for heavy
industrial and technical fabrics.
For proper singeing, the burner is kept very near to the fabric in tangential
singeing, while the flame should meet the fabric at right angle position in the
other two cases.
The recommended conditions for a few typical fabrics are as follow [4]:
2
1. Pure cotton fabric of fabric weight 80-140 g/m – best singeing
position – (c), fabric position – 8 mm from the flame, flame intensity –
150 mm water column, machine speed 90-110 m/min depending on
the machine design.
2
2. Cotton/viscose blended fabric of fabric weight 160-220 g/m - best
singeing position – (c), fabric position – 7 mm from the flame, flame
intensity – 120-130 mm water column, machine speed 80-90 m/min.
2
3. Cotton/polyester blended fabric of fabric weight 70-100 g/m - best
singeing position – (b), fabric position – 7 mm from the flame, flame
intensity – 120-130 mm water column, machine speed 100 m/min.
2
4. Polyester/viscose blended fabric of fabric weight above 250 g/m –
due to heavier texture best singeing position – (c), fabric position – 6
mm from the flame, flame intensity – 160 mm water column, machine
speed 80-90 m/min.
2
5. Lightweight (50-120 g/m ) fabric of pure cotton or blends – best
singeing position – (a), flame intensity – 80 mm water column,
machine speed 100 m/min.
6. Pure woollen fabric of selected varieties - best singeing position –
(b), fabric position – 10 mm from the flame, flame intensity – 70 mm
water column, machine speed 45-70 m/min.
7. Cotton and cotton/polyester corduroy and ribbed fabric – best
singeing position – (b), fabric position – 8-10 mm from the flame,
flame intensity – 150 mm water column, machine speed 100 m/min.
8. Velvet and velour – the fabric is not directly singed by flame but by a
slowly rotating cylinder (roller singeing) heated at a temperature of
about 700-800°C.
The functions expected from a good singeing machine are:
1. It should be capable of burning out all the fibre-ends protruding from

the fabric surface.
2. The singeing effect should be uniform throughout the fabric width
and on both side of the fabrics.
3. In order to ensure safe singeing, the burners should operate only
when the fabric speed attains desired minimum value.
144
4. To minimise the unsinged length of fabric at the start, the drive

should be so designed that the minimum speed is attained very
quickly.
5. The burning of the fibre ends should not be only from the surface,
but also from the interior of the fabric weave. Hence, optimum fabric
speed will be decided by the fabric structure for a particular fabric
sort.
6. The singeing process should not affect fabric properties like tear-
strength, resilience, etc.
7. The machine should be provided with an effective and easy control
of flame height.
8. The burners should be capable of individual swivelling to and from
the fabric, (or inactivating device) and correspondingly the burners
are to be automatically ignited or extinguished, when the machine
attains the desired speed and when it stops or slows down (due to
several reasons) respectively.
9. A set of brush rollers, one each for the front and back of the fabric,
should be provided in order to clean the fabric of any possible
residue of soot after singeing.
10. An efficient static eliminator is necessary at the delivery end to
conduct away any static electricity generated during fabric run.
11. An added device of warning noise or fire alarm in case of a fire.
12. As an added precaution, wet sprinklers and unburned gas detectors
have become necessary due to stringent safety regulations. The
flame should never be yellow, smoky or sooty. This may cause
permanent damage to polyester blended material.
Most singeing machines have:
1. Steam quenching for the sorts not to be wetted e.g. material to be

grey mercerised.
2. Water quenching.
3. Facility for impregnation with appropriate desizing solutions.
Yarn singeing machines are required to prepare bright and lustrous yarns
with smooth surface, as in case of sewing and embroidery threads. The
machine consists of a number of suitably sized gas jet burners equal to the
number of packages to be handled by the machine (generally in multiples of
24). The yarn passing from a big package is allowed to meet jet burner and
the singed yarn is rewound on a smaller package like pirn. Nowadays
electrical burners heated to about 1,100°C are used for the purpose of
assuring greater safety.
145
Like woven fabrics, hairiness is also undesirable in knitted fabrics. The

problem of hairiness can be minimised by controlling factors like yarn quality
and proper yarn count. The main problem for singeing of circular knit fabric
is the opening of the fabric tube in cylindrical form properly during singeing.
The burners must be designed in ring shape and the flame intensity should
be uniform over the entire tube circumference. In Dornier circular knit
singeing machine, after guiding through detwister and circular expander, the
fabric moves upward assisting an exhaust device situated at the top. Eight
swivelling burners are arranged on a ring in such a manner that, even with
width adjustments, the full width of fabric is covered. The flame intensity of
70-100 mm water column is suitable. There is practically no longitudinal
tension in the singeing area. The fabric is finally taken over by the driven
spark extinguishing and plaiting unit [2].
In mills, the singeing room is always separated from the other
departments. Frequent occurrences of fire in the singeing room may be due
to the following reasons:
1. Careless threading in the machine at the start.

2. A momentary slowing down of the speed of the machine.
3. Sudden stoppage of the machine due to machine faults.
4.4.4 Enzyme Treatments

Biotechnology can be defined as the application of scientific and engineering
principles to the processing of materials by biological agents. Ease of
handling, storage and disposal makes enzymes a choice catalyst for any
processing industry. In textile application, the knowledge of specific action of
enzymes (amylase) for starch splitting began around 1857, when malt was
used to remove gum from fabrics before printing. The enzymes have now
been largely used for pre-treatment processes of textile materials. Such
processes include scouring and bleaching of cellulosic materials,
degumming of silk, carbonising, bleaching and shrink-resist treatments of
wool. In stone washing of denim fabrics, the colour of indigo or sulphur
dyed materials is faded at places with the help of an oxidising agent.
Enzymes are nowadays used for such discoloration. Biostoning has
achieved considerable importance for treating casual-wear garments to give
them a washed-down or worn appearance. This is more environmentally
acceptable and it replaces or decreases the amount of pumice stones that
may damage machinery and cause harshness of the fabric.
Enzymes are biological catalysts. They are naturally occurring proteins
capable of catalysing specific chemical reactions, and, being catalysts,
facilitate the reaction without being consumed. The advantages are [5]:
146
1. Enzyme-catalysed reactions are at least several orders of magnitude

faster than chemically-catalysed reactions. While compared to the
uncatalysed reactions, enzymes typically enhance the rates by 106 to
1013 times.
2. Enzymes have far greater reaction specificity than chemically-
catalysed reactions and they rarely form by-products. The high
substrate specificity of enzymes is due to the individual architecture
of the active site where only certain molecules can stereo-fit in.
3. Enzymes catalyse reactions under comparatively milder conditions of
temperature (below 100º C), pressure (atmospheric) and pH (around
neutral). Conversely, high temperatures, high pressures and
extremes of pH are often necessary in chemical catalysis.
4. Consequently, enzymatic treatments offer savings in chemicals and
energy and have less or no impact on the environment. The enzyme
itself is fully biodegradable.
Enzymes consist of complex three-dimensional proteins that are

composed of polypeptide chains. They range from individual proteins with a
relative molecular mass (RMM) of around 13,000 catalysing a single
reaction, to multi-enzyme complexes of RMM of several millions catalysing
several distinct reactions. They are relatively fragile substances and
susceptible to denaturing i.e. degradation due to temperature, ionising
radiation, light, acids, alkalis and biological factors and thereby are
inactivated.
The enzyme catalysis operates first to form an enzyme-substrate complex.
However, the mechanism of enzyme hydrolysis of cellulosic materials is
complicated and is not fully understood. The enzymes have a specific three-
dimensional shape and have a true activity centre in the form of fissures,
holes, pockets, cavities or hollows. These are adsorbed onto the surface of
some substrate in lock and key fashion [6]. At the active site on the enzyme,
hydrolysis of the substrate is accelerated. The products of decomposition of
the substrate are formed and the enzyme is released to be reabsorbed onto
a different location on the substrate. The process continues until the enzyme
is deactivated by conditions in the processing bath. Deactivation may occur
by competitive or non-competitive chemicals called bogies in the processing
bath. The competitive bogies compete with the substrate for enzyme, while
non-competitive bogies are adsorbed on the enzyme causing the shape of
the enzyme to change – both prevent enzymatic catalysis from occurring. All
enzymatic systems function best within a narrow range of pH and
temperature – too far outside the range, the enzyme becomes deactivated
by changes in three-dimensional structure. As the enzyme twists and coils
into a shape that prevents sorption between enzyme and substrate,
catalysis no longer occurs.
147
Chemically enzymes are proteins of high molecular weight e.g. that of

enzyme α-amylase of B. subtilis is about 1,00,000. The enzymes are
biological catalysts. They accelerate hydrolysis reactions and differ from
normal chemical catalysts because they are very specific in action. They are
thermo-labile, have relatively low energies of activation and are usually
active over a narrow range of pH. A starch-solubilising enzyme will not affect
cellulose although both have similar structure. A number of enzymes are
available which hydrolyse starch without affecting cellulose. The liquefaction
and dextrinisation can be readily observed by putting into iodine solution; the
colour of the fabric gradually changes from blue through violet, reddish violet
to colourless. However, enzymes suffer from the disadvantage that their
desizing action is destroyed, if the conditions of temperature and pH are not
favourable. There are very few enzymes, which are not inactivated or
destroyed by temperatures over 75°C. Once destroyed, they cannot be
revived or reactivated. Currently thermo-stable enzymes (e.g. α-Bacillus
subtilis, α-Bacillus licheniformis, etc.) are available which can withstand
temperature up to 90°C. Certain enzymes require specific bivalent metallic
2+ 2+ 2+ 2+
ions (e.g. Ca , Mg , Fe , Mn , etc.) as activators which act probably by
stabilising enzyme-substrate complex or sensitising substrate to the attack
of enzymes. Certain chemicals like alkalis, antiseptics and acid-liberating
agents tend to inhibit the enzyme activity.
Enzymes are principally classified and named according to the chemical
reaction they catalyse, as this is the specific property that distinguishes one
enzyme from another. In other words, they are named by the substrate on
which they act. An enzyme name is assigned not to a single enzyme protein,
but to a group of proteins with the same catalytic property, even if they are
obtained from different sources. Some of the common types of enzymes are
as follow [7]:
Lipases: split fats into glycerol and fatty acids.

Amylases: split starch (amylase) into dextrin and sugars.
Proteases: split proteins into soluble polypeptides and amino acids.
Pectinolytic or pectinases: degrade pectin.
Zymases: convert glucose into alcohol and carbon dioxide.
Cellulases: degrade cellulose to soluble products.
Catalases: convert hydrogen peroxide into water and oxygen.
Saccharidases: convert polysaccharides to glucose.
The application of enzymes in various stages of textile processing may be

summarised as follows [8]:
Desizing: amylase, lipase.

Scouring: pectinase, cellulase.
148
Bleaching: oxidoreductase. xylanase.

Dyeing: oxidoreductase.
Finishing: cellulase, oxidoreductase, lipase.
Composting (biodegradation of textile wastes): cellulase, protease,
nylonase, polyesterase.
Using bioengineering principles, new sources of enzymes are being

discovered, isolated and cultured for commercial use. Major companies
involved in the preparation and marketing of enzymes useful for textile
industry are Dystar, Clariant (formerly Sandoz), Genencor and
Novoenzymes (formerly Novo Nordisk), etc.
The activities of complex enzymes are measured in international unit (IU),
whereby an enzyme acts on an appropriate substrate and the degradation
product is determined for a unit of time. For example, one IU for a cellulase
will liberate 1.0 micromole of glucose from a given cellulosic substrate in one
hour at a given pH and temperature. For a pectinase, one IU will liberate 1.0
micromole of galacturonic acid at a given pH and temperature. Each
enzyme has a characteristic optimum pH and is active over a pH range with
a bell-shaped plot of enzyme activity against pH. At the extremes of the pH
range, the three dimensional structure of the enzyme will be disrupted and
the enzyme loses its catalytic action. The enzyme activities increase with
temperature, but above a particular temperature, the thermal agitation
disrupts the tartiary structure of enzymes.
The roles of surfactants and mechanical agitation are related both to the
enzyme structures and to the characteristic structure of cotton. Nonionic
surfactants are essential for effective enzymatic treatments. They are
compatible with enzymes, while anionic/cationic surfactants may form
complex with enzymes. The presence of nonionic surfactants in the
enzymatic solutions favours enzymes’ biological functions. Mechanical
agitation can increase apparent enzyme activity and efficiency in scouring.
However, enzymes may be denatured by mechanical agitation with high
shear forces. [9].
Enzymes have been used for over 35 year in the textile industry for the
desizing of fabrics. Implementing an enzyme safety program is important for
limiting exposure to enzymes and maintaining employee health and safety in
the workplace. According to the American Soap and Detergent Association
(SDA) document, exposure to enzymes may cause irritation and/or
respiratory allergies. Skin and eye contact with proteolytic enzymes may
cause irritation. Other classes of enzymes are less irritating or pose no risk
of irritation. However, formulation ingredients may be irritants. Exposed
areas should be protected by using hand and eye protection and other
protective fabricating [10].
149
Removal of Surface Fibres

There are three methods to remove surface fibres from 100% cotton woven
and knit goods, namely singeing in the grey state, bio-polishing and home-
laundering the fabrics using detergent containing cellulase enzyme.
Cellulases are multi-component enzyme systems that are commonly
produced by soil-dwelling fungi and bacteria. The effects achieved by these
enzymes are pilling reduction, increase in softness and amelioration of
handle, surface structure, fabric appearance and dyeing yield. The most
important cellulase-producing organisms are fungi of the genera
Trichoderma, Penicillium and Fusarium. The cellulases used are chemically
complex and consist of at least three enzyme systems working
synergistically together. Endo-β-(1,4)-gluconase or endocellulases hydrolyse
cellulose chain molecules randomly, preferentially attacking the internal
regions of the polymer. They generate more chain ends which are further
hydrolysed by Exo-β-(1,4)-gluconases (also termed as cellobiohydrolases)
to produce cellobiose. These exo-cellulases may assist disintegration of
crystalline regions, making the region more susceptible to hydrolysis by
endo-cellulases. The cellobiose and other small oligomers are then
hydrolysed by the third enzyme, β-(1,4)-glucosidase into glucose [8]. Acid
cellulases exhibit the greatest activity generally in the pH range 4.5-5.5 at
45-55°C, whereas neutral cellulases require a pH of 5.5-8.0 at 50-60°C.
Generally a treatment of 45-120 minutes is appropriate, as prolonged
treatment time may increase the fibre loss significantly. Where acid cellulase
predominates, required washing time is short (20-45 minutes), whereas for
neutral cellulase longer wash time (45-120 minutes) is required. Acid
cellulase is sometimes associated with backstaining during bio-stoning,
which may need to be prevented or removed. Similarly, excessive cellulase
dosage and vigorous agitation may also increase weight loss. The
application of cellulase enzyme treatments of cotton is not well established
and further refinements in process technique will emerge in the next decade.
Developments, such as the use of one or more specific enzyme types rather
than three types working synergistically, will depend on commercial
separation of the types of enzyme. The use of co-enzymes to speed up the
process or produce specific effects may also be utilised.
For cotton, the restriction of the enzyme to the fibre surface is easily
achieved, because cellulose is highly crystalline material and possesses
only small amorphous region, making the diffusion of enzymes into the
interior of the fibre nearly impossible. Thus, by regulating enzyme dosage
and choosing the right type of enzyme, the catalytic action of the enzyme
can be confined to the surface of cotton and to the amorphous regions,
leaving the fibres, as a whole, intact. Surface modification of cellulosic
fabrics conferring cooler and softer feel, brighter luminous colour and more
150
resistance to pilling using cellulases, is often known as bio-polishing – a

term created by Novo Nordisk. The same enzymes may also be used for
bio-stoning of denim materials to give a washed-down look by replacing or
reducing pumice stones. This treatment can be applied to knit and woven
cellulosic fabrics such as cotton, viscose, linen and their blends. An
enzymatic stone-wash process requires equipment with sufficient shear
forces and mixing, such as a drum washer. The elimination of superficial
microfibrils of the cotton fibre through the action of cellulase enzymes is
obtained by the controlled partial hydrolysis of cellulose followed by
mechanical treatment, leaving the surface of the fibres free and conferring a
more even look. The improvements in fabric softness and smoothness are
permanent in contrast to the softeners applied to the fibre surface.
Moreover, the water regain is not hampered by the enzymatic treatment.
Although bio-polishing may be carried out at any time during wet processing,
it is most conveniently performed after bleaching. Treating fabrics with
enzyme after dyeing may affect the shade, so some adjustment in dye
formulation may be necessary. It may also be performed in garment form.
Batch processing using washers, jets, becks and winches is extremely
suitable, as pH and temperature can be controlled easily.
Controlled finishing with cellulase enzyme optimises surface properties of
the fabric, but causes a decrease in tensile strength. Commercially a weight
loss of 3-6% and strength loss of about 10% is considered acceptable.
Anionic dyes such as direct and reactive dyes and cationic and anionic
surfactants inhibit cellulase catalytic action appreciably, whereas nonionic
dyes including vat dyes and nonionic surfactants do not show remarkable
inhibition. The degree of inhibition depends on the class of dyes as well as
dye concentration. The inhibitory effect may be due to the ionic interaction
between cellulase and anionic dyes with sulphonate groups, the cross-
linking ability of bifunctional dyes or the large planner structure of vat dyes.
Laundering of knit fabrics with detergent containing cellulase enzymes
helps to maintain a clean surface appearance and the appearance improves
even after multiple laundering. Modern detergents contain a sophisticated
mixture of enzymes to remove stains and to assist cleaning at low
temperature. Proteases, lipases and amylases are generally used to assist
the removal of stains. Cellulases assist in the removal of particulate soils by
removing microfibril from the cellulosic fabrics. Generally, the detergents for
this purpose rely on a mixture of enzymes, strong sequestering agents and
soil-release polymers to provide satisfactory stain removal and soft finish.
While the short fibre ends are hydrolysed by enzymes, additional
mechanical agitation is necessary to complete the process of hydrolysis and
removal of hydrolysed products from the fabric surface, which is best
attained in rotating drum washers and jets.
151
4.4.5 Desizing Process

The yarns, particularly the warps running lengthways throughout the fabric,
are subjected to a high degree of abrasion during weaving. To prevent
breakage or damage of warp yarns due to abrasion, size is imparted to the
warp yarn. The presence of size on the fabric makes it stiff and renders its
treatment with different liquors used in dyeing and finishing difficult.
Therefore, one of the initial steps in wet processing is the elimination of size
and water-soluble admixtures, the operation being called desizing.
The typical sizing materials are:
1. Natural starches from potatoes, maize, rice or topioca.

2. Chemically modified starches (ethers or esters).
3. Organic polymers e.g. polyacrylates, carboxymethylcellulose,
methylcelluose, polyesters or polyvinylalcohol.
4. Solvent-soluble materials e.g. copolymers of methyl methacrylate.
About 75% of the sizing agents used throughout the world consist of
starch and its derivatives because of low cost and high effectiveness as a
sizing material on cellulosic textiles. Starch is difficult to remove, as it is not
soluble in water or in normal scouring liquor. Removal of starch before
scouring minimises the work required in subsequent cleaning processes,
hence reduced concentrations of the chemicals are required in subsequent
scouring and bleaching processes. Moreover, degradation products of
starch with alkali are of reducing nature. Those may reduce the dyes if dyed
materials are to be scoured. Solubility of starch may be promoted by the
action of acids, oxidisers, alkalis and enzymes. If proper care is not taken,
acids and oxidisers not only attack starches but also cellulose itself.
Hydrocellulose and oxycellulose are formed as degradation product and the
fabric becomes weaker.
The desizing process is, therefore, carried out with lower concentration of
desizing agents at lower temperature. The destruction of cellulose is
minimised, but the time required to complete desizing is appreciably high.
The major components of the size are starch, wax and tallow. These,
along with a number of secondary components, are baked to a cake on the
yarn as it is dried at high temperature. This cake sometimes proves
extremely difficult to clear from the yarn. Occasionally, emulsifying agents
are added in the size to facilitate their removal. The term desizing is
restricted to the removal of starch, while wax and tallow are loosened during
desizing and are removed by subsequent scouring process.
Chemically starch is a poly-α-glucopyranose (Section 1.8.1) in which
straight chain amylose and branched chain amylopectin polymers are
present. Both the constituents are insoluble in water, but can be solubilised
152
by hydrolysis of these long chain compounds into shorter ones. Under

favourable conditions, starch can be progressively hydrolysed to the
following products with varying solubility in water:
Starch (insoluble)Æ dextrin (insoluble) Æ dextrin (soluble) Æ maltose
(soluble) Æ α-glucose (soluble)
In desizing, the hydrolysis reaction is carried out up to the stage of soluble
dextrin only and not up to the stage of α-glucose to avoid degradation of
cellulose.
Preparatory processes create 60-70% of the total COD load of the
process-house effluent, of which desizing amounts to roughly 80%. This
means that 50-55% of the total COD load originates from desizing.
About 75% of the sizes used are starch-based and with the exception of
CMC sizes, are not suitable for recycling.
The purpose of desizing is not a complete elimination of all the sizes on
the fabric. Rather, the process must be carried out in such a way that the
subsequent processes can be carried out in the best possible manner and
without difficulty.
The classical desizing process fundamentally involves:
1. Swelling of the highly polymerised size

2. Dissolving
3. Washing off the swollen polymer
The classical desizing process for starch sizes is pad-batch desizing.

Impregnation and padding is done in the trough attached to the singeing
machine followed by long time batching. The advantage of this method is
low investment cost. The difficulties are insufficient liquor pick-up if the bath
is too small, size accumulation in the impregnation bath, messy batching
station (especially with PVA), fabric transfer problem after batching,
stickiness of the fabric, high rinsing water requirement (8-10 l/kg), high
effluent volume of low concentration (1.2-1.5%), longer processing time and
logistics problems.
Water-soluble sizes may be removed on full-width washing machines,
preferably with roller vats. The advantage of this method is that it can be
carried out in common washing machines. The disadvantages are long time
needed for swelling, long washing zone, high rinsing water requirement
(8-10 l/kg) and high effluent volume of low concentration (1.2-1.5%).
The requirements of an optimised desizing process are:
Minimum rinsing water consumption and consequently high effluent

concentration.
Continuous processes for all sizes with no dwell time.
No contamination problem as with the pad-batch process.
153
Size recovery of synthetic sizes.
In a modern impregnator called BEN-INJECTA (Benninger, Germany), the

fabric is guided through two narrow castings where steam and water meet
both sides of the fabric, separately or in a desired mixture. Due to the design
of the steam injector slots and the geometry of the shafts, steam ejects at a
very high velocity on the fabric and thus contains high kinetic energy. Shock
heating of the fabric at the entry of the first casting, combined with strong
kinetic energy from the steam-water mixture, means a high molecular weight
product such as size, can be separated without swelling by lowering of
viscosity due to high kinetics (thixotropical behaviour of size) with no
gumming of the fabric and machine parts. The washing process is
completed in a subsequent short washing zone.
Only counter-flow water from the following compartment at a liquor
circulation of 300 l/min is used i.e. no additional fresh water. The
consumption of water/liquor in the process is low – around 1-3 l/kg with
consumption of 0.4-0.6 kg saturated steam. This results in a highly
concentrated effluent flow – ideal for recycling of synthetic sizes. The sizes
soluble or insoluble in water can be removed to the extent of 85-95%. Starch
sizes may be prewetted with a small amount of enzymes for partial
depolymerisation [11].
Starch desizing methods can be classified as follows:
1. Hydrolytic methods
(i) Rot steeping
(ii) Acid steeping
(iii) Enzyme steeping
2. Oxidative methods
(i) Chlorine desizing
(ii) Chlorite desizing
(iii) Bromite desizing
(iv) Peroxy compounds
Hydrolytic methods consist of degradation of starch into different

intermediate compounds and finally into its monomer glucose. Hydrolysis is
mostly carried out by enzymes, either those inherently present in water or
added externally or by mineral acids. Generally hydrolysis processes are
slow and require significant time, hence they are mostly batch processes.
However, they are comparatively safer than oxidation processes.
Oxidising agents such as chlorine, chlorite, bromite, etc. attack the
glucose ring or the ether linkage forming carboxyl or aldehyde groups. Both
reactions ultimately result in depolymerisation of starch into water-soluble
products. However, cellulose being of similar structure as that of starch is
154
not spared and some degradation of cellulose into oxycellulose is inevitable.

The oxidative desizing processes are, therefore, to be carried out carefully
to minimise such degradation. Oxidising agents used for desizing also have
bleaching actions on cellulose. Hence, partial bleaching occurs during
desizing.
Rot Steeping
This is the oldest and cheapest of the three hydrolytic methods. The main
feature of the method is that no special chemical is required for this
treatment. The fabric is first passed through a padding mangle, in which
warm water at 40°C is kept and the fabric is squeezed to about 100%
expression (% expression or % pick-up is the weight of liquor carried by the
fabric as percentage of its dry weight). The fabric is then allowed to stand for
about 24 hours at 35-40°C or overnight at 60°C in open space or in an open
box. The microorganisms, naturally present in water, multiply and secrete
starch liquefying (hydrolysing) enzymes, which solubilise the starch. The
fabric is finally washed with water, when most of the starch, as well as
water-soluble matters present in the
fabric, are removed. The fermentation
during rot steeping should not be too
rapid, otherwise cellulose itself may be
damaged. The padding mangle (Figure
4.5) consists of a trough, into which hot
water is continuously fed. Two rollers are
placed above the trough and are in
contact with each other under controlled
pressure. One of the rollers is covered
with rubber while the other is made of
steel or ebonite. The grey fabric in open-
width is first dipped in water and then
passed through the nip of the rollers
when it is squeezed to a degree Fig. 4.5 Padding Mangle
depending on the pressure at the nip.
The main disadvantage of this method is that it is a slow process and
prolonged storage requires an enormous floor space for storing the water-
impregnated fabric. There is always a chance of mildew formation during
storage of the fabric [12].
Acid Steeping Method
Dilute sulphuric or hydrochloric acid may be used to hydrolyse or liquefy
starch. The fabric is impregnated with 2.5 g/l acid solution at room
temperature (30°C) followed by storage for about 6-8 hours. Faster desizing
(within 1-2 hours) is possible using stronger solution of acid (say 10 g/l). The
155
process called souring is almost indispensable for low-quality cotton fabric.

Hydrolysis of starch by mineral acid is an exothermic process and the
temperature may rise even up to 50°C. During storage the fabric should not
be allowed to dry, otherwise the concentration of the acid in the fabric will
increase with subsequent damage of the fabric. By acid steeping method,
almost all the starch present in the fabric may be liquefied. A subsequent
wash removes the solubilised starch. The acid-treated fabric should never
be dried before wash, otherwise mineral acid at high temperature reacts with
cellulose forming hydrocellulose.
The loss in weight after acid desizing and washing is always more than
that after rot steeping followed by washing, because the souring process
dissolves nearly all the mineral impurities. The main disadvantage of acid
steeping is that there is always a chance of tendering of the fabric by acid
hydrolysis if proper care is not taken during the process.
Enzyme Steeping Method
Desizing by enzymes is the safest method. In general, enzymatic desizing
agents may be divided into two main types,
1. Dextrinogenic or α-amylases, and

2. Saccharogenic or β-amylases.
They are similar, in that they hydrolyse glucosidic linkages in the starch
molecules, but the point, at which the reaction occurs is different. The α-
amylase attacks the chain at random so that the DP of starch (both number
and weight averages) is rapidly reduced. These are designated as
dextrinogenic and liquefying since the formation of dextrins is accompanied
by a rapid decrease in the viscosity of starch pastes. The dextrins are water-
soluble, hence removable from the fabric [13].
The β-amylases successively removes terminal maltose units from the
reducing, so that the polymer chain is shortened gradually. The presence of
maltose units significantly decreases the number average DP, leaving the
weight average DP unchanged, since the latter average is weighted by the
remaining polymer molecules which are of larger size. With the amylopectin
fraction, the action of β-amylase is arrested at the branch points, so that a
considerable quantity of the original polymer remains. The dextrins, which
remain after the action of β-amylases, therefore, have relatively high
molecular weights and are practically non-reducing.
Starch-degrading enzymes, which may be classified according to their
source of occurrence, are as follows:
1. Enzymes from animal sources such as slaughterhouse waste –
clotted blood, pancreas, liver, etc.
2. Enzymes from vegetable sources
156
(i) Malt extract

(ii) Bacterial
Pancreatic enzymes are prepared from slaughterhouse wastes. The
wastes are first extracted with water and concentrated under vacuum,
followed by precipitation by adding alcohol in which the enzymes are
insoluble. The enzymes are filtered and finally dried. They are to be stored
carefully as they become inactive under acidic and alkaline conditions and
are oxidised by air under moist condition. Malt enzymes are made from
germinated barley, while bacterial enzymes are produced by growing culture
of certain microorganisms on suitable media (e.g. wort-beer prior to
fermentation) under controlled conditions for about a week.
The first textile use of malt appears in 1857, when it was used for removal
of thickeners from printed cotton fabric. Around 1900, a German company
first introduced a malt enzyme or diastase called diastafor for textile use in a
simpler and more efficient manner. Other commercial preparations are
available under the trade names Diastase, Maltoferment, Maltostase etc.
These preparations act upon starch efficiently at a temperature of 60°C and
a pH 5.7. However, on account of feeble acidity, best results are obtained at
pH 6.7. About 2.25 kgs of malt extract is required for every ton of fabric.
Around 1912, a number of pancreatic diastases such as Pancreatin,
Trypsin, Fermasol, Pancreol and Degomma were marketed. The bacterial
diastase was first marketed around 1919 in the form of the well-known
product Rapidase. These possess very rapid action and they are the only
enzymes used for desizing at present. Conventional and much faster
thermostable α-amylases are applicable at 20-80°C and 40-120°C
respectively. The conversion is mostly into soluble starch and dextrin and
practically no saccharification. The optimum conditions for enzyme desizing
are shown in Table 4.1 [14].
Table 4.1 Optimum Conditions for Enzyme Desizing [14]

Diastase/ Amylase pH Temp. °C Time, hour Effects
1 2
Malt 4.5-5.5 55-65 12-24 - +
Pancreatic 6.5-7.5 40-55 12-24 + +
Bacterial 6.5-7.5 65-75 1-4 + +
Bacterial, (Thermostable) 7.0-8.0 100-120 1-2 min + +
1. Sodium chloride, 2. Calcium ion, - no effect, + enhancement.
Time required for desizing depends on the method of application, kind of

fabric (tightness of weaving, weight, etc.) and the temperature and
concentration of the enzyme. The incubation times in various methods are
reported [5] to be as follows:
Jigger: 2-4 ends (60-100°C)

157
Winch: 30 minutes (90-100°C)

Cold pad-batch: 6-24 hours (15-40°C)
Hot pad-batch: 3-8 hours (60-70°C)
Pad-steam: 15-120 seconds (90-110°C)
The amounts used depend on the activity of the product and there are at
least two systems for measuring that activity. The recommendations for
Aquazyme 120 L from Novo Nordisk (120 refer to the strength of the
enzyme) for various machines are as follows:
Quench box: 10-25 g/l

Winch: 2-10 g/l
Jigger: 2-10 g/l
J-box: 20-50 g/l
Combi-steamer: 20-50 g/l
From various studies, the following observations are made:
1. The use of greater amount of enzyme does not ensure complete

conversion of starch.
2. At lower temperature, desizing efficiency is lower and normally
temperature should not be allowed to drop below 40°C.
3. Compared to the pancreatic enzyme, the malt enzyme has a slower
action even with the addition of more enzymes.
4. Whereas bacterial and pancreatic amylases consist of a single
amylase, the malt enzyme has two constituents, α-amylase and β-
amylase, which are found to be in ratio of 1:5 to 1:6. Experiments
showed that conversion of starch by the β-amylase lags considerably
behind that of the α-amylase. The α-amylase attack starch very
rapidly at random points, thereby disintegrating the molecule into
small fragments of low molecular weight dextrin. However, the β-
amylase attaches itself to the non-reducing amylose chain where it
continuously liberates maltose units and finally transforms it to
sugars.
5. Generally, wetting agents are used to facilitate the penetration of the
enzyme into the size film resulting in uniform desizing. However, it
does not have great effect on speed and efficiency of the desizing
agent. On the other hand, some wetting agents (mostly anionic)
reduce thermal stability of the enzyme. Nonionic surfactants are
comparatively safer.
6. Certain compounds like sodium and calcium salts (mostly chlorides)
may be added to amylase solutions to improve its thermal resistance
158
as well as solubility. Pancreatic-amylase cannot reach full activity in

the absence of salts. Malt-α-amylase requires calcium ions to be
effective, so that the sequestering agents should be avoided. On the
other hand, heavy metal ions such as copper, iron, etc. may combine
with the enzyme and inhibit its activity. Bacterial amylases are more
stable to heat than other amylases. The starch itself increases the
stability of such enzymes.
7. The stability of bacterial enzyme is very good at high temperature,
when a high reaction rate may be achieved. This is advantageous in
continuous processing when the dwell time in the J-box may be
reduced to 10-15 minutes if the material is preheated with steam.
Many short-duration enzyme desizing methods have been devised
recently using bacterial enzymes at higher temperature.
Chelating agents should not be used during enzyme desizing process

because calcium ions stabilise the enzymes. Wetting agents and nonionic
surfactants can be used to enhance enzyme penetration and adsorption,
fibre swelling and to promote the removal of waxes, soils and synthetic
sizing agents. Anionic and cationic surfactants may inactivate enzymes.
Lubricants are recommended in jet and rotary washers, to reduce formation
of crease marks and streaks. After enzymatic treatment, the fabrics should
be washed off above 80° C in alkaline liquor followed by a wash in neutral
liquor.
Clariant has developed [15] a cold desizing process with relative
insensitivity to pH fluctuations. The fabric is padded with 2-4 g/l Bactosol TK
liq., 1-2 g/l trisodium phosphate (pH 8.5-9) and wetting agents. It is then
batched for 4-12 hours at room temperature followed by hot and cold wash.
It is often the practice to include some beef tallow or other fat in the size
bath in order to improve the lubricity of the sized yarn after drying. These
fats may have a negative effect on dyeing and finishing operations if not
completely removed. Much time is necessary to remove them during
scouring. It is, therefore, proposed that lipase enzymes be included in the
amylase desizing bath to catalyse hydrolysis of the fat, the hydrolysis
products being glycerol and fatty acid. A synergism between amylase and
lipase is possible that results in even more efficient removal of starch than
would occur with amylase alone.
Chlorine/Hypochlorite Desizing
Gaseous chlorine can be used for degradation of starch. The grey fabric is
padded with water and is passed through a chamber provided with a false
bottom through which gaseous chlorine is blown into the chamber. Chlorine
reacts with water producing nascent oxygen as follows:
159
Cl2 + H2O Æ 2HCl + [O] (4.1)

By controlling the concentration of chlorine and the time of contact, the
formation of oxycellulose may be prevented. Chlorine gas is troublesome to
handle, hence may be replaced with a dilute solution of sodium hypochlorite
or bleaching powder containing 1.5-2 g/l of available chlorine. The fabric
may be impregnated with the solution, squeezed and stored for one hour at
30°C. It is then washed and antichlored.
Typically, for hypochlorite desizing, pad liquor containing 2.5-3 g/l
available chlorine is required. This can be applied in the quench box of
singeing machine or preferably in a saturator. In common with all desizing
operations, it is desirable to obtain a good liquor pick-up, minimum 80%, to
assist size swelling and subsequent removal. Residual hypochlorite is less
detrimental to subsequent peroxide bleach liquor stability than residual
enzymes as in case of enzyme desizing. Hypochlorite can attack ether
bonds and hydroxyl groups and are capable of cleaving C-H bonds,
depending on pH [16].
Chlorite Desizing
Sodium chlorite can be used under acidic condition for oxidising starch
present in grey fabric. Sodium chlorite may be activated by a mixture of
acetic acid and sodium acetate (set at pH 4) at 80°C or with ammonium
sulphate (quantity equal to that of chlorite) at boil. A concentration of 10 g/l
of sodium chlorite is sufficed to complete desizing within an hour. When the
concentration is reduced to 3 g/l, the time required may be about three
hours.
Sodium chlorite requires acidic condition for bleaching, but best desizing
requires alkaline pH. The process should be well controlled, as there is risk
of fibre degradation. In a combined desizing and bleaching process for long
liquor processing, the fabric is first desized under alkaline conditions. Then
the liquor is acidified for bleaching. Good desizing is reported by activation
of sodium chlorite with ammonium sulphate, buffered acetic acid or
photoactivation. Alternate oxidative desizing processes are more suitable
than that with sodium chlorite [16].
Bromite Desizing
Sodium bromite (NaBrO2) or preptone has a powerful oxidising action on
starch. This is due to combined action of bromous acid (HBrO2) and
hypobromous acid (HOBr). Bromine oxide breaks into bromine and oxygen.
Further, bromine hydrolyses forming more hypobromous acid. In addition to
the breakage of ether linkage (i.e. the oxygen bridge joining two glucose
units), sodium bromide opens up the glucose ring by the rupture of C2-C3
link with the consequent formation of a dialdehyde. The dialdehyde is not
soluble in water but in hot alkaline solution, since the adjacent oxygen
160
bridge is highly sensitive to alkali and is broken under such conditions.

Hence, sodium bromite treatment should be followed by a hot alkaline
treatment with or without intermediate washing. It is possible to carry out
continuous desizing with sodium bromite. The fabric is padded in a low
capacity padder (5-50 gallons) with 0.3% sodium bromide, a nonionic
wetting agent and 0.1% sodium carbonate at room temperature. After
padding, the material is stored for 6-20 minutes or more at room
temperature or slightly higher. The fabric is washed and treated with caustic
soda solution in one or two successive J-boxes and rewashed. Best pH for
bromite desizing is 10. Below pH 9 the decomposition of sodium bromite is
rapid, while above pH 11, the oxidation of starch is slow. The maximum
degradation of cellulose occurs at about pH 10 in bromite desizing.
The advantages of bromite desizing are:
1. Room temperature operation, no boiler required and consequently

saving of energy.
2. Low consumption of sodium bromide (0.2-0.3%).
3. Shorter treatment period of 6-15 minutes.
4. Uniform desizing.
5. Bromite also reacts with other impurities resulting in whiter and
cleaner fabric after desizing.
Sodium bromite used to be marketed as an alkaline aqueous solution of

concentration of 60-80 g/l having 78-104 g/l available bromine (similar to
available chlorine). At present, it has no commercial interest in Europe. The
disadvantage of bromite desizing process is that a large quantity is not
consumed for degradation of starch – only about 28% is estimated to be
utilised for the purpose and about 50% reacts with impurities present in grey
cotton increasing AOX value. The recommended continuous and batch
processes use 0.5-1 g active bromine per kg of fabric when the desizing
liquor is applied at ambient temperature [16].
Peroxy Compounds
The possibility of using sodium persulphate or hydrogen peroxide has been
suggested but their commercial use to date is small.
Ammonium perdisulphate (NH4)2S2O8, and acid hydrogen
permonosulphates have been shown to be efficient desizing agents
especially when polyvinyl alcohol (PVA) is used. PVA is water-soluble, but
after heat-setting of the fabric, the PVA size, present on the fabric, gets
polymerised and is difficult to wash off unless a desizing agent is used.
Peroxomonosulphuric acid or Caro’s acid (H2SO5) is prepared by reacting
hydrogen peroxide with sulphuric acid under specific conditions. Potassium
permonosulphate is available as triple salt. The method of desizing is similar
161
to acid desizing. The fabric is saturated with 2 g/l H2SO5, held at ambient
temperature for several hours and then washed off. However, the method is
of academic interest as other peroxygen compounds are cheaper.
Three peroxodisulphates, Na2S2O8, K2S2O8 and (NH4)2S2O8 (commonly
known as persulphates), are available as sodium, potassium and
ammonium salt. All salts are equally effective, but as the potassium salts are
poor in solubility, sodium salts are preferred. Ammonium salts liberate
ammonia from alkaline desizing liquor.
The persulphates improve absorbency of bleached fabric and their use
has continued to the present day. Separate solutions of persulphate and
caustic soda should be fed to saturator maintained at temperature less than
43ºC. After impregnation the material is steamed at 90ºC for 5 minutes. The
concentration of persulphate and caustic soda are 0.3-0.5% and 1-5%
o.w.m. (on the weight of material) respectively. In cold pad-batch method,
the fabric is batched for 4-8 hours with 0.5% persulphate, 0.5% tetrasodium
pyrophosphate and 0.5-3.0% caustic soda before washing off. With soda
ash, inferior results are obtained. The persulphates are not recommended
for kier or other circulating equipment with slow heating rate. For starch-
sized fabrics, 0.35% persulphate with 2-6% caustic soda (o.w.m.) gives
complete desizing at 100ºC within 3-6 minutes. The desizing time is only 30-
60 seconds at 110-130ºC, but there is little advantage of temperature
exceeding 110ºC.
One of the suggested methods of persulphate desizing is to put alkaline
solution of persulphate at 60-90°C into the quench box attached to the
singeing machine when moderate desizing takes place even in 30 seconds.
Clariant method [15] recommends padding at 40°C with 5-7 g/l sodium
persulphate, 40-60 g/l (10-20 g/l for blends) caustic soda and wetting agents
followed by steaming for 1 minute at 100°C and subsequent washing.
Alternately, the fabric may be treated in jigger for several hours. The degree
of starch degradation achieved in persulphate desizing is less than that
obtained with enzymes, but for many purposes it is adequate and
subsequent peroxide bleaching will usually complete the removal of size.
The persulphate-size reaction is believed to proceed through free-radical
mechanism. Some inhibitors like urea, etc. are effective, but only at low
temperature. A high degree of liquefaction occurs with high viscosity grade
polyvinyl alcohol.
The use of persulphate in conjunction with hydrogen peroxide in pad-
steam combined desize, scour and bleach process has been patented.
The starch-degrading property of hydrogen peroxide contributing to size
removal was recognised in early cold pad-bleaching processes.
Polyvinyl alcohol (PVA) is water-soluble, but redissolving of size is
hampered by heat and gelling by caustic alkali. Further disadvantages of
alkaline conditions are said to be the production of chromophores and
162
pungent odour on PVA sized fabric in the presence of oxidising agents.

Desizing of such sizes with hydrogen peroxide is, therefore, to be carried out
under mild alkaline conditions. The recommended pad-steam desizing
method consists of padding with 0.2-0.4% o.w.m. hydrogen peroxide at pH
6-8 followed by steaming at 90-100ºC for 15 minutes. An alternate method
of continuous desizing is a two-bath process. At first, the fabric is treated
with a 0.8% solution of hydrogen peroxide at 90ºC at neutral pH. Without
intermediate rinsing, the fabric passes into a second bath containing 0.5%
caustic soda before final rinsing at 70ºC (minimum).
The relative instability of hot alkaline hydrogen peroxide remained an
obstacle to the combined application of caustic soda and oxidant. One
solution to this problem was the introduction of special grade of hydrogen
peroxide with magnesium sulphate as stabiliser. Magnesium sulphate may
also be added separately in the saturator. This allows preparation of
desizing pad liquors of adequate stability at 60ºC with pH 12 or above. The
stabiliser does not impair desizing when the fabrics are subsequently
steamed at 90ºC. No magnesium sequestering agent should be used. The
fabric may be treated with 1-2 volume hydrogen peroxide along with 7-15 g/l
caustic soda followed by short steaming (3 minutes).
The material is to be saturated with hydrogen peroxide at 60ºC or above
with 80-100% pick-up, preferably with surfactants for better diffusion. It is
then steamed for 8-10 minutes. 2% o.w.m. caustic soda is preferred, but can
be increased to 6% for combined desizing and scouring.
Recommended conditions for oxidative desizing reported elsewhere [14] is
shown in Table 4.2.
Table 4.2 Recommended conditions for Peroxy Desizing

(Quantities in % o.w.m.) Recipe 1 Recipe 2 Recipe 3
Magnesium sulphate 0.005 0.005 0.005
Caustic soda, solid 2-6 2-4 9-12
Stabiliser 0-1 0-1 0-1
DTPA (diethyltriaminepentaacetic acid, 40% solution) 0.2 0.2 0.2
Hydrogen peroxide (35%) 5-15 5-15 5-15
or Sodium persulphate 0.2-0.5 0.2-0.5 0.2-0.5
Wetting agent 0.2-0.5 0.2-0.5 0.2-0.5
Temperature, °C 100 100 120-130
Time, minutes <15 15-60 1-2
The study of pad-steam oxidative desizing system showed that
1. Fibre damage increases as oxidant level increases, it is more

pronounced with persulphate.
2. At a given oxidant level, fibre damage increases with increase in
alkali concentration.
163
3. Cold pad-batch desizing is much less sensitive to variation of alkali

or oxidant levels.
4. Optimisation of alkali and peroxygen level provides desizing with little
fibre damage.
5. Desizing with hydrogen peroxide provides additional bleaching or
whitening effect, but persulphate has negligible bleaching action.
6. It is undesirable to use mixture of persulphate and hydrogen
peroxide at high temperature.
7. When two peroxygen stages are used, minimum oxidant is used in
the unstable desize-scour stage followed by fully stabilised peroxide
bleaching. Sodium silicate or organic stabilisers hamper desizing.
Inorganic per salts such as sodium perborate and sodium carbonate-

hydrogen peroxide (2 Na2CO3, 3 H2O2) are powder products, which on
dissolution provide alkaline solution of hydrogen peroxide. However, the
alkalinity is insufficient for oxidative desizing. The latter product is effective
in foam desizing and bleaching of yarn and dyed fabric.
Organic per acids, such as peracetic acid (CH2COOOH), are more
effective oxidants than hydrogen peroxide at temperature below 60ºC. But
they offer no performance advantage over cheaper hydrogen peroxide or
persulphate.
The demerits of oxidative desizing are [16]:
1. Like all other desizing processes, reduction of COD content in the

effluent by size recovery is not possible. However, after size
recovery, residual size may be quickly and efficiently removed by
oxidative treatments.
2. Another obstacle, but not limitation, is the need for good control of
the desizing system and good equipment for application. Enzymes
show greater tolerances to concentration variations.
3. Adverse effects of metal contamination. Many quench boxes of
singeing machines contain brass components, which are damaged
by oxidants.
Based on availability, cost and effectiveness, only two chemicals are of

prime importance for oxidative desizing – peroxodisulphates and hydrogen
peroxide.
Desizing Efficiency
Starch sizes can be detected by spotting with a solution of iodine in
potassium iodide and this has been converted into a quantitative test.
Different blue-coloured standards can be prepared by interacting fabrics of
varying residual starch and iodine and the colour of the iodine-stained
164
desized sample can be compared to get an idea about the extent of

desizing. However, the results should be interpreted with care as oxidative
damage also gives a blue colour with the reagent.
Desizing efficiency is the starch hydrolysing property of enzymatic
desizing agents and can be assessed [17] in two ways:
1. The first method is suitable for determining the desizing efficiency of
an enzyme as well as the relative efficiency of different enzymes.
The method is based on desizing of starched fabric. It is simple and
quick. However, the method is indirect and the test results are to be
corrected for hydrolysed starch and unhydrolysed starch removed
mechanically along with hydrolysed starch.
In this method, 5 g or more of good quality bleached fabric free
from residual size and finishing materials is taken. Five threads from
each side of the fabric are removed to avoid loss of threads during
subsequent processes. The piece is dried in a stoppered weighting
bottle at 100-105°C to constant weight and weighed accurately.
Starch is applied to the piece by passing it through a solution
containing 10 ± 1% maize starch or potato starch adjusted to pH 6.5-
7.5. The piece is then squeezed to 100% expression by passing it
through a pair of squeezing rollers. The piece is dried in hot air and
weighed in a weighing bottle accurately. 1 g/l enzyme and 1 g/l
sodium chloride solutions in water are prepared separately. Two
beakers are filled with water and the above solutions are taken in
such a way that both the amount of enzyme and sodium chloride is
0.02% of the amount of starch present in the piece and the M:L ratio
is 1:20. Two starched pieces are treated in two separate beakers at
50°C and 70°C for 5 minutes each. The pieces are passed
separately through squeezing rollers and left in separate stoppered
bottles at 38 ± 2°C for 18-20 hours. The pieces are washed 6 times
giving 2 dips each time in 400 ml of fresh water at room temperature.
The two pieces are dried at 100°C in stoppered bottle to constant
weight and weighed accurately. The % loss in weight is calculated on
oven-dry basis as shown in Eqn. 4.2.
% weight loss = W1
– W2 (4.2)
d
where W1 = weight of undesized piece
W2 = weight of desized piece
d = amount of starch in the piece
2. The second method is based on hydrolysis of starch solution. It is
suitable for comparing the relative desizing efficiency of different
enzymes.
165
1% starch solution is prepared by dissolving in water and boiling in

a water bath for about 30 minutes till a clear solution is obtained.
0.1 g dry powdered enzyme is dissolved in 1 litre water at room
temperature.
Four dry test tubes are placed into a rack immersed in a water bath
containing ice. The enzyme solutions amounting 2.5 ml, 5 ml, 10 ml
and 15 ml are added in four test tubes respectively. 5 ml of starch
solution is added in each test tube and made up to 20 ml with cold
distilled water. The rack containing the test tubes is placed in a water
bath heated at 50°C. After 30 minutes the rack containing the test
tubes is transferred to an ice-water bath to inhibit further enzyme
reaction. After 5 minutes 1 drop of 0.1 N iodine solution is added in
each test tube. An orange yellow colour indicates complete
conversion of starch into sugar. The test is repeated in the
concentration zone where complete conversion has occurred and its
immediate lower concentration. The enzyme concentration is by 1 ml
and thus the exact quantity of enzyme required for complete
conversion of 5 ml starch is estimated. The test is carried out
separately for all the enzymes whose desizing efficiencies are to be
compared.
Residual starch in cotton fabric can be measured by boiling the fabric for
about 45 minutes with distilled water, cooling and decanting the supernatant
liquid. The process is repeated until the residue in the beaker shows blue
colour with iodine solution. The decanted liquor is filtered and concentrated
by boiling, cooled and adjusted to 100 ml. 25 ml of the solution is taken in a
flask and 10 ml of 0.5 N potassium dichromate and 5 ml concentrated
sulphuric acid is added. The mixture is boiled for one hour under a reflux
condenser. 6-8 drops of phenyl anthranilic acid indicator is added. The
solution is then titrated with 0.1 N ferrous ammonium sulphate (FAS)
solution until the appearance of a characteristic green colour. The % starch
is calculated by the Eqn. 4.3.
% starch = 400 x (v1
- v2 ) x N x 0.00696 (4.3)
W
Where v1 = ml of FAS required for blank
v2 = ml of FAS required for extract
N = normality of FAS solution
W = oven-dry weight of specimen (g)
One ml of 1 N potassium dichromate corresponds to 0.0096 g of starch.
Desizing of Synthetic Fibres and Blends
Synthetic fibres are stronger, hence increasing strength by sizing is not the
aim. The adhesion of sizing material to the yarn is also difficult. Sizing of
166
man-made fibres with starch creates a lot of problems. The demand for
increasing warp-speed has also led to the development of special synthetic
polymers and paraffin-based lubricants. The main synthetic sizes comprise
of polyvinyl alcohol (PVA), polyacrylic acid, CMC, plasticised acidic vinyl
acetates and acidic methyl acrylate polymers. PVA is the oldest of synthetic
sizes, it dries to form a hard film of poor flexibility. The solubility of PVA may
be impaired by heat applied during sizing, grey heat-setting or singeing.
CMC and water dispensable polyester based sizes are insoluble in acidic
form and can be solubilised by alkali at around 60ºC. To prevent
precipitation by metal ions in the washing bath, addition of sequestering
agent is recommended. To improve the efficiency of size, sometimes a
mixture of various sizes are used. Not only is the quality of weaving
improved by using synthetic polymers, but also minimum use of additives
reduces pollution and improves handle of fabric.
When water-soluble PVA is used as a sizing agent in weaving, no desizing
is necessary. Light scouring with 3-5 g/l nonionic detergent at 95-100ºC for
20-30 minutes is enough to remove the size material. However, high
molecular weight (>1,00,000) PVA is difficult to remove. Polyester sizing
agents are not removed by simple washing treatment. They can be removed
by treating with a solution containing 2-3 g/l nonionic detergent and 1-2 g/l
caustic soda or soda ash (with or without 1-2 g/l sodium tripolyphosphate) at
80-90ºC. The use of soft water or sequestering agent is recommended.
Polyacrylic acid is soluble in mildly acidic or alkaline solution.
The desizing of polyester/cotton blends depends on the nature of size
used. Acrylic copolymer is removed by simply mild alkaline scour. PVA and
CMC are removed by hot wash. A mixture of starch and emulsifying wax is
removed by means of enzymatic desizing followed by alkaline scour. When
acrylic sizes are mixed with starch, their pH of about 9.5 will inactivate
enzymes. In such cases, the fabric may be pre-acidified or acetic acid may
be added to the desizing bath to bring pH at 8. PVA can be easily removed
using hydrogen peroxide in the presence of a metal catalyst under neutral
condition [2].
4.4.6 Scouring of Cotton

Scouring is the most important wet process applied to textile materials
before dyeing or printing. It is mostly a cleaning process in which the foreign
matters or impurities are removed. The impurities may be natural, added or
accidental as discussed earlier. When the impurities are removed, the cotton
becomes absorbent. In fact, the success of a scouring process is judged by
the improvement in wettability of the scoured material.
More specifically scouring is done in order to remove unwanted oils, fats,
waxes, soluble impurities and any particulate or solid dirt adhering to the
167
fibres, which otherwise hamper dyeing, printing and finishing processes. The
process essentially consists of treatment with soap or detergent with or
without addition of alkali. Depending on the fibre type, alkali may be weak
(e.g. soda ash) or strong (caustic soda).
In non-continuous cotton processing (kiering), the M:L ratio is about 1:3;
consequently, the use of a 10-20 g/l caustic soda solution means a quantity
of about 3-6% of the weight of fabric. Under these conditions, the length of
treatment ranges from 2 to 12 hours at temperatures between 100°C and
130°C. In continuous cotton scouring processes based on a 100% pick-up,
the caustic soda concentration should be a minimum of 30 g/l. However, the
steaming time is necessarily less than that in the batch process to attain
higher productivity.
A high-quality synthetic detergent provides a good balance with wetting,
cleaning, emulsifying, dispersing and foaming properties, thus providing it a
good cleaning ability. Anionic, nonionic detergents or their blends, solvent-
assisted detergent blends and soaps are mostly used for scouring. For
accelerating scouring process, wetting agents in conjunction with high
boiling solvents (cyclohexanol, methylcyclohexanol, etc.) are sometimes
used. The function of solvents is mostly to dissolve insoluble fats and
waxes.
When soap is used, a good supply of soft water is to be assured. The
3+ 2+
metal ion (Fe and Ca ) present in hard water and pectin of cotton can
form insoluble soap. The problem is more acute when scouring is carried out
in a continuous process involving padding bath where the M:L ratio is much
lower than batch process, the chelating or sequestering agent may be used
to prevent scum and film formation. Sequestering agents depend on the pH
of the scouring bath. Organic sequestering agents, stable under hot alkaline
conditions are:
1. EDTA
2. NTA
3. HEDTA , N-(2-hydroxyethyl EDTA)
4. DTPA, diethyltriamine pentaacetic acid
5. DHEG, N, N-di(2-hydroxy ethyl)glycine
6. DPTA, diaminopropanol triacetic acid
A number of organophosphonates ATMP (aminotrimethylene phosphonic

acid) or EDTMP (ethylene diamine tetra-methylene phosphonic acid) are
available, which are sequestering agent-cum-detergent, but are unstable at
high temperature.
Builders are added to the kier boiling bath to increase the activity of soap
or detergents. These are generally salts like borates, silicates, phosphates,
sodium chloride or sodium sulphate. Sodium metasilicate (Na2SiO3, 5H2O),
168
can additionally act as a detergent and buffer. The function of the buffer is to
drive soap from water phase to fabric/water interface and consequently
increase the concentration of soap on the fabric.
During boiling of cotton with caustic soda, entrapped air may cause
oxidation of cellulose. This may be prevented by addition of a mild reducing
agent such as sodium bisulphite or even hydrosulphite in the scouring liquor.
Scouring processes for different textile materials vary widely. Among
natural fibres, raw cotton is available in the most pure form. The total
amount of impurities to be removed is less than 10% of the total weight.
Nevertheless, prolonged boiling is necessary as cotton contains waxes of
high molecular weight, which are difficult to remove. The proteins also lie in
the central cavity of the fibre (lumen) which is relatively inaccessible for the
chemical used in scouring. Fortunately cellulose is unaffected by prolonged
treatment with caustic solution up to the concentration of 2% in the absence
of air. Hence, it is possible to convert all the impurities during scouring,
except natural colouring matters into soluble form, which can be washed
away with water.
Scouring of cellulosic fibres other than cotton is quite simple. Bast fibres
like jute and flax cannot be severally scoured owing to the removal of
several non-fibrous components with consequent damage of the material.
These are generally scoured using soap or detergent along with soda ash.
Regenerated cellulosic fibres like viscose are more sensitive to alkali. As
these man-made fibres are much cleaner, scouring with nonionic or anionic
detergents is sufficient.
Since natural impurities such as cotton wax, pectic substances and protein
are associated mainly with the cell wall within the primary wall, the scouring
process aims to remove this wall. The changes caused by the treatment
with boiling alkali have been summarised as follow [18]:
1. Hemicelluloses as well as cellulose fractions with a low DP are

dissolved.
2. Saponifiable oils and fats are converted into soap.
3. Unsaponifiable oils and waxes are melted at the scouring
temperature and are emulsified by the soap formed during
saponification.
4. Pectins and pectoses are converted into soluble salts of pectic acid
and metapectic acid.
5. Proteins are hydrolysed with the formation of soluble sodium salts of
amino acids or ammonia.
6. Water-soluble mineral substances are dissolved.
7. Insoluble dirt is removed and retained in suspension.
8. Sizing and other added impurities, if present, are broken into soluble
products.
169
The required severity of the scouring and bleaching processes will depend
on many factors e.g. the type, colour and cleanliness of the cotton material,
the twist and count of the yarn, the construction of the fabric, etc. The aim of
the bleacher is to remove the non-cellulosic impurities to a sufficient extent
without modification of the cellulose. The impurities, which are most difficult
to remove, are wax, seed fragments and oil stains.
Scouring may be carried out on loose fibres, slivers, yarn or fabric but for
ease of handling, fabric form is preferred. Surgical cotton is scoured and
bleached in fibre form, whereas the yarns to be dyed are scoured in hank or
in package form. The packages used are cones or cheeses. Cotton piece
goods of light or medium weight are mostly scoured in rope form as it is
cheaper to operate, while heavy weight fabrics are best scoured in open-
width. Vigorous scouring is desirable for cotton goods, since they contain
mechanically held particles of cotton seeds, husks and leaves, which may
have escaped the ginning process, and which are supposed to be removed
during scouring. Failure to remove them is detrimental, since their presence
forms dark coloured spots on the fabric and they are dyed differently from
those of the bulk material.
Kier
The boiling with alkali is carried out in specially designed vessels known as
kiers. These may be either open in which the liquor boils at atmospheric
pressure or closed when the liquor is boiled under high pressure and
temperature. Kier boiling essentially consists of circulating hot alkaline
liquor through the fabric, which is stalked inside the machine in rope form.
For this purpose the fabric in open width from the previous processing stage
is passed through a porcelain ring (about 15 cm in diameter) after which the
material is piled inside the kier. Prior to entering the kier, the fabric is often
impregnated with alkaline liquor in a trough, followed by a passage through
a padding mangle to give 100% expression.
The kiers are generally cylindrical vessels made of cast iron or stainless
steel. The conventional cast-iron kier may give severe problem of iron stains
and should not be used for combined scouring and peroxide bleaching as
catalytic decomposition of peroxide is caused by rust. However, these
vessels can be safely used if a lining of ceramic or a mixture of sodium
silicate and cement is applied. Cast-iron pumps, calorifiers and other
external pipes can also be rendered passive by circulating a boiling solution
of sodium silicate and magnesium sulphate.
The conventional cast iron kier may be coated with a mixture of rapid-
setting cement and sodium silicate, 75°Tw (ratio 20:1) with trace amount of
magnesium sulphate, pasted with water. The thoroughly cleaned kier is
painted with the mixture and allowed to dry for about 24 hours. A second
coat is applied and dried for another 24 hours. Then a solution of sodium
170
silicate is sprayed on the surface. After 2 hours of drying, a second spray is

made with about 50 g/l of sodium silicate. The kier is allowed to stand
overnight and then it is ready for use.
°Tw is a measure related to the specific gravity of a solution. The Twaddell
meters, similar to lactometers used for determining purity of milk, are more
convenient to use than specific gravity bottles. For certain solutes, the
specific gravity as well as °Tw of solution varies significantly with the
concentration of the solute. For a particular solute, a relation can be drawn
between concentration and °Tw (or specific gravity).
The concentration can thus be quickly measured with the help of the
twaddell meters. The relation between the specific gravity (S) and °Tw (T)
may be expressed as shown in Eqn. 4.4.
S = 0.005 T + 1
or T = 200 (S – 1) (4.4)
A similar measure is called Baume (°Bé). The relation between the
specific gravity (S) and °Bé (B) may be expressed as shown in Eqn. 4.5.
144.3 144.3
B = 144.3 − or S = ( 4 .5 )
S 144.3 − B
The relation between °Tw and °Bé is as follows:
200 B
T=
144.3 − B
Acetic acid and sulphuric acid show maximum specific gravity at
concentration of 78% and 97.7% respectively. For them, the specific gravity
falls at higher concentration. Table 4.3 shows conversion of various
measures of strength of caustic soda.
Table 4.3 Conversion of Strength Measures of Caustic Soda Solution

Strength Solid Caustic Soda Content (approx.) in Solution
°Tw °Bé g/l g/kg
53 30 300 237
56 32 320 250
62 34 366 280
70 37.5 430 318
76 40 480 347
The simplest, open kier consists of a cylindrical tank with a false bottom
(about 18 inches above the base) in which the fabric is laid down in a
regular fashion either manually, or nowadays by a mechanical piler. The
latter consists of a long trunk, mounted above the kier, which can move
forward and backward. The fabric is passed through the trunk and is laid
evenly inside the kier. Alkaline liquor may also be introduced through the
trunk for simultaneous impregnation. Even distribution of the fabric in the
kier is a vital factor as it helps uniform flow of liquor. Unequal distribution
171
may facilitate formation of channels through which liquor may pass

preferentially. Channels may also form due to movement of fabric during
liquor circulation. Hence, heavy weights are put on the top of the batch,
preferably with an intermediate layer of hessian fabric, to avoid staining.
The capacity of the kier may vary from 500
Baffle plate
kgs to 5 tons. The most popular is of 2 tons
capacity and it may be about 9 feet high and
6.5 feet in diameter. In the simplest form
(Figure 4.6), steam is injected through a hole
at the centre of the bottom of the kier and it
is able to pass up through a central pipe
Puffer
called puffer pipe (about 4-5 inch in pipe
diameter), thereby forcing liquor up with it. False
When steam is first introduced, condensation bottom
occurs. However, when the temperature is
raised sufficiently, the rate of condensation
reduces, the residual steam blows the
column of liquid in the pipe and strikes a
Drain Steam valve
curved baffle plate situated above the puffer
pipe. The liquor is then distributed over the
whole surface of the load of cotton in the kier Fig. 4.6 Kier with Puffer Pipe
and percolates down until it is again
withdrawn below the false bottom, thus keeping up a continuous circulation.
The use of an injector (Figure 4.7) instead of an open pipe gives improved
use of steam for both heating and circulating. It consists of a cavity or
chamber with a conical top. A steam nozzle is
placed at the bottom of the chamber and the
orifice, which is connected directly to the puffer
pipe residing at the top. The cavity is filled with
the liquor from the kier through the side pipe
and the steam enters the nozzle at the bottom.
The steam-water mixture emerges through the
orifice at the top with considerable velocity
causing vigorous movement of the liquor. Water
Liquor circulation entirely by steam is not very
efficient and economical. Moreover, the
condensation of steam causes increase in liquor
inside the kier, which is normally maintained at Steam
three times the weight of material (i.e. M:L ratio
of 1:3). Hence, most of the modern kiers are
equipped with an external calorifier or heat- Fig. 4.7 Steam Injector
exchanger (Figure 4.8). Thus, the dilution of the alkaline liquor by contact
with live steam is avoided. The liquor is withdrawn from the bottom of the
172
kier and forced through a calorifier or heat exchanger by a centrifugal pump.

It is then sent to the top of the kier and spread by the sprayer or distributor
over the material loaded in the kier.
Before material is loaded, sufficient scouring liquor should be run to cover
the false bottom. When the batch is in position, sufficient liquor is introduced
preferably from the bottom, in order to sweep out air. The lid (or manhole
Manhole
Sprayer
Heat Eexchanger
Material
Pump Drain
Fig.4-8 Modern Kier

cover) of the kier is put in place but a valve is kept open to the air. The liquor
is now heated and circulated through the load till the temperature reaches
about 90°C. Steam and circulation are then cut off for a period of 10 to 15
minutes. This is done in order to expel all the entrapped air ,as cotton
impregnated with hot alkaline liquor is oxidised by the air with consequent
damage to the fabric. After the rest period, the temperature is raised by 5°C
when another rest period of 5 minutes is allowed. The temperature is further
raised to boil and a further pause is allowed. The steam is turned on, but an
escape valve is left open so that the air over the surface of the liquor at the
top of the kier can be displaced. The valve is closed when pure steam
emerges which can be judged from the colour of the exhaust (white and
transparent for the presence and absence of air respectively) by an
experienced operator. At the end of the operation, hot rinsing water is run
simultaneously with draining out of residual alkaline liquor to avoid contact
with air. Additionally, a reducing agent like sodium bisulphite is added in the
kier liquor.
Kier-boiling may be carried out either at atmospheric pressure in an open
kier or under pressure in a closed kier. In the latter case, the pressure is
often taken as a measure of the temperature – this is true only if no air is
present in the kier. For example, 20, 30 and 40 pounds per square inch (psi)
2
(1.4, 2.1 and 2.8 kg/cm respectively) pressures are equivalent to
temperatures of 125°, 134° and 141°C respectively. At the end of the boil, a
173
scum may accumulate on the top layers of the fabric, which may be blown
off by overflowing a small volume of liquor through a pipe from the top of the
kier into the drain. Caustic alkalinity at the time of draining should not be
less than 10% of the starting concentration in order to maintain the
impurities in the suspended form.
Lighter fabrics are usually handled in rope form, but heavier materials
show crease marks if processed in rope form. Open-width kiers such as
Jackson kier were therefore designed. In such machines, the fabric is put on
two rollers and wound from one roller to another as in case of jigger dyeing
machine. However, such machines were never popular due to low capacity
and difficulty in handling. Soap and soda, being a milder system, is used for
more delicate fabrics for which caustic boil will be too severe.
Continuous Scouring
Continuous scouring, either in open-width or in rope form, can be carried out
with the aid of various machines, the most important being the J-boxes. Very
large quantities of fabric are necessary to ensure the economic value of
such processes, and it is preferable to have pieces of fabrics of about the
same width and weight stitched together. The large accumulation of fabric,
which is piled in rope form in the J-box, implies that this technique can be
used only for fabrics which are not very sensitive to creasing and crushing.
The disadvantage in case of open-width processing in J-box, is that the
tension applied to withdraw the fabric from the machine may damage the
fabric. The treatment with alkali in this machine is not under pressure;
hence, higher concentration of alkali will be required.
In the Edmeston-Bentz system, the fabric runs through a tank containing a
set of rollers where it is impregnated with hot alkaline solution and then it is
steamed.
Universally popular J-boxes essentially consist of a stainless steel chute
with a high polished inner wall and are suitably insulated with glass wool or
other insulating substances. These, as the name implies, have shapes
similar to that of the letter J. The fabric is fed on the top and withdrawn at
the other end, where the opening is much smaller in order to prevent the
pressure exerted by the column of fabric in the long limb from forcing it out
too quickly. The fabric is piled at the bottom of the chute where it can reside
for about 60–90 minutes and is drawn from the other end at a speed of
about 150-300 metres per minute and is sent to the washing machine. The
production from a large continuous range is of the order of 40 tons per day
and a compact unit as those made by Farmer Norton can scour and bleach
about 500 lbs. per hour. The M:L ratio is 1:1 as compared to that of 1:3-1:5
for a conventional kier. The steam consumption is also much less and
estimated to be about one-fourth to that consumed during kier boiling.
174
J-boxes are of two types (Figure 4.9) differing in preheating arrangements

before storing inside the chamber. In the less popular Dupont or Farmer
Norton type, there is a separate chamber in which the material is heated to
80°C or any other specified temperature before it enters a J-box, which is
sufficiently insulated to ensure that the fabric will retain approximately this
temperature during the whole of its passage. The specially designed heating
D
D
A
B B
C
C
Dupont Type Becco Type

A = Fabric entry, B = Steam, C = Fabric exit, D = Plaiter
Fig. 4.9 Two Types of J-boxes
tube (shown vertical in the figure for simplicity) is about 40 feet in length and
the fabric passes through the tube only for about 8 seconds at a speed of
100 yards per minute. For processing in open-width, the fabric heater takes
the shape of a stainless steel box and the J-box is modified like Gnatt piler
in which there are a series of rollers over which the fabric passes to the
front. In Becco type J-box the steam is injected directly to the machine near
the point of the entry of fabric.
Before sending the material to the J-box, it is passed through a caustic
saturator. The fabric dips into about 4% caustic liquor for 6-8 times. A set of
squeeze rollers is provided to assist exchange of water in the material for
caustic impregnating liquor. The saturator is designed to hold a minimum of
about 300-400 gallons of liquor. The concentration of caustic liquor is to be
to a constant value (varying about ± 5%). The fabric is finally squeezed to
about 100% expression ensuring constant and uniform liquor pickup and
send to the J-box. Using 40-60 g/l caustic soda and keeping maximum
reaction temperature of 98°C, the production speed can reach 180 m/min
taking into account 30-60 minutes dwell time, the capacity of the chamber
must be of the order of 10,000 metres of fabric. After necessary period of
storage, the rope leaves J-box and is washed in hot water.
175
Scouring in J-box suffers from two disadvantages, namely:
1. High pressure scouring is not possible in J-box.

2. Tension required to take out fabric from the J-box may damage the
material, especially in open-width processing.
These shortcomings can be overcome by open-width processing. In open-

width roller steamer, the fabric is first padded through the scouring solution
to at least 100% pick-up at 60ºC with a running speed of 60 m/min, and then
passed through a steamer at 100º-110ºC for about 30 seconds to 5 minutes.
The fabric is then washed in an open soaper at 70-80ºC with counter-flow
arrangement.
The advantages of rope processing over open-width are lower chemical
costs, higher production speed, suitability for a wide range of fabric widths
without stopping the plant, and efficiency and simplicity of the required
equipment. On the other hand, the advantages of open-width processing
over rope processing are suitability for fabrics sensitive to creasing, better
uniformity of treatment, better warp tension control, lower weft distortion and
surface abrasion. The choice between rope and open-width processes
depends upon the nature of the fabric and its construction and upon
production requirements. The open-width processes are preferred for
heavier, higher-twist fabrics such as poplin, duck, twills and drills, in order to
minimise wrinkles and crushing. The rope treatments are used for fabrics,
which do not have creasing problems such as knit-goods, sheeting, broad-
fabrics, shirting, towelling and lining fabrics.
The high-pressure reaction chambers can produce scoured fabric in
significantly higher speed continuously in open-width. In pressure steamer
system, hydraulic sealing heads are subjected to a pressure, which is
slightly above the pressure inside the vessel where the fabric is guided on
rollers. Each sealing head consists of two opposed polytetrafluoroethylene
covered diaphragms and permits continuous cloth feeding and delivery.
Another possibility consists of eliminating the guide rollers and depositing
the fabric on a roller bed system allowing relaxation of fabric inside the
pressure steamer equipped with static lip seals. The Vaporloc machine of
Mather and Platt can operate at 2 atmospheres (30 psi) with a temperature
of 134°C at which both scouring and peroxide bleaching can be achieved in
periods as short as 90-120 seconds. A scouring assembly with a Vaporloc
pressure vessel is shown in Figure 4.10. The material is first treated in a
caustic saturator with 5-9% caustic soda solution containing wetting agent
and other scouring auxiliaries at a temperature of 70°C in open-width. The
material is then sent to the Vaporloc unit where it is treated in open-width for
90-120 seconds at a pressure of 30 psi. The fabric is deposited on a roller-
bed system and thus allows the fabric to be in a relaxed state inside the
176
Vaporloc
Saturator Washer
Fig. 4.10 Vaporloc Scouring Unit

pressure chamber. Finally, it is sent for washing off. Only one washing unit
is shown in the figure, but actually, there are two or three washing units –
one or two hot washes followed by a cold wash. The threading arrangement
as well as the length of fabric, which can be treated at a time, can be altered
by fitting roller frames of varied assembly of driven guide rollers. The
production speed is claimed to be about 120 m/min. A similar machine
called Pressure-lok, developed in the USA, demands complete scouring at a
time of 60 seconds only. A continuous processing pressure chamber
developed by Kleinwerfers operates at 3 atmospheres with a dwell time of
30-180 seconds. The material is impregnated with 60-100 g/l caustic soda at
130-140ºC. The production speed is about 30-60 m/min depending on the
capacity of the machine.
In continuous open-width atmospheric conveyor steamer, the impregnated
fabric is plaited down onto conveyor for necessary time and then taken to
the washing section. Creasing is a problem in such systems; hence, recent
installations are a combination of roller and conveyor systems commonly
known as combi-steamer (Figure 5.3). The impregnated fabric in open-width
is guided over roller assembly for a time sufficient for swelling. After passing
over this tight-strand roller section, the fabric is plaited down onto a roller
bed or conveyor belt with the fabric pile continuously moving so that the
folds in the fabric are never long enough in one position for a permanent
crease to form. The contact of the bottom of the fabric pile with each roller is
also not long enough for drying to occur. A dwell time of about 6-20 minutes
at 100ºC is required for scouring of cotton fabric impregnated with 3-6%
caustic soda. The production speed is around 100 m/min. Vacuum
impregnation (section 7.4.5) of the fabric with the scouring solution before
steaming is sometimes recommended for rapid wetting of the goods. This
machine can be best utilised for combined scouring and bleaching.
Alkaline boiling-off treatments of the fabric are of three kinds:
177
1. Lime-soda boil
2. Caustic boil
3. Soda-soap boil
The lime-soda boil was extensively used in the past but is almost
completely substituted by caustic boil, mostly because the latter is much
simpler. Soda-soap boil is recommended for coloured goods or fabrics
(mostly shirting) containing coloured stripes or patterns. The dyes mostly
used for this purpose are vat dyes as they have excellent wash fastness.
The scouring bath has a strong reducing character because of the presence
of the degradation products of the cotton impurities. They reduce vat dyes
and cause destruction of azoic dyes in the presence of caustic soda
resulting in bleeding or marking off. Hence, such materials are boiled with
soda ash (about 2.5% on the weight of material) instead of caustic soda. In
addition, several mild oxidising agents such as sodium m-nitrobenzene
sulphonate (resist salt), p-nitrosophenol, nitroso-m-cresol, p-nitroso-
dimethylaniline may also be added during boil.
Lime-soda Boil
In the past, lime was used extensively as the alkali to degrade the impurities
present in cotton. The method was cheaper when caustic soda was
comparatively expensive. There is also less risk of tendering of cotton. The
lime-soda boil consists of several steps. Essentially the procedure consists
of boiling with 2-4% (on the weight of material or o.w.m.) milk of lime or
calcium hydroxide solution. The material is packed in a kier along with milk
of lime and boiling is carried out at 30 psi pressure (134°C) for a few hours.
The saponifiable oils are broken down to corresponding alcohols and
insoluble calcium soaps of fatty acids. The pectins and pectates are
converted to calcium pectate and the proteins are broken down into amino
acids. The goods are boiled again with 2% soda ash in the presence of rosin
soap, when the lime soaps react with it resulting in calcium carbonate and
water-soluble alkali soaps.
As a modification, an intermediate treatment with dilute (2%) hydrochloric
or sulphuric acid may be done between the two boiling processes. The acid
or souring treatment is followed by a cold wash when excess acid and
water-soluble matters are removed. The lime soaps are converted into
insoluble free fatty acids, pectates into pectic acid, the calcium being
washed away as calcium chloride or sulphate.
Caustic Boil
Although lime-soda sequence gives satisfactory results, it is tedious and is
replaced by simpler caustic boil. The quantity of lime required is much more
than that of caustic soda. In the light of modern knowledge, caustic soda
178
appears to be the best scouring agent as it saponifies oils, emulsifies waxes,

hydrolyses protein and eliminates pectin. The caustic boil is rated most
efficient since it removes wax almost completely and has the advantage
that, for most fabrics, a single treatment is required. The lime-acid-soda
sequence invariably requires two boils and the second treatment with soda
ash is necessary to complete the removal of wax. When using caustic soda,
the extent to which the wax may be removed is dependent on conditions
such as temperature, time and alkali concentration. The greater part of the
impurities is removed without pressure and a change in the temperature
from 100 to 140°C causes only a small change in scouring loss. The amount
of residual wax decreases significantly as the temperature increases.
Scouring loss increases significantly with increase in concentration of
caustic soda.
The strength of caustic soda solution is generally varied according to the
type of fabric. It is observed that high quantities of caustic soda are mainly
used to remove kities (cottonseed sculps) in the alkaline boiling off process.
The actual need of caustic soda is very little to remove the natural
impurities. American practice, for instance [7], favours 2-3°Tw caustic
solution (0.9-1.35%) for lightweight fabrics and solution of 4-5°Tw (1.75-
2.18%) for heavier material. In textile practice, since the fabric selectively
absorbs the chemical reagents, it is more usual to base quantities on the
weight of material or o.w.m. For a kier, the volume of liquor is about three
times the weight of goods (i.e. M:L ratio is 1:3). Hence, liquor strength of 1-
2% is equivalent to 3-6% on the weight of material.
As in case of laundering, caustic soda treatment does not rely primarily on
the use of surfactants. Nevertheless, a number of kier-boiling assistants are
used to improve the scouring performance. The major role played by these
agents is one of achieving good penetration of the fabric by alkali, and as
such the use of an efficient wetting agent such as Turkey Red Oil (sulphated
castor oil, anionic) or Dedanol OT/OTL (nonionic wetting agent) is essential.
Soaps act as emulsifier for many of the impurities. Solvent-based detergents
assist quicker removal of waxes. Sodium silicate acts as a buffer and retains
the removed impurities in the solution, preventing redeposition on the
material.
The detailed recipes for caustic boiling for various qualities of textile
materials on the basis of industrial experience is given below (% on the
weight of material or o.w.m.):
Cotton check shirting and other fabrics with coloured threads
Open kier boil with 2% soda ash, 0.5% detergent for 8 hours at 60°C
Cotton fabrics before dyeing or printing
Caustic soda –X%
179
Soda ash - 2%
Detergent - 0.5%
Wetting agent (T.R.O., Dedanol OTL etc.) - 0.2%
Sodium silicate - 0.5%
Sodium sulphite - 0.5%
The amount of caustic soda and boiling conditions will depend on the type
of material. A few examples are given below.
1. Cotton fabric having weight of 15-20 mts./kg (lawn, voile, mulmul,

etc.) with 0.5% caustic soda for 4-6 hours at 30 p.s.i. pressure.
2. Cotton fabric having weight of 12-14 mts./kg (cambric, markin etc.)
with 1% caustic soda for 6-8 hours at 30 p.s.i. pressure.
3. Cotton fabric having weight of 8-10 mts./kg (longcloth, poplin, etc.)
with 2% caustic soda for 8-10 hours at 30 p.s.i. pressure.
4. Cotton fabric having weight of 6-8 mts./kg (drill, rib, coating fabrics,
etc.) with 3% caustic soda for 10-12 hours at 30 p.s.i. pressure.
5. Cotton fabric having weight of 3-6 mts./kg with 3% caustic soda
open-width boil for 6-8 hours in Jambo jigger.
Viscose fibre or fabric
2 g/l anionic or nonionic detergent for one hour at 60°C
Typical formulations and conditions for batchwise and continuous scouring

processes reported elsewhere [19] are shown in Table 4.4.
Table 4.4 Conditions for Batchwise and Continuous Scouring Methods

Batchwise machines Æ Kier Winch or jet Jigger Package or beam
Caustic soda solid, g/l 5-10 5-10 5-15 15-20
Wetting agent, g/l 0.5-1 0.1-.02 0.5-1 0.5-1
Detergent, g/l 0.5-1 2 4 2-4
M:L ratio 1: 3-5 1: 15-30 1: 2-4 1: 5-8
Temp, °C 130 95-98 95-98 100-130
Time, hours 4-6 1-2 2-4 3-5
Continuous machines Æ J-box, conveyor, Open-width, Pressure
pad-roll atmospheric steamer steamer
Caustic soda, % o.w.m. 3-6 4-10 6-10
Wetting agent, % o.w.m. 0.1-0.5 0.1-0.5 0.1-05
Detergent, % o.w.m. 0.5-1 0.5-1 0.5-1
Temp, °C 100 95-98 130-140
Time, minutes 30-120 10-30 1-2
For polyester-cotton fabrics, the concentration of sodium hydroxide is to

be reduced to avoid the risk of hydrolysis of polyester. The maximum
allowable concentration depends on the cotton proportion of the blended
180
fabric and the temperature and time of treatment. The addition of suitable
scouring assistants is advised to compensate the reduction of alkali.
Scouring of Knitted Goods
More than 15 million tons of cotton material is prepared world-wide every
year – approximately 60% woven, 30% knitted and 10% yarn.
The processing of knitted goods can be carried out in two forms, viz.,
tubular or open-width (slit) form. In contrast to woven fabrics, knit-goods
have a risk of distortion and the machine should put low tension on the
fabric. Despite the best efforts to process in tensionless condition, the
knitted fabric (especially weft knitted) undergoes lengthways tension or
stretch to some extent. After wet processing, the fabric is to be stretched
widthways so that lengthways stretch is reduced and the structure looks like
original.
Pretreatment of cotton knit-goods should remove 8-13% by weight natural
impurities (fats, waxes, etc.), as well as 1-5% by weight of impurities such as
preparation and knitting oils. The soft handle of knit-goods should be
maintained. Hence, partial retention of natural fats and waxes without
hampering absorbency is advantageous.
Knitted goods have certain advantages over woven goods. These are not
sized, hence easier to prepare. As combed yarns are mostly used, knit-
goods contain fewer seeds. The knitted fabrics allow better penetration of
the liquor because of low twist of the yarn and open structure of the fabric.
Knit-goods are pretreated both in short and long-liquor, continuously or
discontinuously, in circular form, rope form or slit into open-width. The
break-up of world-wide pretreatment methods for knitted goods is reported
to be as follows [20]:
1. Discontinuous long liquor - 60%

2. Semicontinuous pad-batch - 35%
3. Continuous - 5%.
Tubular fabric is first subjected to the process of reversing. The purpose of

reversing is to avoid soiling of the face side of the fabric during processing
and/or handling of the fabric.
For long-liquor batch process, after reversing the fabric is taken into a
winch machine to carry out the process of scouring, bleaching, dyeing and
finishing. Unlike woven fabric, all the above processes for knitted materials
are carried out in the same machine, this may be of different capacities –
100 kg, 200 kg or even 800 kg per batch. The machine takes about 6 to 8
hours to complete all the processes. The M:L ratio for the machine is quite
high (1:10 to 1:20 depending on the design of the machine). The operations
on winches might be more expensive due to high consumption of water,
181
steam, dyes, chemicals, etc. However, it is still preferred by small

processors, as the initial cost of investment is low as compared to modern
soft-flow or overflow dyeing machines suitable for knitted fabrics. Some of
the known makers of such modern machines are Fongs, Tung Shing (Hong-
kong), Thies, Then, Brückner (Germany), Sclavos (Greece), Hisaka (Japan),
Brazzoli, ATYC, Belini (Italy), etc.
Overflow machines are of two types:
1. Workable under atmospheric pressure – suitable for cotton or acrylic

up to 98°C.
2. High temperature model for polyester and blend up to 140°C.
Such machines may be fully automatic or semi-automatic and operate

mostly in rope form. Only a few models operate in sheet form. The machines
are made of multiple chambers or tubes called sections, each having a
capacity of 100 to 125 kg.
After wet processing and before drying, the knitted materials are subjected
to hydroextraction, which is mostly carried out in centrifuge type of machine.
However, the structure of the fabric may be distorted. The crease-marks,
wrinkles and cracking of fabric may occur. The fabric must be subjected to
detwisting before slitting, drying or calendering.
After hydroextraction, the fabric may be dried in a vertical tube dryer. The
machine consists of two or more vertical perforated tubes through which hot
air is blown. The fabric in tubular form is made to slide down on the tube and
pulled out after drying. Some stretching of the fabric is inevitable. Alternately
perforated conveyors may be used through which hot air is blown. The fabric
tubes are placed side by side in a relaxed state on the moving conveyor.
Alternately, modern continuous machines especially developed for drying
of knitted fabric (e.g. Santex of Switzerland, Swastik of India) may be used.
Considerable improvement in quality is assured by the controlled fabric
feeding and expansion using newly developed tubular guides. The overfed
(up to 25%) fabric is supported on a Teflon-coated conveyor and vibrated by
a beating roller. This may be followed by a dryer in which hot air is blown
from staggered nozzles placed above and below the fabric path, which
together with the vibration, create a tumbler drying effect. Natural shrinkage
is allowed without tension. Compactor (shrinkage unit) similar to a
Sanforising machine and calender unit may be synchronised.
The various pretreatment processes carried out on knitted goods are:
(a) Scouring in soda ash or caustic soda.

(b) Acid demineralisation before or after bleaching.
(c) Reduction extraction to remove heavy metal (such as iron) before or
after bleaching.
182
(d) Bleaching – hypochlorite, chlorite or hydrogen peroxide.
The most common method of preparation used for producing cotton

knitted goods has always been the alkaline boiling process, consisting of a
treatment at the boil for a prescribed period of time in a solution of up to 3 g/l
caustic soda, resulting in a weight loss of about 3-10%. Alkaline processes
tend to give the fabric a harsh handle – higher the alkali, harsher the handle.
Alkaline scouring results in an unacceptably high chemical oxygen demand
(COD) in the effluent.
The auxiliaries must not foam, so that they can be used in machines with
high circulation and rapid movement of the fabric and they have minimum
impact on the environment. The key elements of the eco-profile provided by
the European regulatory bodies are that the products should be APEO-free,
have a BOD:COD*100 ratio of more than 60% and bio-elimination (OECD)
should be greater than 70% [20]. APEO (alkylphenolethoxylates) based
detergent/emulsifier may be substituted with eco-friendly fatty alcohol
ethylene oxide adducts.
An American company, CJL, Lurgan is successfully using a process since
1980s involving a short treatment (10 minutes at 100°C) in an acidic bath
containing acetic acid (pH 4.5) and 2 g/l Depsolube (ICI), a self-emulsifiable
lubricant [21]. The success of the acidic scouring process is aided by the
use of only self-emulsifiable type knitting lubricants. The process is not
claimed to be superior to the alkaline scouring process, but is simply a more
cost-effective method of preparation for cotton knit-goods. In case of
polyester/cotton blend, it is also possible to combine scouring with dyeing of
polyester component by this process.
Solvent Scouring of Cotton
In recent years, dewaxing by means of solvents on a commercial scale has
been tried intensively. The wax content in grey cotton fabric reduces from
1.09 to 0.23% when treated with trichloroethylene for 15 seconds and to
0.15% after 30 seconds. Such treated material becomes absorbent on
boiling, presumably because the quantity of residual wax is too small to
reform a layer over the fibre surface.
In solvent scouring process, the fabric in air-dry condition is run into a bath
of boiling trichloroethylene for about 30 seconds and comes out through a
solvent seal. The fabric is then passed through a second chamber, which
contains water at about 90-95°C. The solvent-water azeotrope boils at 75°C.
Hence, in the second bath, the solvent along with some water flashes off
and is reused. The fabric emerges from this compartment through a cold
water seal. Alternately solvent-treated material may be passed through a
steam chamber. The solvent dewaxing process is particularly suitable for
use in conjunction with a continuous peroxide bleach [18].
183
Bioscouring
During alkaline scouring, caustic soda not only removes wax but also leads
to destruction of other primary wall components and even to some damage
to the cellulose, causing high weight loss of cotton and decrease in strength.
Environmental loads (BOD and COD) are higher than necessary. High
amounts of salts are produced during neutralisation of alkali with acid. The
alkalinity and salts are to be removed before dyeing by rinsing, demanding a
large volume of water. Consequently, TDS in the effluent increases
significantly.
For enzyme scouring, pectinase is the only enzyme needed for
wettability/dyeability, while other enzymes may have beneficial effects. The
process is most efficient when run at slightly alkaline conditions.
Pectic substances consist of a polygalacturonic acid backbone, which may
be partially methylated and often has rhamnose, arabinose, galactose and
xylose, and other sugar bonded as side chains. Other impurities such as
protein and wax are interspersed through the backbone and side chains.
Pectinases are able to hydrolyse the glycosidic linkages of polygalacturonic
acid into water soluble galacturonic acid monomers. The same along with
the rest of the pectic substance and other components are then easily
removable.
The pectinase action does not create full wettability alone. Addition of
auxiliaries is necessary. Key factors in a successful application are [1]:
• Combining enzymes with surfactants for good enzyme/substrate

contact.
• Adding calcium binding salt or enzyme compatible chelator for
converting calcium pectate to easy degradable sodium salt. It further
enhances removal of fatty acids.
• Adding emulsifier for removal of wax.
• Raising temperature after the enzyme reaction for emulsification of wax,
preferably above its melting point of 70-75ºC.
• Pretreatment with hot water before pectinase treatment causes wax to
melt, increasing the accessibility of enzymes.
The bioscouring process results in textiles being softer than those scoured
in the conventional caustic soda process. However, the degree of whiteness
is often less and seed coat fragments are not adequately removed.
A study [22] shows that the use of a mixture of nonionic surfactants having
HLB value of 13 and a natural organic solvent D-limonene greatly increases
the scouring efficiency of pectinase enzyme system obtained from
Aspergillus niger. Bioscouring was carried out with 0-10 g/l pectinase in
acetate buffer solution at pH 4.0 at 40°C. The water absorbency of the
184
pectinase-scoured cotton fabric was improved after 2-6 hours of treatment.

The solvent was used to improve the efficiency for the removal of the cotton
wax in the pectinase scouring process. The degree of scouring by this
process is satisfactory, but for complete scouring, the required concentration
of enzyme is very high and the time required is quite long.
Further work [23] showed that the disadvantages of the above aqueous
bioscouring process can be minimised by using a reverse micellar system
(RMS). This is a non-aqueous media of iso-octane containing sodium bis-2-
ethylhexylsulpho-succinate (Aerosol-OT/AOT). The AOT-RMS exhibits a
remarkable property of solubilising a large quantity of water in organic
solvents. The hydrophilic microenvironment within the micelle, called the
water pool, can dissolve several enzymes keeping them active. Those
enzymes are usually insoluble in organic solvents. Aqueous stock solution of
buffer alone (0.1 M sodium acetate, pH 4) or pectinase in buffer was injected
into 50 mmol/l AOT in iso-octane. After injection of aqueous stock solution,
the reverse micellar solution was gently stirred for few minutes until it
became transparent. The bioscouring was carried out at 40°C. The scouring
effect was observed even at low concentration of 0.1 g/l pectinase.
Cellulases are specially suited for scouring of cotton fabrics. Some
pectinase enzyme preparations contain cellulase. The surface of cellulose
structure of cotton, which normally acts as support for the non-cellulosic
impurities, can be hydrolysed by the latter enzyme. Those impurities are
then removed by subsequent washing. However, the combined action of
both types gives greater weight loss and strength loss as compared to the
action of pectinase or lipase alone. Cotton fibres, or their blends with other
fibres, can be treated with aqueous solutions containing protopectinases for
18 hours at 40°C to give scoured yarn with good tensile strength retention.
Pectinases and cellulases are very effective compared to the proteases and
lipases. The change in water absorbency of cotton is rapidly catalysed by
pectinases, cellulases or their mixtures. Pectinases can destroy the cuticle
structure by digesting the inner layer of pectins in the cuticle of cotton.
Cellulases can destroy the cuticle structure by digesting the primary wall
cellulose immediately under the cuticle of cotton. Cellulases break the
linkage from the cellulose side and pectinases break the linkage from the
cuticle side. The result of the synergism is a more effective scouring in both
the speed and the evenness of the treatment. The destruction of the cuticle
during enzymatic scouring of cotton was demonstrated by the results of
Ruthenium Red and Congo Red staining. Ruthenium Red stains proteins
and pectin, faint staining after enzyme treatment indicates that they are
removed in the enzymatic treatments. Physical destruction of cuticle was
also revealed by the scanning electron microscopy (SEM) photographs [24].
Researches are going on towards the development of simultaneous
desizing and scouring by enzymes, replacing two-stage process. [25]. The
185
combined enzyme system may contain amylase, lipase, and pectinase

enzymes to achieve the necessary fabric properties – without the use of
harsh chemicals.
BioPrep 3000L (Novo Nordisk, Denmark) is an alkaline pectinase, free
from cellulases [1]. It works optimally at pH 7-9.5 and at temperature up to
60ºC in exhaust systems and at somewhat higher temperature in pad
systems. A combined scouring and bleaching process for knitted fabric in jet
dyeing machine is as follows:
• Add BioPrep 3000L, nonionic surfactant and a mild chelator at room

temperature.
• Set pH at 8.5.
• Raise temperature to 60ºC and keep for 10 minutes.
• Add more chelator and emulsifier, if necessary.
• Add bleaching chemicals, if bleaching is necessary.
• In dark shades, bleaching may be omitted. Instead, dye and dyeing
chemicals may be added.
• Raise temperature to 70º-95ºC to emulsify waxes and simultaneous
bleaching/dyeing.
• Keep at this temperature for 30 minutes.
• Rinse one to three times – hot, warm and cold.
Residual motes (i.e. husks of the cottonseeds) are not removed, but they
can be easily bleached.
In pad-batch system for woven fabric, a good pH control and temperature
can be obtained. If the fabric is sized with starch, BioPrep 3000L can be
typically combined with amylase desizing.
A combined desizing and scouring pad-batch may be as follows:
• Pad the fabric with a solution of BioPrep 3000L, amylase, nonionic

surfactants and calcium binder with pH set at 8-9.
• Batch at a temperature of 55ºC for 2 hours.
• Rinse in continuous washing machine preferably with chelator and
emulsifier in the first rinse for emulsification of waxes.
• Alternately remove wax in subsequent bleaching process by modifying
bleaching recipe suitably.
• Bleach under reduced alkaline conditions as the material has adequate
wettability.
• Dye in dark shades directly without bleaching.
186
Recently Novo Nordisk has found that BioPreparation can also be applied
in continuous pad steam systems with controlled steam dosages and higher
enzyme dosage.
The advantages of BioPreparation are [1]:
(a) Reduction of caustic soda consumption. Consequently, lesser

amount of acid is required for neutralisation. Water and energy
required for rinsing are also less.
(b) Specific interactions of enzymes retain cellulose structure and
strength.
(c) Softer handle of fabric, less need for softeners.
(d) Less weight loss of fabric. Consequently, BOD and COD in the
effluent are 20-40% of those in traditional process.
(e) Due to less salt formation, TDS is only 20-40% of that in traditional
process.
(f) Mild alkaline condition is safer for blends with silk, wool, etc.
(g) Combined processes are possible by combining various enzymes.
(h) Noncorrosive conditions give a safer working environment and less
wear of equipment.
The challenges of BioPreparation are [1]:
(a) Higher whiteness

(b) Removal of seed fragments
(c) Development of satisfactory continuous pad-steam process
Efficiency of Scouring
The main changes which occur in cotton goods during scouring process are
loss in weight (about 5-10%), loss in length due to shrinkage during boiling
treatment, alteration in yarn count affected by both losses and changes in
tensile strength (generally increase). However, the most important
characteristic of scoured fabric is increased wettability, which is necessary
for subsequent processing. Wettability must be obtained not only in the
capillary spaces between the fibres, but also inside the fibres themselves.
While scouring is beneficial for wettability, when carried out in severe
conditions, it induces fibre deterioration e.g. the creation of cavities in fibres
or dissolution of the cuticle and primary wall.
Since the scouring treatment contributes to the dissolution of a portion of
shorter cellulosic chains, it bestows on cotton higher average degree of
polymerisation than that of native cellulose. Otherwise, this alkali treatment,
in contrast to mercerising, does not induce any profound change in the fine
structure of fibres.
187
The control of scouring efficiency can take place in different ways:

1. Practical tests of absorbency
2. Measurements of
(a) Weight loss
(b) Protein content
(c) Residual wax content
(d) Methylene blue absorption (removal of pectic substances)
(e) Degradation of cellulose by various tests.
The sole aim of scouring process is to impart uniform and sufficient
absorbency to the textile material. A good scoured material should readily
absorb water. Hence, the measurement of absorbency can provide sufficient
indication about the success of a scouring or kier boiling process. The
scoured material is also very clean in appearance. Hence, it is commonly
called that a good scoured material is half-bleached. The whiteness
achieved after scouring may be sufficient for dyeing in deep shades.
Absorbency may be assessed in various ways, the most popular being the
sinking time test (AATCC Test Method 17-1994). A hank of known weight
//
(e.g. 5 g) forming a loop of 45.7 cm (18 ) is tied with a flat cylindrical plate
(25 mm diameter) of small defined weight (say 15-40 g) called sinker. The
sinker is attached to the hank with the help of a hook weighing about 3 g. It
is then dropped slowly on water contained inside a glass measuring cylinder
(500 ml). At first, the hank floats due to entrapped air. Slowly the hank is
wetted and entrapped air is removed. The time required by the hank to go
inside water from floating state is known as sinking time. Low sinking time
indicates rapid wetting because of good scouring. The test may be used for
evaluating performance of wetting agents. Sinking time test can also be
carried out on the fabric cutting it into a specific small size and dropping the
same on the surface of water loosely without putting any thrust.
Another simple test is drop test in which water drops are allowed to fall by
gravity from a burette placed at a certain height from the fabric surface. The
fabric is placed straight on a table without any creases. The time required for
the drops to collapse is noted as wetting time.
A similar test (AATCC Test Method 27-1994) has been recommended for
evaluation of rewetting agents. The fabric treated with a rewetting agent is
mounted in an embroidery hoop. The burette containing either distilled water
or tap water, as desired for the test, is adjusted so that it delivers one drop
of water approximately every 5 seconds. The surface of the taut fabric is
held about 1 cm below the tip of burette and a stopwatch is started just as
the drop falls on the fabric. The watch is stopped when the liquid on the
surface of the fabric loses its specular reflective power. The point is
determined by placing the hoop between the observer and a source of light,
such as window at a convenient angle. A disappearance time of about 10
seconds is considered satisfactory.
188
The LINRA wipe tester is a more sophisticated test apparatus for fabric. In
this test, drops of dye solution are applied to the test paper, which is drawn
under the piece of fabric. The fabric is held in position for a certain time
under constant load. Highly absorbent fabrics rapidly absorb the dye and
very short streaks are shown on the paper. Poor fabric absorbency is shown
up by long dye streaks being spread on the test paper. As with the drop
absorbency test, sensitivity of the test can be modified by using dye
solutions of differing viscosity.
During scouring, cotton material is liable to undergo oxidative degradation,
leading to the production of oxycellulose having reducing aldehyde and keto
group, and acidic carboxylic groups. Such reducing groups impart alkali
sensitivity to cotton, especially at high temperature, with consequent
lowering of tensile strength. The degradation may be assessed by
determining one or more of the following:
1. Copper number, a measure of the reducing groups present in
cellulose.
2. Carboxyl group content.
3. Cuprammonium fluidity, which is a measure of molecular chain
length of cellulose.
4. Tensile strength of the cotton material before and after scouring.
The reducing groups present in degraded material are capable of reducing
an alkaline solution of copper sulphate, when insoluble cuprous oxide is
formed and deposited on the cellulose material. The amount of cuprous
oxide formed is proportional to the amount of reducing groups and is
expressed by Copper Number, which is defined as grams of cupric copper
reduced to cuprous oxide by 100 g of cellulose under standard conditions of
boiling in alkaline medium. About 3 g of sample is boiled under a reflux
condenser with 100 ml of Fehling’s solution and 200 ml of water for 15
minutes. The Fehling’s solution is prepared by mixing two solutions in equal
quantities just before use. One solution is prepared by dissolving 100 g of
crystalline copper sulphate in one litre of water and the other by dissolving
350 g of sodium carbonate and 50 g of sodium bicarbonate. The solution
containing the fibre and the cuprous oxide is then filtered through a Gooch
crucible containing a mat of purified fibrous asbestos and the residue is
washed with water. The whole mass is transferred to a beaker and 1-2 g
ferric alum dissolved in dilute sulphuric acid is added, when ferrous sulphate
is formed from ferric sulphate by cupric oxide in equivalent quantity. This is
dissolved in sulphuric acid and titrated with N/100 ceric sulphate solution
using ortho-ferrous phenathroline indicator. The initial red colour of the
solution turns to green at the endpoint. The copper number is calculated
from the amount of ceric sulphate solution consumed (after deducting the
blank reading for the alkaline copper solution) by ferrous sulphate which is
189
formed by reduction of ferric sulphate with cuprous oxide deposited on the

cellulosic sample during boiling (Eqn. 4-6).
63.5 x V x N x 100
Copper number = (4.6)
W x 100
Where V is the ml of ceric solution consumed after deducting blank
reading, N is the normality of ceric sulphate solution and W is the weight of
the bone dry cellulose sample (0.25 g for normal samples and 0.1 g for
highly degraded samples having copper number greater than 4).
The copper number of pure cellulose is of the order of 0.05, but may be as
high as 0.9 for raw cotton due to the presence of impurities. A well-scoured
and bleached cotton material should have copper number below 0.3 and for
regenerated fibre, the value should be less than 1.2.
The degree of oxycellulose formation can be estimated by several
methods. In one method, the oxycellulose sample is treated with 0.5 N
hydrochloric acid at room temperature for 2 hours and then the material is
washed with distilled water to remove free acid (using methyl red indicator).
The cations other than hydrogen ions, are washed out and only carboxyl
groups are retained in oxycellulose. 0.5 g of cation-free and air dried sample
is added to 50 ml of a freshly prepared aqueous solution containing
potassium iodide (13.63 g/l) and potassium iodate (3.57 g/l) in carbon
dioxide free distilled water together with 20 ml of N/100 sodium thiosulphate
solution in a stoppered conical glass flask. The flask is shaken thoroughly
for about 30 minutes and stored for 24 hours. The excess of thiosulphate is
then titrated with N/100 iodine solution using starch as an indicator. The
end-point is indicated by the appearance of a faint blue colour. During
storage and titration, carbon dioxide free air is blown through the solution,
which is obtained by passing air successively through concentrated
sulphuric acid, concentrated potassium hydroxide solution, two soda-lime
towers and finally bubbled twice in distilled water.
The following reactions take place during estimation:
+ +
5KI + KIO3 + 6H ↔ 6K + 3H2O + 3I2 (4.7)
I2 + 2Na2S4O3 Æ Na2S4O6 + 6NaI (4.8)
The carboxyl content (m. eq. COOH per 100 g) is calculated from the
titration reading as shown in Eqn. 4.9.
Carboxyl content (m.eq. per 100 g bone dry sample) = (a-b) x N x 100 (4.9)
W
where a and b are the titration readings for blank and the sample
respectively, N is the normality of the iodine solution and W is the bone dry
weight of the sample.
The degradation, in terms of reduction of the degree of polymerisation,
can also be assessed by measuring fluidity of the cotton material dissolved
190
in cuprammonium hydroxide solution. The degree of polymerisation of a

polymer is directly proportional to the viscosity of its solution, providing all
solutions are at the same concentration. In Europe and the USA, this
describes the basis of a test for damage in which viscosity of a standard
solution is assessed using a U-viscometer. In the UK, the Fluidity (F), the
reciprocal of viscosity is measured in special X-type viscometers. The
method is more sensitive for detecting chemical damage than loss in tensile
strength. A weighed quantity (sufficient to give 0.5% and 2% solutions for
cotton and viscose respectively) of fibre is finely chopped (1-2 mm in length)
and dissolved in standard cuprammonium hydroxide solution in a standard
capillary viscometer. The viscometer is filled completely to exclude air,
protected from light and agitated for 16 hours. The viscometer and contents
are then brought to 20°C in a thermostatically controlled bath and the rate of
flow through the capillary is measured. Standard viscometers are marked so
that this flow measurement is simply time required to flow between two
points. As each viscometer is pre-calibrated, the fluidity is determined by
dividing a viscometer constant by the time recorded. This gives a direct
-1
calculation of fluidity in terms of pascals per second (Pa s ). Unbleached
cotton shows a fluidity of about two. Generally, bleached cotton with a
fluidity of five or less is accepted commercially. Above a value of ten,
chemical damage shows up as a loss in tensile strength. The standard
unbleached viscose has a fluidity of about ten [14].
In Western Europe, cupriethylenediamine is used instead and the results
are expressed as a degree of polymerisation value. A lower DP value
represents damaged cellulose. The relationship between the two systems is
given by Eqn. 4.10 [26].
log 74.35 + F
DP = 2032 × − 573 ( 4.10)`
F
It is reported that both the methods give low and inaccurate DP values
due to chain scissions of alkali-sensitive oxycellulose in the above two
solvents. In more accurate nitrate method, cellulose is nitrated in a solution
of nitric acid, phosphoric acid and phosphorous pentoxide and dissolved in
butyl acetate.
Physical testing, for example tensile strength, bursting strength and
abrasion resistance measurement, can be used but the results are
influenced by both fabric structure and chemical damage. Tear strength is
also influenced by residual natural lubricants. Staining tests are often useful.
Oxidised cellulose usually has a higher concentration of carboxyl groups
than the unbleached control. These resist staining with C.I. Direct Blue 1 or
give increased uptake of C.I. Basic Blue 9. In Harrison test, a simple test of
oxycellulose, the test sample is immersed in a boiling alkaline silver nitrate
191
solution. Brown to black deposits of silver are produced on the substrate

where there are reducing aldehyde groups.
4.4.7 Combined Processes

Some savings can be obtained by combining scouring and desizing. Further
saving is possible by combining bleaching process with hydrogen peroxide.
However, desizing occurs by free radical mechanism, which should be
controlled to obtain good bleaching without fibre damage. Alkalinity for
peroxide bleaching is usually lower than conventional caustic scouring or
oxidative desizing. With new stabilisers, higher levels of caustic alkali can be
used in bleaching. Though earlier work showed that stabilisers impaired
desizing, now conditions can be selected to give both desizing and
bleaching activity in conditions sufficiently alkaline to give good scouring
simultaneously. For many fabrics, it is possible to obtain a good
preparation by pad-steam continuous method using a padding liquor made
of (% o.w.m.):
Wetting agent: 0.1-0.2

Emulsifier: 0.3-0.5
Stabiliser: 1.5-2.5
Caustic soda: 1.5-2.5
Hydrogen peroxide (35%): 5.0-7.5
The stabiliser may be organic or a mixture of silicate and organic material.

Steaming is usually carried out for 10-20 minutes in open-width. A hot wash
may precede such treatment to prevent excessive size build up in a
saturator or steamer rolls. Size recovery can also be done before bleaching.
The method is not successful for materials with high seed content, when
two-stage method may be suitable. A pre-treatment is first done by padding
with (% o.w.m.):

The material is batched for 4-6 hours followed by padding with (% o.w.m.):
Wetting agent: 0.1 -0.2

Emulsifier: 0.3-0.5
Stabiliser: 0.6-1.0
192
The material is then steamed as before.

The persulphates are used primarily as an alternative additive to the
caustic scour when operating a two-stage process, i.e. scour followed by
bleach, or ambient bleaching processes, particularly cold pad-batch
bleaching.
When using persulphates to improve the desizing action, it should be
appreciated that they can cause an increase in chemical degradation of
cellulose, but the effect is much less than that of excess alkalinity or
temperature. The use of persulphate in cold pad-batch bleaching does not
eliminate the need for high temperature washing off with first washes
containing sufficient alkali to dissolve size residues.
Typically, a modern cold-batch bleach system uses the following
chemicals (% o.w.m.):

Emulsifier: 0.6-0.8
Organic stabiliser: 0.6-1.0
Sodium silicate (sp. gr. 1.4): 0.8-1.5
Sodium persulphate: 0.0-0.4
However, these minimum stage processes are not able to provide

complete preparation in terms of whiteness, seed removal and absorbency,
for all fabrics for all end uses. It will always be necessary for the dyer and
printer to determine the preparation route most applicable and economical
for the individual situation [26].
4.4.8 Mercerisation
Mercerisation refers to the treatment of cotton yarns or fabrics with caustic
soda solution. It is not a fibre purification process, but it induces desirable
changes in cotton yarn and fabric properties. The process, taking its name
from John Mercer, who in 1850 observed that there was a general swelling
and shrinking effect on cotton fabric when treated with caustic soda solution.
Horace Lowe (1889-90) later demonstrated high lustre of mercerised cotton
by maintaining tension during treatment. Considerable quantities of cotton
yarns and fabrics are nowadays mercerised to improve lustre and/or dye
uptake and more recently without tension to produce stretch materials.
The objective of mercerising is to swell the cotton fibre, increasing its
lustre, tensile strength (also retaining tensile strength after easy-care finish),
dimensional stability and dyeability (in terms of uniformity and colour yield).
193
Traditionally, a cold solution of 25-26% by mass of sodium hydroxide is

used, although better penetration and more even treatment is obtained with
the more recent hot mercerising technique. The addition of a wetting agent
to the mercerising liquor gives better penetration and more even treatment
particularly for unscoured materials. The time of impregnation is rarely
sufficient for maximum swelling, so that even with the mercerisation of
bleached cotton, the addition of wetting agent is advantageous. Their
presence is a safeguard against uneven penetration. Normal wetting agents
are not sufficiently soluble in moderately concentrated caustic soda solution.
Until recently, products based on cresylic acid (a mixture of o-, m- and p-
cresols) were popular. Cresylic acid alone is less effective and the wetting
power may be increased by the addition of solvent additives such as
alcohols (e.g. cyclohexanol), ethers, ketones, lower fatty acid amides or
cellosolve.
The presence of such products poses problems because of their toxic and
nonbiodegradable nature. The biodegradable wetting agents include certain
alkylarylsulphonates, some organophosphonates (e.g. sodium
methyloctylphosphonate), alkylated diphenyloxide sulphates (e.g.
dodecyldiphenyloxide sulphate) and especially sulphated aliphatic alcohols
(e.g. 2-ethylhexyl sulphate). The most efficient sulphated alcohols are those
with low molecular weight (chains with 4-8 carbons). Moreover, products
with branched chains are more efficient than those with linear chains. A
cresol-free alternative is sulphated 2-ethylhexanol, which is activated with
about 10% butanol and unsulphated 2-ethylhexanol.
The primary factors affecting maximum degree of mercerisation are the
type of cotton and the growth conditions. A higher degree of mercerisation is
achievable on cotton fibres having finer, uniform and circular cross-section
such as Egyptian and North American varieties. For short-staple flat-type
cotton, the effect is less pronounced. Cotton fabrics are mercerised in grey
or bleached condition or after boiling-off in alkali. Mercerisation is most
efficient after scouring and bleaching – owing to the absence of size on the
fibre, the effect of mercerisation is more pronounced. Moreover, the used-up
caustic solution is not contaminated with sizes. For fabrics bleached in rope
form, subsequent mercerisation aids in removing crease-marks. However,
due to economic reasons, i.e. to save an additional drying cost, grey
mercerisation is frequently practised. The problem of wetting raw cotton
materials is not easy to solve. A larger quantity of good wetting agent is
necessary to assure uniform wetting.
When the aim is to improve dyeability only without much appreciable
change in lustre, a less severe process called semi-mercerisation or
causticisation is carried out. The treatment may be carried out with about
15% caustic soda with or without tension, as the shrinkage after the
treatment is not very high.
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The fabric after scouring is efficiently squeezed and with a water content
of 60%, enters into a large caustic bath containing 300 g/l caustic soda in
the usual process, or 530 g/l in addition mercerisation [27]. Exchange of
caustic soda and water takes place by diffusion, which is accelerated by
increased temperature, due to decrease in viscosity.
To achieve a high degree of swelling, caustic concentration, more than
270 g/l and preferably 350 g/l, is necessary. In the conventional process, a
concentration of 300 g/l is taken in a longer bath, with diffusion aided by
intermediate nips, when exchange takes place. In the addition process,
caustic soda at a concentration of 530 g/l is added to wet the squeezed
fabric and due to higher concentration, concentration difference and higher
temperature, the penetration is quicker and a high degree of mercerisation is
achieved. The optimum time necessary is 35-50 seconds for cold and 25-35
seconds for hot mercerisation at 70°C, depending on the type of cotton,
weave and fabric density. Due to high degree of swelling of cotton fibres,
the fabric gets fixed in its dimension, leading to low degree of residual
shrinkage. When the fabric is not allowed to shrink, the swelling of fibres
leads to internal tension. When impregnated fabric is stretched, the fabric
shows rubber-like elasticity and at levels of 5-10% stretch, there is linear
relation between the stretch force and the resulting elongation. However,
higher the stretch poorer will be the dimensional stability.
Effects of Mercerisation
Mercerisation causes swelling of the fibres. On mercerisation without
tension, the fibres, yarns and fabrics shrink lengthways considerably. The
fibre as well as yarn diameter, increases with corresponding decrease in
metric count. Under tension, the shrinkage can be controlled. On
mercerisation, the convolutions or natural twists of cotton disappear and the
morphological structure changes from twisted ribbon like structure to tubular.
The characteristic hollow channel inside the cotton fibre or lumen almost
completely disappears.
Microscopic examination shows that up to a concentration of caustic soda
of about 7%, the convolutions disappear and the cross-sections become
elliptical but there is no visible swelling. Between 7% and 11% caustic soda,
definite swelling occurs partly inward. At just over 11% concentration, the
inward swelling is complete with the lumens filled, but the primary wall is not
fully extended. Up to 13.5% more outward swelling takes place to a
maximum when the primary wall is fully extended. Finally, further increase of
caustic soda concentration shows no further change. The caustic treatment
neither removes nor damages the primary wall unless it is previously
damaged. The cotton from different sources with different thicknesses of
primary wall will behave slight differently without modifying the general
trend.
195
When a cotton hair is brought into an aqueous solution of sodium

hydroxide of 40°Tw (18%), the cellulose begins to swell immediately. In a
few seconds the hair is elliptical with the major axis of the ellipse about 25-
30% greater than the hair width of the corresponding collapsed hair. On
further swelling, the section rounds off. The wall swells inwards until the
lumen is practically eliminated. When the hair is washed with water,
shrinkage of cross-section begins and on drying, a further and final
shrinkage occurs. The shrinkage proceeds uniformly towards the centre and
the lumen does not recover its original size. Great importance was laid on
the fact that up to a concentration of about 17.5%, the swelling action of the
caustic soda follows the uncoiling, whereas at higher concentrations, the
reverse is the case. As the concentration of 17.5% is the lowest at which
any substantial increase in lustre was observed, Marsh [28] concluded that
the production of lustre is connected with the occurrence of uncoiling after or
simultaneous with swelling.
More recently, swelling evaluations based on precise measurements of
thickness variations of cotton fabric have shown that the swelling would first
increase moderately up to a sodium hydroxide concentration of 120 g/l (11%
w/w), and then to a much greater extent between 120 and 180 g/l. Starting
at 180 g/l (15-16% w/w), the swelling value remains constant up to 300 g/l
(23-24% w/w). The maximum swelling of cotton fibre occurs at about 150 g/l
(13% w/w), while the maximum mercerising effect takes place only at higher
concentrations indicating that the swelling is not the only determining factor.
Mercerisation rather involves largely internal modification in the arrangement
of the fibrils.
Many investigators found that the maximum contraction of cotton yarn
takes place at a concentration of 20% caustic soda solution (45°Tw or
26.5° Bé) at room temperature. The change in the length of yarns is not a
reliable measure of the mercerising effect, as a great deal must depend on
the structure of the yarn.
Due to high affinity, caustic soda solution penetrates into the crystalline
region in addition to amorphous region of the fibre. The intermolecular
forces are weakened and the strength of the material decreases, but
recovers after deswelling and drying. Due to distortion of polymer network
and the change in the crystalline structure, the mercerisation process is
irreversible. The changes in physical and chemical properties are retained
after scouring and bleaching.
The most important effect of mercerisation is on the fine structure of
cellulose fibres. X-ray examination of native and mercerised cotton fibres
shows that a change in the crystal structure takes place, the original
cellulose-I being transformed to distorted crystal cellulose-II on
mercerisation. The comparison of unit cells shows that the planes carrying
the long chains of β-glucose residues have been moved apart due to
196
mercerisation. The extent of conversion depends on the tension applied

during the process. Mercerisation without tension causes complete
transformation, while on mercerisation under tension, mixture of the two
forms is found [13].
Swelling with caustic soda reduces the degree of crystallinity from 70% to
50% when cotton is thoroughly mercerised. The reduction is slightly less for
the treatment under tension. The size of crystallites also changes.
The orientation of the crystallites, as measured by birefringence, changes
little on mercerisation under tension, but significantly under tensionless
condition. The orientation of cellulosic chains decreases in case of slack
mercerisation and increases when mercerisation is carried out under
tension. The change may arise from changes in the spiral angle of the
fibrillar elements and not necessarily from changes in orientation of the
crystallites within the fibrillar structure.
Mercerisation tends to increase the tenacity of cotton fibres. The two
factors held responsible for the fact are the changes in spiral angle and
orientation, but the explanation is controversial. The increase is also
attributed to a strengthening of weak points along the fibre. The weak points
include internal strains (spiral reversals), the places of low cross-sectional
areas and the places of high distortions. The other important factors may be
crystallite length and degree of crystallinity as well as the removal of
cellulose of very low degree of polymerisation. The increase in tensile
strength is significantly higher on fibre bundles than in the case of yarns and
fabrics. The elongation at break decreases and the Young’s modulus
increases significantly on mercerisation under tension. When mercerisation
is carried out without tension, the value of elongation at break is three times
the value of the unmercerised material, thus conferring elastic properties to
cotton fibres. This elasticity is the basis of the preparation of stretch
materials.
Mercerisation is done in yarn and fabric form. It is never done in fibre form,
as in that case no tension-control is possible. Moreover, the cylindrical
mercerised fibres are difficult to spin. Due to fibre swelling, the fibres in the
yarn come closer to each other and become denser, thereby increasing fibre
to fibre cohesion with consequent increase in yarn strength. In other words,
the increase in yarn strength is largely due to consolidation of the structure
rather than increase in the strength of individual fibres. The twist also plays
an important role – the increase in strength is high for low twist yarn and low
for high twist yarn.
If the shrinkage is controlled by applying tension during or immediately
after caustic treatment, the fibres acquire a silky lustre – a valuable property
of mercerised cotton. Due to the change from elliptical to uniform cylindrical
cross-section and untwisting of the fibres, mercerised cotton is lustrous,
closely resembling cylindrical man-made fibres. The lustre depends on the
197
quality of raw material. Long-staple fibre acquires a greater lustre than short-
staple. Twisted double yarn is more lustrous than non-twisted loose yarn.
When mercerisation is carried out without tension, no increase in lustre is
observed. The lustre obtained by impregnating and washing under tension is
same as that obtained by loose impregnation and washing under tension,
but a higher force is required in the latter case. Tensionless impregnation
and washing followed by stretching shows inferior result. Most mercerising
processes allow the material to shrink in the alkali, in order to assist
thorough penetration, and then apply the tension later, either before or
during the removal of the caustic soda. To retain an optimum level of lustre,
it is necessary not to release tension before caustic soda concentration is
lowered to about 60 g/l. For this purpose, the first rinsing must be carried out
under tension. The presence of short projected fibres may hamper lustre
and are to be removed by singeing before mercerisation.
Since the degree of crystallinity decreases with mercerisation, the
resulting fibres have greater absorptive capacity and are more reactive to
chemical agents, which manifest themselves in the acceleration of
hydrolysis under the action of acids and damage by oxidising agents.
Mercerised fibre is more resistant to light and weather effects than non-
mercerised fibres.
Mercerised material requires less dye to obtain the same colour strength
as in case of unmercerised material. The dye consumption is reduced by
about 10-15% in light shades and about 25-30% in deep shades. The
uniformity, purity and brilliancy of the shades are also higher due to the
change of optical properties of the fibre by mercerisation.
The dyes on mercerised materials are faster than that on unmercerised
materials. This is probably due to swelling and opening of the structure with
consequent higher penetration of the dyes.
The temperature of mercerisation also has an influence on the crystalline
structure of cotton. The cellulose-I content and the total crystallinity index
decreases with increase of temperature, whereas the cellulose-II content
follows an opposite trend. With decrease in temperature, the increase is
tenacity is more pronounced.
Hot Mercerisation
Due to rapid and extensive swelling of cotton fibres during conventional
mercerisation at cold, the structure is compacted at the surface of
mercerised yarns or fabrics and further penetration of caustic soda is almost
impossible. This results in nonuniformity of mercerisation effects. Because
of lower level of swelling, mercerisation at elevated temperatures may allow
more even penetration of caustic soda solution into the inner parts of yarns
and consequently better uniformity of the alkali treatment. However, the
conversion of the crystalline structure from cellulose-I to cellulose-II is
198
retarded at high temperature and the yarn assumes a sheath-core

appearance. A reasonable approach is to use a hot caustic soda solution
for better penetration into the textile structure and subsequently to allow the
impregnated material to cool to an adequate temperature in order to have a
good swelling value (i.e. a two-step process) [19].
Technically, hot mercerisation is carried out at 70-100°C for 4-60 seconds
which leads to a uniform high swelling of cotton fibres with a softer feel. One
process of hot mercerisation is to saturate cotton piece goods in caustic lye
(50-58°Tw) for 5 seconds at 97°C under relaxed fabric conditions. The
goods are subjected to controlled hot stretch after caustic saturation. The
hot stretched fabric is cooled under proper control below 25°C followed by
successive tension-controlled washing called stabilisation (up to caustic
soda concentration of 60 g/l) and washing under normal conditions.
Hot mercerised cotton shows more uniform coloration than cold-
mercerised cotton. The total dye uptake is better, but the colour yield is less
pronounced due to less peripheral dye absorption. A better wet crease
recovery is achieved by hot mercerisation and subsequent scouring and
bleaching will be easier and faster. It is claimed that scouring step may be
eliminated or simplified by inserting a steaming step (10 minutes under
atmospheric pressure or 5 seconds at 130-140°C under pressure) between
hot alkali saturation and stabilisation. The desizing process could be
eliminated. However, it should be remembered that the chances of alkali
degradation of cotton by concentrated sodium hydroxide solution are higher
in the presence of air at high temperature.
Yarn Mercerisation with Tension
Before mercerisation, the yarn should be singed, otherwise the projected
fibres will hamper yarn lustre. The mercerisation may be carried out on dry
or wet yarn, the latter coming from a preliminary wetting or scouring
process. However, the excess water must be removed uniformly from the
material to prevent dilution of caustic solution. Irregular distribution of
residual water will cause uneven swelling and consequently uneven dyeing.
Yarns are mostly mercerised in warp form in a truly continuous manner or
batchwise in hank form. Warp mercerisation is done in developed countries
not only for warp yarn, but also for knitting yarn. The process ensures
uniform mercerisation followed by uniform dyeing, though the lustre may be
less than that obtained in hank mercerisation.
The warp mercerisation machine resembles an ordinary warp dyeing
machine – a series of boxes or compartments, as many as eighteen, each of
which is fitted with guide rollers and squeeze rollers. The latter hold the yarn
at proper tension as it passes from one bath to the next. The first two or
three boxes contain boiling water with or without dilute caustic soda solution.
The warps after passing through these boxes, are then squeezed and
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passed through three boxes containing caustic soda solution of mercerising

strength, allowing a contact time of two to five minutes. After first
impregnation, slightly more tension may be applied with the help of rubber
coated rollers, the speed of which determine the extra tension. These rollers
also assist penetration.
The washing is done in three or four subsequent compartments working
with counter-current liquor flow. The washing is started with hot (50-60°C)
dilute (4.5%) caustic soda solution and finished with cold water. After
thorough squeezing, the material is allowed to relax from the previously
applied tension and sent to one or more souring chambers, where it is
treated with dilute sulphuric or hydrochloric acid for a period of at least one
minute. The last five or six compartments are designed for final washing
with water of increasing temperature up to 50°C – the first chambers may
contain sodium carbonate or ammonia to neutralise last traces of acid.
Finally, the yarns are dried preferably by hot air instead of a cylinder, as the
latter are apt to harsh feel.
The warps, good quality combed and singed single or double cotton yarn,
are about 6,000 to 10,000 yards long with 300 to 400 parallel threads wound
into cylindrical balls, all are wound approximately under the same tension.
The yarn comes evenly in contact with alkali, whose concentration must be
uniform and high enough to ensure the required degree of swelling. Warp
mercerising is essentially a large-scale process. In the USA, fine warps of
s
2/60 count are mercerised in these machines in large quantities. The finer
s s
yarns of 2/100 and 2/120 count may also be processed successfully.
The yarns for use as sewing threads, embroidery yarns, etc. may be
mercerised in the form of hank. The hanks (3-5 kg) are cross-wound at
uniform tension and spread on to two parallel rollers of the hank mercerising
machines (Figure 4.11). One of the rollers is fixed while the other can be
moved horizontally to stretch the yarn. The rotation of the rollers causes
uniform impregnation with the liquor. The machine is provided with two trays
carrying caustic liquor and souring acid solution. The trays can be placed
below the rotating rollers and away from them as required. The yarn is
allowed to shrink on immersion in order to facilitate liquor imbibition, the
tension being applied later on the thoroughly impregnated hanks. The yarn
is lowered with continued rotation into caustic soda solution, after being
immersed for about 1-3 minutes, is raised and is allowed to run on the
rollers to squeeze out excess liquor. For controlling the tension applied to
the yarns during mercerising process, different cycles are recommended.
For examples, the yarn may be allowed to shrink on immersion in the alkali
solution in order to facilitate impregnation followed by application of tension.
Alternately a certain degree of tension is applied before immersion, then
increasing it gradually as the hanks come in contact with the alkali solution.
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Water sprayer
Movable Fixed Roller

Roller
Hanks
Tray
Fig. 4-11 Hank Mercerising Machine
In all cases, the stretching of yarns is carried out in such a way as not to
exceed an elongation of 3-5% with reference to initial length.
The caustic tray is then moved away and water is sprayed from top for
washing. When the residual alkali is below 5%, the deswollen yarn will not
shrink further. The acid tray is then brought below the rotating rollers and the
hanks are impregnated by lowering the rollers. The hanks are further
washed and finally dried.
In another type of machine, caustic liquor is sprayed from the top while the
hanks are rotating and the liquor is collected on a tray placed below the
rotating rollers from which it is pumped back to the sprayer.
Higher lustre can be achieved by mercerisation in hank form than in fabric
form as the tension can be applied less effectively in fabric due to the
presence of crimp.
Fabric Mercerisation with Tension
In addition to the enhancement of lustre and dyeability, mercerisation
removes crease marks and neps of immature fibres which otherwise appear
as white specks after dyeing. The fabric is to be singed and desized before
mercerisation.
For continuous mercerisation of fabric, mercerising ranges are employed,
which consist of a sequence of machines for impregnation, washing under
tension, removal of alkali, neutralising, washing, squeezing and plaiting of
fabric. Such ranges can be classified into three types as follows:
1. Stenter type or chain mercerising machine
2. Chainless mercerising machine
3. Chainless and padless mercerising machine
201
On a chain mercerising machine, the fabric is passed through the nip of a

pair of rollers into the caustic soda solution. On emerging, the fabric is
threaded around a dozen of idling rollers to allow time for the caustic soda to
penetrate into the fibres. After plunging through a second trough of alkali
and through the nip of a pair of squeezing rollers, the fabric is fed into the
clips on the two chains of a stenter frame in which it is firmly held. Warp
tension is applied by running the second nip at a faster speed. Tension in
the weft direction is applied by the chains of the stenter frame, which slowly
move away from each other as the fabric proceeds through the stenter. As
the fabric approaches its fully stretched state, it is showered with hot water
to remove caustic soda, which should be brought down below 5% before the
tension is released. During washing, it is desirable that the original woven
width is maintained, so that maximum dimensional stability is achieved.
In chainless mercerising machine, the fabric after padding with alkali is
passed over a set of expander rollers, which are bowed rollers and stretch
the fabric widthways, thereby maintaining maximum width. For many types
of fabric, the machines provide satisfactory mercerisation more economically
than chain machines. With expander rollers, the fabric width is determined
by the tension on the warp and cannot be readily adjusted. The lustre of the
fabric is less than that attained by the chain merceriser.
The zone of the chain mercerising machine, in which the chain is applied,
provides the conditions for good maintenance in width. However, the
effectiveness of lye removal is questionable; though a good fabric width
results from the chain guiding, the anticipated stabilisation may be largely
lost due to the excessive lye content upon leaving the chain. Improvements
can be realised on chainless machines by using more effective expanders,
preferably in the stabilising section, together with more complete lye removal
in the guided fabric width.
While in other fabric mercerising machines, the fabric is allowed to shrink
after caustic treatment followed by stretching, in chainless padless
mercerising machine, the impregnation and washing are done under tension
– the fabric is not allowed to shrink. Instead of forcing caustic liquor into the
fabric by heavy mangle as in other fabric mercerising machines, the liquor is
absorbed from a trough by the fabric, which is held under tension by a series
of rollers in contact with each other. The fabric must be in a very absorbent
state and a highly efficient wetting agent is to be used in the trough. For
fabrics with long staple fibres, longer time of impregnation is allowed as they
have greater tendency to shrink resulting in slower rate of penetration.
In the impregnation section, there are two rows of strong rollers, one
above the other, and the fabric runs alternately around a top and a bottom
roller. The top rollers are covered with rubber and are carried by the bottom
row of rollers, which runs on ball bearings. The fabric runs under tension
over the rollers and the warp tension can be controlled by the drive. The first
202
two lower rollers carry the fabric through caustic solution, which comes
through two-supply pipes immediately above and in front of the first two top
rollers, and flows continuously over the fabric and into the trough. The fabric
runs about 3-4 metres during impregnation, and a further passage of about
5-6 metres round the remainder of the rollers for the alkali to penetrate the
fabric. The fabric then passes through a mangle at a pressure of about 5-8
tons depending on the type of fabric. A further run of about 8 metres
completes duration of about 40 to 60 seconds between the start of
immersion and washing.
The fabric then passes through the washing compartment of a similar
assembly of rollers and washed under tension with hot water. A further
mangling is done after passing through a series of sprays and troughs and
then the fabric passes to a recuperator with five compartments, where
steaming reduces the amount of alkali in the fabric to very small proportions.
In the final compartment, the fabric is sprayed with fresh water and then
heavily mangled to make ready for plaiting on to wagons. The Benninger
padless chainless mercerising machine runs at a speed of about 9 to 26
yards per minute, depending on the type of the fabric. Superimposing fabrics
or running them side by side can increase the production. For heavy fabrics,
the machine is to be run at a slower speed.
Continuous add-on is developed by optimising process and machine-
technology, paying particular attention to the ecological and economic
requirements of today’s market. In contrast to the former common practice
of feeding the squeezed or dry goods into a large bath with the mercerising
caustic concentration, a minimum liquor volume is used in the new process
by utilising the Flexnip (section 5.3.2); maximum pick-up with a
concentration of 500-600 g/l caustic soda is applied to the goods which
already contain about 60% water. After a dwell period of 15-25 seconds,
depending on the fabric with restricted fabric control on the subsequent
rollers, the normal mercerising concentration of 270 to 350 g/l is set up in
the goods through mixing of the initial water present in the fabric before
treatment and the applied caustic liquor. A higher mercerising effect is
obtained at a shorter time. The effect is higher because the required
concentration in the goods is virtually obtained from above by dilution of
applied caustic soda of high concentration with water present on the goods,
higher caustic concentration from outside to inside across almost the whole
of the fibre cross-section. In the former normal mercerising practice, the
required concentration in a large bath is obtained from below. However, in
this case the diffusion process may be slower due to higher viscosity of
more concentrated caustic liquor. The process is, therefore, preferably
operated at 70ºC (hot mercerisation) when the viscosity of caustic liquor is
low. After the diffusion section, the material path runs through a high-
performance squeeze [29].
203
Slack Mercerisation
In recent years, commercially cotton yarn or fabric is mercerised without
tension to impart stretch property i.e. high elongation and high elastic
recovery. These materials are useful for casual wears, skirts, boat covers,
etc.
Slack mercerisation is simple. The cotton fabric being allowed to shrink
without tension in a solution of about 10-15% caustic soda solution at 30°C.
However, the actual processing procedures can be varied and those will
have considerable influence on the stretch qualities in the resulting fabrics.
For some purposes, the weft only is allowed to shrink. The warp either be
held taut or allowed to shrink, followed by stretching in warp direction.
Mercerisation of Knitwear
While woven fabric mercerising is a 140-year-old process, knit goods
mercerising started about 20-30 years ago. It has been established that the
quality improvements due to mercerising can be higher on knit goods than
on woven fabrics. Lustre effects and dimensional stability obtained are
magnificent. Perfectly mercerised knit-goods are characterised by:
• Pill-free surfaces
• Increased dimensional stability in both length and width
• Considerably lower residual shrinkage values than with unmercerised
cotton
• Permanent lustre
• Excellent brilliance and depth of colour
• Silken lustre
• Lower tensile strength loss during high-performance finishing
• Improved wearing properties
The knitted fabric must be fed into the impregnating part of the machine
completely uncurled, under controlled lengthways and widthways guiding.
This requirement must be met without compromise, but it can be satisfied
with a combination of pneumatic and mechanical expanding devices and
exactly controllable draw nips. The guiding elements should be arranged so
that the last fabric expanding and guiding is applied as close as possible to
the immersion point into the liquor. As soon as the fabric is wetted with
liquor, the problem of edge curling disappears.
The circular knitted fabrics can be mercerised in the existing knit-
mercerising machines after slit opening of the tubes. However, some major
problems of such fabrics cannot be solved with existing machines, namely
selvage mark, selvage curling and selvage compacting. Mercerisation may
give rise to different warp thread densities between the middle of the fabric
204
and the edge zones. In chainless machines these differences are mainly
due to the loss of fabric width during mercerising, with the edge zones taking
whole of the shrinkage and entailing an inevitable increase in the number of
warp threads at the edges. The more the fabric is stretched across the
width, higher is the difference in the warp density, though in practice, a
certain difference can be tolerated. Greatest attention is to be given for the
patterned goods, especially with circle effects.
Controlled tension is the important factor for optimum tube mercerising,
lustre and uniformity. During the critical phase of stabilising, when the
caustic is washed out – the tubes must be stretched in their natural tubular
condition. An even stretching is achieved by a steplessly adjustable circular
expander, which is placed inside the fabric tube vertically in the centre of the
washing tower. Spray rings, arranged around the expander, are equipped
with flat spray nozzles through which hot water is sprayed at about 80°C.
The circular expander is held vertical by four concave rollers. The base is
designed as a floating body. The expander stands in the stabilisation bath
and its weight is nearly compensated by its buoyancy.
Liquid Ammonia Mercerisation
Although research reports concerning ammonia on cellulose may be found
since 1861, truly scientific results were only achieved in this field between
1926 and 1937. The cellulose is treated under tension in the presence of an
alkali meaning mercerisation by definition [30].
Researches with liquid ammonia began with Bernardy (1925) who found
that the action of ammonia on cellulose was much weaker than that of
concentrated solution of caustic soda, and the fibre characteristics in the two
cases were completely different. He also observed an increase in volume of
cellulose, but no direct attack by liquid ammonia, as in case of caustic soda.
Some decades had to pass until these results found an industrial application
in 1967.
In its native state, cellulose crystallises in a lattice designated as
cellulose-I. Cellulose-II describes the lattice found in regenerated or alkali-
mercerised cellulose. The treatment with liquid ammonia and hot glycerol
can result in lattices known as cellulose-III and -IV, respectively.
Cellulose and ammonia can form a complex, ammonia-cellulose-II at a
temperature below -30°C and ammonia-cellulose-I around and above
–30°C. The small ammonia molecules, along with its weak surface tension,
favour penetration into the fibre core between the molecular chains of
cellulose, without destroying microfibrils as in case of sodium hydroxide. As
the ammonia molecules are smaller than those of sodium hydroxide,
swelling is also less. Since the internal structure of the crystallites is
affected, hydrogen bonds are broken. In the swollen state the fibre is
deformable and capable of being set in a new conformation by the newer
205
hydrogen bonds, provided the tension is maintained until the ammonia has
been removed.
The ammonia, which has penetrated into the fibre, is removed very quickly
and totally because of its high volatility and extremely high solubility. Like
mercerisation with caustic soda, ammonia produces changes in the
structure of cellulose – reorganisation of the crystalline network with
cellulosic chains rotating and translating around their axle – giving a better
accessible network to reagents.
The differences between the two treatments are:
1. Penetration of ammonia into the fibre and its elimination are nearly
instantaneous (between 15 and 25 seconds). Therefore, the
treatment is very fast.
2. Ammonia is recoverable and reusable after a purifying distillation.
Caustic solution after mercerisation, especially in grey form, is soiled
and this will create pollution problem.
3. Water consumption is reduced to less than half in ammonia
mercerisation.
4. Ammonia is a natural substance and the process may be considered
as ideally eco-friendly.
5. It gives reagent-free textile goods.
The differences in fibre properties are as follows:
1. The properties provided by the traditional mercerising (increased dye

affinity and the change in appearance) are more or less preserved
with ammonia. Improvements in lustre and dye uptake are, however,
less than those of caustic mercerisation.
2. Ammonia, a weak alkali, does not damage the fibre contrary to the
very aggressive caustic soda. Mechanical properties like abrasion
resistance, tensile and tearing strength are improved. Ammonia
treatment increases tensile strength by 40% and the elongation at
break by 2-3%.
3. Less swelling by ammonia causes the fibre to become more plastic
and malleable. The article life is increased and the new appearance
is retained for a longer time. The difference in swelling also explains
the more brilliant aspect of the fibre after caustic soda treatment, and
the satin gloss after the ammonia treatment.
J. & P. Coats Ltd, (Scotland) announced Prograde process in 1969, in

which the yarn is passed through a liquor ammonia bath at -33°C (contact
time 0.7 seconds) followed by a hot water bath (0.1 second at 93°C), where
it is stretched 10-30% as measured against ammonia-swollen length. The
206
yarn is wound on a spool and dried continuously with hot air. The method,
developed primarily for sewing thread, is claimed to be one thousand times
faster than traditional yarn mercerising processes. Prior moisture treatment
(up to 30% of dry weight) improves the effects, especially uniform dye pick-
up.
The ammonia treatment on fabric is done continuously with lengthways
tension. It consists of impregnation of goods with liquid ammonia at
atmospheric pressure (i.e. at the boiling temperature of –33°C) followed by
the elimination of the reagent by evaporation (Sanfor-Set process), or by
rinsing with water (Veramtex process).
In Sanfor-Set process, the evaporation is done by passing over blanketed,
steam-heated dry cans. The residual (5-10%) chemically bound ammonia is
removed by light steaming. The Sanfor-Set or Duralized process combines
liquid ammonia treatment and Sanforizing and is especially suited for heavy
fabrics like denim and corduroy. The combined process is claimed to give
enhanced dimensional stability, softness and smooth drying properties, with
reduced seam puckering, edge fraying and leg twist in garment [19].
Ammonia mercerisation is generally done on desized, kier-boiled and
bleached (without optical brightener) fabric. No strong alkali treatment
should be carried out after ammonia treatment.
Ammonia can also be used as a remarkable solvent for all classical dyes,
which dissolve monomolecularly. Continuous dyeing with liquid ammonia
may be carried out by mangling with the dyestuff dissolved in ammonia at
–33°C. The goods are then steamed in order to fix the dyestuff and to
remove the ammonia. Finally, the material is washed to remove unfixed dye.
Barium Activity Number
The ability of mercerised cotton fibre to absorb more iodine, dyes, moisture
and alkalis, and to undergo oxidation or hydrolysis at increased rates
compared to unmercerised cotton, has been used to develop various
methods of determining the degree of mercerisation. The most successful
method consists of measuring preferential absorption of barium hydroxide
from its dilute solution by mercerised cotton. The extent of this absorption is
more than that by unmercerised cotton under the same conditions. This
ratio, multiplied by 100, is known as barium activity number, barium number
or baryta number.
The mercerised cotton yarn is cut into small lengths, dried over
phosphorous pentoxide for 5 hours and then conditioned at 65% relative
humidity at 31°C before testing. The samples of both mercerised and
unmercerised yarn, each weighting 1 g, are treated with 30 ml of 0.25 N
barium hydroxide solution in 100 ml conical flasks. After 2 hours, 10 ml of
the solution is titrated against 0.1 N hydrochloric acid. A blank is run without
any fibre. If b, s and u are the titration readings for the blank, mercerised
207
and unmercerised samples respectively, then the barium activity number N

is given by Eqn. 4.11.
b−s
N= × 100 ( 4.11)
b−u
Appropriately large number of conditioned samples are taken, taking into

consideration the moisture regain of the samples. Thus, if the moisture
regain is 8%, 1.08 g of the conditioned cotton is weighed to get 1 g of the
bone dry cotton. The barium activity number of good mercerised cotton may
be around 150-160.
4.5 PREPARATION OF PROTENEOUS MATERIALS
Animal or protein fibres are very irregular in composition. They contain a

significant amount of non-fibrous impurities – about 50% in case of wool and
about 15-30% in case of silk. These fibres are very sensitive to alkali and
are damaged quickly on alkaline wet treatment at high temperature
(especially wool). Hence, these fibres are scoured with large amount of soap
or detergent, with little or without alkali at low temperature. The time of
treatment is also much shorter as compared to that in case of cotton.
4.5.1 Scouring of Wool

The methods employed for scouring cotton would rapidly destroy wool due
to high alkalinity (especially caustic alkalinity) and high temperature. In
addition, mechanical pressure applied in wet state should be low in order to
avoid felting of the material. As a result of considerable experimental work to
reduce felting, several new scouring machines have been developed in the
industrial stage, including the SOVER solvent process, the UNISEARCH
and the CSIRO jet machines, WIRA improved scouring machine and the
widely accepted Fleissner machine [31]. In practice, with all the improved
wool-scouring machines, reduction in felting is achieved at the expense of
cleanliness, and it is now accepted that if a scouring machine is well
operated, no worthwhile reduction in felting can be achieved without some
reduction in cleanliness. Owing to the changes in industrial practice, the
cleanliness has become of overriding importance. The conventional
scouring machine in one of its modern forms, is consequently the best type
of machine to use for scouring wool. Felting in conventional scouring
bowls is minimised by using high wool feed rates. In the thick layer of wool
in the bowls, adjacent fibres and staples provide mutual support and inhibit
felting movements.
208
Wool scouring may be regarded as an extraction process in which the

contaminants are extracted from wool by a detergent action, the most
effective way being continuous counter-current extraction. The evolution of
scouring methods over the last decade has been towards the ideal steady-
state, continuous process. Steady-state is disturbed by the heterogeneity
created by dirt. It settles from the liquor in the scouring bowls, eventually
building up to such an extent that the bowls are to be washed out once in
one or two week, or even after 8 hours for very dirty wool. Steady-state
operation is attractive from the point of view of effluent disposal – water
consumption is lower, hence lower amount of effluent is to be treated.
Wool may have to be scoured at various stages during its manufacture –
as raw wool fibre, in sliver or yarn form, or in the form of woven or knitted
fabric. Unlike raw cotton, containing wax, raw wool is greasy, difficult to spin
and it must be scoured before spinning. Good and careful scouring is
important for subsequent processes, as the greasy wool is more difficult to
process. Although scouring of cotton in fibre form is done only for special
purposes, the scouring of wool fibre is a standard and widely used process.
Even if wool is already scoured in fibre form, additional mild scouring in yarn
or fabric form is necessary to remove residual fatty matters and oils or
lubricants added during spinning or weaving process.
Raw wool contains about 40-50% impurities, hence fibre scouring process
is quite troublesome. Complete removal of wool wax is not desirable at the
fibre stage. The fibre should retain a small portion (between 0.4% and 0.6%)
of the wool wax after scouring, in order to avoid brittleness causing fibre
breakage during subsequent spinning process. Sometimes spinners of
woollen yarns prefer a residue as high as 3%. The feedback parameters of
scouring are residual grease content of the wool and the subjective
assessment of quality – colour, brightness, felting, loftiness, etc.
The efficiency of scouring is judged by measuring residual fatty matters in
scoured wool. The measurement is made by extraction with petroleum ether
or dichloroamine in soxhlet apparatus. A known quantity of scoured wool is
taken in the stoppered bottle fitted with a condenser. The vapour of the
solvent is condensed and returned back to the bottle. The extraction is
continued for about three hours. The extracted solvent is then evaporated
on a water bath and the residue is dried and weighed. The method is
accurate, but time-consuming. Faster but less accurate measurement is
possible with a special apparatus based on a similar principle. Another
simple test is the turbidity test in which a fixed quantity of treated wool is
stirred with a fixed quantity of a standard detergent solution and the turbidity
is compared with that of the standard.
The disposal of highly contaminated waste liquor is much more
complicated than that of cotton scouring.
209
Fibre Scouring
Wool fibre scouring machines are of three types [12, 18]:
1. Swing Rake machine
2. Harrow machine
3. Paddle machine
The first two are widely used in England and other European countries,
while the latter is a continental system for scouring shorter and dirtier wool.
In the first two English methods, a number of prongs move raw wool
continuously through a series of shallow bowls or rectangular tank filled
with the scouring liquor. Each bowl is fitted with a perforated false bottom
over which the material moves. In the swing rake machine [18] (Figure
4.12a), individual prongs or rakes (B) move separately and cause greater
degree of agitation. The forks are moved by cam (J) and crank
arrangement (C) in such a manner that the prongs first descend into the
liquor and press the wool down. They then move gently horizontally
carrying wool through the liquor. At the end of the sweep, they rise vertically
out of the liquor and return to the original position. The usual length of
sweep is about 9 inches, but sometimes a 12-inch sweep is used. The
swing-rake machine cleanses dirty wool better, but the vigorous mechanical
action is liable to cause some degree of felting or matting of the fibres. The
rakes can be adjusted to act in unison or may be timed to exert an
individual sweeping movement by operating at different periods. This
irregular motion brings about more agitation of wool and so produces better
J
J J J J
C G A H G
A
B B B
D F D F
E E
(a) Swing Rake Type (b) Harrow Type
A = Feeding Conveyor,
K K K B = Swing Rake, C = Crank,
G D = Bowl with Perforated False
A Bottom,
E = Sediment Outlet,
F = Output Conveyor,
D F G = Squeeze Rollers,
E H = Harrow, J = Cam,
K = Paddle.
(C) Paddle Type
Fig. 4.12 Three Types of Wool Fibre Scouring Machines

210
cleansing action, but only suited to coarser wool. Finer wool may tend to
felt if severely treated, and the fibres break during subsequent mechanical
processing. In the harrow machine [18] (Figure 4.12b), the prongs are all
mounted on one frame called harrow (H) and move together. This provides
a comparatively gentle form of propulsion and is, therefore, particularly
suitable for finer qualities of wool, which felts easily. Some systems of
scouring raw wool of medium quality include both methods, first the swing
rake and then the harrow. In continental method [12], the paddle (K) action
((Figure 4.12c) gently swishes the wool along the bowl in which it has a
longer period of immersion at a much lower temperature than in the English
method. The continental system is a closer approximation to true
emulsification. In the English method, the wool wax is partly removed by
melting with subsequent wash. The English system operates at a
temperature of 50° to 55°C for a total period of 10 to 15 minutes, whereas
in the continental method the temperature is 28° to 38°C and the time of
treatment is longer (20 to 25 minutes).
In the Fleissner machine, wool is conveyed through the scouring bowl by
a series of suction drums [19].
The feeding device (A) for the bowls (D) generally consists of an endless
blanket made of leather or lattice wire on which the wool is evenly spread.
The greasy wool trends to float in the liquor. Hence, an immersion roller or
box called ducker is fixed at the entry into liquor. The roller or the box is
perforated and beneath the liquor. The wool is forced to dip into the liquor
and is moved forward.
At the end of the bowl, the wool has to be carried forward and upward to
the squeezing rollers (G) by an accessory called lift. Belgium lift operates
like a small grab – some of its forks dipping into the wool and lifting it onto a
small conveyor (F), which carries it to the nip of the rollers. An alternate
technique, side lift consists of a series of slides with projecting spikes,
which carry the wool to the squeezing roller. Now the most common
transfer mechanism is the washplate. Scouring liquor overflows from the
bowl and washes the wool down a plate inclined towards the squeezing
bowls. The washplate is perforated at its end to assist drainage of liquor
from the wool.
The function of intermediate squeezing is to minimise the carry-over of
liquor from one bowl to the next. Where water usage is high (15-20 litres
per kg of greasy wool), the amount of carry-over has little effect. However,
in modern plants with water usage less than 5 litres per kg, the carry-over
has an important effect on overall scouring effectiveness. The bottom roller
is always metal (stainless steel) usually knurled or otherwise roughened to
assist in gripping of wool. The top roller may be covered with a resilient
material such as rubber or polyurethane, lapped with several layers of wool
or other fibrous material.
211
An uniform layer gives more even drying. Hence, the provision of a feed
hopper between the final squeezing rollers and the dryer is becoming
increasingly common. Drum dryers are more popular than conveyor dryers
because the higher velocity in the former gives quicker and more uniform
drying. In modern dryers, the operating temperature, residence time of
wool and exhaust rate of air can be readily adjusted.
In all three systems, the wool is scoured in troughs or bowls with
perforated false bottoms (D), which permit the heavy impurities to escape,
by settling into the compartment at the bottom of the bowl. Side
compartments are provided at the end of the bowl, to receive the liquor
from the squeezing rollers. As the dirt settles and the fats rise, the
intermediate purer liquor may be fed back into the bowl for reuse. All but
the first bowl in a set are self-cleaning as above.
Wool scouring machines are generally made in standard widths of 28, 36
or 48 inches and in lengths of 30-40 feet, to suit requirements. There are
generally three or more bowls arranged in a line to scour the wool. Modern
scouring machines designed for the middle range of merino wool are
typically six bowls long. A conventional five bowl scouring machine is
shown in Figure 4.13 [19]. Nearly all scouring machines would have three
scouring bowls, i.e. bowls in which the bulk of the contaminants are
removed. The remaining one or two bowls would be rinse bowls to which no
detergent is added. In the ideal system, the first bowl cannot be a suint
bowl, since the purpose of a suint bowl is negated if it receives a counter-
current flow of hot detergent liquor from the second bowl. However, it is
possible to add a suint bowl to the front of an ideal system.
Detergent Detergent Detergent

Raw Clean
wool wool
1 2 3 4 5
Water
Clean water
Rinse
Centrifuge
Cream Sludge Liquor
Effluent
Fig. 4.13 Conventional Five Bowl Wool Scouring

The successive bowls of a set are generally arranged in one straight line.
Many types of bowls are available and in some of them, it is possible to
impart additional motion to the rakes, opening the wool and agitating it
212
during the scour. The process must be gentle to avoid felting and owes a
great deal of its efficiency to the open nature of the loose wool, which
assists penetration and permits the escape of the scouring liquor.
The first bowl is responsible for the major part of the cleaning and the later
bowl for further cleaning and rinsing of wool. The bowls mostly operate in
counter current principle. When the scouring liquor in the first bowl becomes
too dirty for further use, it is withdrawn from time to time or continuously
drained through the outlet. When self-cleaning bowls are not used, the first
bowl is to be emptied out after every 24 hours and refilled with liquor from
the second bowl followed by strength adjustments of the scouring agents.
For an ideal steady-state system, water, introduced at the last bowl, flows
back successively to the previous bowls and finally dirty water is discharged
from the first bowl. However, if a self-cleaning device is attached to the bowl,
the scouring liquor will be cleaner.
The dirty liquor from the first bowl may be clarified by a centrifuge and
used again. The liquor may be taken to the centrifuge (Figure 4.13), where
cream, clear water and sludge are separated as top, middle and bottom
layers respectively. Usually, cream production from the centrifuge is
controlled by setting the size of the gravity disk, a dam over which the
middle layer flows. The cream is treated with boiling water and is sent to the
clarifier centrifuge for separating wool grease. The clear liquor after filtration
may be send back to the bowl, while sludge to the sludge-bed of effluent
treatment plant. Dirty-water from the centrifuge, as well as rinsing water from
fourth bowl, is sent to the effluent treatment plant. Advantage can be taken
of the contaminant removal device by reducing either the number of bowls
or the counter-current flow rate. Some of the important operating
relationships in the ideal system are [19]:
1. The higher the number of bowls, the lower the counter-current flow
rate required.
2. The more efficient the contaminant removal device, the lower the
counter-current flow rate required (or the smaller the number of
bowls required).
3. The effects will be same as above when the flow rate round the
contaminant removal loop is greater.
In practice, the approach to the ideal system is limited by several factors.

Although good scouring is possible in machines with 1-3 bowls, the
consumption of detergent, water and heat are high. In order to reduce water
consumption, nowadays, very small bowls are used in higher numbers
(seven or more).
However, for many years to come, most wool will be scoured in
conventional four-, five- or six-bowl machines. The minimum water
213
consumption in these machines is about 2–4 litres per kg of wool and

additional 4-10 litres per kg in the rinse bowl.
The WRONZ (Wool Research Organisation of New Zealand) scouring
system has several distinctive features, the most important features on
liquor system are [19]:
1. The use of modified scouring bowls that permit the controlled

desludging of main bowl and side bowl.
2. Full counter-current flow through the machine, with discharge from
one point only.
3. The use of a large gravity settling tank in conjunction with the first
bowl.
4. Like CSIRO jet scouring machine, all liquor circulation is from the
bottom of the bowls or side bowls, thereby delaying the accumulation
of sludge.
5. Problems associated with abrasion caused by circulating bowl-
bottom liquor are avoided by introducing a heavy solids tank (HST),
in which the liquor settles before passing to the grease centrifuge.
The Lo-flo system has been designed as pollution reduction process. In

this system, the first bowl has been substituted by three small bowls. The
bowls operate with very high dissolved solids and the liquor from them
circulates in turn through the centrifuge. The liquor discharge from second
bowl may be zero with some wool types.
From chemical point of view, there are various methods of purifying loose
wool and these are determined to some extent by the type of material to be
cleaned, and the nature and amount of the impurities. The main methods of
purification are:
1. Emulsion scouring
2. Suint scouring
3. Solvent extraction
4. Freezing
The contamination on wool are of two types, easy to remove and hard to
remove. CSIRO (Australia) observed that once the easy-to-move
contamination has been removed, it should be separated from wool as
quickly as possible to avoid redeposition on the fibre, which is harder to
remove a second time. Scouring is thus recommended to be carried in two
stages. The first step is a wash and soak/rinse. Hard to remove
contamination requires longer time to swell, after which it can be removed
easily by a second scouring. This is the basis of two stage scouring.
214
CSIRO reinvestigated the operation of suint scouring. This is the practice

of operating a cold or warm first bowl (20-30ºC) where mainly the potassium
salts of suint have a detergent action. CSIRO modified the suint bowl by
addition of some chemicals so that the bowls can remove a considerable
percentage of the heavy solids present, while leaving wool grease, which is
not soluble at low temperature. By operating a modified suint bowl prior to
two-stage scouring, CSIRO developed a three-stage scouring process
called Siroscour.
Emulsion Scouring of Wool
Wool wax is difficult to saponify under conditions, which would not damage
the wool fibres. However, it may be readily emulsified, particularly at a
temperature slightly higher than its melting point (40-45°C). Emulsion
scouring with soap is the most common method of cleaning loose wool.
Scouring, most popularly know as wool washing, is done with 2-4% soap
and 2% sodium carbonate, calculated on the weight of the wool. At present,
wool scouring is most economically done with nonionic detergents. After
emulsion scouring the separated wool wax is contaminated with detergent
and suint. For this reason, the product is called wool grease, as distinct from
wool wax.
In the emulsion scouring process, generally soft water and a soap of high
emulsifying power should be used. Soft water prevents formation of metallic
soaps. The scouring liquor should also prevent the redeposition of the dirt
and grease on the scoured wool, after being emulsified by the soap. A
neutral soap is preferred as the hydrolysed alkali may be adsorbed by wool
causing discoloration, harsh feel and alkali damage. A small amount of alkali
may be beneficial for scouring, but no free alkali should be left on wool at
the end of scouring.
The melting point of the soap used for the scouring wool should not
exceed 27-30°C. The harder soaps, such as those from palmitic and stearic
acids, are more difficult to remove from wool and their residues tend to give
a harsh feel to the scoured material. On the other hand, soaps from oleic
acid are very water-soluble and do not gelatinise on cooling. The best soap
is potash-olive soap, but cheaper alternatives are also available. A
satisfactory substitute is the soda soap made from oleine, which is
sufficiently free from solid fatty acids.
The detergent action of soap is due to reduction of surface tension
between the scouring liquor and the wool grease. However, such reduction
with increase in concentration is not significant when the concentration of
soap is above 0.4%. Moreover, the stabilising effect due its action as a
protective colloid is maximum at the concentration around 0.2-0.3%.
Therefore, it is not beneficial to increase the concentration of soap above
0.4%. In fact, in the first bowl the concentration of soap is kept around
215
0.7-0.8% as a safety measure. It seems desirable to have sufficient soap in

the first bowl to start emulsification process, after which the natural
impurities in the wool are, to some extent, self-emulsifying. The
concentration is reduced to 0.4% in subsequent bowls.
The wool grease is frequently acidic. Moreover, hydrolysis of soap and
subsequent adsorption of alkali by wool may hamper detergent action and
free fatty acids may be produced and deposited on the wool during final
rinse. The addition of alkali improves detergency and saponifies the fatty
acids in the grease, converting them into soap. The alkali mostly used is
sodium carbonate and its concentration varies from works to works and with
the type of wool to be processed, but 0.25% is common. Although the lowest
surface tension effects are exhibited by soap at pH 8-10, yet the
emulsification and suspension power falls off rapidly below pH 9 unless the
concentration of soap is increased. Although optimum pH of the first bowl
should be of the order of 10, this is rarely in practice. The suint salts have a
high buffering action so that substantial alkali should be added to maintain
the desired pH, particularly in view of the neutralisation of some of the alkali
by the fatty acids in the wool wax. The liquors of the later bowls are much
cleaner and, therefore, more sensitive to alkali.
The temperature of treatment should not be above 52°C particularly when
sodium carbonate is present. With sulphated alcohols, in the absence of
alkali, the temperature may be allowed to rise to 70°C. The concentration of
soap and sodium carbonate in the four bowls, as well as temperature and
time of treatment, are shown in Table 4.5.
Table 4.5 Wool Fibre Scouring Liquor Composition and Conditions of

Treatments
Bowl Soap (%) Alkali (%) Temp. Time
1* 2* 1* 2* °C Minutes
First 0.8 0.75 0.27 0.25 49 3
Second 0.4 0.5 – 0.1 46 2.5
Third 0.37 0.25 – 0.1 43 2
Fourth Water only 40 1.5
1* - Priestman, Woollen Spinning, Longmans Green, London, 1924.
2* - Schofield, Finishing of Wool Goods.
° C - Minimum temperature, tolerance +3°C [18].
Nowadays soap has been largely replaced by anionic or non-ionic

synthetic detergents for the scouring of wool. These products are cheaper
and insensitive to hard water. Although synthetic detergents are as effective
in hard water as in soft water, little if any, relaxation in water quality
standards can be tolerated when the detergents are used for wool scouring.
Of particular importance are traces of iron, manganese and other heavy
216
metals. Even when the concentration is lower than 1 mg/l, they can be
absorbed by wool fibres in sufficient quantity to cause discoloration or to
adversely affect the dyeing of wool. Traditional water-quality standards
should be retained, irrespective of the detergent system used [19]. The
minimum water consumption in conventional 4-6 bowl machines is about
2 litres per kg for coarse wool and 4 litres per kg for fine wool, plus an
additional 4-10 litres per kg in the rinse bowls. The primary alkyl sulphates
were used formerly. However, they have been subsequently replaced by
comparatively cheaper secondary alkyl sulphates derived as a by-product of
petroleum cracking.
Among nonionic detergents, octa/nona-ethoxylated nonylphenols are
preferred for detergency, although ethoxylated straight-chain alcohols are
used where better biodegradability is required. The advantages of nonionic
detergents over soaps include greater efficiency under neutral conditions,
stability in hard water, lower cost and more efficient removal of grease.
These are easily desorbed in difficult rinsing conditions (e.g. in yarn
cheeses), although they are not as efficient as soap for the suspension of
dirt. Instead of sodium carbonate, sodium sulphate may be used as a
detergent builder, preserving neutrality of the medium. A guide recipe with
detergent is shown in Table 4.6 [18].
Table 4.6 Treatment Conditions for Wool Fibre Scouring with Synthetic
Detergents
Bowl Detergent Sodium Carbonate Common Salt pH °C
First 0.25% 0.25% – 9.0 54
Second 0.2% 0.2% 0.4% 10 52
Third 0.12% 0.02% 0.5% 10 49
Fourth 0-0.1% – – – 46
Grease Recovery
The major portion of wool grease extracted during emulsion scouring is
recovered by centrifuging the liquor of the first scouring bowl. A widespread
practice is to heat the liquor before centrifuging. Some workers claim that
the temperature of centrifuging has no effect on grease recovery, while
others believe that the recovery is better at higher temperature. For a
scouring machine operating in an efficient manner with a counter-current
flow of 5-6 litres per kg, grease recovery will be in the range of 30-50%,
depending on wool quality. When counter-current rates fall to 2-4 litres per
kg, recovery is likely to be 40-60%. The grease quality is always lower at
higher recoveries. In Lo-flo process, the first one or two conventional bowls
are substituted with a number of small bowls. The water input to the small
bowls is reduced to less than one litre per kg, thereby increasing the
dissolved solid content to 10% or more. This causes the liquor to destabilise
217
and grease recovery is roughly doubled compared to a conventional

scouring machine.
Comprehensive scouring systems have been developed by the WRONZ in
their minibowl technology and by CSIRO with their Siroscour processes.
These techniques employ minimum volumes of water without sacrificing final
wool cleanliness. In minibowl technology, small scouring bowls of advanced
design are used to obtain maximum scouring efficiency. Because of the
design of bowl, the minimum flow-down is about 1.5 litres per kg. At these
water-input rates, the liquor is at least partially destabilised and grease
recovery is significantly increased.
Even though a good amount of wool grease is recovered by centrifuging, a
large quantity is discharged with effluent water. Wool wax has a bad effect
on plant and animal life in rivers and tends to clog up the beds in sewage
disposal systems. The commonest method of purification of wool scouring
effluents is acid cracking, followed by hot pressing. The effluent is collected
in a settling tank where the solid dirt can sink to the bottom. The suspension
is then transferred to large wooden vats where sufficient sulphuric acid is
added to bring the pH of the liquor to about 3.5. Stirring is made with
wooden paddles or jets of steam or air.
The soap present in the waste liquor is decomposed into sodium sulphate
and free fatty acids. The emulsion of wool wax is also broken due to the
removal of the dispersing agent, soap. The residual dirt settles at the
bottom. The fatty acid and wool wax float to the surface, which is skimmed
off. The clear liquor is discharged. The skimmed material is mixed with the
sediment that still contains some fatty acid and wax. The mixture is then
heated with steam to 93°C and pumped into a heated filter press where
water and molten fatty matters are separated from dirt. The filtrated liquor is
dried when Brown Yorkshire Grease is obtained. The fatty acids can be
converted into soap by boiling the material with ammonia. The aqueous
emulsion thus formed is treated with magnesium sulphate when the soap is
precipitated. The wool wax floats on the liquor surface.
Calcium chloride may be used to precipitate soap and sodium carbonate
as lime soap and calcium carbonate. The precipitate, along with wool wax, is
separated by filtration. The disadvantage of the process is that the wax is
not collected in a very pure form. The method is not applicable for synthetic
detergents.
The wool wax, a valuable source of cholesterol and lanolin, is mixed with
free fatty acid when collected by acid cracking process. With specially
designed centrifuge, it is possible to remove the gross dirt before
transferring the waste liquor into conventional centrifuge operating at about
6,000 rpm. This will recover about 30-40% of the wool wax from the waste
liquor. The wool wax thus recovered is much better in colour and quality.
218
However, the aqueous discharge still contains some soap and wax, which
must be separated by acid cracking process.
Suint Scouring of Wool
Since time immemorial, it is known that the potassium salts present in the
impurities of raw wool and originating from perspiration, possess detergency
property. The old-fashioned method of scouring wool is to steep in water
and use the liquor as detergent, often reactivated with lant or stale urine and
pig-dung. The process generally operates in five stages:
1. De-suinting (16°C)
2. Grease removal (60-70°C)
3. Rinsing (0.1% soap, 40°C)
4. Soaping (0.3% soap, 40°C)
5. Rinsing (0.1% soap, 32°C)
Cold suint is used in the first bowl for treating the dusted wool and the
liquor is purified by sedimentation or centrifuging. In the subsequent two or
three bowls, clear suint solution is used at 60-70°C when wool grease is
removed by emulsification. Suint liquors vary in pH from 5.5-8.4. The bulk of
the grease and dirt is removed in the first two bowls, and soap is only
required at a later stage to remove the small amount of remaining impurity.
This means that the soap bowl is not rapidly contaminated and may be used
over long periods. The last bowl contains only water.
The suint scour is very economical and gives brighter and whiter wool,
which is more open and lofty than that obtained from soap scour. Although
the optimum dirt-suspending power of suint is at pH 7, the maximum grease-
suspending power occurs at pH 10, so that the suint scouring can be
improved by the addition of alkali.
One of the great problems of suint is the removal of the dirt, which is liable
to foul the desuinting liquor and deposit on the fibres containing the wool
wax and stain them. Precautions must be taken to settle the dirt instead of
being dispersed during pumping. It is more difficult to separate the dirt and
the grease from the suint liquor. Normally the liquor is withdrawn and
centrifuged so that the dirt settles at the bottom and the wool wax rises at
the top. The suint solution may then be drawn off and allowed to settle in
tanks before reuse in scouring. The wool wax obtained by this method is
purer and, therefore, more valuable than that obtained from the emulsion
scouring.
Modern requirements of low water consumption and effective effluent
treatment cannot be made if a suint bowl is used and it seems possible that
suint scouring will become increasingly rare in the future.
219
Solvent Scouring of Wool

Organic solvents are used to extract wool wax commercially in a limited
scale. The method is in practice in Belgium and the USA. Though the
process may be costlier than aqueous scouring, the advantages are lesser
felting and lesser entanglement of wool, and complete separation of the wax
without contamination with fatty acids derived from soap used in aqueous
scouring. However, solvents do not remove suint and dirt and an additional
step of aqueous scouring is necessary. Wool wax may be removed from
wool by benzene, carbon tetrachloride, solvent naphtha or white spirit.
Chlorinated hydrocarbon solvents are convenient, but usually cheaper
petroleum solvents of high boiling point are used. The latter require
adequate precautions against fire. Solvent scouring of wool can also be
carried out using perchloroethylene in which 8-18% water on the weight of
wool has been emulsified with a surfactant. Solvent and wax may be
separated by distillation and the solvent is reused. In spite of significantly
higher yield, the wax is of less commercial use due to its brown colour.
In conventional method, wool is packed into a kier, which is evacuated of
air and the solvent is introduced. The extraction is generally effected in
three stages, first with a solvent that has been already used for the scouring
purpose twice, then with a solvent used once, and finally with a fresh
solvent. The residual solvent on wool is removed by blowing warm air
through the kier, and passing it through a condenser where the solvent is
recovered. The suint is not removed by solvent treatment and, therefore. an
additional treatment with warm water in a special bowl or desuinting
machine is necessary.
In a modern method developed by CSIRO, raw wool is conveyed over
perforated drums beneath jets ejecting solvents under considerable
pressure. Under such pressure, extracted grease and dirt are removed. The
fibre is subsequently passed under water jets. The squeeze rollers are used
to remove excess liquor between successive treatments.
Solvent scouring offers clear pollution control advantages; a system
based on hexane (de Smert process) and another using 1,1,1-
trichloroethane (Toa/Asohi process) are in commercial operation in Taiwan
and Japan.
Freezing Method
A partial cleaning of wool is possible by freezing technique. A mild scouring
is necessary after this treatment. When raw greasy wool is cooled to a
temperature of -30 to -45°C, the fats freeze and become hard and brittle, but
the wool fibre itself is not affected. After cooling for sufficient time, it is
subjected to vigorous agitation when the frozen grease breaks up into fine
powder and falls away with considerable quantity of vegetable and mineral
220
matters. The raw wool is fed into the top of a refrigerator through a pair of
rollers, which act as a seal. The wool falls on a conveyor and is allowed to
stay in the chamber for about 3-7 minutes, and is then passed on a cleaning
machine, which comprises a cylinder with steel pegs on its surface.
Some fibre breakage may occur due to mechanical treatment, but after
milder scouring, a softer handle, lofty appearance and better colour is
obtained as compared to conventionally scoured material. The weight
reduction may be between 10% and 18%, and grease removal is about 30-
57% [18]. It is, therefore, possible to reduce the number of scouring bowls
or to increase the capacity of scouring bowls. As vegetable matters are
removed largely, carbonisation i.e. the process of removal of vegetable
matter, may not be necessary for most varieties of wool except fine felt wool.
Back Washing
Although wool is cleaned or scoured in the form of loose fibre, the sliver or
fibre strand prepared by the carding machine often possess a dirty
appearance. A subsequent washing treatment called back washing is
necessary. After carding, the fibres are more uniformly distributed. The
fibres in the carded sliver present a better form for cleaning the inadequately
cleaned wool and the dirt from the interior of the fibrous lumps are
accessible in case of sliver. The wool also acquires dirt during mechanical
operations up to the carding stage.
The back washing plant (Figure 4.14) consists of a small two-bowl
scouring machine equipped with a continuous drying system and a gill box
to apply oil. The first bowl consists of soap and hot water and occasionally
little ammonia. A mild cleaning takes place. A second bowl containing hot
water is placed a little above the first bowl and the liquor is allowed to flow to
the first. About 16-30 slivers are guided through the bowls by revolving
brass rollers submerged inside the liquor.
Dryer
First Second
Gill
Bowl Bowl
Box
Fig. 4-14 Back Washing Plant
The dryer consists of a steam-heated cylinder, or perforated cylinder

through which hot air is passed. Generally, the dryer consists of about six
221
standard size cylinders, or in multi-cylinder machines with about 40 small

cylinders of 4-inch diameter fitted around a large cylinder. Hot-air dryer
without cylinder is also used. After back washing, the fibre may become
brittle due to insufficient residual grease. About 3% of a suitable oil-emulsion
is applied in the gill box to protect wool during subsequent operations.
Woollen Yarn Scouring
Although the oil content of wool is reduced to 0.4-0.6%, it is customary to
add olive oil or specially prepared mineral oil during spinning. Manufactured
products may therefore contain about 5% oils in worsted yarns, to as high as
20% or more in carpet yarns, together with dirt picked up during
manufacture. The lubricants used in wool fibre during spinning and weaving
may be of the following types [32]:
1. Water-miscible polyglycol lubricants; these are mainly used on carpet

yarns and can be scoured with neutral nonionic detergents.
2. Mineral wool oil (mineral oil with nonionic lubricant) normally
extracted with using a nonionic detergent with or without little alkali.
3. A combination of mineral oil, olein fatty acids and triglycerides.
Partial removal is possible with synthetic detergent and sodium
carbonate. However, complete removal as required for various
finishes (e.g. shrink-resist) is possible only with soap and alkali.
4. Natural vegetable and/or animal oils are mostly used on woven
worsteds and the scouring is traditionally done with soap and alkali,
but there is a gradual trend towards neutral systems.
A high proportion of wool is dyed in the yarn form for the production of
woven fabrics with coloured designs. These yarns are, therefore, to be
scoured in yarn form.
Some types of woollen yarn tend to curl and distort during the scouring
process and others may be entangled or felted. Hence, some permanent
set is to be imparted to the yarn before scouring. The commonest method is
to stretch the yarn on a frame and then immerse it in boiling water, or treat it
with steam for 30 to 60 minutes followed by cooling in stretched condition.
Yarn may be scoured in hank form or in packages such as cones and
cheeses. Various methods may be adopted for scouring of woollen hanks.
The frames used for permanent setting may be lowered into the scouring
liquor and the hanks are rotated by some mechanism. Subsequently the
same bowl may be used for dyeing. Alternately, an endless rope or chain of
hanks may be made and scouring is carried out in Dolly scouring machine
(Figure 4.18) as in case of piece goods.
Large-scale scouring of wool in hank form may be done in tape or brattice
scouring [18]. The tape scouring machine (Figure 4.15) is simpler in
222
T2
H H H
N N
B1 B2
T1
Fig. 4.15 Tape Scouring Machine

construction, cheaper and ideal for small batches. The hanks are trapped
between the upper and lower members of two endless tape belts (T1 and
T2) and are passed through two or three consecutive bowls (B1 and B2)
containing detergent solution and rinsing water. A series of nip rollers (N)
situated inside the liquor promotes removal of the oil and dirt. Pairs of heavy
rollers (H) are placed at the entry and exit of each bowl to keep the belts in
position and to squeeze out the excess liquor. The duration of treatment in
the bowl is short and, therefore, a detergent of high emulsifying power and
solubility should be used.
It is difficult to specify the bath compositions, as the conditions are
variable. The first bath may contain 0.5% soap and 0.1% sodium carbonate
and the second bath only water. For three-bowl machine, the additional
second bath may contain 0.25% soap only. The concentrations are
maintained by intermediate additions. Nonionic detergents like Lissapol N (5
g/l) can be used instead of soap. Final rinsing with water may be omitted,
because the retained detergent will not hamper subsequent processes.
Brattice scouring machine (Figure 4.16) is used for scouring greater
quantity of woollen yarn. There may be two to five bowls. The yarn is laid on
a brattice or conveyor belt (B), made of stainless steel slats fitted one inch
apart. The brattices are submerged under scouring liquor. The first brattice
moves forward with the hanks and at the end of the brattice, the hanks fall
S S
T
B B
Fig. 4.16 Brattice Scouring Machine

223
on a second brattice, below the first one, which moves in the backward
direction. As the hanks reach the end of the second brattice, they fall on a
third brattice moving forward. At the end of the third brattice, they pass
through a pair of squeezing rollers (S) before entering next bowl. During the
submerged passages along with the brattices, the hanks are held firmly in
position between two adjacent brattices. The bowls work on counter-current
principle. The heavily soiled liquor is continuously discharged from the first
bowl and a corresponding amount of clearer detergent solution is transferred
from the subsequent bowl. In the first bowl, the liquor is continuously
pumped and delivered to a tray (T) situated over the top brattice. The tray is
perforated at the bottom through which the liquor is sprinkled on to the
hanks of yarn laid on the brattice.
The yarns wound on packages like cheese, may be scoured and dyed in a
package dyeing machine. Synthetic detergents are more preferrable than
soap, as these are more water-soluble and less liable for the formation of
insoluble deposits. Complete rinsing in this machine is difficult, but residual
detergents have no adverse effect on subsequent processes. The scouring
may be done for 20-30 minutes at 50-55°C with 0.2% detergent solution.
Crabbing and Blowing
It is necessary to scour woollen woven or knitted fabric to remove residual
wax and fatty matter as well added lubricants. However, before scouring, the
material is to be set with hot aqueous
solution to prevent shrinkage during
scouring and milling resulting in C
cockling and crows footing i.e. width
distortion of the design and weave. For B
A
greasy material alkaline solution is
preferred. The process is known as
H
Crabbing. In the simple crabbing
process (Figure 4.17), the fabric
previously wound under tension in a Fig. 4.17 Crabbing Machine
roller (A), is rewound on to a second
roller (B) by passing under tension through a trough of hot water (H). The
second roller moves in touch with another roller fitted on its top (C). As the
roll of fabric builds up on the lower roller, pressure is applied from the upper
roller, which operates in slots to allow for the increasing diameter of the
lower roller. Pressure is applied on the upper roller with the help of levers,
wheels, weights, etc. The process may be repeated in a second trough. The
application of heat and pressure in the moist condition is responsible for
setting the fabric in a smooth and even manner. The duration of Immersion
in hot water may be 5 to 15 minutes, followed by natural cooling or by
running through cooled water. Double crabbing by making the upper layer
224
of first crabbing as the inner layer during second crabbing is often advisable
for more even treatment throughout the length of fabric. The crabbing
process is often replaced or followed by a faster blowing process in which
the fabric is wound on a perforated roller through which steam is blown for 1
to 3 minutes under a pressure of about 0.1-0.5 MPa (1-5 atm). The process
is repeated after rewinding the fabric so that the external layers form the
interior of the roll. Machines are also available in which crabbing and
blowing can be carried out consecutively.
In crabbing and blowing process, all fabric irregularities like creases, etc.
and all latent strains from spinning and weaving are removed. A little
widthways shrinkage occurs. The fabric is set in a smooth and regular state
capable of withstanding subsequent processes. The fabric becomes uniform
and lustrous in appearance and thinner in handle. The weave is clarified.
Where the weave is pronounced, a cotton wrapper is interposed between
the layers of wool to avoid marking during the process. For most goods,
interlayer wrapper is not essential and its use will increase the treatment
time. It also requires frequent washing.
Potting process is similar to crabbing and is used for high-quality woollen
fabrics. The fabric is wound carefully onto a cotton-wrapped perforated iron
or steel roller and the roll is placed in a tank of cold water. The temperature
of water is raised slowly to either 75-80°C or the boil and the treatment is
continued for 3-5 hours. After cooling and rewinding to reverse the fabric,
the operation is repeated.
The set is permanent only up to the temperature of treatment. The study
shows that such short treatment in steam or hot water does not impart
permanent set but, on the contrary, leads to super-contraction. A long time
is necessary to break cystine linkages and rebuild in new position. The
cystine linkages break as follows:
/ /
R-S-S-R + H2O→ R-SH + HO-S-R (4.12)
The permanent set is acquired in the relaxed state by the formation of new
linkages through the condensation of the amino acids and the products of
hydrolysis of the original cystine linkages:
/ // / //
R -S-OH + H2N-R → R -S-NH-R + H2O (4.13)
Woollen Fabric Scouring
The scouring in rope form is mostly done in Dolly scouring machine
(Figure 4.18) resembling a winch dyeing machine [18]. The machine
consists of a pair of heavy squeeze rollers (R) and guide rollers (G). A
trough (T) situated under the squeezing rollers to collect the liquor
expressed by them. Two valves (W) are fitted into the trough so that the
collected liquor can either be returned to the vessel (V), or be discharged.
225
G G
D
T
W W
V
Fig. 4.18 Dolly Scouring Machine

The discharge is necessary when the scouring process is nearing
completion and the liquor is considerably soiled.
The pieces of fabrics (about 60-70 metres for worsted fabric) are made
into an endless chain, which is threaded, in rope form, through the squeeze
and guide rollers. Twelve or more ropes can be processed simultaneously
keeping the ropes side by side and separated by dividing rods (D). The M:L
ratio may be as low as 2:1, which is much smaller as compared to that
employed for scouring of cotton. For certain varieties, however, a higher
ratio is maintained so that the fabric floats in the liquor, which opens it
somewhat, and prevents watermarks.
Scouring liquor composition depends on the nature of the oils to be
removed. Lubricants, prepared from hydrolysis of natural oils and fats,
require sodium carbonate (about 3-4% on the weight of material) in the
scouring bath at 35-40°C. Low quality woollen goods contain as much as
15-20% oil and require treatment with 4-5% of sodium carbonate. It may be
necessary to repeat the operation with lesser alkali before final rinsing.
Worsted goods generally contain very low amount of oil. About 0.5-1.0%
o.w.m. of soap or synthetic detergent is usually adequate. To ensure
alkalinity, sometimes 1% sodium carbonate or ammonia is added.
Carbonisation
The most unwanted cellulosic impurities, which remain entangled with raw
wool are burrs and broken seeds of various plants. These are to be
removed after the scouring process, otherwise these may damage spinning
machines like card fabricating and combs. Yarns with burrs are difficult to
weave and dye evenly.
The burrs can be removed by burr rollers, which operate in conjunction
with opening rollers or cards. The burr rollers are about 4 inches in diameter
and carry steel blades set close to the card rollers where the wool is held
226
and the burrs are flicked off. In another type, the burrs are crushed between
smooth and fluted rollers applying pressure suitable for the type of burr.
The mechanical methods are capable to remove cellulosic impurities to
the extent that the wool can be spun and woven without any problem and
the chemical carbonisation process can be carried out in fabric form for
complete removal of vegetable matters. Carbonisation in fabric form is
preferred because the wool qualities beneficial to spinning and weaving are
preserved until fabric formation.
Carbonisation of woollen fabric may be carried out before or after dyeing.
The advantage of carbonising before dyeing is that the acid can be carried
forward to the dyebath as dyeing is done in acidic pH. However, carbonised
goods do not always dye evenly. If carbonisation is done after dyeing,
considerable care is necessary to ensure that the shade does not change
after acid treatment.
Carbonisation may be done for unscoured wool, but penetration will be
poorer and higher amount of acid will be required. Generally, wool fabrics
are carbonised between scouring and milling processes. Carbonised wool
takes longer time to full or mill. However, for acid milling, the acid from the
carbonisation process may be allowed to remain in the goods. After milling,
the burrs and other water-insoluble impurities are fastened in the fabric and
are difficult to remove.
The cellulosic matters can be converted into hydrocellulose in two ways:
1. Dry carbonisation with hydrochloric acid gas.

2. Wet carbonising with either by:
(a) Immersion in 5-7% sulphuric acid solution (5-6°Tw) in presence
of 0.01-0.02% nonionic wetting agent at room temperature,
followed by squeezing to 75-80% liquor retention, giving an acid
uptake of 5% (o.w.m.). Typical running speeds in continuous
impregnation tank are 5 m/min for heavyweight and 25 m/min for
lightweight fabrics. The fabric should be dried to a 10% moisture
content at temperatures up to 90°C and baked for 3 minutes at
130°C. Crushing is done discontinuously for 60 minutes.
(b) Immersion in aluminium chloride (12°Tw) or magnesium chloride
solution (10-15%), drying followed by heating at 120°C. Both the
salts liberate hydrochloric acid at high temperature, the ideal
reaction being:
AlCl3 → Al(OH)3 + 3 HCl (4.14)

MgCl2 → Mg(OH)2 + 2 HCl (4.15)
In dry carbonising, the concentrated hydrochloric acid is allowed to drip

into a heated metal retort and the liberated gas passed into a brick chamber
227
in which the previously dried fabric is exposed inside a revolving perforated

drum and the temperature is maintained at 90°C. The rags are then
transferred to a shaker, which beats out the powdered hydrocellulose. The
rags are then washed and neutralised with soda ash solution.
The wet carbonising process is more usual. In this process, the fabric in
open-width passes over the usual opener and then uniformly wetted by
immersion in a water bowl followed by squeeze rollers or vacuum slot.
Alternately, the fabric may be wetted in rope form and then hydroextracted.
The wetted fabric is then passed through the tank containing acid, under a
series of rollers and may even pass between squeeze rollers in the middle
of the tank. The concentration of carbonising agent varies with the weight of
the fabric and its vegetable content. Lightweight goods of low cellulose
content may require only 2°Tw sulphuric acid. The fabric is finally squeezed
and passed over a suction slot to remove excess of acid. The liquor pick-up
should be about 40% and the acid contained should not be more than 5% of
its weight. Earlier the treatment used to be carried out with 2-4% boiling
sulphuric acid. However, presently the treatment is carried out at cold. The
same acid bath may be used for months with addition of acid and water as
required. However, after sometime the salts coming from wool exert
buffering action and consequently more acid will be required. At the start,
7°Tw fresh acid may be adequate, but after some months, the concentration
may have to be increased to 10°Tw for complete carbonisation. Surfactants,
stable under the condition of hot acidic treatment, help the wetting and
penetration of the wool, ensuring more uniform treatment with less damage
to the wool. Alkylnaphthesulphonates as well as some specific nonionic
surfactants are used. The acid-impregnated fabric is sent to the drying-
baking section of the continuous range. This consists of 4 to 6 chambers.
The first part of the drying unit consists of fans and blowers and the
temperature is below 60°C. The final heating may be at a temperature of
95-100°C. The time required may be 20 minutes for drying and 10 minutes
for baking.
The hydrocellulose formed is brittle and may be removed simply by
mechanical means. The dried fabric, still hot, is passed through a rotary
milling machine without any liquor in it, when the hydrocellulose readily falls
away. Sometimes no additional treatment is necessary. Before milling, the
acid retained in the fabric is to be removed by washing with water. Final
neutralisation may be made with 2% soda ash, but this may affect the
colour.
For dyes sensitive to sulphuric acid, aluminium or magnesium chloride
may be used. When these are employed for carbonising, it may be
necessary to rinse the fabric after heating and dry milling, with hot dilute
hydrochloric acid, followed by washing with water, rinsing with ammonia and
again with water. The magnesium chloride leaves a basic chloride or
228
oxychloride in the wool, so that scouring may be necessary after

carbonising.
A study [33] showed that the temperature and humidity during drying
influences the affinity for dyes. With sulphuric acid, the affinity increases for
basic dyes and decreases for acid dyes after carbonisation. The reverse is
the case with aluminium chloride. The drying should be as rapid as possible.
The washing of freshly carbonised fabric with hot 3% sodium sulphate
removes more sulphuric acid than when washed with water only.
The amount of sulphuric acid required for carbonisation can be reduced by
the action of cellulytic and pectinolytic enzymes. Various studies show that
acid carbonisation may be replaced by treatments with enzymes, namely
cellulases, ligninases, hydrolases, lyases and oxidoreductases. Proteolytic
enzymes alone, or in combination with hydrogen peroxide, can increase the
whiteness and hydrophilicity of wool compared with the oxidative treatment
alone.
Felting and Milling
During processing of wool, all precautions are to be taken to prevent felting.
The felting properties of wool are due to three factors.
1. Scaly surface structure
2. Ease of deformation
3. Recovery from deformation
Wool has a scaly surface. The scales project slightly from the stem of the
fibre and point towards the tip of the fibre. Wool fibres, therefore, possess a
property called directional frictional effect (D.F.E.), the result of which is that
the coefficient of friction of one wool fibre against another is greater when
the tips are pointing in opposite directions than is the case when their
longitudinal orientation is similar (Figure 4.19). Though felting is primarily
believed to be caused by projecting tips of the scales, some other keratinous
substances devoid of scales also show D.F.E. Therefore the phenomenon is
considered to be an inherent property of keratin itself. The ease of
deformation and high power of recovery is responsible for the mass
contracting in bulk by a series of self-contracting mechanism. Felting, milling
or fulling is the thickening, accompanied by loss of area of woollen materials
when they are subjected to vigorous agitation in aqueous medium. Felting is
Less friction More friction
Fig. 4.19 Directional Frictional Effect of Wool

229
caused by a degree of irreversible movements of fibres in relation to each

other brought about by the D.F.E. The elasticity of wool plays an important
role causing unidirectional movement responsible for felting. The tendency
of felting reduces with reduction of elasticity. When two adjacent fibres are
compressed and relaxed many times and then the compressive force is
withdrawn, the D.F.E. will prevent them from returning to exactly the same
positions as before. Consequently the fibres are entangled and a compact
mass is formed. The study shows that the root ends of the fibres tend to
thread themselves through the fibres arranged parallelly and under
compression, they buckle up. Since the root of the fibre plays a significant
role, either hardening of this zone of fibre or conversely softening of the tip
promotes shrinkage and thereby felting. The experimental evidence
confirms the phenomenon.
The shrinkage of wool is at its lowest between pH 4 and pH 8 and it
increases rapidly on either side. The curves showing shrinkage and
elasticity (the amount of work required to stretch the fibre by a specific
amount) against pH have very similar shapes. Hence, the shrinkage is
considered to be closely related with the elasticity of wool fibres. Between
pH 4 and 8, adjacent polypeptide chains may be bound together by salt
linkages making the structure comparatively rigid. Below pH 4 and above pH
8, the salt linkages are broken and the fibres can expand or contract under
the influence of alternate compression and relaxation.
The ability to felt is the most important characteristic of wool. For certain
varieties of woollen materials, purposeful felting is done. The process is
called milling or fulling. The object of milling is to felt the fabric partially so
that it becomes fuller and denser, the pattern of the weave structure
disappearing to an extent depending on the severity of the process. The
process consists of applying a squeezing action to wet fabric in order to
promote fibre migration and interlocking, leading to shrinkage and felting.
Milling is a finishing process and not a preparatory process. However, when
alkaline milling is used, a certain amount of scouring takes place and it is
possible to combine scouring and milling together.
The original term for felting process is fulling, which is still used in the
USA. The British term milling is used for all compressive processes, which
cause felting. The woollen material coming from looms or the knitting
machines are thin, porous in structure and lack rigidity. Milling closes the
interstices and makes a solid fabric with higher strength. Milling is continued
until a specific density or weight per square yard/metre is attained. Milling
processes can be divided into three types [34]:
1. Grease milling
2. Acid milling
3. Soap milling
230
Greasy woollens are often milled in sodium carbonate alone, which

saponifies the grease into soap. Grease milling is a cheap but dirty method.
The greasy fabric is run through a liquor containing 25-30 g/l soda ash and
then squeezed to a M:L ratio of 1:1 or 3:2. The fabric is then milled to the
required cover and dimensions before washing. It is seldom used for
medium and good quality fabrics.
Some goods such as felt hats and blankets are milled under acidic
conditions (pH 3) using dilute sulphuric acids. Acid milling is especially
suitable for dyed goods as many of the dyes applied on wool have poor
resistance to neutral and alkaline treatments. Acid is preferred as a milling
medium because:
1. The resultant fabric has a greater tensile strength.

2. The process occurs more rapidly and to a greater extent.
3. A greater degree of extensibility and stretch of the milled fabric.
4. Less fibre degradation, less flocking and heavier fabrics than with
grease or soap milling.
5. Less bleeding or cross-staining at low pH.
6. Minimised washing off, resulting in lower water consumption.
Alkaline milling conditions are still, however, largely used for woven piece
goods, the maximum milling takes place at around pH 10, using soap. The
high-melting point soaps, such as those based on tallow and palm oils, are
preferred to give the required gelatinous solution and lubricating properties.
Sodium or potassium soaps are dissolved to give a 5% solution in hot water.
Such solutions have to be applied warm, as soap solidifies on cooling. For
carbonised fabric, thorough neutralisation is necessary, otherwise there may
be flocculation of fatty acids. The soap acts as a lubricant and decreases the
inter-fibre friction, permitting more rapid shrinkage than with alkali alone. For
producing heavily consolidated fabrics such as meltons and billiards, soap is
essential. During lengthy soap milling, however, certain fabrics cease to
shrink further. In these cases, the fabric is washed in a washer and then
returned to the milling machine. Excessive lubrication by soap can block the
felting process by reducing the influence of directional frictional effect.
There is gradual trend towards milling in almost neutral conditions, for
which milling aids based on nonionic and anionic surfactants are useful.
Some wool yarns are milled nowadays simply by tumble drying wet yarns,
whilst knitted garments are milled in rotary type machines using nonionic
surfactants with sodium bicarbonate or polyphosphates.
Normally milling is carried out in a rotary milling machine in which the
scouring and milling can also be made simultaneous. The fabric is
processed in endless rope form and is passed through the milling liquor
followed by a pair of heavily loaded squeeze rollers and then into a spout
231
where compression takes places. The spout is rectangular in cross-section

and the topside is pivoted at one end and free at the other. The pressure on
the spout can be varied by applying weight to the pivoted top. The relaxation
takes place as the fabric leaves the spout so that the necessary alteration of
pressure and expansion is brought about.
4.5.2 Processing of Silk

Silk is obtained in the form of cocoon, an elliptical mass spun by silkworms.
The following sequence of operations is carried out to obtain silk filaments
from the cocoons:
Cocoon testing & selection

↓
Stifling or drying by sun, steam stifling or hot air conditioning
↓
Storing
↓
Sorting
↓
Cooking by methods like:
1. For Mulberry by soap-soda, enzyme or water
2. For Tussah and Muga by soda or enzyme
Using machines like open single bath, three pan (bath) system, or
pressurised vessel
↓
Brushing or deflossing by hand or mechanically
↓
Wet reeling
↓
Re-reeling (for standard hank)
Raw Mulberry silk is white, golden yellow or yellow-green in colour, while

wild silk is light to deep brown in colour. Raw silk does not possess the
lustre and softness for which this fibre is known. The gummy substance
called sericin covering the fibrous material, fibroin, imparts a harsh handle
and must be removed in order to bring out the supple and lustrous qualities.
Although sericin and fibroin, the two components of raw silk, are both
protein, they differ considerably in their relative compositions of various
amino acids and accessibility. The process for removal of sericin is known
as degumming, boiling off and less commonly scouring. Degumming of silk
involves the cleavage of peptide bonds of sericin, either by hydrolytic or
enzymatic methods and the subsequent removal of sericin from the silk
232
fibroin. Since the sericin acts as a protecting coating in mechanical

processes such as spinning, knitting and weaving, its removal is delayed
until the completion of the mechanical processes, depending on the product.
However, a slackened thin uneven structure of such degummed fabric is not
acceptable for high-quality silk fabric. Hence, the recent trend is to degum in
yarn form followed by application of easily removable sizes, which are
subsequently removed by desizing.
Degumming also removes accompanying substances like fats, oils,
natural pigments and mineral components. The thorough and uniform
removal of these impurities is important not only for uniform dyeing, but also
for good printing. Sizes such as starch must also be removed with some
qualities (e.g., schappe). According to the origin of silk, its natural colour is
very lightly to heavily marked (e.g. by chlorophyll, carotin). With some wild
silk, this natural coloration may be very strong, affecting not only the gum.
The main degumming agent is soap. Boiling off or degumming of silk is
carried out just below boil (90-95°) in soap solution with or without alkali
according to the quality of the fibre. The removal is based on the water
solubility and higher alkali sensitivity of the sericin as compared with the
fibroin at pH values from 9 to ca. 11.5 [35]. Some hydrolysis of sericin
probably occurs. Stronger alkalis may attack fibroin. On the other hand,
prolonged degumming time is required in the absence of alkali. During
degumming, alkali is taken up by the sericin and the free acid from the soap
is formed. This may be deposited on the fibre, reducing the rate of
degumming and protecting it from hydrolysis. Alkali is often added to
maintain or to restore the pH of the baths, but it is rarely used alone,
because it makes silk harsher in handle. For complete removal of sericin,
sodium carbonate may be added. If the pH exceeds 11, the fibroin is
attacked. Silk can also be degummed with strong acids – the gum is
completely removed at a pH 2.5 after 30 minutes of treatment. However,
acid degumming is not commercially successful. Protein-splitting enzymes
are also able to degrade sericin.
The gum content varies according to the quality and origin of silk.
Cultivated mulberry or Bombyx mori silks have about 20-30% gum and wild
silk Tussah or Tasar 5-15%. The complete removal of sericin results in a
considerable weight loss. Hence in certain varieties, the gum is not
completely removed.
1. In Ecru silk, only 2-5% gum is removed, the object in this case is to
extract the small quantity of wax that is present rather than to degum
the silk. The handle of ecru silk resembles that of raw silk being
relatively harsh, but even so, it is suitable for warp threads.
2. In souple silk about 8-15% gum is removed. Souple silk is fuller and
softer in handle and is used for weft.
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3. In Cuite or boiled off silk the gum is completely removed.
During the process, care must be taken to avoid entanglement or fracture

of the fine filaments, particularly while processing in yarn form. The
mechanical stress on the silk is kept to a minimum so that the silk threads
are not spliced. Otherwise, severe and irreparable damage may be caused
in subsequent processes such as dyeing and printing which involve further
mechanical treatments. To prevent surface rubbing and haphazard
movements, the material may be put into bags. The machine should have
an extremely polished surface to prevent fibre rupture due to abrasion. Like
other animal products, silks of different varieties vary considerably in
properties. The correct degumming method for each type of silk article
should be carefully selected. Improperly pretreated silk may become yellow
during storage under the influence of light. Four different degumming
processes are used in practice:
1. Traditional method with soap (Marseilles)

2. Degumming with synthetic detergents
3. Enzymatic degumming
4. Acid degumming
Acid degumming process has not been commercialised yet. However, it is

claimed that the degumming at pH 1.0-2.9 with organic acids such as
tartaric and citric acid, gives a product with superior tensile strength than
that obtained by soap degumming.
Traditional Degumming with Soap
The traditional method with soap is still the one mostly used, especially in
China and India. However, slowly the processes using synthetic detergents
or enzymes are becoming popular. The advantage of soap degumming is
that an especially soft handle is produced. However, the treatment time is
very long (2-6 hours) and prolonged treatment may damage the material.
Continuous processing of piece goods is hardly practicable. As soap is
used, soft water is a decisive factor for good results.
The best soaps for degumming silk are made from olive oil commercially
sold as Marseilles soap, which is now somewhat expensive, as a result, the
less effective oleic acid soaps are being used largely. Tallow soaps are
difficult to remove after degumming. Soap from cottonseed or coconut oil
has been suggested, but they leave an unpleasant odour in the material.
Grove-Palmel [36] stated that no soap that has hard fat for a base can safely
be used, and no soap whose 1% solution will gel when cool is suitable. He
further stated that the following three kinds of soap are excellent for
degumming:
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1. A pure oil soap containing 65% fatty anhydrides, 8% combined alkali,

25% water and less than 0.3% of free sodium hydroxide.
2. Monopol soap, made from sulphated castor or linseed oil, containing
65-75% fatty anhydrides, 3% combined alkali, 12-15% water and no
free alkali.
3. Marseilles soap, made of olive oil containing 60-63% fatty
anhydrides, 7% combined alkali, 26-30% water and up to 2.3% free
sodium hydroxide.
When neutral olive soap is used with a small amount of alkaline reagents
such as sodium carbonate, phosphate or silicate, the pH of the liquor should
not fall outside the range of 9.2 to 10.5. The concentration of soap is
generally not less than 20-30% of the weight of the material, which works
out at 5-7 g/l for a M:L ratio of 1:30-40. Often higher amounts are employed
corresponding to 30 to 50% of the weight of silk. Unless the concentration of
soap is adequate to remove and to retain the impurities in suspension, there
is always a danger of the scum and gummy matter being deposited on the
silk again. The danger may be obviated by the addition of a dispersing agent
e.g. sulphated alcohol.
The temperature of the degumming bath generally lies between 90 and
95°C; higher temperatures up to boil are apt to bring about some yellowing
of the silk and inferior handle. A further difficulty of high temperature is that
due to bubbling, the material is vigorously agitated leading to chafing and
lousiness. The rate of degumming is found to be three times faster at 93°C
than at 82°C. A degumming time of 90 to 120 minutes at boil is considered
to be sufficient and economic.
The addition of alkali to soap solution increases the rate of degumming
and makes the process economical since the quantity of soap and time
required are reduced. High-grade olive oil soap liquor gives a starting pH of
9.2-9.5, which rapidly falls to 8.5. The addition of alkali tends to maintain pH
at the effective point. With up to 0.18% free alkali, no weakening of fibre
occurs. However, the resultant silk acquires a yellowish tinge.
The material may be immersed in water overnight so that the gum swells,
thus becoming easier to remove.
The details of the conventional working method for boiling off Mulberry silk
is as follows:
1. Soaking overnight or for 6 hours in a bath with 3-5 g/l Marseilles

soap and 1-2 g/l wetting agent.
2. Boiling off for 2-6 hours at 90-95°C in a bath containing 8-10 g/l
Marseilles soap at pH 9.5 with soda ash. For schappe silk, the same
bath may be used, but only for 1-2 hours.
235
3. Repeat the treatment in a second bath like the first one for 2 hours, if
necessary.
4. Rinsing first at 50°C with ammonia and then two rinsing, one at 40°C
and another at cold.
A rapid method of degumming with soap is to treat for 1-2 hours at 90-
95°C at pH 9.5-10 in the following bath:
8-10 g/l Marseilles soap

1 - 2 g/l wetting agent
1 g/l soda ash
1 g/l sodium tripolyphosphate.
For ecru silk, the silk is immersed overnight in a weak (4-5%) solution of
formaldehyde at 20°C or treated with 15% formaldehyde solution at 75°C for
1 hour for hardening of sericin. Then the silk is treated in a weak soap
solution carefully so that the gum is not attacked.
The partial degumming of souple silk does not take place perfectly in
alkaline soap bath, but in an acid bath, as in the following bath sequence
[35]:
1. Degrease at 30-40°C in a weak alkaline soap bath.

2. Treat at boiling temperature either in a sulphuric acid/magnesium
sulphate solution or sulphuric acid/soap bath for 1-3 hours.
3. Rinse thoroughly.
4. If still sticky, treat briefly in another soap bath at 30-40°C.
Souple silk thus obtained should not be treated with hot alkaline bath
afterwards.
Degumming with Detergent
Synthetic detergents are increasingly replacing soap, especially in Europe.
The traditional degumming requires a huge quantity of soap, the pure soap
itself is very costly nowadays. The use of soap also demands the use of soft
water, otherwise a considerable amount of soap will be wasted by reaction
with hard water. A variety of synthetic detergents is widely available and will
be comparatively economic, as lesser amount of synthetic detergent will be
required. Moreover, the time of treatment is considerably shorter enabling
continuous processing of piece goods. The synthetic detergent should be
carefully selected because the same soft feel as that achieved with
Marseilles soap is not always obtained.
A method recommended by Clariant [35] is as follows:
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1. The material is treated with 2.5-5 g/l Sandopan SRS liquid at pH

11.2-11.5 (with caustic soda) at boil for 30-120 minutes.
2. The material is subsequently rinsed with water at 80°C. The
processing may be discontinuous or continuous.
Enzyme Degumming
The method is regularly used in China. The treatment time is somewhat
longer than with synthetic detergent, but shorter than soap. It is considered
to have a mild action on the fibres and is claimed to produce uniformly
degummed material with soft handle and reduced lousiness. The
recommended proteolytic enzymes are trypsin (of animal origin), pepsin and
papain (of vegetable origin). They hydrolyse peptide bonds formed by the
carboxyl groups of lysine and arginine. Enzymatic degumming is not a single
step process. The gum must be swollen before the enzyme treatment. An
additional treatment with mild alkali is necessary to remove natural wax, soil
and lubricant oils.
Trypsin, a proteolytic enzyme secreted by the pancreas, is most active at
pH range 7-9. Ammonium bicarbonate (0.1 mole/l) is considered to be a
good buffer. For tryptic digestion, 1-2% enzyme on the weight of material at
37°C for 1-4 hours is considered appropriate.
Papain, obtained from vegetable source, papyrus latex, is most active at
pH between 5 and 7.5 at 70-90°C. Original poisonous activators potassium
cyanide or hydrogen sulphide are being replaced with sodium thiosulphate,
alone or an admixture with sodium hydrosulphide.
A bacterial enzyme, alkalase, is very effective in hydrolysing sericin. It
may completely hydrolyse sericin in one hour at 60°C and pH 9.
Clariant recommends the following steps:
1. Treat at boil for 1 hour with a liquor containing:

0.5 g/l soda ash
0.5 g/l Glauber’s salt
3 g/l wetting agent
2 g/l sodium silicate
2. Treat at 40-45°C for about 1 hour with another liquor containing:
1-5 g/l protein enzyme
1 g/l soda ash
2 g/l Glauber's salt
3. Treat at boil for about 1 hour in a bath similar to the first bath.
Degumming of Wild Silk
Wild silks i.e. Tussah (Tassar), Muga and Eri silk, are obtained from wild
surroundings i.e. from forests without any sort of breeding or cultivation and
237
is naturally coloured pale brown to dark brown. They differ from Mulberry silk
both chemically and physically and hence their processing differs
considerably. Generally, with Tussah silk, the gum is not present in the
same regular form as with bombyx mori silk. It is often embedded in the
strongly fibrillated fibre and is therefore difficult to remove completely.
However, very recently some new varieties of Tussah silk are produced
mostly in China which are very close in properties to the Mulberry silk and
they both can be processed in the same manner.
A conventional process is as follows:
The wild silk requires an initial scouring in a M:L ratio of 1:30 (minimum)
and 10% (by weight of silk) soda ash. The temperature is raised to 40°C
within 15 minutes, running the hanks vigorously initially and slowly later on.
The bath becomes dirty brown. The hanks are treated for half an hour at
40°C when about 10% weight loss occurs. The hanks are hydroextracted
and entered in a fresh bath containing 10 to 15% soda ash at 45°C. The
temperature is raised to 85-90°C in about half an hour and the treatment is
done for one hour. The hanks are washed and treated with 10%
hydrochloric acid for 15 minutes, which brightens silk. The material is then
washed well, soaped with 3-5% soap at 40-45°C for half an hour and again
soured with hydrochloric acid. Souring may reduce strength slightly but
elasticity and gloss improve considerably.
A simplified method which may not be very satisfactory but used by some
processors, is to boil directly at 90-95°C for 2-6 hours with 3-5 g/l Marseilles
soap and 2-8 g/l soda ash.
Afterwards it is rinsed thoroughly in hot and cold water.
A combined method recommended by Clariant [35] is as follows:
1. Soaking at 40°C for 30-60 minutes in a solution of wetting agent.

2. Desizing at 70°C for one hour with a liquor containing:
5 ml/l Bactosol MTN liq. (enzyme)
4 g/l common salt
0.5 g/l calcium chloride
1 ml/l wetting agent
3. Soda bath: treating with 3-4 g/l soda ash for one hour at 80°C. The
amount of soda ash may have to be increased depending on the
gum without impairing soft handle.
4. Boiling off: treating for 2-8 hours at 80°C with 8-10 g/l Marseilles
soap pH 9.5-10 with soda ash.
5. Rinsing at 50-60°C with 1 ml/l ammonia followed by cold rinsing.
Degumming Machines
Silk may be degummed in the form of hanks, or as hosiery or as woven
238
piece goods. The greater part of silk is treated in hank form. The machines
and equipment should be appropriate for the particular physical form, as the
silk material is very delicate and liable to be damaged even with little
mishandling.
When the degumming is to be carried out in hank form, it is allowed to
hang freely in the bath. During the process, the fibres swell and become
sticky, but the gum soon starts to dissolve and reveal the smooth, soft and
lustrous silk fibres. There are various methods for the treatment of hanks or
skeins of silk. One of the simplest methods is to suspend the silk on smooth
wooden rods in a rectangular vat of the soap solution and turn the hanks by
hand from time to time. Modern vats may be made of stainless steel instead
of wood. The silk may also be treated in two stages. The first stage of
degumming may take place in hank form on poles, after which the hanks are
packed in fabric bags or pockets. The hanks are stretched in between the
stages, thereby entanglements are removed and the handle and lustre are
improved.
In much improved hank-spraying machines (Figure 7.4), the hanks are
hung on perforated arms above the bath but are not immersed in it. The
chances of filament entanglement are thus minimised. The liquor is
circulated from the bath through the perforated arms holding the hanks. The
liquor enters into the hanks through the perforations and falls to the bath
below. The arms are occasionally turned. In foam boiling-off process, the
hanks hang from a rotating arm and are not submerged in the degumming
bath. The hanks are allowed to touch a concentrated soap bath, the foam of
which meets the silk and causes degumming.
In hank dyeing machines, the hanks are turned on a four-rod or double-
rod assembly of porcelain or stainless steel. The rotation of the rods can be
regulated. In these machines, hanks can be maintained in stretched
condition and thus, any entanglement can be avoided.
Though the principle of degumming silk fabrics is same as that for yarn,
the silk fabrics due to its fragile nature cannot be treated in rope form in the
ordinary way. The use of a stagnant bath will probably be best for sheer
delicate fabrics of silk. Silk fabrics cannot be safely treated in a jigger unless
the fabric has strong selvedges, but this will complicate the processing
because of rolling and of festooning across the weft. Differential shrinkage
and extension causes creasing and other irregularities.
In the simplest pack system, the fabric pieces are hung on bamboo or
smooth metal rods so that the goods remains submerged in the bath. With
many delicate fabrics, the simplest method of treatment is on the star frame
on which the fabric is wound and dipped into a soap bath. Well-known types
of star machines include:
• Vertical simple star in which the goods hang from above only.
239
• Vertical double star in which the goods are attached from below on
hooks as well as hanging from above.
• Horizontal double star used for very sensitive articles such as heavy
taffeta and tightly woven fabrics; also known as velvet star.
Depending on quality of the material, heavy shrinkage may occur during

degumming. Hence, the star machines are so designed that the hooks can
be moved along the arms of the star, thus allowing for shrinkage.
In continuous machines, there may be one or two large baths, depending
on their capacity. The goods are hung in loops on rods, which remain fully
submerged in the bath and move continuously forward. The fabric-fed is
carefully controlled to avoid creases. The protruding threads are
automatically cut off so that they do not catch on the rods and wind round
them. Using synthetic detergents, the treatment time can be reduced to
about one hour.
Degumming Faults
One of the difficulties encountered in degumming is that the reagents not
only remove the sericin and free parallel filaments of fibroin, but they also
penetrate the filaments. Due to an uneven structure, there is a danger of
separating the fibrillae. Further processing may break them, causing
lousiness of yarn. The broken filaments are apt to be of a much lighter
shade than the rest of the material after dyeing.
Improper treatments during processing may cause mechanical damage to
silk. As stated earlier, the silk threads can be very easily chafed at the
surface causing lighter shade after dyeing. The darker the colour, the
greater the contrast becomes visible. The material may have a chafed
surface or locally chafed marks, which appear like white particles, stuck to
the surface.
Weighing of Silk
Since silk is an elegant and expensive material, the substantial weight loss
during degumming is compensated wholly or partially by a process called
weighting. The degree of weighting is normally expressed by a term par –
10% below par means 10% lighter than original silk, while above par means
greater than original weight. More than 25% above par is common for
necktie silk. Silk may be weighted up to 300% of its original weight.
Weighting may improve certain properties of silk yarn such as [35]:
• Fullness and better handle

• Elegant lustre as in case of necktie silk
• Better flame retardancy
• Better washability, crease resistance and less splitting
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5% above par weighting with tin salt is sufficient for flame retardancy and
antistatic properties. Depending on the process and amount of weighting,
some disadvantages are:
• Lower dye affinity
• Brittleness and chances of yarn splicing
• Substantial strength loss and increased loss on storage
• Lower dischargability of dyes
At the beginning of 1980s, crepe woven fabrics and materials with
beautiful draping properties were in larger demand and weighting became
of less importance except for necktie fabrics. However, weighting may
become popular depending on fashion trends and fibre costs.
Different substances and materials are used for weighting of silk yarns
and fabrics, which can be broadly classified into three types, namely:
(a) Vegetable
(b) Mineral
(c) Polymers
The vegetable and mineral materials can also be combined.
Vegetable materials, namely tannins or special plant extracts (Persian
berries), are hardly used today. Such weighting may be combined with
dyeing by natural colour, such as logwood.
Mineral weighting with tin (IV) salt is still the classic method. Tin (VI)
chloride solution (19°Bé/30°Tw) is applied at room temperature for 60
minutes. After rinsing, it is treated in a second bath with disodium hydrogen
phosphate (6°Bé/9°Tw) at 60-70°C for 60 minutes. The material is washed,
acidified and treated in a third bath with sodium silicate (8°Bé/12°Tw) at
60°C for 60 minutes. The processing cycle may be repeated until the
weighting is adequate. Finally the fabric is washed and soaped. The
chemistry of reaction is not well established. The possible reactions are
[37]:
Sncl4 + 4H2O ↔ Sn(OH)4 + 4HCl (4.16)
Sn(OH)4 + Na2HPO4 Æ Sn(OH)2HPO4 + 2NaOH (4.17)
Sn(OH)2HPO4 + Na2OSiO2 Æ (SiO2)SnO2 + Na2HPO4 + H2O (4.18)
Recently various polymer treatments have been developed by a number
of research institutes. These weighting processes are mostly done by
polymer grafting.
Some silk processors have adopted these methods especially for
neckties silk. Experience has shown that up to 50% weight increase by
grafting with methacrylic amide in the presence of ammonium persulphate,
showed no appreciable impairment of handle. The polymer treatment also
modifies dyeing properties, hence it is not clear whether weighting should
be carried before or after dyeing.
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A working method on hank spray dyeing machine is as follow [35]:

An aqueous stock solution of 20% methacrylic amide and 1% ammonium
persulphate is prepared. The treatment bath is prepared with 10-20% of the
above solution and the material is treated at a M:L ratio of 1:4 – 1:10 at 50-
60°C for 2 hours. Depending on the M:L ratio and temperature, 40 to 200%
weighting can be obtained.
4.6 PREPARATION OF SYNTHETIC MATERIALS

The various processing stages of polyester, nylon and acrylic fibres are
described below:
4.6.1 Heat-setting of Synthetic Fibres

Unlike natural and regenerated fibres, the yarns and fabrics manufactured
from synthetic fibres require a special preparatory operation called heat-
setting. During this operation, the material is subjected to thermal treatment
in tensioned condition in hot air, steam or hot water medium. Unless this
treatment is done, these materials will shrink when treated with aqueous
solution in loose condition, and as a result the linear dimensions and the
shape of ready-articles change. The magnitude of shrinkage is dependent
upon structural parameters such as orientation and crystallinity of the fibres,
previous history of treatments and tensions applied, and external variables
like temperature, time and tension applied during shrinking. The amount of
thermal shrinkage exhibited by any particular fibre product reflects its
history: the draw-ratio, the tension developed during other processes and
any heat-treatment that has been applied. Unset fabrics also tend to form
creases, which are difficult to remove during subsequent processing.
Setting process releases the strains imposed during drawing, knitting or
weaving processes, minimises creasing during wet processing and imparts
high degree of dimensional stability. In order to achieve a satisfactory
degree of set in synthetic thermoplastic fibres such as polyester and nylon, it
is necessary to supply sufficient energy to the fibre to weaken or to break
inter-chain bonds and allow new bonds to be formed whilst the material is
held to optimised dimensions. Thus the material must be heated to a
temperature close to the thermoplastic point of the fibre and some degree of
widthways or lengthways tensions are normally imposed on the fabric.
The setting process consist of two stages [38]:
1. Heating of the material to a specific temperature depending on the
fibre type, ensuring breakage of intermolecular bonds and equalising
internal stresses in chains.
2. Cooling of the material resulting in the restoration of intermolecular
bonds, the fibre being in new state, free from internal stresses. The
242
quicker the cooling and the lower the temperature, the better is the
stabilisation effect.
The main techniques of setting are [38]:
1. Dry-heat setting (or simply, heat-setting/thermo-setting)

2. Steam-setting
3. Hydro-setting
Dry-heat setting is generally carried out on synthetic fabrics in pin or clip

stenter machines equipped with one or more heat-setting sections in which
a temperature of approximately 170-230°C can be maintained either by
indirect oil or electrical heating.
Steam and hydrosetting are used mainly for setting of yarns such as
nylon. Saturated steam as the setting medium is probably most widely used
on garments, but is also applicable for certain types of knitted fabric. Steam
setting is carried out by using saturated steam at a pressure of 10-25 psi for
nylon 6,6 and 5-15 psi for nylon 6. Flash heating of material is avoided as
this can cause variation in dye affinity. The moisture in the steam is
controlled within a small limit. The principal difference as far as the dyer is
concerned, is that the steam setting reduces the rate of dyeing much less
than that with dry heat-setting. On the other hand, the steam-set dyed
fabrics have slightly less wash fastness than that of dry-heat set fabric.
Since dry-heat setting reduces dyeing rate, small variations in heat-setting
conditions may gives rise to unevenness during subsequent dyeing,
commonly known as barre effect.
Recently steam injection stenters have become increasingly popular. In
these machines, high-pressure steam is injected and they offer the following
advantages:
1. By expelling air from the setting chambers, the oxidative

degradation, stiffening and yellowing of nylon is minimised.
2. The rate of heat transfer to the fabric is increased.
3. Higher setting temperatures can be attended without hampering
fabric qualities, thereby the materials can be run at higher speed with
shorter dwell period.
The upper limit of the heat-setting temperature is determined by the

temperature of fibre softening, while the lower limit is determined by the
minimum temperature necessary for destroying a certain part of
intermolecular bonds. The lower limit for polyamide and polyester is about
100°C. The lower the temperature, the longer should be the time of
treatment.
243
Substances promoting fibre swelling cause a partial destruction of

intermolecular bonds and loosening of the structure. Consequently, a lower
temperature is required for heat-setting of swollen fibre. These substances
include water and, therefore, steam setting or hydrosetting is carried out at a
lower temperature than that for dry heat-setting.
Stabilisation is a reversible process. The greater the difference between
the stabilisation temperature and the temperature to which it is to be
processed, the higher will be its dimensional stability. For example, if setting
is carried out in boiling water at 100°C, the stabilisation will complete
disappear after subsequent treatment in boiling water, but will be maintained
if setting was carried out in steam at 130°C. The fabric may be subjected to
setting at various stages of processing, namely grey state, after scouring or
after dyeing during finishing. If grey heat-setting is done, heating energy can
be saved as the fabric is at dry state, while after scouring or dyeing the
fabric is to be dried before heat-setting. However, during grey heat-setting,
the impurities present in the fabric like size, lubricants and other substances
will be firmly embedded in the material and will be difficult to remove during
scouring. The optimum conditions for setting various textile fibres in water,
steam and dry-air are shown in Table 4.7 [13].
Table 4.7 Optimum Temperature and Time for Setting of Textile Fibres
In water In steam In hot air
Fibre °C Minutes °C Minutes °C Minutes
Triacetate – – – – 190-220 0.5-2
Nylon 6 100 120-180 108-121 10-30 175-190 0.25-0.5
Nylon 6,6 100 120-180 115-130 10-30 190-215 0.25-0.5
Polyester 100 120-180 140 10-30 180-220 0.33-0.66
The difference of the setting process of triacetate, as compared to those of

nylon and polyester, is that there is very little tendency for the yarns to
shrink on heat-setting. This means direct-contact heat-setting machines
such as heated cylinders can be used to a greater extent for triacetate than
for other synthetic polymer fibres.
Heat-setting processes result in increase of density and crystallinity of
nylon. Application of tension assists in development in crystallinity. When
heated under tension, the orientation increases. Crystallinity and crystal size
increases more readily at a low temperature for steam-set samples as
compared to dry-heat set samples [38]. The modulus of the fibre increases
on dry-heat setting and it decreases with steam setting. Steam setting
increases dye uptake of nylon and decreases on dry heat setting.
Steam and hot water can serve as excellent media for the setting of nylon
as the setting can be achieved at significantly lower temperatures and
consequently less fibre discoloration or stiffening occurs. Nylon materials
244
can be relaxed in hot or boiling water. However, the setting is done under
some degree of restraint in order to conform to dimensional requirements
and to avoid fabric creasing. Nylon materials can be treated with saturated
steam in autoclave. Weft-knitted fabrics are calendered to approx. 2 inches
higher than the required finished width and batched under slight tension
onto perforated tubes prior to loading in autoclave. The setting circle
commences by a vacuum extraction followed by injection of saturated steam
at the desired temperature for 10 minutes. This is followed by vacuum
extraction and a further prolonged steaming cycle of 10 minutes. For nylon
hose and tights, autoclaving under the same conditions is done for only 1-3
minutes.
Polyester yarns are normally set by relaxation in saturated steam. Short-
staple polyester yarns are commonly twist-set by steaming them whilst they
are still on the spinner’s ring tubes and the temperature should be restricted
to 110°C to avoid distortion of the tubes. Some 3-4% shrinkage can be
tolerated in cheese type packages. However, yarns with high potential
shrinkage, such as ordinary polyester filament yarns, and yarn containing a
component (e.g. viscose) that swell in the dyebath, must be heat-set before
winding. Yarn steaming is carried out in an autoclave fitted with a vacuum
pump, so that the chamber can be evacuated before and after steaming.
Pre-evacuation aids the penetration of the yarn package by the steam. The
sequence of evacuation-steaming-evacuation may be repeated. Polyester
garments and hosiery can be stabilised by the above steaming process.
Different varieties of polyester fabrics are normally set by dry-heat. The
sequence, scour-heatset-dye is the safest and most satisfactory for all types
of goods. However, setting being in the central position of processing
sequence, the expense of drying would be higher as the fabric is to be dried
twice.
For materials that are perfectly clean in loom-state, it is possible to use the
sequence, heatset-scouring-dyeing. The sequence is very useful for warp-
knitting industries. When heat-setting is a final process, as in the routine
scour-dye-heatset, the conditions of the setting may alter the handle of the
fabric.
Clip stenters and pin stenters are used for heat-setting, but the latter is
preferred for the purpose, because of its versatile dimensional control. The
conditions chosen for stentering vary considerably between different types
of polyester materials as shown in Table 4.8 [38].
The high thermal shrinkage of typical unset polyester filament materials
leads to a thin and impoverished handle when high tension is applied. The
best uniform finished effect is produced by restraining 4-5% of the potential
shrinkage and by allowing an increasing degree of relaxation shrinkage to
take place in the stenter. Staple-fibre fabrics shrink less than filament
fabrics. For worsted spun goods, 3-5% relaxation shrinkage is allowed in
245
both warp and weft. The free weft shrinkage of a typical polyester-cotton
shirting fabric is 4% at its normal setting temperature, but this is restrained
by 2-3% to ensure the removal of creases and to gain control over weft
straightness [39].
Table 4.8 Heat-setting Conditions for Different Polyester and Blended

Fabrics
Type of Fabric Temp. (° C) Time (Seconds)
100% Polyester 180-220 20-40

Texturised 160-180 30
Polyester-cotton 190-210 20-40
Polyester-wool 170-190 30
Polyester-acrylic 190-200 30-60
Cationic dyeable 170-180 20-40
The initial increase in the heat-setting temperature causes a decrease in

the uptake of disperse dye. After reaching a minimum dye uptake, in the
temperature range of 170-200°C, the dye uptake increases. The initial
decrease in uptake may be due to lowering of amorphous volume per crystal
as a result of coming closer of parallelised chains in the amorphous region
during formation of new crystals. In the later stages of crystallisation, the
crystallites increase in size and become perfect. Consequently, the
amorphous region per crystal increases. In the temperature range of 180-
200°C, the dye uptake is less sensitive to heat-setting temperature. Hence,
the variation in dye uptake due to local fluctuations of temperature will be
lowest. Therefore, this is the most preferred temperature range for heat-
setting of polyester materials.
Acrylic and modacrylic fibres cannot be heat set in the conventional sense
since the fibres are readily stretched or deformed at temperatures above
approx. 75°C. A degree of stability, which is sufficient for practical
purposes, can be achieved by passing such fabrics through a stenter at
120°C. Higher temperatures may be required when processing blends of
acrylic or modacrylic fibres. Knitted fabrics produced from a feeder blend of
acrylic and texturised polyester fibres, for example, are usually heat set at
about 160°C. Certain acrylic and modacrylic fibres are very sensitive to
heat, and the temperatures above 120°C, or even lower temperatures may
cause discoloration if treatment time is lengthy [40].
The handle of acrylics bears a greater resemblance to wool than that of
any other man-made fibre. High bulk yarns, which have great appeal for
certain purposes, can be made from polyacrylonitriles. When the fibres are
hot-stretched, the whole of the elongation is not stable and, under the
influence of steam, a relaxation of between 15% and 20% takes place.
246
Thus, if stretched and unstretched filaments or staple are spun together and
subsequently steamed, one component will shrink and the other will not.
This brings about a buckling effect in the non-contracting component,
causing the yarn to increase considerably in bulkiness.
4.6.2 Scouring of Synthetic Fibres

The scouring procedures for synthetic fibres are relatively simple since the
fibres contain fewer impurities, most of which have at least some degree of
water solubility, the most important being sizes and lubricants. The major
sizes used are polyvinyl alcohol, carboxymethylcellulose and polyacrylic
acid, all of which are completely or partially water-soluble.
Scouring of Acetate Fibres
Secondary acetate and triacetate fibres can be scoured with soap or
synthetic detergent usually at 60-75°C, this being sufficient to remove soil,
oil, colouring impurities and any antistatic agents. Anionic synthetic
detergents such as polyoxyethylene sulphates are preferred for all synthetic
fibres that are to be subsequently dyed with disperse dyes, since nonionic
detergents with low cloud point may hamper stability of disperse dyes at
high temperature. Addition of a sequestering agent will be helpful for hard
water. In case of fabrics, relaxation of knitting or weaving tensions occurs
during scouring under minimum tension at high temperature.
For acetate fibres, normally alkali should not be used as these ester fibres
may get hydrolysed. The secondary acetate loses its lustre by excess alkali.
A finish called S-finish is applied on triacetate fibres in which the material is
treated with 3 g/l caustic soda solution for about 1½ hours at 80-90°C [39].
The process reduces acetyl content of the fibre from its normal 62% to 59%.
The saponification mostly occurs at the surface and thus gives rise to a thin
skin. The advantages claimed are improvements in handle and drape,
resistance to soiling and glazing-stiffening during ironing, antistatic
properties, gas fading fastness, wet and dry rubbing fastness.
Scouring of Nylon
Polyamide and polyester fibres are generally adequately scoured using an
alkyl polyoxyethylene sulphate and sodium carbonate.
With polyamides or nylons, nonionic synthetic detergents (1.5-2 g/l) with
the addition of an alkali (0.5—1.5 g/l sodium carbonate or trisodium
phosphate) are suitable. Anionic detergents like fatty alcohol sulphonates
behave like acid dyes and are adsorbed by the fibre. Their presence on the
fibre will slow down dyeing and may reduce the exhaustion of the dyebath. If
the material is to be dyed with acid dyes, a nonionic detergent is to be used.
Clariant recommends the use of crypto-anionic (i.e. anionic/nonionic hybrid
247
surfactants) ethylene oxide condensate or modified polyglycol ether with or

without solvent (Imerol XI and Sandopan DTC of Clariant). The presence of
solvent imparts stain-removing properties. When scouring is carried out in
jet dyeing machines, low-foaming detergents should be used, as excessive
foam generated would create problems in subsequent dyeing process.
When hard water is used for scouring, some salts of heavy metals may be
retained by nylon fibres, presumably by combination with the free carboxyl
end-groups, which the fibre contains. The temperature of scouring varies
according to whether the material is already heat-set or not, being 70-80°C
for the unset and 95-100°C for heat-set. High temperature may cause
deterioration of the setting. For heavily soiled materials, scouring is
preferably done before heat-setting in order to avoid setting in of the
contaminants, however, the unset materials are prone to distortion and
creasing.
If cationic spin-finish is present, the material is to be subjected to an acid
wash at 50-60ºC for 20 minutes with 1-2 g/l nonionic wetting agent (e.g.
Sandozin NIS, Clariant) and 1-2 ml/l formic acid (85%).
After scouring, the nylon fabric should be washed thoroughly before drying
and heat-setting. The fabric should not be dried unevenly after scouring and
before heat-setting, as this could lead to irregular results in dyeing,
particularly with anionic product.
Scouring of Polyester
It is not always necessary to scour polyester fibre materials before dyeing.
Loose stock, slubbing and some types of yarns are supplied in clean state
and usually bear low quantities of processing aids which are compatible with
disperse dyes. Such products can be simply washed with water or may even
allowed to remain in the dyebath. However, some products are heavily
soiled, waxed or sized. Some may contain cationic processing aids. These
must be removed before dyeing. If sizing agents are not removed easily, an
additional step of enzymatic desizing is to be carried out. The processor
should know the exact contaminants present and take appropriate action.
For most normal purposes, the scouring bath should have 1-2 g/l
synthetic detergent or soap (alone or admixture with nonionic surfactant)
and 2 g/l soda ash. For lightweight materials in rope form or unset filament
materials, the temperature should be below 60°C. For other materials,
scouring may be done at boil for 20-30 minutes or 4 to 5 ends in a jigger.
For heavily soiled materials, the scouring time should be extended.
Otherwise the soiled scouring liquor should be dropped and the process is
to be repeated with a fresh bath. A soil-suspending agent like sodium
tripolyphosphate may be added.
The same conditions may be maintained for polyester-viscose blends. For
blends with cotton and linen, the concentration of alkali should be doubled.
248
For pad-steam or pad-roll processes of polyester-cotton blends, the

padding liquor should contain 20-40 g/l soda ash and 5-8 g/l detergent. For
heavier polyester long-staple fabrics or polyester-wool worsted fabrics,
scouring may be done in rope form in dolly or a similar scouring machine.
The worsted fabrics require somewhat vigorous scouring than all-wool
fabrics. The scouring may be done with 3-4% (o.w.m.) soap and 20-30 g/l
soda ash at room temperature for 20-30 minutes, followed by rinsing at
40°C. The process may be repeated two to three times.
Nowadays some polyester fibres are subjected to causticisation
treatments with sodium hydroxide in the presence of a cationic surfactant to
give a lighter fabric with a silkier handle. The process causes localised
saponification of polyester surface.
Scouring of Acrylic Fibres
For acrylic fibres, anionic surfactants should be avoided, because they may
restrain the uptake of basic dyes. These fibres are scoured with an
ethoxylated alcohol, either alone or with a mild alkali such as sodium
carbonate or phosphate. The removal of lubricants (frequently anionic), oil
and dirt prior to dyeing is recommended and sometimes essential. The best
method depends on the type and quantity of substances to be removed.
Sometimes a short cold rinse is sufficient. Usually a weak alkaline treatment
with nonionic detergent (0.5-1% o.w.m.) and ammonia (0.5-1% o.w.m.) may
be carried out at 80°C. Phosphates can be used as an alkaline agent.
Addition of a solvent-based detergent helps removal of oil and grease, if
present. After scouring, a thorough rinse at 50-60°C is necessary to remove
any residual alkali.
REFERENCES
1. N.K. Lange. 2000, International Dyer, February, 18-21.
2. S.R. Karmakar. 1999, Chemical Technology in the Pre-treatment Processes of
Textiles, (Amsterdam, Netherlands: Elsevier).
3. H.K. Rouette. 2001, Encyclopedia of Textile Finishing, Vol. 3 (Amsterdam, Holland:
Springer)
4. R.S. Bhagawat. 1991, Colourage, XXXVIII (1), 57-66.
5. Cavaco-Paulo and G.M. Gübitz (Eds.). 2003, Textile Processing with Enzymes
(Cambridge, UK: Woodhead).
6. E.J. Nolan. 1998, Colourage Annual, 87.
7. V.A. Shenai. 1984, Technology of Bleaching, (Vol. III), 4th Edn (Bombay, India: Sevak
Publications)
8. Holmes. 1998, Colourage Annual, 41-56.
9. Y. Li, and I.R. Hardin. 1997, Text. Chem. Colorist, 30 (9), 23-29.
10. Enzyme Technical Association. 2000, TCC & ADR, 32 (1), 26-27.
11. H.P. Weber and J. Ströhle. 1997, International Dyer, March, 9-13
249
12. J.T. Marsh. 1979, An Introduction to Textile Bleaching (New Delhi, India: B.I.
Publications)
13. R.H. Peters.1967, Textile Chemistry, Vol. II (Amsterdam, Netherlands: Elsevier)
14. J. Shore (Eds.). 1995, Cellulosics Dyeing (Bradford, UK: SDC)
15. Sandoz (India) Ltd. 1982, Colour Chronicle (April/June), 6.
16. K. Dickinson. 1987, Rev. Prog. Coloration, 17, 1-6.
17. ISI Handbook on Textiles, SP: 15-1981 (New Delhi: Bureau of Indian Standards,
1981).
18. E.R. Trotman. 1968, Textile Scouring and Bleaching (London, UK: Charles Griffin).
19. M. Lewin and S.B. Sello (Eds.). 1983, Chemical Processing of Fibres and Fabrics, Vol.
1. In: Fundamentals and Preparation, Part A, (New York: Marcel Dekker).
20. D. Angstmann and M. Bradbury. 1998, International Dyer, March, 11-18.
21. S. McCaffrey and G.K. Santokhi, JSDC , 115 (1999) 167-172
22. K. Sawada, S. Tokino, M. Ueda and X.Y. Wang, JSDC, 114 (1998) 333-336.
23. K. Sawada, S. Tokino, and M. Ueda, JSDC, 114 (1998) 355-359.
24. Y. Li, and I.R. Hardin, Text. Chem. Colourist, 29 (8) (1997) 71-76.
25. S.R. Karmakar. 1998, Colourage Annual, 75-86.
26. P. Ney. 1982, Melliand Textilber., 63, 443.
27. S. Graif. 1996, Textilveredlung, 77, 594. Reported by W.B. Achwal, Colourage, XLIV
(1997) 29-31.
28. J.T. Marsh. 1979, Mercerisation (New Delhi, India: B.I. Publications, by arrangement
with Chapman and Hall Ltd, London).
29. W. Schumacher. 1998, Colourage Annual, 135-140.
30. D. Hazard. 1994, International Textile Bulletin, 40 (3), 50-56.
31. Textile Recorder. 1964, 81, 69.
32. J. Shore (Eds.). 1990, Auxiliaries, Volume 2. In:Colorants and Auxiliaries, (Bradford,
UK: SDC).
33. Ryberg. 1934, Am. Dyestuff. Rep., 23, 230.
34. Bearpark, F.W Marriott and J Park. 1986, A Practical Introduction to the Dyeing and
Finishing of Wool Fabrics (Bradford, UK: SDC).
35. Silk and Colour.1985, Brochure No. 9307.00.88 (Bastle, Switzerland: Sandoz Ltd).
36. F. Grove-Palmel. 1928, Oil and Fat Ind., 5, 194.
37. F. Sadov, M. Korchagin, and A. Matetsky. 1978, Chemical Technology of Fibrous
Material (Moscow, USSR: Mir Publisher).
38. A.L.N. Rao and R.S. Gandhi. 1991, Orientation Programme in Chemical Processing
for Senior Executives, Book of papers, The Textile Association (India), Bombay, p 58.
39. D.M. Nunn. 1979, The Dyeing of Synthetic-Polymer and Acetate Fibres (Bradford, UK:
SDC).
40. P. Cusack. 1975, Rev. Prog. Coloration, 6, 13-17.
Chapter
Preparatory Processes II
(Whitening) 5
5.1 INTRODUCTION
After desizing and scouring processes, the textile materials are in very
absorbent form and can be dyed without much problem. But the materials
are still yellowish or brownish in colour, which may affect the tone and
brightness of the shade obtained by dyeing, particularly for light shades. For
white goods, the degree of whiteness required is much more stringent.
Whiteness of scoured goods is far below satisfactory because none of the
above preparatory processes can remove the colouring matters. The textile
substrates possess these substances naturally, or these may be acquired
from the substances added to facilitate processing or dropped accidentally.
The quantities of such materials are normally very negligible but they are
firmly embedded into the textile materials. Their removal requires a special
step of preparatory process called bleaching. The main object of bleaching
is the removal and/or destruction of natural and adventitious colouring
matters with the production of pure white materials. The natural colouring
matters present in various textile materials are different. But a method of
bleaching may be suitable for a number of textile fibres, though the
conditions and the extent of bleaching required may be different in different
cases. For example, Egyptian cotton is darker in colour and more difficult to
bleach as compared to American varieties. One must be careful while
choosing the bleaching agent as the textile material may be damaged in the
presence of a particular bleaching agent, under certain pH range and
temperature.
In a broader sense, the term bleaching encompasses a series of
operations designed to produce a clean, white material including three
distinct processing stages, namely desizing, scouring and whitening. The
first two stages have already been discussed in the last chapter.
Cotton contains portions of the husks of the cotton ball, called motes,
which are trapped between the cotton fibres during picking. During ginning
these motes are further reduced in size and entangled with the fibres.
Caustic scouring softens, decolourises and erodes some of these particles,
251
allowing their removal during the washing operation following scouring and
bleaching; other particles simply get bleached and remain in place.
Bleaching agents convert coloured impurities into colourless particles.
Colour is imparted by a chromophore, i.e. a moiety usually involving
alternating carbon-carbon single and double bonds. Bleaching destroys
these double bonds by addition (saturation) or rupture. Once the free
electrons of a double bond are tied by substitution or by rupturing the double
bond, electromagnetic radiation is not absorbed and is reflected in the
visible region of the spectrum and colour ceases to exist [1].
Sun bleaching was the main form of whitening until the Romans used the
fumes of burning sulphur to bleach wool. Until the middle of 18th century,
the Dutch virtually had monopoly of bleaching in Europe. The Dutch method
of bleaching of linen consisted of steeping for several days in liquor made
alkaline with the extract of burned seaweed. The cloth was then well rinsed
till clean and spread on grass fields for sunlight and air exposure for several
weeks. These operations are called bucking and crofting respectively. These
two processes were repeated five or six times, after which the cloth was
soaked in sour buttermilk for several days, rinsed well and crofted again.
The whole sequence of processes was repeated once or twice until the
desired degree of whiteness was obtained. In 1756 or thereabout, sulphuric
acid replaced buttermilk and the steeping time for souring was reduced from
8 weeks to 12-24 hours.
Many coloured compounds, when acted upon by reducing agents,
become colourless due to structural modification. The oldest such
substance used for bleaching of wool, and to a lesser extent for silk, is
sulphur dioxide. The Romans used to stretch cloth on a cage-like frame
followed by burning sulphur underneath the frame. The degree of whiteness
was adequate, but lacked permanence. Moreover, this was not useful for
cellulosic materials.
The discovery of chlorine by Scheele in 1774 and the observation of its
bleaching action revolutionised the methods of treating linen and cotton. In
1799, Tenant commercially manufactured bleaching powder by the use of
dry hydrated lime and chlorine gas in Glasgow. Since around 1830,
bleaching powder is the chief agent for the bleaching of vegetable fibres.
Labarraque commercially manufactured the solution of chlorine in aqueous
caustic soda solution in 1820.
In the late 1890s, a firm later known as Dupont first produced peroxide
bleached materials. Their sodium peroxide process was mainly for wool and
silk. The electrolytic process for manufacture of hydrogen peroxide was
developed in the 1920s and by 1930, several mills were experimenting with
peroxide bleaching.
Bleaching with peroxides seems to have passed through three phases in
its history, the first being the early use of barium peroxide and the solutions
252
of hydrogen peroxide which could be made from it. This came to an end at
about 1912, when sodium peroxide became available in commercial
quantities. Since about 1927, however, the concentrated solutions of
hydrogen peroxide are being manufactured from various routes. It fact, it is
the only oxidative bleaching agent for wool and silk, but is also safe for all
textile fibres – hence the name universal bleacher.
Since its introduction as a commercial product in 1939, sodium chlorite
has achieved an ever-increasing place amongst the bleaching agents for
cellulosic fibres, especially linen. Sodium chlorite is active under acidic
condition. Hence, this is useful for white cotton goods where the natural
softness can be preserved by eliminating scouring process. With the
invention of synthetic fibres, especially polyester, sodium chlorite gained
popularity as a bleaching agent. These fibres are unstable in alkaline
conditions under which other bleaching agents are normally applied.
Peracetic acid, made available in 1948 by BECCO, is widely adopted for
bleaching polyamides and acetate rayon.
Even after bleaching, the whiteness may fall short for white goods.
Whiteness can be further enhanced by treating with a blue pigment or dye,
which suppresses the yellowish tinge of the materials, or with an optical
brightening agent, which allows more light reflection from the textile surface
by converting ultra-violet light of the illuminating source into visible light.
5.2 REDUCTIVE BLEACHING AGENTS

Many colouring matters can be reduced to colourless compound by reducing
agents. However, on exposure to air and sunlight, the reduced colourless
components get oxidised and the yellowish tint reappears.
Before the invention of hydrogen peroxide, sulphur dioxide was the only
bleaching agent for wool. Woollen goods were exposed to sulphur dioxide in
an enclosed chamber called stove, and the process was known as stoving
[2]. The goods are scoured and hydroextracted, and in wet condition hanged
on wooden poles inside the chamber. The chambers are made with acid-
resisting cement and specially made bricks, or with a wooden double wall
filled with sand in between. No metallic parts like iron nails should be
incorporated. The material is loaded through a small front door and the
residual sulphur dioxide gas is removed through an exhaust fan at the back
of the stove. The front door has sufficient ventilation to allow enough air to
enter so that the sulphur kept in a pot in one corner of the chamber burns
slowly over a period of 6 to 8 hours. The exposure is generally done for
about 8-12 hours.
The goods should be slightly alkaline before the treatment, as under acidic
or neutral condition there will be very little bleaching. The material should be
253
uniformly wetted. Low moisture will cause local drying, while too wet cloth
will cause draining to the lower part of the load. The presence of
adventitious dirt or traces of iron will cause brown staining. The roof of the
chamber should be insulated, as water condensed on the roof reacts with
sulphur dioxide forming sulphuric acid, which falls on the material causing
formation of holes. Some baffle plates are to be placed over the sulphur
oven, which prevents deposition of sublimed sulphur on the cloth surface.
At the end of treatment, the material is to be treated with 1-2% of sodium
sulphite at 40°C. Sulphur dioxide is converted to sodium bisulphite, which is
readily removed by washing. Sodium carbonate should not be used, as the
material will be slightly discoloured.
The method is primitive, but quite efficient. However, stoving may create
several practical problems such as incomplete bleaching due to shortage or
incomplete burning of sulphur, uneven bleaching due to poor circulation of
sulphur dioxide gas, etc.
After the commercial production of sodium hydrosulphite or sodium
dithionite in 1905, it has become the most widely used reducing agent in
textile bleaching and dyeing. As it is in solid form, it more convenient to
transport, store and handle as compared to gaseous sulphur dioxide.
The sodium dithionite is manufactured by first passing sulphur dioxide
through an aqueous suspension of zinc dust.
Zn + 2SO2 = ZnS2O4 (5.1)
The zinc dithionite thus formed, is treated with caustic soda or soda ash,
when zinc hydroxide or carbonate is precipitated leaving an aqueous
solution of sodium dithionite.
ZnS2O4 + 2NaOH = Na2S2O4 +Zn(OH)2 (5.2)
The filtrate is further purified and treated with a mixture of common salt
and alcohol, when needle-shaped crystals of sodium dithionite will separate.
The crystals are dehydrated at 60°C.
Another method of commercial production is based on the reaction
between sodium formate and sulphur dioxide, or alternately between
ammonium formate and sodium metabisulphite.
Na2S2O5 + H.COONH4 ↔ Na2S2O4 + (NH4)HCO3 (5.3)
Sodium dithionite is reasonably stable, provided it is kept in dry and cool
surroundings. When acted as a reducing agent in aqueous solution it is
converted into sodium bisulphate.
Na2S2O4 + 4H2O = 2NaHSO4 + 3H2 (5.4)
254
The best bleaching action is obtained at 50°C at a pH of 7. The solution is

very unstable unless the pH is above 10. However, excess caustic soda
may convert it into sodium sulphide and sulphite.
3Na2S2O4 + 6NaOH = Na2S + 5Na2SO3 + 3H2O (5.5)
During preparation of the solution, water should not be added into the
powder, but the powder itself is to be sprinkled into water preferably in the
presence of soda ash. Faster bleaching or stripping of dyes can be obtained
at higher temperatures.
Animal fibres, wool and silk can be bleached with 4 g/l sodium dithionite at
40-50°C in the absence of any metal other than stainless steel. Iron or
copper salt, if present, will be reduced to their respective sulphides causing
greyish coloration, which are very difficult to remove. No open steam pipe
should be attached to the vessel as rust may enter into the vessel along with
steam. The material should be completely immersed in the liquor, if required
with the help of wooden rods. The bath is allowed to stand for 4-6 hours,
after which the material is rinsed thoroughly. The reductive bleaching of
wool is mostly carried out with stabilised dithionite at pH 5.5-6.0.
When sodium or zinc formaldehyde sulphoxylate is used, the bleaching is
carried out at pH 3 and the temperature is maintained at 90ºC for 30
minutes. The process tends to make the handle of wool harsher and leave
sulphurous odour.
For upgrading the base colour of naturally yellow carpet wool before
dyeing, acid reductive bleaching may be carried out. After bleaching the
bath is to be boiled for 15 minutes to destroy the residual reducing agent.
The dye is then added directly in the bleach bath and normal dyeing process
is carried out. The process is effective for producing bright pastel shades on
wool.
Sulphur-containing bleaching agents may damage cystine groups of wool.
A safer and effective reductive bleaching agent is thiourea dioxide,
(NH2)2C=SO2 , which can be applied at pH 7 at 80ºC for one hour. A
sequestering agent must be included in the bath, to prevent metal-catalysed
decomposition of this reductive bleach. It has less effect on the physical
properties of the fibre than other reductive bleaches. The active bleaching
species in thiourea dioxide bleaching is sulphinic acid.
(NH2)2C=SO2 + H2O Æ (NH2)2C=O + H2SO2 (5.6)
Arifoglu and Marmer described [3] a novel oxidative-reductive bleaching
system, which involves first bleaching with hydrogen peroxide for 60 minutes
at 60º C and then adding thiourea, adjusting pH to 4.5-5.5 to generate
thiourea dioxide in situ.
H2N-C(SH)=NH + 2H2O2 Æ (NH2)2C=SO2 + 2H2O (5.7)
255
The reduction bleaching is carried out with thiourea dioxide, thus

generated, for 25 minutes at 60º C followed by washing.
However, this method may cause considerable wastage of reductive agent
due to large excess of hydrogen peroxide usually left in the bleach bath.
Moreover, thiourea (not thiourea dioxide) is classified as carcinogenic.
In an alternate method, after peroxide bleaching, organic catalysts are
added to decompose the residual peroxide. Iron or copper salts may cause
excessive damage and discoloration of wool, while Co2+ is the only cation
reported to cause no damage or discoloration. Thiourea dioxide or methane
sulphinate is then directly added to the bath with necessary pH adjustment.
Thiourea may be replaced with trisodium salt of trithiocyanuric acid
(TTCA, s-triazine-2,4,6 trithiol i.e. 3 sulphur ions on carbon atoms in triazine
ring). It is not carcinogenic, but more expensive than thiourea [4].
5.3 OXIDATIVE BLEACHING AGENTS

Oxidative bleaching agents are used much more than reductive bleaching
agents. Earlier atmospheric oxygen was utilised in dew bleaching process.
The medial process of bleaching was to lay the material out in a field for
exposure to air and sunlight. In ancient days this slow process was the only
method for bleaching of cotton and linen goods.
Slow atmospheric oxidation is not commercially viable. Hence, a number
of chemical oxidation processes are being utilised for bleaching of various
textile fibres. The most important oxidative bleaching processes are:
1. Hypochlorite bleaching,
2. Hydrogen peroxide bleaching,
3. Sodium chlorite bleaching.
5.3.1 Hypochlorite bleaching

Hypochlorite bleaching is a low-cost process using simple chemicals. It may
be carried out in small as well as large batches of fabric in a variety of
machines. However, the process suffers from several disadvantages:
1. There is a risk of fabric damage if the pH is low.

2. The process is slow and is to be carried at low temperature. Hence, it
is difficult to carryout as rapid continuos operation.
3. There is a chance of yellowing of bleached fabric on storage.
4. Relatively high concentration of chlorine and salt in the effluent
process water is objectionable from ecological point of view [5].
Two chemical compounds are utilised in hypochlorite bleaching –
bleaching powder and sodium hypochlorite. The bleaching mechanism with
256
chlorine-containing compounds is based on saturation or rupture of double

bond. The first mechanism is hydroxychlorination to a chlorohydrin (Eqn.
5.8), the second mechanism is chlorination to form 1,2 dihalide (Eqn. 5.9)
and a third mechanism involves oxidation by electrophilic substitution, which
destroys carboxyl chromophores [1].
Bleaching powder is commercially manufactured by treatment of chlorine
gas with slaked lime. Sodium hypochlorite as a bleaching agent has virtually
Cl OH
C=C + HOCl Æ C C (5.8)
Cl Cl
C=C + Cl2 Æ C C (5.9)
replaced bleaching powder, which varies considerably in composition and

also is difficult to dissolve. Sodium hypochlorite is available as a clear
solution and contains about 14-15% available chlorine. It may be prepared
by electrolysis of sodium chloride when chlorine gas and sodium ion is
formed. The latter reacts with water forming caustic soda. The cathode and
anode are kept in close proximity so that the chlorine gas liberated reacts
immediately with caustic soda forming hypochlorite and chloride of sodium
(Eqn. 5-10).
2NaOH + Cl2 = NaOCl + NaCl + H2O (5.10)
Sodium hypochlorite can also be prepared by the action of gaseous
chlorine with a solution of caustic soda. The reaction is same as the
electrolytic process with a large amount of sodium chloride remaining as a
by-product. The reaction should be carried out at a temperature below 27°C
as at high temperature a useless by-product, sodium chlorate forms.
6NaOH + 3Cl2 = 5NaCl + NaClO3 + 3 H2O (5.11)
The chlorine gas is passed through 20% solution of sodium hydroxide at a
rate that the available chlorine content will be about 14-15% within 5 hours.
The tank is made of cement or steel, lined with vinyl chloride. To keep the
temperature below 27°C, cooling coils made of titanium can be immersed in
the liquid. For adequate stability, the final pH should not fall below 11 either
with unconverted caustic soda or with soda ash used as an admixture. In
continuous manufacturing process, the feed of chlorine gas is regulated by
redox-operated control.
257
Estimation of Chlorine
An approximate method of estimation of available chlorine from the °Tw,
measured with a hydrometer is shown in Table 5.1.
Table 5.1 °Tw vs. available chlorine of Bleaching Powder Solution
°Tw Available Chlorine (g/l)
0.5 1.40
1.0 2.71
2.0 5.58
5.0 14.47
10.0 29.6
15.0 45.7
20.0 61.5
A simple method of estimation of hypochlorites as available chlorine is

titration with sodium thiosulphates, though the estimate falsely includes
chlorates as available chlorine.
About 25 ml of sample is diluted with 500 ml water of which 5 ml is taken
in a conical flask containing approx. 50 ml water. A few crystals of
potassium iodide are added followed by dilute acetic acid, when a quantity
of iodide equivalent to the available chlorine will be liberated. This is titrated
with N/10 sodium thiosulphate (24.815 g crystalline thiosulphate per litre)
until a pale straw tint appears. Some soluble starch is added when a deep
blue colour appears, which is discharged by further titration with thiosulphate
solution.
1 ml N/10 sodium thiosulphate ≡ 0.00355 g of available chlorine (5.12)

The error due to chlorates may be avoided by titrating with N/10 sodium
arsenite solution (made by dissolving 4.95 g of pure arsenious oxide and 25
g of crystalline sodium carbonate in 200 ml of water). A quick method of
estimating available chlorine is to measure the pressure generated by the
oxygen liberated by reaction of hypochlorite with hydrogen peroxide.
Effect of pH and Temperature
Being a salt of weak hypochlorous acid with an electrolytic dissociation
constant equal to K = 3.4 × 10-8, sodium hypochlorite is hydrolysed in
aqueous solution as follows:
NaOCl + H2 O ↔ HOCl + NaOH (5.13)
As a result, in spite of alkaline reaction (the pH of 0.01 N solution of
NaOCl is 9.7), solutions of sodium hypochlorite contain free hypochlorous
258
acid, whose amount decreases with increase of pH and increases with

decrease in pH.
The basic equilibrium reactions of hypochlorite solutions at different pH
values are:
At pH > 5, HOCl ↔ H+ + OCl¯ (5.14)
At pH < 5, HOCl + H+ + Cl¯ ↔ Cl2 + H2O (5.15)

Since bleaching is carried out above pH 8, the active species appears to
be OCl¯ ion, or as suggested, its complex with hypochlorous acid. With
decrease of pH, the proportion of undissociated hypochlorous acid
increases until it reaches a maximum at pH 5. While decreasing pH from 10,
the fraction of hypochlorous acid increases from 0.003 to 0.21 at pH 8 and
0.99 at pH 5. The redox potential of hypochlorite solution was studied at pH
between 2 and 13. A strong maximum can be observed around pH 7.
Calcium hypochlorite releases free hypochlorous acid on hydrolysis. The
composition of equilibrium mixture depends on the pH of the solution. Above
pH 8, calcium hypochlorite predominates but between pH 6.5 and pH 5, a
significant portion is hydrolysed into hypochlorite. As pH falls below 2.5, an
ever-increasing quantity of free chlorine liberates. Freshly prepared
bleaching powder or calcium hypochlorite solution has a strongly alkaline pH
of about 11, as it is saturated with calcium hydroxide. On standing or
agitation, the atmospheric carbon dioxide precipitates calcium hydroxide as
carbonate, thereby decreasing pH. As a result, the concentration of
hypochlorous acid, and thereby bleaching power, increases. The so-called
aged liquor, therefore, bleaches better than a fresh solution. However,
hypochlorous acid is a strong oxidising agent and can degrade the cellulosic
materials due to formation of oxycellulose. Therefore, long-standing bath of
bleaching solution, of which pH has fallen below 8, should either be
discarded or made alkaline by addition of more calcium hydroxide.
Addition of electrolytes like calcium chloride or sodium chloride
immediately activates bleaching liquor by increasing rate of backward
reaction of calcium hydroxide and chlorine (similar to Eqn. 5-10). But the
activation is for the first fifteen minutes and after that it has no effect.
Hypochlorous acid tends to decompose with the formation of hydrochloric
acid, which brings a marked fall in the pH, even in a buffered solution. The
pH will, therefore, fall to a certain extent even during bleaching cycle. Ridge
and Little [6] recorded pH values of bleaching powder and sodium
hypochlorite solutions containing 3-5 g/l available chlorine stabilised with
various buffers, which are shown in Table 5.2.
259
Table 5.2 pH Values of Buffered Hypochlorite Solution.

Buffer pH range
For bleaching powder
8-10 g/l sodium sesquicarbonate 7.5 – 8.5
3-7.5 g/l sodium bicarbonate 6.8 – 7.3
For sodium hypochlorite
1-1.5 g/l lime 11
5-10 g/l sodium carbonate 10-11
5 g/l sodium sesquicarbonate 10
10 g/l sodium bicarbonate 8-6
5 g/l boric acid 8-8.5
It is well known that hypochlorite bleaching is more rapid at high
temperature. Hypochlorite solutions are themselves stable at boil at pH 11.
When hypochlorite solutions are buffered to pH 11, the rate of bleaching is
increased by a factor of 2-3 times for every 10°C rise in temperature. It is
possible to bleach at 60°C without serious damage of material, the treatment
time should be only 6.8 minutes, whereas an equivalent treatment at 40°C
requires a period of 49.4 minutes. Under practical conditions, the time will be
very short for accurate control. Alternately, the concentration of hypochlorite
solution may be reduced. The bleaching may be carried out at 70°C for 1
hour in a solution of 0.9-1.6% o.w.m. chlorine at pH between 8.6 and 12.8
using 10-30 g/l sodium hydroxide.
There is always a risk of tendering of materials due to formation of
oxycellulose while bleaching with hypochlorite. When hypochlorite solutions
attack cellulose, they not only produce chain scissions (i.e. degradation of
the polymer), but also introduce new functional groups (i.e. aldehydes,
ketones and carboxyls). The oxidation is generally regarded as non-specific,
no position in the anhydroglucose unit is preferentially attacked. The non-
specific oxidant continues to attack the primary oxidation products and
produces a highly heterogeneous series of substances [7]. Severe loss in
tensile strength as well physical damages like formation of holes may occur.
It has long been known that when hypochlorite-oxidised cotton is placed in
aqueous alkali, the solution acquires a yellowish or even a dark brown-black
colour especially on boiling. The phenomenon has been studied
systematically by Lewin and co-workers [5]. Leuco vat dyestuffs and metallic
deposits (cobalt, iron, chromium, nickel, copper, manganese hydroxides,
etc.) accelerate the oxidation of cotton with hypochlorite probably by free
radical formation.
The extent of oxidation may be assessed by measuring copper number,
cuprammonium fluidity, etc. as discussed in Section 4.4.6.
After-treatments
After bleaching with bleaching powder, some calcium carbonate, formed by
reaction of calcium hydroxide with atmospheric carbon dioxide, is deposited
260
on the material. Hence an after-wash with mineral acid, called souring, is

essential to remove such deposits. The same treatment is also used for
removal of residual chlorine after sodium hypochlorite bleaching. The
material is finally washed to remove traces of acid, which may otherwise
form hydrocellulose.
Though residual hypochlorite is removed by acid treatment, the main
purpose of this treatment is to remove insoluble deposits and metallic stains
acquired by the materials during previous processes. If a considerable
quantity of hypochlorite is present on the cloth during acid treatment, the
material may be damaged due to lowering of pH with consequent increase
in free hypochlorous acid. In some industries, acid treatment is done to
remove residual chlorine for the sake of economy; but the material is to be
thoroughly washed before acid treatment. Generally, a treatment time of half
an hour to one hour with 1% sulphuric acid at room temperature is sufficient.
A better method for removal of residual chlorine, particularly after
bleaching with sodium hypochlorite is to treat the material at 40°C for
15 minutes in liquor containing 2 to 2.5% on the weight of material (o.w.m.)
a reducing agent like sodium sulphite, bisulphite, hydrosulphite or
thiosulphate. Rinsing once in water should follow the treatment. The
reducing stage is needed for the removal of entrapped hypochlorite as well
as the chloramines, which may split into hydrochloric acid and cause
hydrolysis of cellulose. The reducing stage also stabilises whiteness.
Bleaching Process
A small quantity of cellulosic material may be bleached with sodium
hypochlorite or bleaching powder solution in a small rectangular tank made
of stone, porcelain or tiled cement structure called bleaching cistern (Figure
5-1). The treatment tank is placed little above the floor with two small
storage tanks at the floor level. A three-way valve connects the top tank with
either of the storage tanks or the drainage line. One storage tank contains
bleaching powder or sodium hypochlorite solution, while the other contains
souring/antichlor solution. A pump lifts the bleaching liquor at first and
sprays it over the materials loaded in the treatment tank. The liquor
percolates through the material and returns back to the tank through the
three-way valve. After completion of the bleaching cycle, the pump is
stopped and water is sprayed. Water washes the material while percolating
through it, and it is finally discharged through the drainage line. After
thorough washing, the pump starts circulation of souring/antichlor liquor and
the liquor after passing through the material, returns back to the tank
containing souring solution. It is finally washed with water. The material
should be uniformly packed manually or with a mechanical piler in a
bleaching cistern, otherwise the liquor will flow preferentially through
channels of least resistance. For bleaching in large quantities, a similar
261
bleaching cistern may be used, but for easier handling of materials, the pits
may be underground so that the materials can be handled or inspected from
ground level. Two successive cisterns may be used for bleaching followed
by washing-antichloring.
Water
Treatment
tank
Souring Bleaching
solution solution
Pump
Drain
Fig. 5.1 Bleaching Cistern
When bleaching small quantities in long liquor (M:L ratio about 1:5-10), a
solution containing 1.5 to 2.75 g/l of available chlorine may be used for a
treatment time of 2 hours. However, for a circulating system as above, the
M:L ratio may be as low as 1:1 and the available chlorine falls rapidly in the
early stages. A liquor containing 8 to 10 g/l of available chlorine may be
used in such cases and the circulation may be continued for 6 to 10 hours.
The conditions for hypochlorite bleaching vary with the kind of fabric, the
extent of bleaching required and the machines to be used. A typical kier
bleaching formulation consists of hypochlorite solution having 2-4 g/l
available chlorine, 0.1-0.2% wetting agent, 2-4 g/l sodium carbonate and
necessary sodium hydroxide to bring pH at 11.5. The M:L ratio is 1:3 to 1:7
and the time of bleaching is 3-4 hours at 20°C. The fabric is washed with
cold water. The fabric is then successively treated with 8-12 g/l sodium
sulphite and formic or acetic acid solution (souring) with intermediate and
final cold wash. The same formulation may be used in jigger, both for cotton
and cotton-polyester but the time of treatment is reduced to 1-2 hours.
For pad-batch, J-box and conveyor processes, the recipe may be same as
above. The liquor pickup should be 70-120% and the time of treatment 1-2
hours. In fully continuous open-width process, the time of treatment may be
reduced by using more concentrated hypochlorite solution having 10-15 g/l
active chlorine and 5-8% sodium carbonate [5].
262
For bleaching in package dyeing machine and in winch with M:L ratio of
1:10 and above, both the active chlorine content and sodium carbonate
concentration should be 1-2 g/l and the time of treatment should be 1 hour.
Sodium hypochlorite solution is strongly alkaline and is usually saturated
with sodium chloride. Hence, these salts tend to crystallise out. For
bleaching, the commercial product is diluted to give a solution containing
between 1 and 3 g/l of available chlorine.
Before hypochlorite bleaching, the material is to be thoroughly scoured to
remove all the impurities. If the proteins are not removed, they will form
chloramines during hypochlorite treatment. Such compounds will
decompose under hot alkaline conditions during washing with the formation
of brown substances. Hence, improperly scoured hypochlorite bleached
materials may lose its whiteness after several washes.
5.3.2 Peroxide Bleaching

Although hydrogen peroxide is costlier than hypochlorites, the former has
several advantages, which have contributed to its greatly increased use
during recent years. The advantages are:
1. It is a universal bleaching agent and can bleach most of the textile
fibres without damaging the materials.
2. It is eco-friendly. As the decomposition products of hydrogen
peroxide are oxygen and water, bleaching can be safely carried out
in an open vessel. No AOX is generated even in the presence of
salts.
3. Hydrogen peroxide does not react with proteins. Hence, a permanent
whiteness can be achieved without preliminary alkali treatment.
4. As peroxide bleaching is done under alkaline conditions at or near
boil, both scouring and bleaching can be combined. In fact, it is the
only bleaching agent, which can be used for the combined process.
As desizing is also possible with hydrogen peroxide, it is possible to
combine all the three processes. The presence of natural impurities
during peroxide bleaching is advantageous as they exert a stabilising
effect upon hydrogen peroxide, preventing excessive loss of oxygen.
Earlier it was thought that prolonged alkali boil is necessary for
removal of wax so that the cotton materials become absorbent.
However, recent studies show that for imparting absorbency it is not
necessary that the wax be completely removed. The rupture of
primary cell walls of cotton fibre where wax is situated may be
sufficient to impart absorbency. The presence of hydrogen peroxide
in combined processes accelerates rupture of cell walls. Hence, the
absorbency is attained much quicker than separate scouring and
bleaching processes.
263
5. This has also lead to the introduction of continuous processes, as

peroxide bleaching can be completed within an hour or so. It allows
versatile processing such as batch or continuous, hot or cold, rapid
or long dwell.
6. As peroxide bleaching is done at or near boil, the broken seed or
other vegetable matters are removed during the treatment and
consequently the cloth appearance after bleaching is much better
and fuller than hypochlorite bleached material.
7. Another important advantage of hydrogen peroxide bleaching is that
there is little risk of tendering due to over-bleaching.
8. Coloured goods dyed with vat dyes can be safely bleached with
hydrogen peroxide.
9. No souring or any other after-treatment is necessary after peroxide
bleaching.
10. It is compatible with most dyes and FWAs.
The difficulties of peroxide bleaching are:

1. Instability of hydrogen peroxide solution at high alkalinity and in the
presence of metallic impurities.
2. The use of a stabilising agent is indispensable for the reason that
peroxide ensures whitening in conditions where it is rather unstable.
These substances regulate the release of oxygen, which does not
have any bleaching action and may cause fibre damage. Sodium
silicate, though a most widely used stabiliser, is liable to deposit on
the fabric and on the equipment.
3. The use of multiple chemicals needs careful control.
4. The process is comparatively expensive.
Manufacture
The classical method of preparation of hydrogen peroxide is to react an
aqueous suspension of barium peroxide with sulphuric acid, when insoluble
barium sulphate forms and a clear solution of hydrogen peroxide may be
separated by filtration.
BaO2 + H2SO4 = BaSO4 + H2O2 (5.16)
The solution can be concentrated up to 45% by evaporation under
atmospheric pressure at 70°C. The product is, however, not very pure and
residual traces of metallic ions may cause catalytic decomposition. Hence, it
was not possible to produce stable solutions for commercial purposes, until
phosphoric acid replaced sulphuric acid.
The first electrolytic process developed in 1908 consists of electrolysis of
ammonium bisulphate when ammonium persulphate is formed at the anode.
264
2(NH4)HSO4 = (NH4)2S2O8 + H2 (5.17)

The compound hydrolyses at high temperature as follows:
(NH4)2S2O8 + 2H2O = 2(NH4)HSO4 + H2O2 (5.18)
By passing steam through its solution, hydrogen peroxide is vaporised and
fractionally distilled to a solution of approximately 35%. Alternatively, a
saturated solution of potassium sulphate may be used for electrolysis.
Potassium persulphate thus formed is acidified when hydrogen peroxide is
liberated.
Due to high cost of electricity, electrolysis processes are very expensive at
present. Hence, newer chemical oxidation processes are being tried. The
oxidation of iso-propyl alcohol and 2-ethyl anthraquinol are being widely
used in industry.
(CH3)2CHOH + O2 Æ (CH3)2C(OH)2 Æ (CH3)2C=O + H2O2 (5.19)
The more popular, 2-ethyl anthraquinol is dissolved in a mixture of an
aromatic hydrocarbon and cyclohexylether. It is reduced with hydrogen in
the presence palladium catalyst. The solution is then filtered and oxidised by
blowing air through the solution. Hydrogen peroxide is separated by
extraction with water. The quinol dissolved in aromatic hydrocarbon does
not mix with peroxide.
Sodium perborate, a solid product, when dissolved at room temperature
releases hydrogen peroxide.
4NaBO2·H2O2·3H2O + H2O = 4H2O2 + Na2B4O7 +2NaOH (5.20)
The caustic liberated provides required alkalinity for the liberated
hydrogen peroxide to act as a bleaching agent. The addition of 2% (o.w.m.)
sodium perborate to normal scouring liquor, will provide sufficient whiteness
to carry out dyeing in light or medium shade in many cases. In some
detergent formulations, a small quantity of sodium perborate is added to
impart whiteness on washed goods.
The precise chemical structure of sodium perborate is doubtful. There is a
doubt whether it is a true per-salt, NaO·O·B·O·4H2O or a salt containing
hydrogen peroxide in a form analogous to water of crystallisation,
NaBO2·H2O2·3H2O. It is a free-flowing white crystalline powder yielding 10%
by weight of available oxygen.
Strength of Hydrogen Peroxide
Hydrogen peroxide is available in liquor form. The strength of its solution
may vary widely and is expressed in terms of the volume of available oxygen
liberated from one unit volume of the liquor. Thus if 1 ml of solution liberates 1
ml of oxygen at S.T.P., the solution is equivalent to one volume solution. The
265
relationship between volume strength and percentage composition of hydrogen

peroxide is shown in Table 5.3.
Table 5.3 Relationship between Volume Strength and % Strength of
Hydrogen Peroxide
Volume Strength % Strength
1 0.3
10 3.0
100 27.5
131 35
197 50
At present it is more common to express strength by percentage weight of
hydrogen peroxide. Textile bleaching grade hydrogen peroxide is mostly of
27.5% and 35% strength.
The strength of hydrogen peroxide can be measured by titration with N/10
potassium permanganate in the presence of an acid.
2KMnO4 + 3H2SO4 + 5H2O2 = K2SO4 + 2MnSO4 + 8H2O + 5O2 (5.21)
Peroxide solutions of concentration of 10 volume or stronger are to be
diluted. Dilute sulphuric acid (1:5) is added. Usually 2 ml (V) of sample is
taken in a flask containing 100 ml dilute (10%) sulphuric acid. The
standardised permanganate solution is run from a burette until a permanent
pink colour appears (A ml). The actual normality of potassium
permanganate may be estimated by titrating with 0.1 N sodium oxalate
solution containing 20% sulphuric acid (in the ratio of 10:1). The end point is
faint but of a permanent pink colour. The actual normality is the ratio of
volumes of oxalate and permanganate solution multiplied by the normality of
oxalate solution.
Each ml of the N/10 permanganate is equivalent to 0.0017 g or 0.114
volume of hydrogen peroxide, or 0.5605 ml of gaseous oxygen. The
following simple strength calculations may also be made [7]:
A/V x 4.86 = g/l H2O2 (35%), A/V x 3.4 = g/l H2O2 (50%)
A/V x 4.28 = ml/l H2O2 (35%), A/V x 2.86 = ml/l H2O2 (50%) (5.22)
The above titration cannot be accurately measured when the solution is
discoloured. In such cases, volume of oxygen liberated by catalytic oxidation
of manganese dioxide can be measured.
Bleaching Action
In peroxide bleaching, the carbon-carbon double bond is destroyed by
epoxidation and hydroxylation (Eqn. 5.23) [1].
Earlier bleaching action of hydrogen peroxide was thought to be due to the
liberation of nascent oxygen, but this explanation is no longer valid. Under
266
O OH OH
—C=C— + H2O2 Æ C——C Æ C—C (5.23)
Epoxidation Hydroxylation
certain conditions, particularly with regard to pH, hydrogen peroxide

decomposes into hydrogen and perhydroxyl ion (HO2-), which is thought to
be responsible for bleaching action. The very recent work [8] has strongly
–
implicated the superoxide radical anion (•O2 ). Hydrogen peroxide solutions
normally require the addition of an activator to bring about bleaching. The
most common activator is alkali, which presumably encourages the
formation of the perhydroxyl anion, this then reacts further with hydrogen
peroxide to give the superoxide ion (5.24).
Alkalinity favours the liberation of perhydroxyl ions i.e. the rate of forward
reaction is increased due to neutralisation of H+ ion released forming water
(H++ OH¯ ÆH2O). However, excessive alkalinity makes hydrogen peroxide
unstable.
In the presence of catalysts, the alternate reaction takes place evolving
oxygen.
OH
H2O2 H+ + HO2¯
+
H
HO2¯ + H2O2Æ •OH + •O2¯ + H2O (5.24)
2H2O2 Æ 2H2O + O2 (5.25)

The liberated oxygen has no bleaching power and the catalysts, therefore,
cause wastage of hydrogen peroxide.
With increase in temperature, the stability of hydrogen peroxide
decreases. For natural and man-made fibres, the time of bleaching will be
too long unless the temperature is higher than 80°C. In practice, the
treatment is done at 90-100°C for 1-1½ hours, but in a pressurised vessel
the temperature may also be raised to 120 to 130°C, with reduction in
treatment time as short as 20 minutes. However, the evolved oxygen
accumulates at the top of the enclosed vessel, which can cause tendering of
the material due to oxycellulose formation at high temperature.
Hydrogen peroxide is decomposed catalytically by traces of many metals
such as copper, iron, manganese, chromium, etc. and their oxides. This is
accompanied by increased degradation of cellulose.
The oxidation of cellulose by hydrogen peroxide takes place
simultaneously with its decomposition. Bleached cotton appears to have a
267
catalytic effect on the decomposition. The rates of decomposition and

oxidation increase with pH, but at the higher pH values the decomposition
rate increases faster. Very little oxidation occurs at pH 7 and with HCl-
extracted cotton, indicating that traces of a catalyst is required for the
oxidation reaction. The main functional groups formed on the cellulose by
oxidation appear to be ketones, while very few aldehyde and carboxyl
groups were also found. The ketone groups, thus formed, are inactive and
do not bring about yellowing and colour reversion. The attack on cellulose is
not directed at random to all carbons of the anhydroglucose units of the
chains, it is directed mainly to the C3 hydroxyl groups.
The catalytic effect of metal ions is not limited to the decomposition of
hydrogen peroxide. Simultaneously the fibres are attacked, DP and the
tensile strength decrease considerably. Localised concentration of the
catalyst accelerates the oxidation of the fabric to such an extent that
pinholes or razor cuts are formed in the fabric. These are due to local
dissolution of the cellulose of very low DP values [5].
Stabilisers are necessary to slow down the decomposition of both
hydrogen peroxide (Eqn. 5.25) and the active bleaching agency. The most
common stabilising agents have been the colloidal sodium silicates. The
formulae of silicate are best represented in terms of the ratio of sodium
oxide to silica, as in sodium metasilicate (Na2O:SiO2) and orthosilicate
(2Na2O:SiO2). These silicates, however, are in crystalline form in which the
ratio is 1 or greater. In the colloidal forms originally preferred for peroxide
bleaching the ratio is less than 1. For example, in the so-called alkaline
glass form the ratio is 1:2; whilst in the so-called water glass form, it varies
from 1:1.6 to 1:1.38. The colloidal silicates are efficient and economical
stabilisers, but care is needed to ensure efficient washing-off in order to
avoid deposits of silica on the fabric and equipment. Although such colloidal
forms have been preferred, the crystalline meta- and ortho-silicates can also
be used and may provide easier wash-off. The mechanism by which these
stabilisers work is complex, although the elements of buffering action and
sequestering of transition-metal ions, such as those of iron (III) and copper
(II), which otherwise catalytically degrade hydrogen peroxide, undoubtedly
contribute. Magnesium ions also play an essential part in the mechanism
and must be added (as sulphate) if they are not already present in the
system sufficiently. A small quantity of magnesium salt must be present, if
sodium silicate is to act as a stabiliser. Hard water containing at least 2°
hardness will usually supply the need. Hardness between 2° and 7° would
give satisfactory results. If soft water is used, 0.1 to 0.2 g/l magnesium
sulphate is to be added. Sodium silicate may impart harshness to the
material due to the deposition of insoluble silicon compounds. This may
create a problem in circulation in the package dyeing machine. To avoid
such precipitation, additional alkali may be added to bring the ratio of
268
Na2O:SiO2 around 2.25:2.75. To avoid a risk of degradation of cellulose, a

mixture of sodium hydroxide and sodium carbonate is used as alkali. The
major disadvantage of silicate stabilisers is that they form hard scales on
equipment. They also have tendency to deposit on fabric causing poor
handle.
Water-soluble impurities in raw cotton can have a considerable stabilising
effect on hydrogen peroxide solution. It is, therefore, preferable to bleach
unscoured cotton, unless the material is heavily soiled.
Theoretically, sequestering agents should be the best stabilisers –
stabilisation may be affected by elimination of heavy metal ions responsible
for free-radical formation. The various types of sequestering agents used in
textile processing are:
1. Polyphosphates
2. Polyhydroxy-carboxylic acids
3. Aminopolycarboxylic acids
4. Phosphonic acids
5. Polyacrylic acids
It is important to recognise that whilst transition-metal ions catalyse the
destruction of peroxide, the alkaline-earth element stabilise it. In the
absence of calcium and magnesium, even silicates cannot act as bleach
stabilisers [9]. Proteins also exert a stabilising influence and can inactivate
slight traces of copper in the bleaching liquor. Other stabilisers include
magnesium silicate or hydroxide, trisodium phosphate, sodium
pyrophosphate, tetrasodium pyrophosphate and commercial non-silicate
stabilisers (e.g., a mixture of sodium oxalate and sodium pyrophosphate).
Nowadays organic chelating agents are also used as stabilisers. A very
important function of stabiliser is to maintain the internal pH of the fibre,
irrespective of the pH of the liquor, between 8.0 and 8.5. So far as the
buffering is concerned, sodium silicate and non-silicate mixed stabiliser
mentioned above are most effective.
The recent peroxide stabilisers are blends of several materials, mainly of
the following chemical types or their mixtures:
1. Alkali e.g. silicate, caustic soda or sodium carbonate
2. Organic sequestering agents, e.g. EDTA, DTPA, heptonate or
phosphonate
3. Inorganic salts e.g. magnesium salts
4. Dispersants e.g. acrylates or phosphonates
5. Protein degradation products
6. Certain surfactants
7. Polymeric materials or colloids e.g. acrylic polymers
Magnesium and calcium salts are more stable at high temperature as
compared to free aminocarboxylic acid. Polycarboxylic acid mainly acts as a
dispersing ion-exchanger. Phophonates are good complex formers with
269
good dispersing properties. Nevertheless, due to pollution problem, they are

now substituted by acrylates.
DTPA as sodium or magnesium salt and its hydroxy derivatives have good
sequestering property as well as stability to oxidation. However, EDTA and
DTPA are now replaced by heptonates and gluconates [10].
Clariant has developed a new organic stabiliser called Stabiliser SIFA [11].
The main features of the new stabiliser are:
1. Perfect stabilisation of hydrogen peroxide under severe conditions
i.e. long steaming times (20-30 min) of a non-scoured fabric as in
case of continuous combined scouring-bleaching process.
2. It is bio-eliminable and phosphate-free.
3. Progressive whiteness – the degree of whiteness of cotton rises
along with increasing concentration of the stabiliser. Thus the
product can be exploited in two ways. A higher degree of whiteness
can be achieved with the same amount of peroxide with conventional
stabiliser. Alternately, the same whiteness can be achieved using
lesser quantity (20-30% less) of hydrogen peroxide.
4. Astonishing synergism during simultaneous bleaching and
brightening treatment. Stabiliser SIFA exercises a strong influence
on the effect of optical brighteners. The resulting degree of
whiteness is higher.
5. Sodium silicate can be replaced entirely, thereby avoiding deposition
problems.
6. Stabiliser SIFA inactivates the metal cations (iron ions), thus
preventing undesirable decomposition of peroxide and damage of
material.
7. Stabiliser SIFA is especially suitable for the bleaching techniques
with maximum application at 150% (see page 280).
Hydrogen peroxide is not an active bleaching agent for cellulosic fibres
under neutral and acidic conditions. On the other hand, excessive alkalinity
will cause instability and decomposition of hydrogen peroxide with liberation
of oxygen. Compounds, which increase pH values such as sodium
hydroxide, sodium carbonate and ammonia, are activators. In order that
bleaching is completed within reasonable time, it is necessary to adjust pH
of the bleaching liquor between 10 and 10.5 for cotton, while for wool it is
between 8 and 9. For cotton, a mixed alkali of sodium hydroxide and sodium
carbonate is used. But for wool, these may be harmful – sodium
pyrophosphate, tetrasodium pyrophosphate or sodium silicate may be used.
However, if sodium silicate is used, the material should be thoroughly rinsed
after bleaching in order to avoid harsh feeling.
By incorporating TAED (tetra-acetyl-ethylenediamine), a peroxide
activator, into the bleach bath, peroxide bleaching can be performed at both
lower temperature and alkalinity with significant benefits in terms of refined
270
fibre quality [12]. TAED is a colourless, odourless, stable, safe and

biodegradable substance. In the detergent industry, it is used for many
years in combination with a persalt to provide effective bleaching by the
production of the peracetic anion (CH3COOO–) using temperature and
resident time at which peroxide alone would be ineffective. The bleach bath
may be set at pH 10, which upon addition of TAED reduces to 7. After a
period under beneficially low pH conditions, the pH is subsequently raised to
pH 10.5 to complete the cycle. Good whiteness may be achieved on cotton
and blends at a temperature as low as 60°C.
Acetic anhydride and highly concentrated formic acid can activate
hydrogen peroxide by forming peracetic and performic acids respectively.
However, peracetic acid has unpleasant odour and the danger of explosion.
The bleaching solution is sensitive to temperature and catalysts. Many other
acylating organic compounds are described in patent literatures. Ammonium
persulfate activates hydrogen peroxide in the cold bleaching of silk [5].
Bleach activators are added to promote the oxidation potential of alkaline
hydrogen peroxide. These generate peracids, which allow bleaching to be
conducted at lower temperatures and for reduced time, resulting in energy
savings and less fabric damage. The bleaching activators commonly used in
laundry detergent are TAED and NOBS (nonanoyloxybenzene sulphonate).
Other cationic bleach activators have also been studied recently. Their
affinity for the negatively charged surface of cotton minimises hydrolysis in
the bleach solution and maximising oxidation at the relevant sites on the
substrate. A new cationic bleach activator, N-[4-(triethylammonio-
methyl)benzoyl]caprolactam chloride in hot peroxide bleaching system. has
been studied recently [13]. It was observed that temperature has the
greatest influence on the whiteness of cotton fabric, followed in turn by the
bleach activator concentration and time. By adding the activator in the
bleach bath, it is possible to achieve satisfactory whiteness and wettability at
lower temperature. Less chemical damage at lower temperature is beneficial
for delicate components, for example, wool in cotton/wool blends. The
above activator and 6-(N,N,N-trimethylammonio)hexanoyl caprolactam p-
toluenesulphonate are found to produce satisfactory whiteness within 8
hours batch time in cold pad-batch bleaching. The predicted optimum recipe
consists of 10 g/100 ml H2O2 (35%), 2.9 g/100ml chelant
(diethylenetriaminepentakis(methylphosphonic acid, 50%) and 0.585 and
0.76 g/100ml of two activators respectively [14].
A trace amount of residual hydrogen peroxide (several ppm) can cause
dyeing problems, such as unevenness and batch-to-batch variation of dyed
shades and poor dyeing, depending on the stability of the dyes. The reactive
groups and/or chromophore of many reactive dyes get oxidised.
271
Currently, many cellulosic dyeing and finishing plants are using three or
four rinses to remove peroxide or are using reducing agents such as sodium
bisulphite, the excess of which may adversely affect the shade.
H2O2 + Na2SO3 Æ Na2SO4 + H2O (5.27)
The advantage of catalase enzyme [15] is that it attacks only hydrogen
peroxide and nothing else. The reaction is as follows:
H2O2 + catalase Æ 2H2O +O2 + catalase (5.26)
The reaction rate is extremely fast and under optimum conditions one
mole of catalase is able to decompose 500 million moles of hydrogen
peroxide in one minute. The catalase is free to decompose more hydrogen
peroxide as long as the desired pH and temperature are maintained. The
need to neutralise before adding the dye is beneficial since catalase is most
active in the pH range of 6-8.
Normally, when using catalase, the number of rinses can be reduced
drastically. The catalase is applied in the dyebath prior to adding chemicals
and dyes. This is acceptable because catalase acts on hydrogen peroxide
only and no other chemicals. The steps to be followed are:
• After bleaching, the bath is cooled to 70-80°C and if needed, the
machine is drained.
• It is then refilled and pH is neutralised with acetic acid, the amount of
which is decided by the residual caustic soda.
• After running for 10-15 min, the pH is checked and adjusted to 6.5-7.5
before draining.
• The bath is refilled, catalase is added (amount depending on the
concentration of the product) and run for 10 min.
• The dyes, electrolyte, chemicals and alkali can be added to the machine
without draining the liquor.
Preparation for Bleaching
The goods are to be desized before bleaching to prevent excessive fouling
of the bleaching liquor. Some enzymes can cause catalytic decomposition of
hydrogen peroxide. Hence, enzyme desized materials are to be thoroughly
rinsed. Acid desizing is preferred as it not only hydrolyses starch, but also
removes metallic salts present in the fibre. The iron stains, if any, are also
removed which may otherwise cause catalytic decomposition of hydrogen
peroxide causing damage (e.g. hole marks) to the cellulosic materials.
Since cotton is a natural fibre, it is not a uniform material in its physical
dimensions, chemical constitution or even colour. Cotton is a natural product
obtained by various methods of cultivation and harvesting. Moreover, this
natural product has its origin in many different countries, the condition of the
soil and the climate of which have a considerable influence on the quality of
272
the end product. The raw cotton does not, therefore, have typical qualities
as would be desirable for carrying out efficient processes in industry. Metals
like Ca, Mg, Fe, Cu and Mn are present in varying quantities in cotton of
different origin. Cotton cultivated in dry regions is less contaminated, while
heavy rainfall during maturing period may cause high contamination with
soil. The mineral content varies widely as a result of variation in the nutrients
in the soil, which depends on the year and place of growth. Especially iron
content has been tested to vary from 205 ppm for Indian cotton to 4 ppm for
Egyptian cotton. During spinning process, the metal content may increase
due to breakage or wear of machine parts [16].
Increased metal content of textile materials can lead to lower level of
whiteness, unacceptable level of strength loss and in the worst case,
pinholes in the prepared fabric. The reactions are often self-propagating.
Proper preparation of materials is, therefore, necessary.
Metal catalysts can be removed by demineralisation with inorganic acid.
But the process is time-consuming and thorough rinsing with large volume of
water is necessary after such treatment.
Demineralisation and bleaching can be done in the same bath using Sirrix
2UD liq. (Clariant), which is bio-eliminable, phosphate- and solvent-free. At
low applied amounts (1 to 5 g/l), Sirrix 2UD liquid is capable of doping the
amylase enzyme by protonising it, thus activating it for the bio-conversion of
starch with simultaneous protection against hazardous substances like iron.
The acid medium buffered in this manner promotes demineralisation and
depigmentation of heavily pigmented cotton, thus improving both the result
of desizing and the final quality of goods. At higher amounts over (10 g/l),
this product is capable of hydrolysing and cracking synthetic polymer sizes
as well as ionising peroxide catalysts, thus achieving greater reliability of the
bleach [11].
Another product which also plays an important role in bleaching is
Sandoclean PC (Clariant), a detergent with high cleaning and rapid wetting
power. The product is based on linear fatty alcohols of natural origin. It
permits bleaching chemicals to penetrate into the interior of the fibre, hence
very much suitable for recently developed maximum application techniques.
The process can be universally applicable on woven and knitted goods on
jigs, jets and winches [17]. The method is as follows:
• Set bath at 40ºC with 1.5 ml/l Sirrix 2UD liq. and 1.5 ml/l Sandoclean PC
(Clariant).
• Raise temperature to 50ºC and run for 10-15 minutes.
• Add 6 ml/l caustic soda (32%) and run for 5 minutes.
• Add 3 ml/l hydrogen peroxide (35%).
• Raise to boil and run for 10 minutes.
• Hot rinse twice.
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• Cold rinse and peroxide scavenge with 0.1-0.2 Bactosol SAP liq.
(Clariant).
• Neutralise with 0.5-7.5 ml/l Sirrix 2UD liq. (Clariant).
CIBA has developed a similar product called Invatex ED [18], which is
further compatible with desizing enzymes. Pad-batch enzymatic cracking
may be followed by pad-steam bleaching.
• Pad (100% pick-up) at 20-90ºC with a liquor containing:
2-6 ml/l Ciba Tinozyme ADC (enzyme preparation)
3-5 ml/l Ciba Ultravon CN (surfactant)
1-3 ml/l Ciba Invatex ED (demineraliser)
• Batch for 2-24 hours at room temperature
• Hot wash
• Pad (100% pick up) with a liquor containing:
10-14 ml/kg Ciba Tinodarite CBB
2-4 ml/kg Ciba Ultravon CN
15-25 g/kg caustic soda solid
30-60 ml/l kg hydrogen peroxide (35%),
• Steam (saturated) for 20-30 minutes
• Hot wash
Batch Process
Cotton yarns may be bleached in hank form in a kier and in cone or cheese
form in a package dyeing machine. The fabrics in rope form are mostly
bleached in a kier. Alternately smaller batches of fabric, especially heavier
varieties, may be bleached in winches.
Conventionally cotton materials are bleached in kiers. The conventional
cast-iron kiers, though used largely, may cause catalytic decomposition of
hydrogen peroxide, if rust is present. A lining of sodium silicate and cement
is perfectly satisfactory and many old-fashioned kiers are lined with ceramic
to render them suitable for the process. Cast-iron pumps used for
circulation, calorifiers and external pipes, can be rendered passive by
circulating through them a boiling solution of sodium silicate and magnesium
sulphate. The kier is coated with rapid-setting cement, sodium silicate and
little magnesium sulphate as described in Section 4.4.6. The kier is allowed
to stand overnight and a mixed solution of sodium silicate and magnesium
sulphate is boiled and circulated through the pump and calorifier for about
one hour in order to inactivate the cast iron components. Finally the liquor is
run off and the kier is ready to use. The stainless steel kier will be
undoubtedly the best choice, but at the same time will be very costly.
Bleaching time can be shortened by using a high-pressure kier, but when
boiling at atmospheric pressure, bleaching can also be completed within a
reasonable time.
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It is not possible to give a standard recipe for peroxide bleaching of cotton

because of the variation of M:L ratio in the particular machine, water quality,
the quantity and the nature of impurities present in the materials and the
extent of whiteness required. For full white material, higher amount of
peroxide, alkali and silicate are used than those required for materials meant
for dyeing. In most cases the scouring is done simultaneously with the
peroxide bleaching using a suitable surfactant.
A guide recipe (% o.w.m.) for kier scouring and bleaching may be as
follows [2]:
Magnesium silicate - 0.05 g/l
Sodium silicate - 2-3%
Caustic soda - 0.3-0.8%
Soda ash - 0.6-1.0%
Hydrogen peroxide (35%) - 3-5%
Wetting agent - as required.
Instead of caustic soda and soda ash, only caustic soda (0.6-1.4%) may
be used.
The chemicals are dissolved in a separate tank and are added in the
same order as shown in the recipe. The solution is pumped into the kier
which is then filled to about one-third of the capacity with water. The material
is then loaded with simultaneous circulation of liquor. When the kier is half
filled, the steam is turned on so that the temperature is about 50°C when the
loading is complete. Sufficient water is then added to ensure that the load is
completely immersed. Then the temperature is raised to 65-70°C in a time
not less than 30 minutes, after which both the steam and liquor circulation
are turned off for about 10-15 minutes when entrapped air is allowed to
escape. The temperature is further raised to 80°C and once again the steam
and circulation are closed for 10-15 minutes. The kier is then closed and the
temperature is raised to 110°C. The bleaching is then continued for 1 to 3
hours. For an open kier, the time required may be 5 to 8 hours.
Hydrogen peroxide is never completely consumed. At the end of bleaching
cycle, 2% o.w.m. soda ash is added and the liquor is circulated for further 1
to 2 hours at 80-90°C. This is followed by rinsing.
A general guide recipe for bleaching of unscoured cotton and cotton-
polyester blends in a winch machine or any other long-liquor machine (M:L
ratio 1:10-20), is as follows:
Sodium silicate 79° Tw – 7 g/l
Sodium hydroxide – 0.5 g/l
Sodium carbonate – 1.8 g/l
Hydrogen peroxide (35%) – 1-2 g/l
Wetting agent – as required
Temperature – 90-95°C
Time – 1-2 hours
275
To avoid precipitation, 50% of sodium silicate may be substituted by

trisodium phosphate or an organic stabiliser.
Yarn packages are normally bleached and dyed in package dyeing
machines. In these machines the liquor is circulated through the yarn
package which has a filtration effect. As a result it is quite common that
insoluble silicates are precipitated on the material. The bleaching should be
carried out with soft water or otherwise a sequestering agent like sodium
hexametaphosphate or E.D.T.A. is added. After bleaching, the material is to
be washed with soft water at 90°C followed by a cold wash with soft water.
The guide recipe given above for long-liquor machine may be used and the
concentration of hydrogen peroxide may be increased, depending on the
whiteness required without changing the concentration of other chemicals.
The quantity of sodium silicate may be halved by adding an equal quantity of
trisodium phosphate or doubling the quantity of caustic soda.
The recipe for jigger machine recommended [5] as follows:
Sodium silicate (79°Tw) – 4-10 g/l
Sodium hydroxide – 1-1.5 g/l
Sodium carbonate – 1.8 g/l
Hydrogen peroxide (35%) – 1.5-3.5 g/l
Temperature – 80-100°C
Time – 1-3 hours
Semi-continuous Process
Cotton or other cellulosic goods can be bleached by overnight storing at cold
or in a hot chamber for 12 hours, after padding or impregnation with a strong
hydrogen peroxide solution. The whiteness is not as good as kier-bleached
material, but may be sufficient for dyeing pale or bright shades, or for the
materials, which may be damaged on boiling with aqueous solution. The
recipe for padding liquor may be as follows [2]:
Sodium silicate – 20 g/l
Caustic soda – 5 g/l
Soda ash – 5 g/l
A single or double padding may be carried out with 100% expression. The
material should be covered with a polyethylene sheet during storage to
avoid evaporation causing localised increase in peroxide concentration.
Residual peroxide remaining in the spent liquor can be activated by 1%
soda ash or caustic soda solution at 80-90°C.
In semi-continuous pad-batch process, the fabric may be impregnated in
open width in the bleaching liquor typically containing 0.5-0.8% caustic
soda, 2-3% sodium silicate, 0.8-1.2% hydrogen peroxide, all on the basis of
276
o.w.m. It is then preheated by passing through a steam or infrared chamber

and made into a circular batch consisting of about 2,000 metres fabric on a
rotating roller. It is then held in a steam-heated reaction chamber for a given
time prior to washing off [5].
Continuous Process
Continuous processes were developed with the advent of hydrogen
peroxide as a cost-effective alternative to hypochlorite in the late 1930s.
Peroxide can be used continuously after a shorter alkali boil-off. In order to
allow time for the chemicals to work, a first in, first out system, called a
J-box, was developed to replace storage pits based on first-in, last-out
systems, which used to give uneven results. J-boxes are primarily used for
rope form, but with the advent of synthetic fibre blends with cotton, open-
width systems were developed because blended fabrics and fabrics of
heavy construction are sensitive to crease marks while packed in J-boxes.
Rope-form processing machines are suitable for lightweight or wide fabrics,
terry towelling and knits [1].
For continuous processing, the bleaching time should be short and easily
controllable. Higher temperature or pH around 7 may accelerate
hypochlorite bleaching process. But in both cases there is a risk of serious
degradation of cellulose. However, hydrogen peroxide bleaching can be
completed within 60 to 90 minutes without damaging the material. To
complete this dwell period at high temperature, a storage chamber is
necessary. The Gnatt piler, a precursor of J-box, was not satisfactory for the
purpose, because it was made of wood.
Continuous bleaching with hydrogen
peroxide was successful only when J-boxes
made of stainless steel, titanium or ceramic
were available. In J-box, the material is fed at
the top and withdrawn at the bottom, where
the opening is much smaller so that the cloth
cannot be forced out quickly by the pressure
exerted by the column of the cloth. The output
of J-box is between 150 and 300 m/min. The Fig. 5.2 Saturator or
two types of J-boxes (Dupont or Farmer Impregnator
Norton and Becco type) differ by the method of preheating before storage
(Section 4.4.6).
The saturator or impregnator device (Figure 5.2) is an extremely important
part of a bleach range. It must evenly and rapidly impregnate the fabric with
the treatment chemicals. The most common open-width application is a
single box with four or six dips and nips before final squeezing to the desired
wet pickup. Two-stage impregnation units force initial impregnation into the
277
fabric using a roller nip with 10-tons pressure, and a second series of dips
before expression with a nip under a pressure of 5-tons.
A sequence of continuous scouring and bleaching using two synchronised
J-boxes is as follows:
(a) Impregnation with 4% caustic soda solution at 70°C.
(b) Heating the impregnated cloth at about 100°C and storing in J-box
for about 60 minutes.
(c) Washing off caustic soda at cold.
(d) A second cold water wash.
(e) Padding with a hydrogen peroxide solution containing:
Caustic soda – 2 g/l
The solution will have a pH of about 10.9 and in case of any sign of
instability, 0.2 g/l magnesium sulphate may be added.
(f) Heating the padded cloth at about 100°C and storing in J-box for
about 60–90 minutes.
(g) Final wash.
The rope bleaching ranges are based mainly on the J-box, which is
considered the workhorse for this industry. The main variations between the
rope bleaching ranges are the types of J-box, the number of stages and the
type of washer used. The rope systems require fewer chemicals and permit
a higher production rate than the open width machines. The large J-boxes
can store up to 2,000 kg fabric. Dwell times of 30-60 minutes are possible,
and the speed of production of about 180 m/min can be reached. The rope
systems are suitable for a large variety of fabric widths and the equipment
involved is simple and efficient.
Open-width continuous equipment includes J-boxes, roller steamers and
conveyor steamer. The open width bleaching processes have been
developed in recent years at a rapid pace. These processes are of particular
importance for the polyester-cotton blends, which are very sensitive to
creasing. The quality of processed goods may suffer in these machines due
to uneven heating and the energy consumption is high. But these machines
have revolutionised bleaching processes as treatment time has been
brought down very significantly. Roller steamers with 50-200 metres
capacity allow very short reaction time because of rapid and uniform
heating. In roller steamer systems, the impregnated cloth is passed through
a closed steamer over a number of rollers. The machine is ideally suited for
highly crease-prone fabrics. They suffer, however, from high chemical cost
and the high cost of frequent replacements of various machine parts. The
conveyor steamers with 200-500 metres capacity permit the processing of
more relaxed fabrics by plaiting it without tension on the conveyor; longer
dwell time results in more efficient use of chemicals. The scouring and
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bleaching recipes for cotton fabrics in three continuous steamers having

varying dwell periods are shown in Table 5.4 [19].
Table 5.4 Scouring and Bleaching Recipe for 3 Continuous Steamers
having Varying Dwell Periods
Chemicals (g/l) Dwell Time in the Steamer (minutes)
20-30 10-15 2-3
Scouring
Caustic soda 20-30 30-40 80-100
Scouring aid 3-8 5-10 10-15
Wetting agent 2-3 2-3 2-3
Bleaching
H2O2 (35%) 20-30 30-40 40-60
Sodium silicate 5-10 12-15 15-20
Caustic soda 4-6 5-7 6-8
Wetting agent 0.5 0.5 0.5
Most of the recent installations are a combination of roller-conveyor

steamer (Figure 5.3) [1]. The enlarged roller preheater and conveyor
sections, needed to prevent packing creases, can be used separately or in
tandem. The fabric path may be changed without rethreading. Thus, there
will be maximum flexibility with regard to retention time. The fabric passes
over a number of rollers on entry to the heated chamber to ensure level
heating and to start the reaction in a flat, creaseless condition. After
prestabilising in this way, the fabric is rippled on to a conveyor consisting of
a large number of driven rollers, all of which are close together. Such a
conveyor, also called as roller bed, keeps the fabric pile continuously
Roof with vent, heating pipes and perforated steam pipe
60 metres tight strand section
Exit 4 metres roller bed section
Steam
WetWet
or dry or
bottom heated
dry entry
Fig. 5.3 Combination roller-conveyor steamer

moving so that the folds in the fabric are never long enough in one position
for a permanent crease to form. The contact of the bottom of the fabric pile
279
with each roller is also not long enough for drying to occur. Such types of
steamers are also known as roller bed steamers.
With classic wet-on-wet applications, various measures are necessary to
obtain uniform and reproducible effects. Continuous processing demands
highly concentrated liquors and keeping the concentration of the products in
the saturator constant. Often these liquors are at the limits of stability and at
the end of operation, 500 to 2,000 litres of residual liquor are released in
wastewater. Modern ranges operate with a maximum wet-on-wet application
of 150% giving residual liquors of less than 10 litres, without the
disadvantage of saturator. The pretreatment cycle is considerably simplified
and the quality of bleaching goods and operating reliability is improved. The
basic logic is simple: the higher the application value, the more efficient the
bleaching effect.
Proper impregnation means uniform application of chemicals dissolved in
water over length and width of a wet or dry fabric web. To achieve a uniform
reaction during steaming, the distribution of the treatment chemicals must be
homogeneous across the fabric structure. Optimum liquor impregnation
makes certain demands on modern plant, such as:
• Uniform and reproducible liquor pick-up

• Controllable and high add-on liquor application
• High liquor exchange
• Low liquor content in the system
• Metering of individual components
Intensive impregnation can be achieved by BEN-IMPACTA (Benninger

AG) [20] similar to BEN-INJECTA (Section 4.4.5). The fabric is guided
through two narrow shafts. Due to high turbulence caused in these narrow
shafts and on the other hand, by the heavy cross-flow and by the liquor
circulation plus temperature up to 60°C, there is an intensive liquor-
exchange and a uniform distribution of the chemicals. The chemicals
penetrate inside the fabric. No additional penetration zone is needed and no
loss of chemicals occurs in the system. A small quantity of liquor ensures
fast liquor replacement and quick adjustment during lot or process change.
Liquor pick-up is regulated by adjusting the application pressure of a two-
roll squeeze, made of two ground soft rollers of 55° shore hardness. The
pressure roller is dynamically balanced and its weight plays no part i.e. the
centre of gravity of the roller is over the pivot point. The undesirable nip
opening after a seam is prevented by a proximity switch. The controllable
add-on is 30-65% (60% in-feed moisture content) and can be adapted to the
liquor carrying capacity of the fabric.
High liquor addition from BEN-IMPACTA gives optimum bleaching
conditions so that a separate scouring step is not required. The
280
accompanying substances are better dispersed or dissolved in the liquor

and there are less chances for crease marks. Water is metered
automatically as needed. The chemicals can be metered in proportion to the
fabric weight processed in g/kg or ml/kg.
Because of high liquor exchange, BEN-IMPACTA can be used for high
pick up application in front of the steamer and also for cold pad-batch
bleaching. The possibility of a cold bleach operation in the same range,
besides the one-pass desizing-scouring-bleaching process, is possible with
better whiteness.
In the conventional system, cooled goods squeezed to 70% pick-up pass
through the saturator with approximately 1,000-litre capacity and are then
padded with an application of 90%, giving a difference of squeezing effect of
20%. So as to prevent liquor from becoming diluted by the continuous
passage of the fabric, the feed liquor must be reinforced by a factor of
100:20 = 5. In the new maximum application technique, the desized,
washed and still hot (90°C) fabric passes into the new, approximately 10
litre-capacity unit producing a liquor addition of approximately 80%, giving a
final pick-up of 70% + 80% i.e. 150%. The feed liquor is much less
concentrated (by a factor of 100:80 i.e. 1.25) and thus considerably more
stable. In the conventional process, it is necessary to monitor the
concentrations of soda ash and hydrogen peroxide metering, to ensure the
reproducibility of the effects. Equilibrium is established very slowly and it can
rapidly change. With the maximum application, the liquor is replenished in
fractions of a second. The system results in not only better final quality of
the goods, but also better uniformity, reproducibility and reliability in
continuous bleach [11].
Maximum application is the new state of wet-on-wet impregnation. A
number of maximum impregnation systems have been developed recently, a
few systems developed in Germany are:
• Booster and BEN-IMPACTA systems (Benninger AG)

• Flexnip system (E. Küsters)
• Dip-sat Varic system (Max Göller)
• Raco-Yet system (Ramisch Kleinewefers)
• Super-Sat system (Babcock)
• Optimax system (Menzel)
All these ranges have a common function, i.e. maximum increase of

application when impregnating the goods with the bleaching liquor before
steaming. They all prevent creasing and chafing in the steamer and make
alkaline scour boiling unnecessary. A shorter production cycle means higher
final quality.
281
The specific novelty of Booster system (Benninger AG) is the inclusion of

a special low liquor trough following the classical saturator for maximum
application impregnation. The bleaching liquor can be conveyed from the
saturator to the trough by means of a pump. This system can be fitted with
conventional saturators so that the fabric enters the steamer with 150%
pick-up.
Flexnip applicator (Küster, Germany) [21] is based on the concept of
Add-on, meaning application of liquor without any exchange of substances.
No interaction occurs between liquor and textile materials during application
so that the changes in concentration in wet-on-wet processes or tailing
effect in case of substantive products do not occur. It consists of a V-shaped
trough formed by two foils sealed off at the sides and the bottom by
pneumatic pressure systems. The fabric is drawn down through this trough,
wet or dry and leaves the bottom slot with an evenly applied pressure on
both sides. The trough is loaded according to the specific liquor pick-up
thereby avoiding drop formation. Application is truly additive – there is no
recycling of mixed or depleted liquor. Immersion time is only 0.15 seconds at
100 m/min. An extremely fast turnover of the trough liquor prevents
concentration variation and cooling or heating of the liquor by the fabric. The
bleaching liquor application is identical from first to the last metre of the
fabric. 10% saving in chemical cost is reported in one step bleaching. The
desized, still hot (90°C) fabric with a moisture content of about 70% passes
downward into a 10 litre capacity trough in which the bleaching bath is
renewed in a matter of seconds. Emerging at the bottom, the fabric passes
between two flexible squeezing rollers that adjust the total pick-up to 150%.
In case of mercerisation and causticisation, add-on application results in a
constant concentration of caustic soda and auxiliaries.
Dip-sat Varic (Göller, Germany) system generates a high degree of
humidity on the fabric leading to very efficient swelling of fats, waxes and
cotton seeds in single step bleaching process. This system can be
incorporated into any existing range and is based on a free liquor add-on,
i.e. impregnation without squeezing the fabric. The substrate absorbs
maximum of liquor and the excess liquor runs back to the first trough. An
automatic system controls the concentration of chemicals. The desized
fabric passes in this manner through the Dip-Sat system with a capacity of
10 litres and a moisture content of 60% and then runs horizontally into a
steamer with a maximum application of approximately 140%.
Raco-Yet (Ramisch Kleinewefers, Germany) [21] is a machine for single
step desizing-scouring-bleaching process with a process time of about
1-3 minutes. The unit consists of inlet, applicator, reaction storage unit, post-
scouring machine and automated chemical metering station.
Raco-Yet utilises a mixing nozzle, in which steam, chemicals and water
are mixed and ejected as heated aerosol, which is applied to the fabric
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structure and the capillaries of the fabric. The chemicals and thermal energy
act simultaneously. Liquor feed is proportional to the fabric weight, liquor
application, fabric speed and width – the individual parameters are stored in
the programmable controller.
The individual flat spray jets overlap, ensuring uniform liquor application
over the fabric width. Two nozzle beams are used for both sides of fabric,
adjustable to suit the fabric width in order to minimise chemical losses.
The aerosol comprises five components – soft water, water glass (sodium
silicate) as stabiliser, caustic soda, special multifunctional auxiliary and
hydrogen peroxide.
The application housing is connected to a reaction storage unit via an
overflow chute so that the chemicals cannot overflow into the storage unit.
The storage unit is designed for tight-strand fabric guidance to ensure that
the average treatment time of 2 minutes is maintained.
If size recovery is required, a pre-scouring stage for full or partial desizing
is required prior to Raco-Yet applicator. Otherwise dry, grey fabric can be
fed directly into the applicator.
Although chemical costs are higher in this process, total production costs
are lower due to reduction of process steps.
The combination of the Pre-Yet and Raco-Yet units with identical jet-spray
technology allows multi-phase processing of desizing, scouring and
bleaching. Pre-Yet spray removes synthetic sizes within 30-40 seconds
using only water, which should preferably come from the first washing
section. Water-insoluble starch sizes can be removed by using HT enzymes.
The impregnation is followed by temperature shock of 102ºC. Another
advantage of spray method over immersion method is that all enzymes are
directed at the fabric – contrary to the latter method, very little amount of
enzymes remain unused in the wash baths.
After liquor application, the fabric passes through a steam section, which
can be used either as a steamer or as a normal washing section. The
passage takes about 1 minute at 100 m/min. After the size is completely
swollen in the steam zone, it can be removed by a high-performance
RacoVac vacuum unit, which removes size and dirt in concentration up to
7%. Two-sided suction is recommended for dense fabrics like tarpaulin, etc.
This is advantageous over squeezing roller in removal process.
In Optimax system (Menzel), after strong pressure is applied to a
compressed fabric, a strong decompression takes place, which causes the
liquor to be sucked into the goods like a sponge. The desized, hot washed
fabric is squeezed off between two Rovatex rollers and then absorbs the
liquor found in the nip formed by the two rollers. Two small rollers prevent
the loss of liquid. The fabric travels upwards. Before it enters the steamer,
two rollers regulate the maximum application value. The system is flexible
since it allows minimum to maximum application values.
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Bleaching of Viscose
High-wet-modulus (HWM) viscose fibres and normal viscose, in particular,
are more vulnerable than cotton to chemical damage. They must, therefore,
be bleached under milder conditions than those used for cotton. Moreover,
the raw fibres are whiter than unbleached cotton and their coloured
impurities are more easily removed. Sodium hypochlorite, hydrogen
peroxide, sodium chlorite and peracetic acid can all be used for viscose
rayon. The most common bleaching technique is probably with hydrogen
peroxide. For the bleaching of yarn or fabric in a long liquor, the treatment
may be done with 0.5-1 vol hydrogen peroxide for 1 hour at 50-70°C.
Sodium silicate, soda ash, detergent and preferably a sequestering agent
are added. In cold pad-dwell process, the desized viscose fabric is padded
with warm alkaline (soda ash and sodium silicate) peroxide solution, so as to
achieve a pick-up of 0.4% o.w.m hydrogen peroxide (35%) and is then
batched.
HWM fibres are bleached whiter and are degraded less during bleaching
as compared to normal viscose. In all cases of bleaching, with sodium
hypochlorite in particular, the crystallinity is reported to increase [5]. The
reported optimum conditions for peroxide bleaching is at pH 10 and 85°C for
one hour with 0.6-1 g/l sodium silicate as stabiliser.
Combined Hypochorite-peroxide Bleaching
For better whiteness at low cost and to avoid problems due to improper
scouring, lightly scoured materials may be given hypochlorite bleach at cold
followed by hydrogen peroxide bleaching. The combined process is known
as full bleach in textile trade.
The advantages of this method are:
1. A high degree of whiteness can be achieved on heavily discoloured

materials.
2. The danger of degradation of cellulose by hypochlorite is remote due
to the presence of impurities in improperly scoured materials.
3. The hydrogen peroxide with its virtually negligible degrading action
completes the bleaching.
4. The hydrogen peroxide acts as anti-chlor, destroying residual
hypochlorite and chloramines.
5. The method is very useful if kier-boiling is not possible due to
economic or technical reasons such as treatment of cotton-rayon
mixtures.
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A combined bleaching process for cotton yarn in package dyeing machine

is as follows [2]:
1. The yarn is scoured at boil for 30 minutes with soda ash and
detergent.
2. The material is rinsed, cooled and bleached below 40°C in liquor
containing sodium hypochlorite solution with 1.5 g/l of available
chlorine.
3. The liquor is drained and the material is rinsed with cold water.
4. The machine is filled with bleaching liquor containing:
Trisodium phosphate – 1.6 g/l
Caustic soda – 1.7 g/l
Soda ash – 0.3 g/l
Magnesium sulfate – 0.03 g/l
5. The temperature is raised to 90°C and the circulation is continued for
45 minutes.
6. The material is washed with soft water at 90°C.
7. Final cold wash with soft water.
Combined bleaching with hypochlorite and peroxide is increasingly

winning favour increasingly in modern continuous pretreatment, at the
expense of the two-stage process with alkaline scouring and peroxide. The
main reason for this is the gradual disappearance of the unjustified fear of
hypochlorite in the textile industry. The continuous process too, is based on
the fact that the cheap hypochlorite does the lion’s share of the bleaching,
raising the whiteness from grey to 75-80%, and leaving only 5-10%
improvement to be achieved by the costly peroxide stage. Because the
residual chlorine on the cloth activates this second stage too, significant
saving of peroxide is thus achieved. Occasional fibre damage is
encountered during batchwise hypochlorite bleaching in jiggers, winches
and rope bleaching, but these systems differ fundamentally from continuous
pre-treatment in open width – greater control in continuous systems largely
eliminates the possibilities of fibre damage.
Overdosing even up to twice the proper amount of active chlorine causes
no damage of cellulose with continuous pre-treatment, because the dwell
time is short (7-10 minutes instead of more than 30 minutes in batch
process) and the available chlorine remains restricted due to a M:L ratio of
1:1.
Apart from its chief application for cotton and blends, the combined
process is suitable for other fibres like jute, flax, etc. For coloured materials,
the problem of colour bleeding during bleaching may be overcome by mild
hypochlorite bleach followed by a cold peroxide bleach.
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Combined Scouring and Bleaching of Cotton

The advantages of this process are increased production with reduction in
labour cost and reduced treatment time, lower consumption of water, steam
and electricity. The loss in weight and strength of material is less. The
disadvantage is increased chemical cost as a higher dose of hydrogen
peroxide is required. The declining price-rates of peroxide with increasing
cost of utilities may make the process more economical. In the presence of
hydrogen peroxide, the scouring process is accelerated and less time is
generally required to achieve good absorbency of the material.
The process may be carried out in conventional machinery by treating
grey, desized or mercerised fabric directly with caustic soda, soda ash,
scouring aid, hydrogen peroxide, sodium silicate or other peroxide stabiliser
at or above 80°C for 4-6 hours, depending on the type of fabric and
machinery used for the process. To adopt the process, the scouring-aids
play an important role. Many solvent-based compositions are available in
the market. The solvents remove wax and grease and the emulsifier
incorporated removes the impurities and keeps them in suspension. A major
portion of such composition is nonylphenol ethylene oxide condensate.
However, objections are being raised against these products due to water
pollution problem by solvents. Eco-friendly solvent-free products are
composed of high HLB anionic surfactants, anti-redeposition agents and
very powerful hydrotope.
A very popular machine for carrying out combined scouring and bleaching
of lightweight woven fabrics is the jigger. This is basically a dyeing machine,
processing cloth in open width form. However, dyeing jiggers are of less
capacity (50-100 kg per batch), whereas jiggers used for combined
scouring-bleaching are of high capacity – jumbo jiggers (300-500 kg per
batch) . The trough of the jumbo jiggers may be V-shaped or rectangular to
accommodate very thick cloth wound rollers. This is a low cost machine
suitable for small process houses. Synthetic and blended shirting, suiting,
cotton poplin and drill fabric can be successfully prepared for dyeing.
Scouring and bleaching can also be carried out successively in this
machine.
In a jigger (Figure 5.4), the material is wound, in open width, over two
rollers (A) standing above a shallow trough containing liquor. The rollers, by
rotating in clockwise and anti-clockwise directions alternately, pull the cloth
backward and forward through the liquor, complete immersion being
ensured by guide rollers (B) at the bottom of the trough. Only a few metres
of the cloth piece are immersed in liquor at a time, making it possible to work
with exceedingly short liquor. The reversal of the direction of rotation of the
rolls is controlled either automatically or manually with the help of levers.
There is an additional roller (C), which may be placed on the cloth-wound
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roller. The purpose of this roller is to squeeze out liquor from the cloth at the
end of treatment. The rollers may be made of stainless steel or ebonite.
Delicate knit goods and pile fabrics require low tension and minimum
machine contact to prevent damage. Batch operations are possible on
winches, low-tension jets and large vats called beck.
A A
B B
B B
Fig. 5.4 Jigger Machine
5.3.3 Chlorite Bleaching

Since its commercial production in 1939, sodium chlorite has achieved an
ever-increasing demand as a bleaching agent for cellulosic fibres.
It has several advantages:
1. It is the only bleaching agent which is applicable under acidic

condition. This is advantageous for white cellulosic goods, which can
be bleached without scouring. The natural oils and fats remain intact
and hence, natural softness is preserved for such goods. The weight
loss is also low.
2. As a bleaching agent, it is versatile and may be used not only for
cotton but also for many other fibres and their mixtures. It is
particularly useful for rayons, which require milder and prolonged
bleaching. Sodium chlorite is also used for bleaching of synthetic
fibres like polyamide and polyester.
3. When applied under recommended conditions, high whiteness is
achieved without degradation of cellulose.
4. Traces of ions do not catalyse bleaching reactions and do not bring
about degradation of cellulose.
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5. Rinsing after bleaching is simpler as no fibre-substantive alkali is used

as in case of hypochlorite and peroxide bleaching.
However, sodium chlorite bleaching has the disadvantage of the strong

corrosive action exercised by bleaching chlorite solution on the equipment,
so that the equipment is to be made of ceramic, plastic or special steel
equipment. If normal stainless steel equipment is used, certain corrosion
inhibitors are to be added and enough precautions are to be taken for its
longer life. Chlorite bleaching is to be carried out in a closed vessel with tight
sealing of the equipment and good ventilation is to be maintained in the
bleaching room as noxious chlorine dioxide evolves during bleaching.
Manufacture
Sodium chlorite is a fine white, slightly hygroscopic powder and when mixed
with a small quantity of alkali, can be stored in solid form for an indefinite
period.
Sodium chlorite is produced by reaction of chlorine dioxide with sodium
peroxide:
Na2O2 + 2ClO2 = 2NaClO2 + O2 (5.28)
It may also be prepared by passing chlorine dioxide gas through a solution
of sodium hydroxide.
2ClO2 + 2NaOH = NaClO2 + NaClO3 + H2O (5.29)
The undesirable sodium chlorate is converted to sodium chlorite by
reaction with hydrogen peroxide or sodium peroxide.
NaClO3 + H2O2 = NaClO2 + H2O + O2 (5.30)
The resulting solution containing sodium chlorite only is evaporated and
the residue is dried and packed. The product should be stored in a dry place
in a sealed container. If allowed to dry on cellulosic matters like straw, wood
or textiles, sodium chlorite causes spontaneous ignition. Sodium chlorite
solution (300-325 g/l) is safer to handle. The powder form is white or yellow
in colour containing about 80% sodium chlorite. It is readily soluble in hot
and cold water.
Chlorine dioxide is obtained by reaction of chlorates with hydrochloric
acid. At first step, chloric acid is formed which reacts with hydrochloric acid
in two stages:
HClO3 + HCl = HClO2 + HOCl (5.31)
HClO3 + HClO2 = 2ClO2 + H2O (5.32)

An unwanted side reaction may be as follows:
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HOCl + HCl = H2O + Cl2 (5.33)

In order to suppress this side reaction, a reducing agent like sulphur
dioxide, methyl alcohol or formaldehyde is used.
HOCl + H2SO3 = HCl + H2SO4 (5.34)
Commercially chlorine dioxide is manufactured from sodium chlorate,
which is further obtained from electrolysis of sodium chloride solution. All
the processes are based on treatment of sodium chlorite with a reducing
agent in the presence of an acid. In the Mathieson process, 46% solution of
sodium chlorite and concentrated sulphuric acid is continuously fed into a
reaction vessel. A mixture of sulphur dioxide and air is blown
simultaneously. The chlorine dioxide thus formed may be used directly or
may be dissolved in a absorption tower with a downward flow of chilled
water.
Estimation
Like sodium hypochlorite, sodium chlorite liberates iodine from an acidified
solution of potassium iodide, which can be titrated with N/10 sodium
thiosulphate using starch as an indicator.
1 c.c. of N/10 sodium thiosulphate ≡ 0.00226 g of sodium chlorite.
Bleaching Action
Sodium chlorite is a medium-strength acid and hydrolyses in water to a
limited extent [5]. It is only active in acidic solution. Chlorous acid
decomposes into chlorine dioxide, chlorate, chloride and oxygen in acidic
solutions:
– – –
5ClO2 + 2H+ = 4ClO2 + Cl + 2OH (5.35)
– – –
3ClO2 = 2ClO3 + Cl (5.36)
The reactions depend on the pH. Above pH 5, the solution decomposes
slowly and at pH above 7 it becomes virtually stable. Below pH 5, the
decomposition mainly produces chlorine dioxide and chlorate. A small
amount of chlorine dioxide is decomposed into chlorine and oxygen.
Addition of sodium chloride to sodium chlorite solution increases the
efficiency of bleaching possibly by reducing chlorate formation with
simultaneous release of chlorine, which synergistically increases bleaching
efficiency of chlorine dioxide.
289
Chlorine dioxide is believed to be responsible for bleaching. However,

some study also showed that sodium chlorite can bleach under conditions
where no chlorine dioxide can exist. Agster believes that chlorine dioxide
does not directly act as bleaching agent; bleaching occurs only in the
presence of water when it is converted to chlorite and chlorate. According to
Peters, the chlorite ions must be at least partly responsible for bleaching [5].
Chlorine dioxide is more hazardous than chlorine and causes corrosion of
the equipment. Hence, its liberation should be controlled and should be
equal to the rate at which it can be consumed by the impurities in cotton.
Under optimum condition sodium chlorite does not degrade cellulose. But
significant degradation may occur when it is used in large excess or when
the pH is high.
The optimum condition for bleaching is at pH 4 at a temperature of 85-
95°C for a period of 30 minutes to 6 hours. The required concentration of
sodium chlorite is 5 g/l in long liquor, 20-30 g/l in pad-batch process and 70
g/l in continuous units like J-box.
At pH between 2.5 and 3.5, the liberation of chlorine dioxide would be
more rapid than its potential consumption in the bleaching process. A study
[22] showed that pH 4.5 represents a reasonable practical compromise
between the utilisation of the chlorine dioxide produced and time cycle
required for the operation. At pH 2.6 about 34% of the sodium chlorite is
wasted by conversion into chlorate, the wastage will be negligible above pH
8.5. However, at such high pH the bleaching will be too slow and the
degradation of cellulose will be very high. For practical purposes, the
optimum pH will be 5.5, but for the sake of greater productivity, the
bleaching is mostly done in the range of pH 4 to 4.5. At higher pH values
less chlorine dioxide is evolved, which means a reduction in toxic hazard
and vessel corrosion.
Acids can be used as activators in sodium chlorite bleaching. Mineral
acids like hydrochloric and sulphuric acids are not used due to their
corrosive nature, harmful effect on cellulosic materials and difficulty in
maintaining pH. Organic acids such as formic or acetic acid are, therefore,
preferred. Various sodium salts such as sodium dihydrogen phosphate,
disodium hydrogen phosphate, disodium pyrophosphate, tetrasodium
pyrophosphate, sodium formate and sodium acetate can be used as buffer.
The phosphates exert a protective action against the corrosive effect of
chlorine dioxide on stainless steel. The activator should also increase the
utilisation of chlorite by decreasing the formation of chlorate.
Various compounds, which hydrolyse in hot aqueous solutions such as
diethyl tartrate and ethyl lactate, can be used as activators for pad-steam as
well as long liquor batch processes. Ammonium chloride, sulphate and its
aliphatic caboxylic acid salts may also be used. The evolution of chlorine
dioxide will be slow (causing less environmental pollution) as these
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compounds will hydrolyse slowly at high temperature throughout the

bleaching cycle. However, they need high temperature of treatment and
higher concentration of sodium chlorite than organic acid activators.
Formaldehyde may also be used as activators. There is almost
quantitative decomposition of sodium chlorite with the formation of chlorine
dioxide, when goods are impregnated with a solution containing sodium
chlorite and formaldehyde and stored overnight in an airtight container or
cover. The probable, but controversial reaction may be as follows:
2 NaClO2 + HCHO = NaClO3 + HCOOH + NaCl (5.37)
Most metals are rapidly corroded by acidified solutions of sodium chlorite.
Wooden vessels have reasonable resistance. Complete resistance may be
achieved with ceramic-lined glass, stoneware and titanium plants. Stainless
steel containing 2 to 5% molybdenum in addition to the normal content of
18% chromium and 8% nickel may be used following certain precautions.
The resistance depends upon the formation of very fine surface films of
metallic oxides. The surface irregularities may cause local breakdown of the
protective film and a well-polished surface is of utmost importance.
Occasional pacification can be made by treatment with 10 to 20% nitric acid
for 10 to 30 minutes. The treatment may be made after every fourth to sixth
bleach. Hydrogen peroxide is also capable of restoring the protective film.
A stainless steel plant will be serviceable for an almost indefinite period, if
chlorite and peroxide bleaching processes are carried out alternately or
even if peroxide bleaching is done occasionally. Sodium nitrate is also
effective as a protecting agent or corrosion inhibitor. Some commercial
inhibitors are based on inorganic fluorides. They act as a buffer at pH 4 and
suppress the evolution of chlorine dioxide. The inorganic fluoride forms an
iron-fluoride complex, which protects stainless steel and reduces the risk of
yellowing of the materials by the trace contaminated-iron.
Batch Process
Although it is possible to use a detergent stable at pH 4 during bleaching, It
is common practice to scour the desized goods first. There are a number of
pretreatments used in practice which range from an enzyme desizing and a
soda ash scour to a 2-3 hours boil in 10-30 g/l sodium hydroxide in the
presence of wetting agents.
Chlorite bleaching may be carried out in a kier using liquor (% o.w.m.)
containing [2]:
Sodium chlorite (80%) – 1-2%
Sodium dihydrogen phosphate – 0.25-0.5%
Wetting agent – 0.1-0.25%
Formic acid is then slowly added with stirring to bring the pH between 3.8
and 4.2 (about 1-1.2 ml per litre). The liquor is circulated cold for 20 to 30
291
minutes and then the temperature is raised to 80 to 90°C over a period of 1

to 1½ hours. The temperature is maintained for a further 2 to 3 hours with
occasional checking of pH, which is to be within the specified range. This is
followed by the treatment with soap and soda ash and finally washed with
water. For very compact materials, two consecutive bleaching treatments
may be necessary.
For bleaching in package dyeing machine or in winch, the composition of
the liquor may be as follows:
Sodium chlorite (80%) – 2-4 g/l
Sodium dihydrogen phosphate – 1 g/l
Sodium nitrate – 1-2 g/l
Wetting agent – 1-2 g/l
Required amount of formic acid to bring pH to 3.8-4.2.
After running for 10-15 minutes at cold, the temperature is raised to 80-
85°C and maintained for 1-2 hours. This is followed by soaping and
washing.
Semi-continuous Process
The consumption of sodium chlorite can be greatly reduced by employing
pad-roll process. The fabric is padded with a solution containing:
Sodium dihydrogen phosphate – 3–5 g/l
Wetting agent – 2-3 g/l
Sufficient formic acid to maintain pH between 3.8 and 4.2.
It is heated in a steam chamber and then rolled up in a heated condition in
a sealed heat-retaining chamber for 4-8 hours. After completion of
bleaching, the cloth is taken out and given an anti-chlor treatment with
bisulphite or soda ash scald.
The simple cold pad-stack method is advantageous for small-scale
production using only padding mangle and polyethylene bags or sheets. The
scoured material is impregnated with a solution containing:
Sodium chlorite (80%) – 10 g/l
Sodium carbonate – 1 g/l
Wetting agent – 3 g/l
Formaldehyde (40%) – 2-3 ml/l
The fabric is padded with 85-100% expression. It is then covered with
polyethylene sheet and kept overnight without external heating.
Formaldehyde is to be added just before padding. After storing, the goods
are run through liquor containing 1 g/l soap and 5 g/l soda ash at a
temperature of 80°C.
Continuous Process
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The batch process of sodium chlorite bleaching may be uneconomical as

compared to other oxidative bleaching agents due to high consumption of
sodium chlorite. The consumption reduces significantly in continuous
method, based on padding and subsequent storing at 95°C for 90 minutes in
a J-box. Prolonged alkaline scouring is not necessary, as it does not form
chloramines as in case of sodium hypochlorite. This avoids the risk of
degradation of cellulose and colour variation due to varying extent of
scouring at different portions of the fabric. Thus, a uniform whiteness is
obtained as compared to other oxidative bleaching agents.
The cloth is first lightly scoured in a J-box with 2 g/l detergent with or
without caustic soda/soda ash followed by washing. The consumption may
be only 1.2% (o.w.m.) as compared to 2% or more in batch process. The
padding liquor may contain:
Sodium dihydrogen phosphate – 3-5 g/l
Wetting agent – 0.5 g/l
Sufficient formic acid to maintain pH 3.8-4.2.
After emerging from the J-box, the cloth is passed through a continuous rope
washing machine and washing may be carried out with cold water or a hot
soda ash scald.
Bleaching of Synthetic Fibres
Acetate fibres are usually sufficiently white and require no bleaching, unless
very bright pastel colours are to be dyed or a super-white material is
required. Hypochlorite may be used for bleaching secondary acetate, but
yellowing may occur on heat-setting. Hydrogen peroxide or peracetic acid
may be used at 60°C or sodium chlorite at 80°C. In case of hypochlorite or
chlorite bleaching, the treatment should be followed by antichloring.
The polyamide fibres are largely bleached with sodium chlorite. It gives
better whiteness than that obtained by hydrogen peroxide or peracetic acid.
It does not have any harmful effect on the fibre. The bleaching liquor may
contain:
Sodium chlorite (80%) – 0.5-2.0 g/l
Tetrasodium pyrophosphate – 0.5-1.0 g/l
Wetting agent – 0.5-1 g/l
Sufficient formic acid to maintain pH between 3.8-4.2
The bleaching is carried out at 80-85°C for 30-60 minutes. After bleaching,
the material is washed with hot and cold water followed by antichloring with
1-2 g/l sodium bisulphite at 20-55°C for 15 minutes. The material is finally
washed with cold water.
100% polyester fabrics contain few impurities and have a naturally good
white colour. Sodium chlorite has some bleaching effect on polyester – other
293
bleaching agents are ineffective. It does not cause damage to the fibre and
indeed, there is a slight increase in the degree of crystallisation. The
bleaching may be carried out with 1-5 g/l sodium chlorite for about 1 hour,
best at 98-100°C and practically at 90-95°C, to minimise the evolution of
intolerable chlorine dioxide.
Acrylics also possess good natural whiteness and for extremely good
whiteness, bleaching may be carried out with sodium chlorite solution
containing:
Sodium chlorite – 1.5 g/l
Stabiliser (polyphosphates, formates,
borax to control release of chlorine dioxide) – 1-2 g/l
Oxalic or formic acid to bring pH between 3.8 and 4.2 – 2 g/l (approx.)
Nonionic detergent and fluorescent whiteners stable to chlorine dioxide
may be incorporated in the bleaching bath for simultaneous scouring and
optical whitening respectively.
The use of oxalic acid provides stability of whiteness of the bleached
fabric to light and heat. Oxalic also prevents interference of metallic ions,
especially iron. However, it has now proved to be toxic. The bleaching is
carried out at 90°C for one hour followed by antichloring.
5.3.4 Peracetic Acid Bleaching

In recent years, this compound has come into use, particularly for the
bleaching of synthetic fibres. It is the acetyl derivative of hydrogen peroxide:
CH3COOH + H2O2 ↔ CH3·CO·OOH + H2O (5.38)
The more concentrated the acetic acid, greater will be the yield of
peracetic acid. About 1% sulphuric acid acts as a catalyst when the yield of
peracetic acid increases significantly. The best result is obtained by mixing
acetic anhydride and 90% hydrogen peroxide at room temperature in the
presence of a catalyst.
In an improved method of manufacture, acetaldehyde is oxidised in the
presence of air, ozone and an inert solvent such as ethyl acetate at 0°C.
The unreacted acetaldehyde is removed by distillation and then recycled
into an oxidising unit. The remaining solution of acetaldehyde mono-
peracetate in ethyl acetate is heated to 100°C in vacuum. The solvent is
volatilised and the mono-peracetate breaks down into peracetic acid.
Peracetic acid is available as a clear, colourless, fairly stable solution of
36-40% strength. A typical commercial composition may be 36 to 40% of
peracetic acid, 3 to 6% of hydrogen peroxide and the remainder acetic acid
and water. Highly concentrated solutions are difficult to handle, as the acid
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is volatile and has a pungent irritating smell, though not toxic as chlorine
dioxide.
Bleaching Action
Peracetic acid bleaching may be carried out both with industrially produced
peracetic acid, and so called equilibrium peracetic acid, the mixture of
acetic anhydride and hydrogen peroxide, which form peracetic acid in the
bleaching bath. Storage, handling and changing price relationship between
the two components continually tend more towards the use of equilibrium
peracetic acid [23].
A free-radical mechanism cycle can be assumed for peracetic acid
decomposition in the bleaching bath, the perhydroxyl radical acting as an
active bleaching species. The radicals are formed according to the equation
below:
CH3·CO·OOH Æ CH3COO· + ·OH (5.39)
The stability of peracetic acid is not quite as high as that of stabilised
hydrogen peroxide. Peroxide bonds are rather weak and can be broken to
give a supply of free radicals, which are possibly responsible for attacking
cellulose during bleaching.
As the character of this acid is chemically similar to hydrogen peroxide, it
is expected that free radicals may be produced in greater numbers in the
presence of ions such as copper, iron, etc. To avoid damage to the cloth, a
sequestering agent (e.g. diethylenetriamine-penta-acetic acid) may be
added to remove these catalytically active ions which can be absorbed by
some of the synthetic fibres [24]. Other stabilisers of peracetic acid are
sodium hexametaphosphate and sodium pyrophosphate.
Bleaching Conditions
Peracetic acid has been put forward in recent years as a suitable bleaching
agent for many fibres – nylon, viscose rayon, cellulose acetate and even
cotton as a possible substitute of hydrogen peroxide. It is particularly
recommended for bleaching nylon, which has become yellow during heat-
setting process. Degradation of nylon by peracetic acid is not significant and
is not dependent on pH.
Bleaching may be carried out on nylon for about one hour at 80°C using 3
g/l peracetic acid (36-40%), 0.2 g/l sodium pyrophosphate and wetting agent
at a pH between 6.0 and 7.5 with dilute caustic soda.
It is possible to bleach viscose and acetate fibres satisfactorily at pH of 6-
8, no damage by saponification will occur to the acetate fibres.
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For cotton fabric, optimisation was carried out [23] on the basis of degree
of whiteness, loss of DP, weight loss and economic considerations for
bleaching of cotton fabric with peracetic acid. The stated optimum conditions
are:
Concentration: 15 g/l of 15% peracetic acid
Stabiliser: 3 g/l sodium hexametaphosphate
pH value: 7
Temperature of treatment: 70°C
Time of treatment: 60-70 minutes
The degree of whiteness is comparable with that obtained with sodium
hypochlorite. The fibre damage is less and AOX value (chlorine containing
compound) is low.
5.3.5 Enzymatic Processes

Oxidoreductases, enzymes that catalyse oxidation or reduction reactions,
may find use in enzymatic bleaching process. Although some degree of
colour removal is possible through the use of selected enzymes, seed
coatings remain a severe problem.
5.3.6 Combined Preparatory Processes

The modern approach to integrated chemical pretreatment involves
combined desizing-scour-bleach operation using continuous open-width
pad, steam, wash off, dewater and dry sequence. Alternately, enzyme
desizing may be carried out by amylases, separately followed by alkaline
oxidation using caustic soda, hydrogen peroxide and a wetting agent. A one-
step process for desizing, scouring, bleaching and slack mercerising
process is described below [25]. The cotton fabric is impregnated in a mixed
solution containing sodium hydroxide (10-30%), hydrogen peroxide (20 g/l)
and trichloroethylene (50 g/l) for 3 minutes, followed by curing for 30
seconds at 120°C. The physical properties of the treated material are similar
to those obtained using a conventional two-step approach. Potassium or
sodium peroxodisulphate may be incorporated in the recipe while carrying
out integrated processing. However, oxidative treatment gives rise to
oxidative damage and complete removal of the primary wall of cotton.
Careful monitoring is essential to minimise fabric damage [26].
The use of a single product simplifies recipes and promotes easier
handling. A unique product, Ciba Tinoclarite FS (CIBA) has been developed
for one stage Flash Steam procedure for desizing, scouring and bleaching. It
is a phosphorous-free combination of a bleach processor, dispersant,
wetting agent and detergent. Within 2-4 minutes of steaming (saturated),
with tight strand guidance throughout, loom-state goods are brought to
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whiteness suitable for dyeing. This is advantageous especially for crease-

prone fabrics. The recommended recipe for padding is as follows:
Ciba Tinoclarite FS – 15-30 ml/kg
Caustic soda solid – 30-50 g/kg
Hydrogen peroxide (35%) – 45-90 ml/kg
Similarly, Ciba Tinoclarite PD is developed for cold pad-batch peroxide
bleach. No other auxiliary is required except the bulk chemicals like
hydrogen peroxide and caustic soda [27].
5.3.7 Bleaching of Knitted Goods

The machines used for the bleaching of knitted fabrics have undergone
great development and changes in recent years.
Warp knits used for fishing nets, industrial fabric, etc. usually require
100% synthetic filament yarns and do not normally require bleaching. The
vast majority of knitted structures are weft knitted fabrics produced in 100%
cotton and much less commonly polyester, polyamide, polyacrylonitrile. The
fabrics may be called jersey, rib or fleece, depending on how the loops lie.
The bleaching stage is made easier by having goods with an open
structure, which promotes liquor penetration and absorption. The open
structure also allows easier washing out of residual chemicals. Since knitting
yarns are unsized and usually combed to reduce seed and trash content,
normally there is no need for any treatment prior to bleaching. The knitting
lubricants, which replace the size on woven fabrics are usually self-scouring,
but sometimes they may create problems with foam and stains in wet
processing or on the knitting machine, which need to be treated with
solvent-containing auxiliaries.
Outside India, a country that has traditionally favoured it, hypochlorite
seems to have been negligibly used for bleaching of knitted fabrics. A major
problem with hypochlorite is the ease with which it loses available chlorine,
making the bleaching process quite variable unless the activity is measured
just before use. In any case, the recent restrictions on absorbable
organohalogen compound (AOX) generation effectively rule out its use as a
single-stage bleach.
The acidic nature of sodium chlorite bleaching process made it ideal for
knitted fabrics, as the natural fats and waxes of the fibre were not scoured
out, enhancing the soft, voluminous handle of the goods. In 1970, Ney and
Patrick reviewed the use of chlorite on the J-box and this became known as
the Packsystem. Later the J-box was especially made of titanium, a material
less prone to corrosion than stainless steel. However, the system was
never popular for cotton, although it is still used for processing bast fibres.
A combination of hypochlorite and peroxide bleaching gives maximum
whiteness, whilst a combination of scour and peroxide bleach gives least
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whiteness. The first of the combined hypochlorite-peroxide processes was

the Böhme C-S or activated bleach, where the fabric was treated with
hypochlorite and then without washing off, treated with peroxide. This
combined process gave very high whiteness. In the modified process,
hypochlorite process is carried out for several minutes at cold in a scray or
Gnatt piler and after washing off, the fabric is peroxide bleached by pad-
steam process. Adequate whiteness is achieved with 20 ml/l hydrogen
peroxide (35%) and 30 minutes steaming. The process is seldom used on
knit-goods, but is normally used for woven fabrics in India [28].
For ecological reasons, processes involving chlorine are not acceptable in
various part of the world. On the other hand, the reproducibility of whiteness
is poor with hydrogen peroxide. It also lacks bluish tint of hypochlorite
bleach. However, it is still possible to an acceptable level of whiteness for
dyeing in pastel shades, or even full white by using a special metal
extraction procedure before peroxide bleach, with especially developed
auxiliaries like Lusynton SE (BASF), Eulysin S (BASF) or Sirrix 2UD liq.
(Clariant) (Section 5.3.2). Cold pad-batch bleaching gives insufficient
whiteness and insufficient removal of calcium or magnesium salt produces a
negative effect in subsequent dyeing process.
The major problems of impregnating tubular goods in pad-batch method
are the ironing in of the edge, and build up of the batch either on rolls or in
trucks. The Reaktol mangle of Jawatex, the dy-Rol mangle of Tub-tex and
the applicator of the Calator Airtex unit, all seem to offer suitable
alternatives, but there is still some concern about the edge creases and
more and more dry slit goods are cold-pad-bleached using a small volume
trough to apply bleach liquor and a Bianco guider to roll the fabric onto a
perforated beam on an A-frame. The goods are wrapped in a plastic sheet
and rotated for the bleaching time (usually overnight). The plastic sheet is
then removed, the beam connected to a hose and the fabric is beam-
washed. Alternately, slit fabric is batched dry onto the perforated beam. A
pair of such beams is then connected to the delivery side of a pump and
warm bleach liquor is passed from a common reservoir through both beams.
The suction side of the pump is connected to the swallow trays mounted
near the base of the perforated beams. A typical saturator recipe for cold-
patch process (assuming 100% pick-up) is as follows:
Magnesium sulfate – 0.1 g/l
Wetting agents – 2-5 g/l
Organic stabilizer – 0-15 g/l
Sodium silicate (79ºTW) – 10-15 g/l
Caustic soda solid – 10-20 g/l
Hydrogen peroxide (35%) – 40-60 ml/l
For continuous processing of knit-goods, J-boxes are no longer in use.
Several other machines have been developed, such as spiral winches,
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Galaxy (Brückner, combination of a J-box and flattened open-width tube),

Uni-Wash washer (Aroili), Spray-Tex jet washing unit and Traflo-Tex suction
drum washer (Babcock). The actual bleaching in the last two machines are
carried out in a reservoir called Store-Tex unit [29].
Store-Tex compartment (Babcock) is used for storing fabric on roller bed
and steaming of knitted and woven fabric in scouring and bleaching
processes, which require lengthy treatment and dwell times. The fabric
enters via a low-lying lock in the base of the unit and leaves the
compartment through a water-lock. Used as a steamer, the Store-Tex
compartment can be controlled with saturated steam (free of air, controllable
up to 100º C). The excess steam is drawn-off from the fabric entry lock
through extraction ducts. A system for operation with a defined steam-air
mixture is also possible. When a wetting trough is used, the admixture of
chemicals takes place in the wetting trough. The deposited fabric on the
roller bed can be either sprinkled from tangential conical nozzles or
moistened by means of pouring channels. A circulating pump returns the
liquor from the floor to the nozzle via a steam-jet heater. For short batching,
Mini-Store unit is developed. To cater optimally for the various tasks, fabric
types and operating requirements, the Store-Tex unit can be used in
conjunction with Spray-Flow and Convi-Tex C (Babcock, Germany)
compartments [28].
All reactive dyeing systems may be considered as an extension to
scouring because of alkaline fixation conditions. The scouring effect that
takes place during the dyeing stage will be a function of the alkali used for
fixation and the fixation temperature. Integrated pretreatment and dyeing
processes favours hot dyeing systems such as eXceL – controlled coloration
with Procion H-EXL dyes. The scouring (eXceL Scour) may be carried out at
60ºC for 30 minutes with special auxiliaries. This is immediately followed by
dyeing without intermediate wash. The carry-over products have a minimum
impact on the Procion H-EXL dyeing. Similarly, eXceL Bleach process has
been developed for pale or pastel shades. These provide a Load to Unload
concept for dyeing cotton knit-goods with reactive dyes systems.
Knitted cellulosic goods are generally not sized. Such materials can be
lightly scoured with 4-5 g/l soap or 2 g/l synthetic detergent and 1 g/l soda
ash at boil for 30 minutes and then bleached with sodium chlorite in a winch
machine with a liquor containing:
Sodium dihydrogen phosphate (anhydr.) – 1 g/l
Sodium nitrate – 1 to 3 g/l
The goods are allowed to run in this liquor for 5 to 10 minutes, after which
sufficient formic acid (about 0.5-1 g/l) is added to bring the pH between 3.8 and
4.2. The temperature is gradually raised to 80-90°C at which it is maintained
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for 1½ to 2½ hours. The pH is to be checked from time to time and adjusted,

if necessary. The process is very suitable for white goods, as natural softness
will be retained due to light scour. If the goods are to be dyed, a subsequent
anti-chlor treatment is to be carried out with 0.5 g/l sodium bisulphite and 0.1-
0.2 g/l formic acid for 15 minutes at boil. The degree of whiteness may be
improved by a sodium carbonate treatment, with or without previous bisulphite
treatment using 1-2 g/l sodium carbonate and 1 g/l soap at 80-90°C for
15-30 minutes.
5.3.8 Bleaching of Coloured Goods

In certain varieties of fabrics, coloured threads are used in warp or weft e.g.
saris, check shirting etc. Such fabrics may be required to be bleached if they
are soiled during weaving. Generally bleaching is done with hypochlorite at
cold. Dyes of all classes are not stable under the bleaching condition. Vat
and azoics are suitable for the purpose.
Processing of coloured goods is to be done with certain precautions. The
dyes may bleed in the processing liquor. These may get reduced during
alkaline scouring by the residual starch or get oxidised by the bleaching
agent.
The fabric is first desized by a powerful desizing agent such as enzyme,
and thoroughly washed to remove solubilised starch. Mild alkali boil is done
at 60-70°C using 0.5% soda ash and 0.5% soap, or detergent along with
resist salt (sodium salt of m-nitrobenzene sulphonic acid), to prevent
reduction of the dye. After thorough washing, mild bleaching is done with
bleaching powder solution or sodium hypochlorite solution (2 g/l available
chlorine) for 30-60 minutes, followed by souring. Colored goods can also be
bleached in kier using lower amount of hydrogen peroxide (maximum 4%),
soda ash (1-1.5%) and required quantity of sodium silicate at about 80°C.
5.3.9 Bleaching of Jute

Although jute fibres contain considerable amount of impurities, jute materials
are generally bleached without prior scouring due to its alkali sensitivity. Jute
differs from linen in its high lignin content (about 11-12% dry weight). The
lignin, together with hemicellulose, provides inter-cellular binding material
known as middle lamella, holding the fibres together. In contrast to linen, it is
neither desirable nor necessary to delignify jute. Jute is effectively bleached
by hydrogen peroxide while most of the lignin remains.
A consequence of the presence of lignin in bleached jute is that its
whiteness is not fast to light and there is gradual reversal to the original
colour (photo-yellowing). Though the best varieties of jute are sufficiently
white to allow dyeing without bleaching, it is difficult to achieve light-fast
dyeing in pale and medium shades. The presence of UV radiation in sunlight
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in the range of 330-370 nm causes yellowing. Lignin breaks on UV

exposure, leading to the formation of orthoquinones and other
chromophores (i.e. chemical groups, which absorb visible light resulting in
colour sensation) [30].
In order to produce different degrees of whiteness ranging from pale
cream to milk white, jute fabric may be bleached and oxidised by controlled
treatment with selected oxidising agents. The treatments with calcium or
sodium hypochlorite and hydrogen peroxide are done under alkaline pH,
sodium chlorite and potassium permanganate under acidic pH, peracetic
acid in neutral or slightly acidic pH.
Bleaching Processes
Jute may be successfully bleached with sodium hypochlorite solution having
3-7 g/l available chlorine, using sodium carbonate to maintain pH of 10-10.5
at room temperature for 1-2 hours. It is advisable to add 1-2 g/l wetting
agent, when the material is directly bleached without scouring. It is then
washed and antichlored with 0.2% sodium sulphite for 20 minutes at 50°C.
Sodium chlorite is suitable for bleaching and delignification of jute. It
removes more lignin than hydrogen peroxide. Treatment of jute fabric with
acidified 4% (o.w.m.) sodium chlorite solution, pH 4-4.5 at 90°C for
90 minutes improves the whiteness of the materials.
The bleaching with hydrogen peroxide causes a markedly lower loss of
weight (10% as against 17.9% in chlorite bleaching according to one study)
and a slightly lower loss in strength. A typical recipe for bleaching jute with
hydrogen peroxide in a jigger (% o.w.m.) is as follows:
Hydrogen peroxide (50%) – 3-6%
Sodium silicate – 6-8%
Caustic soda – 0.5-0.7%
Nonionic detergent – 0.2-0.5%
Chelating agent – 0.05%
pH: 11
Temperature: 80-85°C
Time: 2 hours
Sodium metasilicate may be used instead of sodium silicate, and trisodium

phosphate (1.5-2%) instead of caustic soda. After bleaching with hydrogen
peroxide the fabric should be thoroughly rinsed with hot water and cold
water, preferably followed by a treatment with 2 -3 g/l acetic acid. The
brightness of peroxide bleached jute material was found to increase when
pre-treated with an enzyme mixture containing cellulase and xylanase.
The conventional hydrogen peroxide bleaching requires treatment at high
temperature, which may damage jute materials. Cold bleaching may be
carried out by treating the material with a solution containing 6% hydrogen
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peroxide, 4% caustic soda, 4% sodium silicate, 2% soda ash and 1% soap,

followed by 24 hours storing at room temperature. The whiteness achieved
may not be very high.
A common practice is to achieve light-fast bleached jute materials in two
stages – first with sodium hypochlorite at pH 6, and subsequently with
hydrogen peroxide. Another light-fast bleaching process involves treatment
with an acidified solution of potassium permanganate, followed by discharge
of excess permanganate using a mild reducing agent.
Hutex bleaching
A number of approaches have undertaken to minimise the yellowing of
bleached jute. Among these, the most important process is Hutex bleaching
developed by IJIRA [31]. The process consists of three stages:
1. Chlorination
The jute fabric is treated with sodium hypochlorite containing 0.6%
available chlorine at pH 6 and at room temperature in a covered
jigger for 6 ends (end means complete one passage of the whole
length of cloth in the machine). Sodium hypochlorite liberates
nascent chlorine, which converts lignin at the surface of the fabric
into chlorolignin.
2. Extraction
The chlorinated fabric is rinsed in cold water for two ends and then
treated with 5% sodium sulphite solution at 70-75°C in a jigger for
45 minutes. This antichlorination step may be avoided, as residual
chlorine will be removed by subsequent hydrogen peroxide
treatment.
3. Bleaching
Bleaching is done with 3% hydrogen peroxide, 2.5% sodium
hydrogen phosphate and 1% sodium silicate for 1 hour at 70-75°C
at pH 10.
Extensive damage to fibres, violent evolution of hazardous chlorine gas

and high process costs are major drawbacks of the process. Chlorine
liberation may be reduced by adding 0.1% ammonium oxalate. In acid bath,
a strong tendency for chlorine retention by lignin is also reported.
Miles [32] suggested a treatment of bleached cloth with 2-8 g/l nickel
sulphate in acetic acid-sodium acetate buffer (pH 6) at 90-95°C for ½ hour to
improve photo-stability. The use of UV absorbers such as 2,4
dihydroxybenzophenone can prevent photochemical degradation of undyed
and dyed jute.
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5.3.10 Bleaching of Flax

Linen or flax is bleached either as yarn or in the form of cloth. Scouring and
bleaching may be preceded by singeing, and the appropriate desizing
process employed to remove the warp size. Usually there is no difficulty in
making linen materials absorbent, because the rate at which linen absorbs
water is significantly greater than that for cotton or viscose. This has been
attributed to the presence of nodes in the fibre.
Normally it is not possible to obtain a good white in one operation.
Whiteness is achieved in several stages and the choice of procedure
depends on the result required. The processes used are milder than those
used for cotton. However, the overall procedure is more complicated.
Unlike cotton, flax contains a small amount (about 2%) of lignin. This
component may be bleached with sodium chlorite or with hypochlorite under
acidic conditions, after which the lignin may be dissolved in dilute alkali. For
bleaching of yarn in a package dyeing machine, a scour is given with 8-10%
o.w.m. soda ash at a temperature of 95°C for two hours. The yarn, after
thorough hot and cold wash, is treated with hypochlorite solution containing
3-5 g/l available chlorine at room temperature for 30-45 minutes. The yarn is
then washed several times with dilute soda ash solution (0.5% o.w.m.).
Alternately, the yarn may be treated with 4% sodium chlorite solution at
80°C for 45 minutes maintaining pH of 3.8-4.2. The bleaching effect is better
in this case with lesser weight loss.
After chlorination, the yarn is treated with 0.5% (o.w.m.) hydrogen
peroxide along with soda ash and sodium silicate at 80°C for 60 minutes.
The process of chlorination, followed by peroxide bleaching, may be
repeated for a second time, if required. For very good whiteness, finally
alkaline hypochorite bleach may be carried out. The linen yarn may also be
bleached in hank form.
As caustic boil will be too harsh for flax, flax fabric is first boiled with lime
in a low-pressure kier for 8 to 12 hours. This is followed by soda ash boil for
about 6 hours. The fabric is then thoroughly washed and treated with
bleaching powder solution. As fabric processing machines are robust and
largely open, treatment under acidic condition may cause toxic hazard due
to liberation of chlorine gas. Hence, bleaching powder treatment is done
under alkaline condition. As in the case of yarn, the fabric may be treated
with 2-3% (o.w.m.) sodium chlorite at 80-90°C for 3-4 hours as an
alternative.
The fabric is then treated with soda ash and subsequently with 2%
(o.w.m.) hydrogen peroxide under alkaline conditions at 80°C for 4-5 hours.
Due to hard nature of some fabric, it may retain some metallic particles,
which could damage the cloth during peroxide bleaching. To prevent this
damage, 0.0025% (o.w.m.) sodium cyanide is added during soda boil.
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5.3.11 Bleaching of Wool

Approximately 10% of total world production of wool is bleached, although it
is difficult to quantify the amount of top-up bleaching in the last bowl of the
scour. The wetted wool carries hydrogen peroxide added to this bowl to the
dryer, where most of the bleaching takes place. Hydrogen peroxide is
virtually the only oxidative bleaching agent for protein fibres like wool and
silk. Hypochlorites have poor bleaching action and give rise to yellow
coloration and seriously tender wool in alkaline solution. Sodium chlorite
gives a pinkish white shade, which requires after-treatment with sodium
bisulphite.
While bleaching cotton with hydrogen peroxide, temperature may be
raised to 100°C or more and little regard is given to alkalinity. For wool and
other protein fibres, the control of alkalinity is most important as high
alkalinity may cause breakdown of polypeptide chains with consequent loss
in strength. The minimum alkalinity required to activate hydrogen peroxide is
sufficient to damage the fibre if the temperature exceeds 60°C. The
recommended pH is 8-8.5, which is much lower than that maintained during
cotton bleaching. Degraded wool fibres, such as chlorinated wool, are more
sensitive to alkali.
Iron or copper causes catalytic decomposition of hydrogen peroxide. If the
woollen material contains traces of such metals, there will be immediate
tendering of the material. However, the defect can be noticed during use
only. Adding sequestering agents in the bleaching bath can eliminate the
action of metallic catalysts. Under damp and slightly alkaline state, mildew
and enzymes may develop on the materials. Some of the enzymes also
cause rapid decomposition of hydrogen peroxide with the evolution of
oxygen. A vigorous effervescence appears on immersion of such materials
in peroxide liquor. The microorganisms can be destroyed by passing such
materials through a solution of hypochlorite having available chlorine less
than 40 p.p.m.
The rate of decomposition of hydrogen peroxide, and hence the rate of
bleaching can be retarded by stabilisers and accelerated by activators. The
most important function of the stabiliser is to maintain the internal pH of the
fibre, irrespective of the pH of the liquor, between 8 and 8.5. As far as the
buffering is concerned, sodium silicate and non-silicate mixed stabiliser,
Stabiliser C (probably a mixture of sodium oxalate and sodium
pyrophosphate) are the best. With sodium pyrophosphate, there is a
tendency for the solution to decrease in pH during bleaching from the
adjusted pH value of 8.5. With trisodium phosphate, on the other hand, there
is an increase of pH value depending on its concentration.
The compounds, which increase pH values such as sodium carbonate and
ammonia, can be used as activators. Higher alkalinity is harmful for wool,
304
whereas low alkalinity will slow down the bleaching process. The alkalinity
should be checked periodically and adjustments are to be made if
necessary. Sometimes wool is pretreated with acid which is to be
neutralised with alkali. The neutralisation is slow and sometimes the liquor
shows alkalinity even though the cloth is still acidic.
Caustic soda and soda ash are excluded for adjustment of pH of
bleaching liquor. Ammonia has no stabilising property and tends to cause
excessive loss of peroxide, especially in standing bath. Sodium silicate,
sodium pyrophosphate and tetrasodium pyrophosphate are commonly used.
They exert buffering action as well as precipitate undesirable metallic ions.
Environmental concerns regarding phosphates are likely to intensify the
search for alternative stabilisers.
Some progress has been made using silicate-based stabilisers. Sodium
silicate is safe for wool. However, the material is to be thoroughly washed
after bleaching.
As heavy damage to wool occurs during poorly controlled alkaline
hydrogen peroxide bleaching, an alternate process is to bleach under
weakly acidic condition using peracid activator. BASF offered an activator,
Prestogen W for carrying out bleaching at pH 5 for about 1 hour at 80ºC.
Hydrogen peroxide and peroxy compounds damage wool fibres, due to
progressive oxidation of disulphide bonds ultimately forming cysteic acid (R-
S-S-R + [O] Æ RSO3–). Alkali solubility tests are normally employed to
assess the degree of damage incurred during bleaching process.
Subsequent dyeing processes can aggravate this initial damage, hence pre-
bleached material should be dyed at as low a temperature as possible.
Normally pastel shades are produced on bleached ground and dyeing at
80ºC is adequate. Moreover, Oxidatively bleached wool should not be boiled
since it undergoes hydrothermal yellowing at a faster rate than unbleached
wool.
Batchwise bleaching may be done in a tank composed of stainless steel,
ceramic or wood. No direct contact of material should be made with the
steam coil. Wool may be bleached with 0.3-1.2% (w/w) solution of hydrogen
peroxide depending on the whiteness required, the discoloration of wool and
the time permissible to complete the bleaching. The bath may be prepared
as follows:
Sodium silicate - 7 g/l

Soda ash - 2 g/l
Hydrogen peroxide (35%) - 3-6 g/l
Wetting agent - as required
pH is adjusted to 8.5-9.
or
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Tetra-sodium pyrophosphate - 2 g/l

EDTA (30 %) - 1 g/l
Hydrogen peroxide (35%) - 2-4 g/l
Wetting agent - as required
The temperature of the bleaching liquor can be constantly maintained at

50°C and the material is allowed to stand for 4 to 16 hours. Recent
optimisation has intended to reduce bleaching time to an hour. For overnight
bleaching, the initial temperature should be 54°C and may be allowed to
drop to 40°C by the next morning.
A very large proportion of unused hydrogen peroxide remains in the spent
liquor (as high as 90%) and should be reused. The material after bleaching
is passed through a squeezing roller from which the expressed liquor returns
back to the tank.
After bleaching under alkaline condition, a good rinse with weak acid
solution (1 ml per litre acetic or formic acid) is desirable. Wool, that is slightly
acidic, retains whiteness better during drying.
Woollen goods containing coloured threads dyed with acid dyes cannot be
treated with alkaline solution. These are, however, very fast under acidic
condition. Moreover, alkaline treatment impairs handle of the said materials.
Bleaching under acidic condition causes less degradation of wool. The
method can be synchronised with the scouring of loose wool. After passing
through the scouring bowls, the fibres travel through a bowl made of
stainless steel containing 0.5 to 4 volumes of hydrogen peroxide. A liquor
may be made up with:
Formic acid - 1.2 ml/l

Hydrogen peroxide (35 %) - 2-4 g/l
The pH is adjusted to 4-4.5 with formic acid or soda ash. After squeezing,
low cross-bred wool should retain 4-5% of its weight of hydrogen peroxide
(35%). For better quality of wool, the retention of only 1.5% is suffice.
After bleaching, the goods may be dried immediately, but ageing for 12-24
hours is preferred. No bleaching takes place before the wool is placed into
the dryer where the water is evaporated, leaving the peroxide behind.
Bleaching occurs during the subsequent few days. Acid bleaching is
particularly suitable for blankets.
An interesting process developed by IWS [33] and BASF involved
bleaching wool with hydrogen peroxide solution (40 g/kg of 350 g/l H2O2) in
presence of formic acid (2 g/l) by a cold pad-batch process. Overnight
batching gave excellent bleaching effects and bright pastel shades could be
obtained by including anionic dyes in the above pad liquor. The mechanism
behind the process probably is that the disulphide groups in keratin react
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with hydrogen peroxide or the superoxide anion to form peroxysulphinic

acid, RSOOH, which like carboxylic peracids, may act as an active
bleaching species.
Recently studies have been made for bio-bleaching of wool under both
oxidative and reductive conditions. The studies showed that hydrogen
peroxide bleaching in the presence of protease preparation, Bactosol SI
(Clariant) considerably improved whiteness and hydrophilicity. A number of
protease enzymes are commercially available in the market, which are
regularly added to laundry detergents to aid in the removal of protein-based
stains. However, they are mostly unstable to hydrogen peroxide. Alkaline
proteases with improved stability to peroxide have been subsequently
prepared such as Durazyme 16.0 L (Novo Nordisk). As no significant
whiteness improvement was achieved before 1 hour of enzyme addition, it
was suggested that the whiteness enhancement effect might be due to initial
rapid etching of the wool fibres, making them more susceptible to
subsequent bleaching. Hence, it is advisable to pretreat wool before
peroxide bleaching so that the enzymes unstable to peroxide can be used.
The enzyme treatment was carried out for 1 hour at 50°C and pH 9.0. The
bath was cooled to 45°C before adding hydrogen peroxide and ammonia to
pH 8.5-9.0. Whiteness improvement was similar to that obtained in the
simultaneous treatment, though slightly inferior. The addition of the protease
enzyme (about 0.5-1%) shortens bleaching time by half for the same
whiteness. Similarly, an appreciable increase in whiteness can be achieved
under reductive conditions by treating wool with the protease papain,
applied in the presence of a mixture of sodium bisulphite and sulphite at pH
6.5-6.9. The process is fairly cheap and rapid as compared to peroxide
bleaching, but requires optimisation. In both oxidative and reductive modes,
a weight loss of at least 3% can be expected. Though such a weight loss is
quite acceptable with cotton when treated with cellulase, it may be
excessive for wool, which is much more expensive.
Some wool fibres, such as Karakul or Canary, are heavily pigmented. It
can be said that wool lots completely free of dark fibres do not exist. The
colour of pigmented material is not uniform. Single pigmented fibre can
cause expensive imperfections in light coloured wool products. This applies
even more for speciality animal fibres, such as white mohair, cashmere and
alpaca. The degree of contamination of white wool by coloured fibres has a
significant influence on its commercial value, especially when the wool is to
be processed into light and pastel coloured articles. Manual removal is time-
and cost-intensive. The colour of dark fibres ranges from black through
shades of brown to light yellow.
Pigmented fibre bleaching is the most delicate and risky wet operation –
any mistake in controlling of the bleaching process can cause serious fibre
damage.
307
For heavily pigmented or naturally discoloured animal fibres, ferrous

mordant bleaching is carried out. The most efficient pigment bleaching with
minimum fibre damage is provided by the use of metal catalysts in a
mordanting step proceeding peroxide bleaching. In industrial practice iron
(II) salts are used as mordants. The pigmented wool is first treated with a
solution of iron (II) sulphate, rinsed and finally bleached with hydrogen
peroxide. The presence of iron (II) ions in the melanin pigment cause
hydrogen peroxide to undergo radical decomposition, leading to oxidising
species that are far more aggressive than the perhydroxyl anions, which are
regarded as bleaching agents under alkaline condition. These radicals bring
about not only a complete disruption of the melanin pigment, but are also
very efficient in the decolourisation of the dye formed.
The pre-mordanted wool is rinsed when the iron (II) ions are removed from
the keratin, but not from the melanin pigment granules. Rinsing prevents the
unacceptably severe damage to the fibre produced on adding hydrogen
peroxide to destroy the melanin granules by a free radical degradation
process. The iron (II)-melanin interaction is apparently much stronger than
the iron (II)-keratin interaction. Thus, in addition to the selective absorption
of iron, selective desorption becomes an important factor in optimising a
pigment bleaching process. A cold rinse may remove little iron, while a hot
rinse (20 min, 80ºC) using 0.5 ml/l hypophosphorous acid solution will
remove most of iron from the unpigmented wool. Adding a small amount of
NTA (Nitrilotriacetic acid) to the rinsing bath has an advantageous effect on
bleaching.
The same bleaching effect can also be obtained by using iron (III) ions.
Nevertheless, the absorption is not selective, resulting in heavily damaged
fibre during bleaching.
Increasing the concentration of iron (II) ions above 0.035 mol/l did not
significantly enhance the iron uptake by the pigmented fibre. The pH range
of 3-3.5, a temperature of 80ºC and treatment time of 60 minutes were
found appropriate [34]. The presence of chelating agents such as EDTA,
etc. impaired selectivity of absorption.
A reducing agent is used to prevent iron (II) from being oxidised to iron
(III). Sulphur-containing reducing agent like sodium dithionite may induce
scission of disulphide bonds of wool. The damage can be minimised by
adding a protecting agent like formaldehyde.
The wool may be mordanted by immersing for 2 hours at 65-95°C in a
solution containing:
Sodium hydrosulphite – 2%
Ferrous sulphate – 3%
Ammonium sulphate – 1%
Formaldehyde – 4%
308
Required acetic acid to bring pH 5 to 6.

Formaldehyde acts as a protecting agent preventing damage of keratin.
The pH is to be checked from time to time and to be maintained slightly
acidic. At the end of 2 hours, the liquor is run off and wool is well rinsed with
water.
Hypophosphorous acid is an excellent stabiliser for iron (II) ions under
mordanting conditions with least damage of cystine of wool [34]. Addition of
formaldehyde is not necessary. The mordanting may be carried out with
10 g/l FeSO4, 7H2O and 3-4 ml/l hypophosphorous acid (50%) and pH
adjusted to 3-3.5 with formic acid. The treatment is carried out at 80ºC for 60
minutes followed by rinsing for 20 minutes at 80ºC.
The second step consists of bleaching with hydrogen peroxide. The
solution is prepared as follows:
Sodium pyrophosphate - 5 g/l

Hydrogen peroxide (35 %) - 5-10 g/l
Soda ash - sufficient to bring pH between 8 and 9, but not more than 1 %
on the weight of wool.
Alternately the pH may be set with ammonium hydroxide. The method can
also be used for bleaching various speciality hair fibres and feathers.
After bleaching, the deposits of ferrous hydroxide are removed by treating
with 3 to 5% solution of ammonium bifluoride on the weight of wool at 70°C
for 1 to 1½ hours.
Alternately, the removal of residual iron and further bleaching may be
carried out by adding thiourea in the bleaching bath. Excellent whiteness
had been reported [3] when combined oxidative and reductive bleaching
was carried out by this method. Bleaching was first done for 60 minutes at
60ºC at pH 9.5 with 20 ml/l hydrogen peroxide (30%), 10 g/l tetra-sodium
pyrophosphate and a wetting agent. Then 5.4 g/l thiourea was added
directly in the bleaching bath. Vigorous reaction was observed with a drop of
pH to 2-3 and an increase in temperature by 5-7ºC. The pH was then
adjusted to 7-8 with slow addition of soda ash and the bleaching was
continued for 25 minutes at 60ºC, rinsed and dried. The reaction of thiourea
with residual hydrogen peroxide after bleaching and necessary pH
adjustment created a highly reductive agent that reduced any ferric species
to ferrous form and was easily washed away because of much lower affinity
to white wool.
The dyeing properties of mordant-bleached wool are different from those
of normal wool. The uptake of acid dyes is slower, indicating the presence of
a relatively large number of sulphonic acid groups in the modified wool. Light
fastness of the dyed shades also diminishes.
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5.3.12 Bleaching of Silk

Woven silk from the cultivated silkworm is slightly yellowish after
degumming. This natural colour is desired by some fashion designers as a
soft white or natural shade. The colour of silk is dependent on the amount of
residual sericin, since it carries the colour. Over the years more and more
white textile fabrics are on demand. With silk as well, the brightest possible
white is sometimes desired. The desired degree of whiteness can be
relatively easily achieved with mulberry silk, but with tussah silks, depending
on their origin, a light to pronounced yellow-brown tint is unavoidable and
pale dyeing and printing may be affected by this colour. Bleaching is
therefore especially important for tussah silk.
The removal of sericin often produces whiteness adequate for dyeing. The
bleaching agents used for silk are the same for wool. The usual agent is
hydrogen peroxide; sulphur dioxide stoving having fallen into disuse. A
reducing agent, sodium hydrosulphite is sometimes used for bleaching of
silk (Section 5.2). However, the whiteness is insufficient and temporary.
Chlorine containing compounds may cause discoloration, which may be due
to oxidation of tyrosine residues. [24].
Bleaching of silk with hydrogen peroxide can be carried out in more
severe conditions than wool, since silk is not easily degraded. The material
is to be carefully checked for metal spots, which may cause catalytic
degradation of hydrogen peroxide. Most varieties of silk are bleached by
steeping, but winch machines may be used for fabrics. The treatment is
carried out with 0.55% w/w hydrogen peroxide solution made alkaline with
sodium silicate and ammonia to give a pH of 10, or with addition of
tetrasodium pyrophosphate and EDTA at 60-75°C for 2-4 hours. For
overnight steeping, the concentration of hydrogen peroxide may be reduced.
Over-bleaching should be avoided as yellowing may occur. An alternate
recipe for mulberry silk is as follows:
Hydrogen peroxide (35%) – 15-20 ml/l

Stabiliser AWNI (Clariant) – 0.5 g/l
Imerol XN (wetting agent, Clariant) – 2 g/l
pH 9 with trisodium phosphate
The material is immersed at 40°C and treated at 90°C for 1-2 hours,
rinsed with hot and cold water.
For tussah silk the recipe is as above, but with 20-30 ml/l hydrogen
peroxide (35%). The treatment time is 4 hours or more. If the tussah silk has
strong self-colour, the material is treated for 30 minutes at cold with 2-3 g/l
potassium permanganate.
The material is then treated for 45 minutes at cold in a fresh bath containing:
310
Sodium hydrosulphite – 15-25 g/l

Sulphuric acid (conc.). – 0.4 ml/l
The material is thoroughly washed with hot and cold water.

With tussah silk it is often impossible, depending on its origin, to attain the
same degree of whiteness within a single piece or from piece to piece. As
goods of similar whiteness cannot be obtained, it is advisable to check the
pieces well and classify them in different processing categories.
Sometimes degumming and bleaching are done simultaneously for
mulberry silk. A 0.3% (w/w) hydrogen peroxide solution containing 0.85 kg of
olive soap and 0.06 kg of sodium silicate per 100 litres of water using M:L
ratio of 1:15 can be used. The temperature at the beginning is kept at 75°C
and is gradually increased to 90°C. The treatment is completed within 2-3
hours. The hydrogen peroxide concentration may be increased to 0.55 %
(w/w) depending on the extent of discoloration of silk.
For maximum whiteness, peroxide bleach is given after degumming
followed by a reduction bleaching along with fluorescent brightening agent.
The exhaust method of reduction bleaching is to treat the fabric with:
Sodium hydrosulphite – 2-5 g/l

Leucophor PAT (Clariant) – 0.5-4% (o.w.m.)
for 1 hour at 70°C.
After 45 minutes, pH is adjusted with formic acid to 3.5 and continued the
treatment for further 15 minutes, rinsed with warm and cold water.
5.4 WHITENESS
White is the colour for purity, freshness and cleanliness. Whiteness is,
however, not only psychologically associated with purity, but also an
indicator of freedom from contaminants. Whiteness of a product diminishes
as it acquires dirt and other impurities and as such, it is a measure of the
quality of the product. Both wool and cotton, in natural form, are dirty; that is
not white, and tend to lose strength and degrade rapidly [35]. Whiteness is
defined to be an attribute of visual sensation according to which a given
stimulus appears to be void of any hue and greyness [36]. The gamut of
stimuli that give rise to the perception of whites and near whites in colour
space depends markedly on observing conditions, but is always very small
as compared to the whole gamut of colours perceived. In three-dimensional
colour space, whites occupy an area near the top of the colour solid.
Depending upon the conditions of perception, there are about 5,000
311
distinguishable colours called white and 30,000 more called ish whites - that
are bluish white, greenish white or reddish white [37].
White is perceived as a unique colour by an observer. There are, of
course, a variety of whites and no specific recognised line of demarcation
between white surfaces and light-coloured near-white tints. ASTM
(American Society for Testing and Materials) Designation E313-79 specify
near whites as colours having Munsell value greater than 8.3 (luminous
reflectance 65%) and Munsell chroma no greater than 0.5 for B hues, 0.8 for
Y hues and 0.3 for other hues - Munsell is a visual colour specifying system
[38]. In physical terms, a white surface is one which reflects strongly (>50%)
throughout the visible spectrum. The higher and more uniform the spectral
reflectance, the whiter is the appearance of the object. Geometrically, a
white surface reflects diffusely in all directions. Mirrors, though reflect
strongly throughout the visible spectrum, but only in one direction, hence are
not called white.
The difference is, of course, that white materials have high scattering
coefficient as well as low absorption coefficients.
White is a colour like blue, green or red and can be determined precisely
by colorimetric methods. The characteristic, which distinguishes white
samples from those called coloured, is their high lightness combined with
very low colour saturation. White samples are often more difficult to assess
than coloured ones because white, besides being objectively quantifiable, is
also a subjective connotation of quality which is greatly influenced by
personal taste.
5.4.1 Improvement of Whiteness

Natural fibres like cotton and wool absorb more light in the blue region of the
visible spectrum than in the others owing to the presence of impurities, i.e.
natural colouring matters. Consequently, they take on a yellowish or
brownish cast. Whiteness of such substances can be improved in three
ways:
1. Increasing blue reflectance of the substrate by destroying the
colouring matter with strong reducing or oxidising agents in the
process called bleaching. The function of bleaching is to remove blue-
absorbing yellow contaminants.
2. Even the most thorough bleach cannot remove all traces of yellowish
cast. Therefore, an additional whitening stage is essential. The age-
old practice is to treat the bleached material with a very small
amount of a blue or violet dye – an operation known as bluing – to
boost the visual impression of whiteness. The most widely used
colorant for the purpose is a water-insoluble pigment available
commercially in finely powdered form called Ultramarine Blue (C.I.
312
Pigment Blue 29/ 770077) or dispersed in liquid form. The pigment is

bright blue to bluish green in colour. It is fast to acid and alkali, but
unstable in lime. It is prepared by fusing kaolin, soda ash, Glauber’s
salt, sulphur, carbon and kieselguhr in the absence of air in red-hot
condition for 7-10 hours. It is a polysulphide of sodium or potassium
aluminosilicate of unknown composition. The polysulphide linkage
causes the colour of the pigment. The quantity required is very small
and depends on the actual strength of the commercial product. The
treatment is generally done at room temperature for a very short
period. This treatment is very popular for domestic washing of white
goods. A common complaint against such product is patchy
appearance of the treated materials. The present trend is, therefore,
to use a water-soluble dye having no affinity for the substrate, say, a
blue or violet acid dye for cotton. These dyes absorb light in the
green-yellow portion of the spectrum and reduce lightness. Since at
the same time, they shift the shade of the yellowish material towards
blue, the eye records an increase of whiteness. The blue colour of
the dye offsets the yellow colour of the material, resulting in a neutral
very-light grey, but our eye does not quickly notice the greyness. A
high white base or good bleaching of the material is therefore
advisable, which reduces the amount of blue dye required.
Consequently, the lowering of lightness is minimal resulting in lesser
greyness. The dyes should be as brilliant as possible to keep the
absorption region narrow and cause minimum loss of lightness. The
commonly used dye is Milling Violet 5B (C.I. Acid Violet 49/42640).
3. The third way is to use fluorescent brightening agents (FBAs),
fluorescent whitening agents or optical whitening agents. Unlike
dyes, FBAs offset the yellowish cast and at the same time improve
lightness, because they do not subtract green-yellow light, but rather
add blue light. FBAs are virtually colourless compounds which, when
present on a material, have the ability to absorb mainly invisible
ultraviolet light in the 300-400 nm range and remit violet to blue
fluorescent light. The emitted fluorescent light is added to the light
reflected by the treated material, by that producing an apparent
increase of reflectance in the blue region. Dazzling whiteness is
perceived especially on a well-bleached material. Slight improvement
in base whiteness enhances whiteness of FBA-treated material
significantly. Figure 5-5 shows reflectance curves of unbleached raw
cotton (R), bleached (BL), bleached and blued (BB), and differently
tinted FBAs treated cotton materials – violet (V), blue (B), blue-green
(BG). The curve for physically ideal white (IW) is also shown for
comparison.
313
140
120 B
IW
%Reflectance
100
80 BL
BB
60 V BG
R
40
20
0
350 400 450 500 550 600 650 700
Wavelength (nm)
Fig. 5-5 Reflectance Curves for Raw

and Treated Cotton Materials
5.4.2 Fluorescent Brightening Agents

200 years ago, linen bleachers already knew that the effect of lawn
bleaching could be improved with the help of horse chestnut extracts. This is
due to the fact that the inner bark of horse chestnut contains aesculin or
esculinic acid, a glucoside which is a derivative of coumarin having a blue-
violet fluorescence. However, the effect obtained was not fast to washing
and light. It took many years before these disadvantages could be largely
eliminated and first commercial optical brighteners were released. These
products were derivatives of diaminostilbene disulphonic acid (5-1), which
have affinity for cellulosic fibre. Products having different constitutions have
an increasing share in the market for textile fibres of varying chemical
compositions and sources of origin.
Fluorescence is produced by the absorption of radiation having a high
energy, on the part of the molecule, which re-emits this radiation as a
radiation of lower energy, i.e. of longer wavelength, and the difference in
energy being transferred into kinetic energy. Fluorescence is mainly linked
with the aromatic character of a molecule, but an aromatic ring alone is not
enough to impart the property of an optical whitener. Most of the whiteners
will hardly fluoresce in powder form; their fluoresce will only appear in
solution. There are certain types which will not fluoresce in solution and
which will only show the property after they have been applied to the fibre.
314
Fluorescence, therefore, is dependent not only on the structure of the

molecule, but also on its condition.
In fact, an optical whitener does not increase brightness of a textile fabric
to an appreciable extent. The basic effect is the compensation of a blue
defect i.e. whitening without additional greying which occurs with a bluing
dye, such as ultramarine blue.
Apart from the fact that the compound must meet certain demands in respect
of dyeing properties, like satisfactory light and wash fastness, the fluorescence
effect, which is required to compensate the yellowish shade of the fibre, is of
supreme importance. On comparing different textile goods treated with
different whiteners and possessing approximately the same brightness,
differences in hue can be detected, since the human eye is particularly
sensitive to differences in whiteness. If an optically whitened fabric with a
reddish-white shade is compared with another fabric having a greenish-white
shade, both will appear to be equally bright in sunlight incident from northern
direction, but the greenish shade will appear more bright than the reddish one
in bright sunlight. Fabrics treated with neutral white shade will appear slightly
superior to the reddish and slightly inferior to the greenish shade in sunlight,
whereas opposite effect is obtained in reduced light. While an optically
whitened smooth material of a reddish shade may appear equal in brilliance to
that of a similar material with a greenish shade, it will be seen that in the case
of a rough surface the reddish material will be judged to be more bright [39].
Chemistry and Properties
About 20% of total production of FBAs is used for application on textile

materials and are based on more than 30 fundamental chemical structures.
The largest consumption is for production of detergents (about 45%)
followed by application on paper (about 35%), in both cases the number of
fundamental structures are less than 10.
An FBA is a dyestuff, but in place of the chromophoric system which is a
characteristic for dyes, it contains a fluorescing system and like a normal
dye, has certain substituents which promote the affinity, depending on the
type of fibre on which it is applied. The products suitable for cotton are more
or less substantive (i.e. having affinity for the substrate) and are derivatives
of diaminostilbene disulphonic acid (5-1). Tinopal BV (Geigy), C.I.
Fluorescent Brightening Agent (FBA) 1/40630, was one of the early
products, which achieved great success. It was made by treating the sodium
salt of 4,4/–diamino stilbene-2,2/-disulphonic acid with cyanuric chloride
(DASC), then reacting with ammonia and finally heating with aqueous
formaldehyde. It has good affinity for cellulosic fibres and has sufficient blue
fluorescence to give commercially acceptable whites. Acid-stable, acid dye-
type DASC whiteners are applicable on wool and polyamides.. The triazinyl
315
derivatives (TS) such as Blancophor B (Bayer) (C.I. FBA 32/40620) and

Tinopal BV are decomposed by hypochlorites. FBAs should be stable in
hypochlorite, if simultaneous bleaching and whitening is to be carried out.
American Cyanamide found that 2:8-disulphonic acid of benzidine sulphone
possesses good greenish fluorescence and is stable in hypochlorite
bleaching liquors. However, the fluorescence is relatively weak. Various
other structures have been proposed for stability in hypochlorite. Some are
based on triazoles such as 2-(4-sulphostilbyl) naphthotriazole and bis-
(triazolyl)stilbene derivatives (NTS). The stilbene derivative may be present
in two form - trans and cis forms. The non-substantive cis form is rapidly
formed from trans form under the action of light. The solution of this product
should, therefore, be protected from light. A great number of products are
based on 7-aminocoumarin (5-2). Aminocoumarins have been specially
marketed for application to wool and nylon. These are water-soluble
compounds, which are widely used on cellulose, polyamide and wool fibres.
There are also interesting representatives among the products based on 3-
phenylcoumarins (5-3). Many of the currently used FBAs are derived from
heterocyclic compounds, which contain nitrogen atoms.
With the advent of synthetic fibres, such as polyester and acrylic, a new
range of products was required that would behave as disperse dyes and not
contain any groups giving water solubility.
Polyester fibres are highly hydrophobic substances and only dispersions
of insoluble fluorescent compounds can be used. They are mostly applied
along with finishing agents by pad-cure method. The affinity for the fibres is
not great – high temperature and the addition of auxiliaries assisting dyeing,
called carriers, are often necessary. Bisbenzoxazole compounds (5-4) and
many other heterocyclic compounds are suitable, provided none of the
substituent groups are sulphonic groups.
Most of the acrylic fibres have affinity for cationic FBAs. Type (5-4) will be
suitable provided the R and R / are amino or substituted amino groups.
Basic naphtho-triazol stilbene, oxacyanines and pyrazoline derivatives are
being used [2].
Since the FBAs behave like dyestuffs, they will be subjected to the
influence of all factors which are important in dyeing, such as concentration,
period of treatment, temperature, liquor ratio, hardness of water, salt
content, pH, method of application, chemical and physical properties of
substrate.
316
Since the shade of an optically whitened fabric depends on the

concentration of the optical whitener, it is only possible to attain a definite
maximum whiteness which is different for every optical whitener and which
is defined by certain fixed conditions of application – the quantities are
optimum quantities. If the quantities are increased above optimum, the
whiteness will not become more intense; on the contrary, it will become
weaker, in spite of the fact that when measured with a fluorometer, the
fluorescence continues to increase. The explanation is that the maximum
visual whiteness is produced with that concentration of the FBAs on the
fibre, which just suffices to compensate the yellow hue of the substrate. An
excess over this critical quantity can promote reflection at selective
wavelengths causing a deviation from pure white. This is one of the reasons
why it is so problematical to compare different FBAs and also why it is of
fundamental importance to know the optimum quantities of application of
each optical whitener, as well as its range of application.
H2 N –CH=CH– NH2
=O
H2 N O
SO3 H SO3 H
(5-1) (5-2)
O O
C—CH=CH— C R
/
R
=O N N
O
(5-3) (5-4)
Application Methods
FBAs may be applied either by exhaustion or by padding methods. Natural
fibres require prior bleaching for an acceptable white. The man-made fibres,
on the other hand, are usually sufficiently white themselves to render
bleaching unnecessary.
Cellulosic fibres generally require between 0.05 and 0.6% (o.w.m.) FBAs,
when applied from long liquor by exhaustion methods. The most commonly
used are Tinopal 2B, BV, ABR (C.I. FBAs 24, 1 and 15 respectively),
Blankophor CE, BE, RA, BA, (C.I. FBAs 118, 115, 204 and 113 respectively)
etc. Though they have varying salt sensitivity, the electrolyte commonly
used is 5 g/l anhydrous Glauber’s salt or common salt. The goods are
entered into cold liquor, the electrolyte and the FBAs are added and the
temperature is raised over a period of 15 minutes to 60-80°C depending on
the optimum temperature for the product. A further treatment for 30 minutes
317
will be sufficient for complete exhaustion. For padding process, 0.05 to 2 g/l
FBAs is necessary depending on the nature of the substrate and the degree
of whiteness required. Fastness to light and washing of FBAs applied on
cellulosic substrates are not very high. However, this does not matter much
as most domestic detergents contain FBAs and in consequence, losses are
compensated during washing.
Amongst the FBAs used for wool and silk are Tinopal WG (Geigy), Uvitex
WGS (Ciba) and Blankophor WT (Bayer) (C.I. FBAs 54, 56 and 48
respectively). They all contain sulphonic acid groups and behave towards
protein fibres like acid dyes. About 0.02 to 0.2 percent (o.w.m.) of FBAs is
applied from an acid dyebath having pH between 3 and 5 by addition of
organic acids. The treatment is carried out at 40°C for 20 minutes.
Marked yellow discoloration of wool treated with FBAs may occur on
exposure to sunlight. The effect is more pronounced on moist wool. The
discoloured wool is much browner than untreated wool. The conclusion
made from several studies is that an oxidation product of the protein causes
the yellowish colour, the oxidation reaction is probably catalysed by the
FBAs. The presence of reducing agents has an inhibiting effect. The
addition of hydroxylamine sulphate to the treatment liquor brings a
significant protecting action.
FBAs suitable for cellulose, as well as those suitable for protein fibres, can
be applied on polyamides from acidified liquors. Moreover, this fibre has an
affinity for disperse dyes. Good exhaustion can, therefore, be obtained with
suspension of insoluble fluorescent compounds. Tinopal WG and
Blancophor WT have good affinity for polyamides and can be applied from
liquors acidified with 2% formic acid (85%) which should bring the pH to
between 3.5 and 4. The quantities required vary from 0.05 to 0.5% and the
temperature range recommended for application is 40°C to 70°C.
Leucophor PC (Sandoz, presently Clariant) (C.I. FBA 134), an anionic
stilbene derivative, has affinity for cellulosic, protein and polyamide (both
nylon 6 and 6,6). It can be applied from a normal acidic bath (pH 4) or from
a reductive bleach bath at 80ºC for 30-60 minutes containing 0.2-0.5%
Leucophor PC Pdr., 1 g/l sodium bisulphite and adequate formic acid to
bring pH at 6.
The disperse FBAs such as Tinopal PG, Tinopal ET and Uvitex ERN (C.I.
FBAs 152, 156 and 135 respectively) are available in paste form. They are
applied from neutral liquors at high temperature of 70 to 80°C. The rate of
exhaustion is slower and a treatment for 30 to 45 minutes at the specified
temperature is necessary.
Polyester fibres have no affinity for water-soluble FBAs. However, they
have affinity for disperse FBAs. The rate of exhaustion is slow and the use
of auxiliaries, called carriers, is recommended. Diphenyl and chlorinated
hydrocarbons such as di and tri-chlorobenzenes are effective carriers, but
318
are banned now. The treatment is done for about 30-60 minutes at boil. The
temperature is to be raised slowly to avoid faster initial pick-up causing
unlevelness. If pressurised machinery is available, the treatment may be
carried out at high temperature of 130°C. The optical whitening agent can
also be applied successfully on polyester by pad-bake method. The fabric is
run through a padding liquor containing 1-30 g/l optical whitening agent. It is
then dried and cured at 120-160°C on stenter machine. The fastness to
washing and light of optical whitening agent on polyester are of high order.
Most of the acrylic fibres contain anionic groups conferring affinity for
cations. A few fluorescent compounds containing amino, substituted amino
groups or nitrogen-containing heterocyclic components, which can form
quaternary salts, are cation-active products. They have affinity for acrylic
fibres. The cationic FBAs are applied from liquors containing 3-5% formic
acid to bring pH of 3 to 4. The treatment is carried out at a temperature of
95-100°C for 30-40 minutes. The exhaustion can be improved by treating at
a temperature of 110°C in a pressurised vessel.
Quite a good number of FBAs are stable in bleaching liquor. Hence, they
can be applied at bleaching stage, thus eliminating a separate treatment
step. The stability of various products towards oxidising bleaching agents is
as follows:
1. Products, stable to hypochlorite and sodium chlorite, are Tinopal GS,
Tinopal RBN, Uvitex RS (C.I. FBAs 47, 59 and 41 respectively).
2. Products, stable to hydrogen peroxide, are Tinopal GS, Tinopal WG,
Uvitex VR, Uvitex BT, Leucophor R, Fluolite C (C.I. FBAs 47, 54,
142, 19, 30 and 23 respectively).
Some of the products are unstable in hypochlorite solution, but cannot be
attacked if they are already absorbed by the fibre. It is therefore
recommended to add them during scouring.
If for any reason, the optical whitening agent is to be stripped off the
fabric, the treatment may be carried out for about 20 minutes in a cold liquor
containing 0.25 to 0.50 potassium permanganate and 0.5% concentrated
sulphuric acid.
5.4.3 Instrumental Assessment of Whiteness

Whiteness can be assessed by a variety of instrumental methods. The
simplest method is based on physical data such as reflectance or emission
at a particular or a range of wavelength. The colorimetric or psychophysical
methods are based on values that integrate the reflectance of the material,
the illumination and the human eye. Like all other colours, whites can be
clearly defined by just three parameters. However, attempts to rank white
samples unidimensionally, i.e. to fit them into a scale, have been going on
for decades. The methods evolved are of course ambiguous, in that the
319
samples differing completely in appearance may be allotted the same

whiteness rating. However, the use of a single number in terms of a
whiteness formula is very convenient for routine quality control. Therefore,
such formulae are universally used. Whiteness formula covers a wide
spectrum ranging from a simple, measured physical quantity to a complex
algorithm based on colorimetric parameters. The common feature of the
formulae is that they describe areas of equal whiteness in the colour space.
Each whiteness formula has a specific whiteness bias, i.e. preferences,
directly comparable with the varying whiteness preferences of human
observers.
Physical Methods
A widespread method of expressing whiteness is to relate it to the level of
reflectance at one given wavelength in the visible region of the spectrum.
The whiteness formula, then, may simply be written as:
W=R (5.40)
where R represents the measured value.
The best known methods of this type are SCAN (Scandinavia) and TAPPI
(USA) (also known as paper brightness) which recommend reflectance at
457 nm as the measure of whiteness. When such special filter is not
available, the reflectance at 460 nm may be considered. Unbleached 100%
cotton woven fabrics usually have a reflectance of about 55% at 460 nm.
This increases to 83-85% for fully bleached fabric. Lower reflectance, say
78-82%, is generally acceptable as a preparation for subsequent dyeing.
The method is very simple and easy to assess, but can be used only for
the material not treated with FBA because such materials have roughly the
same spectral curve and differ mainly in intensity. When reflectance at 460
nm is considered, it falls on the long-wave flank of the fluorescent peak.
Different FBAs produce tinting of different hues (red-violet, blue or blue-
green) and the fluorescent peak shifts. Moreover, the self-colour of the FBA
interferes with whiteness when the material is overloaded with it.
Therefore, the above method may be used only for samples containing the
same FBA and when the concentration of FBA is lower than the overload
level. Otherwise, the result will contradict the visual impression of
whiteness. The effect of shading dyes is not generally determined by this
method, because such dyes have maximum absorption between 550-600
nm.
A large number of whiteness calculations are based on measuring the
reflectance at two wavelengths – one at the short wavelength for blueness
and another at long wavelength for redness. The methods were originally
devised for non-fluorescent white to determine the general level of
reflectance, and decreased reflectance in the blue region due to the
320
yellowish cast. The typical formulae of Harrison and Stephansen are as

follows:
W (Harisson) = 100 - R670 + R430 = 100 - (R670 - R430) (5.41)
W (Stephansen) = 2R430 - R670 = R430 - (R670 - R430) (5.42)

The bracketed term refers the difference between the reflectance levels in
the yellow and blue region and aimed to measure the yellowish cast, which
lowers whiteness. Harisson's formula considers the value of 100 for
physically ideal white.
To determine the effect of FBAs, sometimes the reflectance values at 460
nm with and without UV absorption filter are measured. The difference
between these two measured values is used to characterise the degree of
fluorescence whitening, often denoted as ∆UV value. However, this value
cannot be considered as a measure of visually perceived whiteness,
because this consists of both base white and fluorescence.
Colorimetric Methods.
A colorimetric system places every colour in a defined place. It has three
dimensions because a colour can change visually in three directions - hue,
saturation and lightness.
White materials, because of their high reflectance values throughout the
visible spectrum, are always high in all three tristimulus values X, Y and Z.
For whites, their absolute magnitudes vary between 80-130. However, the
stimulus value, which is most important and receives the greatest attention
is Z, relating to the reflectance at the blue end of the spectrum. Its spectral
sensitivity function stands by itself separate from other functions. Because of
such separation, any tipping of spectrophotometric curve from flatness is
more likely to change the value of (Z/Y) than to change the value of (X/Y).
These two ratios determine chromaticity. This tendency of Z to differ from
the other two-stimulus reflectance factors for whites has major visual impact
on yellowness [34]. The reflectance at 430 nm and 670 nm in the whiteness
formula described earlier can be replaced by the value B and G measured
by a tristimulus colorimeter as follows:
W (Taube) = G - 4(G - B) = 4B - 3G (5.43)
The quantity (G - B) (in percent) denotes an index of yellowness which is
given four times weighting over G (in percent), the luminance factor
representing an index of lightness. ASTM designation E313 [40] also
recommends Taube's index as whiteness index and defines G and B
parameters as follows.
Luminous directional reflectance factor, G is proportional to the light flux
reflected by the specimen for source C when viewed under specified
321
geometric conditions by a receptor whose spectral response duplicates the

CIE luminosity function. The light flux is expressed as a percentage of the
light that would be reflected under the same geometric conditions if the
perfectly reflecting, perfectly diffusing ideal white standard substitutes the
specimen. CIE recommends the use of the term reflection factor, the
capacity to reflect light in specific directions instead of directional
reflectance. G is equivalent to CIE tristimulus value Y.
Blue directional reflectance factor, B is defined in the same manner as G,
except that the receptor is required to duplicate spectrally the CIE blue
response function. B is equivalent to CIE tristimulus value Z multiplied by
0.847 (i.e. B = 0.847 Z).
AATTC (American Association of Textile Chemists and Colorists) method
110-1979 recommends the same whiteness index with G and B as green
and blue reflectance respectively for CIE illuminant C and CIE 1931 2°
standard observer, measured by tristimulus colorimeter.
MacAdam incorporated colorimetric purity, pc into the whiteness formula
as follows:
W (MacAdam) = (Y - kpc2)1/2 (5.44)
where Y is the luminance factor and k is a constant.
Among uniform colour scale systems, Hunter L, a, b system has been
used widely for whiteness assessment. Among the three dimensions, b
dimension measuring yellowness-blueness is most important. Bluing
decreases L, but increases blueness as well as whiteness of the product.
The a dimension is of least importance for whiteness. White colours can be
graphically represented in two-dimensional L-b diagram as shown in Figure
5-6. Yellowness-blueness, b is represented horizontally and Lightness, L
vertically. The figure shows change of lightness and yellowness at various
stages of processing of a white material, i.e. the locations of raw or grey cot-
ton (G), bleached (B), bleached and blued (BB), bleached and FBA treated
(FB) materials. The probable locations of yellowish (YW), greyish (GW) and
brownish (BW) whites are also shown. The bluish whites fall on the second
quadrant with negative values of b. They are not shown in the figure.
Hunter developed the following whiteness formula on the basis of L and b
values, which was incorporated in his colorimeter.
W (Hunter) = L - 3b (5.45)
The formula gives three times weighting on yellowness over lightness for
overall whiteness perception and the influence of redness-greenness
parameter on whiteness is neglected. Hunter further proposed a similar
whiteness index as follows:
W (Hunter) = 100 - [(100 - L)2 + 10b2]1/2 (5.46)
322
However, Stensby was in favour of incorporating all three parameters.
95
FB
Lightness, L
YW
B
90
85 BB G
GW BW
80
0 5 10 15 20
Yellowness-blueness, b
Fig. 5-6 Locations in L-b Diagram of White

Materials at Various Stages of Processing
W (Stensby) = L - 3b + 3a (5.47)
To be valid for the complete white colour space, a whiteness formula
should be based on full colorimetric information as that of Stensby. The
three psychophysical parameters can unite all colorimetric information, i.e.
spectral properties of the light source, the object's reflectance or refractance
and eyes' sensitivities.
If the CIE tristimulus system is adhered, all formulae have the general
form:
W = f(X,Y,Z) (5.48)
The difference will be the signs and magnitudes of the factors for the
individual tristimulus values.
Berger formula, once most widely used in Europe, is as follows:
W (Berger) = 0.333Y + 1.060Z - 1.277X (5.49)
The formulae may also be in terms of Y,x,y values where lightness and
chromaticity components are separated and can, therefore, be differently
weighted.
CIE has recommended the use of the following formula for comparison of
whiteness of samples evaluated for CIE standard illuminant D65.
W (CIE) = Y + 800(xn - x) + 1700(yn - y) (5.50)
323
Where xn, yn are the chromaticity coordinates of the perfect reflecting

diffuser, for which the value of the index will be 100. For the samples treated
with FBAs, the value of the index will be greater than 100.
The hue of the white sample may change towards blue, red or green
depending on the quality of the FBA. Therefore, the hue imparted by the
FBAs is additionally measured by the tint factor TW defined as follows:
TW (CIE) = A(xn - x) - 650(yn - y) (5.51)
The whiteness and tint formulae are the same for CIE 2° and 10° standard
observers except for the value of A, which are 1,000 and 900 respectively.
The formulae are valid for (5Y - 280) > W > 40 and 3 > TW > -3 .
If TW ≈ 0 , the hue is blue with dominant wavelength 466 nm.
If TW = + , the hue is green.
If TW = - , the hue is red.
Most of the whiteness formulae are derived empirically on the basis of
correlation with visual sensation of whiteness. The performance of the
formula depends on the material under test, white perception capability of
the observers and the illumination used. The validity is lost when the
conditions are changed.
The exact contribution of hue, saturation and lightness to the whiteness is
not known. When selecting a formula, it is important to realise that each has
its own specific weighting of the three colour characteristics. In the light of
experience, it is possible to choose the formula correlating most closely with
the tint preference of the panel of observers. The formula chosen for marked
blue-green preference is of Berger, while Stensby’s formula is specifically
suitable for assessing samples with violet preference. The preferred
deviation towards blue alone is known as neutral preference.
5.5 TESTING OF BLEACHED MATERIALS

A well-prepared substrate should have:
1. A high, uniform whiteness which is stable on storage
2. A high, uniform absorbency for aqueous solution
3. Low chemical damage
The damage due to bleaching may be measured in terms of fluidity in
cuprammonium hydroxide solution or cupriethylene diamine. An increase in
fluidity (the inverse of viscosity) indicates degradation of cellulose. The
methods of assessment have been discussed in details in Section 4.4.6.
REFERENCES
1. G.N. Mock. 1985, Bleaching, In: Enclyclopedia of Polymer Science and
Engg, Vol. 2, 2nd Edn (New York, USA: John Wiley) 310-323.
324
2. E.R. Trotman. 1968, Textile Scouring and Bleaching (London, UK:

Charles Griffin).
3. M. Arifoglu and W.M. Marmer. 1990, Textile Res. J., 60, 319-327 and
549-554.
4. W.N. Marmer, J.M. Cardamone, B.G. Ping, and F. Casado. 1993, Text.
Chem. Colorist, 27, 75.
5. M. Lewin and S.B. Sello (Eds.). 1984, Fundamentals and Preparation, In:
Chemical Processing of Fibres and Fabrics, Vol. 1. Part B (New York,
USA: Marcel Dekker).
6. Ridge and Little. 1942, J. Text. Inst., 33, 33 and 59.
7. L.F. McBurney. 1954, Cellulose and Cellulose Derivatives, Part 1, 2nd
Edn (New York, USA: Interscience).
8. J. Dannacher, and W. Schlenker. 1990, Textilveredlung, 25, 205.
9. J. Shore. 1990, Colorants and Auxiliaries, Vol. 2 (Bradford, UK: SDC).
10. S.R. Karmakar. 1999, Chemical Technology in the Pre-treatment
Processes of Textiles (Amsterdam, Netherlands: Elsevier).
11. S. Fornelli. 1994, Colour Chronicle (Mumbai, India: Sandoz) (January –
March)
12. J. Mathews. 1999, JSDC, 115, 154-155.
13. S. Lim, N.C. Gürsoy, P. Hauser and D. Hinks. 2004, Color. Technology,
120, 114-118.
14. N.C. Gürsoy, S.Lim, D. Hinks and P. Hauser. 2004, Textile Res. J., 74
(11), 970-976.
15. P. Niels. 2000, TCC & ADR, 32 (5), 23-24.
16. W.S. Hickman. 1996, Rev. Prog. Coloration, 26, 29-45.
17. A.K. Lotze. 2001, International Dyer (February), 15.
18. B. Jakob and L. Vermeersch. 2000, International Dyer (October), 10.
19. B. Mahapatro and others, Book of papers on Orientation Programme in
Chemical Processing for Senior Executives (Mumbai, India: Textile
Association)
20. H.P. Weber and J. Ströhle. 1997, International Dyer (March), 9-13.
21. Anonymous. 1995, International Dyer (April) 22.
22. Higginbotham and Leigh. 1962, J. Textile Inst., 53, 312.
23. W. Hellwich. 1997, Int. Tex. Bull., 43, 37-38.
24. R.H. Peters. 1967, Textile Chemistry, Vol. II (Amsterdam, Netherlands:
Elsevier).
25. K.S. Huang and M.S. Yen. 1997, JSDC, 133, 95-98.
26. I. Holme. 2001, International Dyer, (February), 8-9.
27. B. Jakob and L. Vermeersch. 2000, International Dyer (October), 10.
29. K. Meyer. 1999, International Dyer (February), 7-12.
30. D.P. Chattopadhyay. 1998, Colourage XLV (May), 23-36.
325
31. IJIRA, IJIRA Process of Bleaching, Indian patent No. 110,628 (1967),
B.P. 1,221,527 (1968).
32. L.W.C. Miles. 1985, J. Text Inst., 76, 415.
33. J.F. Graham, R.R.D. Holt and D.M. Lewis. 1979, Colourage, 26, 48.
34. A. Berek. 1994, Rev. Prog. Coloration, 24, 17-25.
35. R.S. Hunter. 1975, The Measurement of Appearance (New York, USA:
Wiley-interscience).
36. G. Wyszecki and W.S. Stiles. 1982, Color Science: Concepts and
Methods, Quantitative Data and Formulae, 2nd Edn, (New York, USA:
John Wiley).
37. K.L. Kelly and D. Judd. 1955, The ISCC-NBS Method of Designating
Colors and a Dictionary of Color Names, NBS Circular 553
(Washington, USA: NBS) November, 156,181.
38. A.K. Roy Choudhury. 1999, Modern Concepts of Colour and
Appearance, 1st Edn (Enfield, USA: Science Publishers).
39. Bayer AG. 1970, Blankophor in the Textile Industry In: Bayer Farben
Revue, Sp. Edn. No. 7E (Leverkusen, Germany: Bayer)
40. ASTM. 1987, Standards on Color and Appearance, 2nd Edn,
Designation E 313-79, (West Conshohocken, PA, USA: ASTM).
Chapter
Dyes and Dyeing 6
6.1 INTRODUCTION
From prehistoric times, man has been fascinated by colour. Colour is
everywhere. The clothes we wear, our surroundings, both natural and man-
made are abundant with colour. The dyes, more accurately known as
colorants, are highly coloured substances and can be used to impart colour
to an infinite variety of materials described technically as substrates.
Substrates can be subdivided into textile and non-textile, or fibrous and non-
fibrous materials. The coloured materials may originate from animal,
vegetable or mineral sources or may be abstract. The colouring matters of
animals and plants, the dyes used for coloration of textile, plastic, etc. are
organic chemicals. The colouring materials for ceramics, glasses, rocks,
jewels, etc. are inorganic substances. Abstract colours are those produced
by purely physical effects of dispersion, refraction or scattering of light, no
actual colouring substances being present. The examples are the colour of
sky, sun, insects, birds etc.
th
At the beginning of the 19 century, the natural dyes dominated the world
market whilst synthetic dyes were almost unknown. The only synthetic dye
that was known at that time was picric acid discovered in 1771, which too
had a very little share of the total dye production.
th
Until the end of the 19 century, the colouring materials were all obtained
from natural sources. The majority were of vegetable origin; plants, lichen
and trees, though a few were obtained from insects and molluscs. Over
thousands of years a large number of natural dyes had been used, but only
a dozen or so proved to be practically useful, as most of these natural
colouring matters are very unstable. The extraction of dyes from natural
sources was a slow, inefficient, wasteful and very labour intensive process.
Sources of supply were unreliable and standardisation was non-existent.
The resulting dyes were rarely pure compounds and since the proportions in
the mixture were variable, reproducibility was a serious problem. Many of
these dyes did not have strong affinity for the fibre and pre-treatment with
metallic salts was essential.
327
The 19th century saw a dramatic reversal of this situation. Within fifty
years of Perkin’s discovery of Mauveine in 1856, the synthetic dyes
accounted for over 90% of the dyes used. These spectacular changes were
initiated by a relatively new science, organic chemistry. W.H. Perkin was not
intentionally working towards preparing synthetic dyestuffs but towards
quinine, the anti-malarial drug. He attempted the preparation of quinine by
the oxidation of allyltoluidine with potassium dichromate in sulphuric acid.
He failed and turned his attention to the simplest aromatic amine, aniline.
Again he obtained a very unpromising mixture, a black sludge, but on boiling
his reaction mixture with ethanol, he obtained a striking purple solution,
which deposited purple crystals on cooling. Perkin recognised that this new
compound might serve as a dye, later to be called Mauveine. Perkin had
been very fortunate. Not only did his discovery arise from testing an
erroneous theory, but it also required the presence of substantial toluidine
impurities in starting aniline.
By 1850, the empirical formula of an organic compound could be easily
established, but the structure of these organic molecules remained a
perplexing problem for the organic chemists. Kekule’s most remarkable
single contribution to organic chemistry was his paper, published in 1865, on
the structure of benzene. The solution of the structure of benzene made an
enormous impact on both organic chemistry and the dyestuff industry. The
immediate impact of unrevealing chemical structures was the manufacture
of two important natural dyes, alizarin and indigo, by chemical synthesis.
Simultaneously new classes of synthetic dyes were developed such as
xanthenes, phenolthiazines and sulphur dyes. Meanwhile, a significant
progress had been made in azo dyes. Caro in 1875 discovered Chrysoidine,
a dye still used today, by diazotising aniline and coupling the diazonium
compound with m-phenylenediamine, the first azo dye for wool. Congo Red,
made in 1884, was the first dye which had direct affinity for cellulose and
could be applied directly on cotton without using any mordant, as the natural
colouring matters used in those days invariably required a mordant.
th
The second half of the 19 century had seen the introduction of many new
classes of dyes by British chemists. Since then, very few new chromogens
have been added to the range of available dyestuffs. Chromogen is the term
used to describe that complete arrangement of atoms which gives rise to the
observed colour. The term chromophore describes the various chemical
units (building blocks) from which the chromogen is built.
In the forty years after 1875, the Germans progressively built up their
dyestuff industry and used to produce 90% of the World’s dyes, whilst the
British remained stagnant. The period since the First World War has seen a
big expansion in the dyestuffs industry during which time USA, Japan,
Britain, Germany and Switzerland have become major manufacturers [1].
328
Two remarkable developments in the post-war period made by Scottish

Dyes Ltd. (later ICI) are copper phthalocyanine in 1927 and fibre-reactive
chlorotriazinyl dyes in 1954. With the introduction of hydrophobic fibres like
polyester and polyacrylonitrile, new classes of dyes were developed. But
they are merely modifications of dyes that were already available.
In fact, a high percentage of the present organic chemical industry (such
as pharmaceutical, agrochemical, etc.) is an offshoot of the dyestuff
industry. Hence, just as Perkin is rightly acclaimed the Father of the dyestuff
industry, so the dyestuff industry itself could be called the Mother of the
modern organic chemical industry.
Traditionally, synthetic dyes were known as coal tar dyes because the
aromatic organic raw materials containing six-member ring structures of
carbon atoms used for dye manufacture were originally obtained from coal
tar. Major raw materials are benzene, toluene, xylene, naphthalene and
anthracene – these are now largely supplied by the petrochemical
industries. The raw materials are first converted into dye precursors called
dye intermediates by unit processes such as nitration, sulphonation,
halogenation, reduction, oxidation, amination, etc. The manufacture of dyes
from these intermediates is a multistage batch process and various chemical
reactions such as diazotisation, etc. are carried out. Commercial products
must be standardised to give acceptably consistent shades, depths of shade
and other physical properties, and they often contain as little as 10-20% of
actual colorant.
6.2 PROPERTIES OF DYES
The colouring matters used for coloration of textiles, plastics, etc. as well as
for paints, printing ink and other colorant preparations, may be broadly
classified into two categories – dyes and pigments. The dyes are soluble in
water or made soluble during application and have affinity for one or more
textile fibres under precise conditions of temperature and presence of
specific auxiliaries. The pigments are water insoluble. They are mostly used
for paints, printing inks and plastics. They can also be applied on textile
materials, by adding in polymer melt or solution, or by applying on fibre
surface with the help of an adhesive type substance called binder. The
pigments may be classified as follows:
1. Inorganic pigments, such as various metallic oxides, hydroxides,
chromates or other salts, are mostly used for paints and similar colour
preparations.
2. Organic pigments, such as insoluble azo or polycyclic keto
compounds, are mostly applied on textiles.
329
3. Toners are sparingly water-soluble azo compounds precipitated as

barium, calcium or magnesium salts.
4. Lakes are water-soluble dyes precipitated as metallic salts.
5. Complex of basic dyes with selected inorganic acids such as
phosphomolybdic acid, phosphotungstic acid and
phosphomolybtungstic acid resulting in fluorescent pigments, which
are used for printing of textiles and for making poster or signal colours.
6. Metallic co-ordination complexes of organic compounds e.g. copper
phthalocyanine.
Many thousands of dyes are developed for coloration of a great number of
textile and other materials, and the colour of such materials has to withstand
extremely varied external conditions. The manufacturers are producing
newer dyes and discarding some older dyes everyday. The dyes are,
therefore, to be classified into different groups for systematic application and
recording. The classification may be on the basis of the chemical groups
present in them or most popularly on the basis of their methods of
application, such as direct, acid, basic, vat, disperse etc. A particular dye-
class may be suitable for one or more fibre type.
Dyes used for textile materials must possess the following four principal
properties [2]:
1. Intense colour.
2. Solubility in water, either permanently or temporarily during dyeing.
3. Affinity or substantivity towards textile fibres so that they are absorbed
and retained by them. Reactivity of certain dyes with fibres assures
firm retention.
4. Adequate fastness, i.e. ability to withstand the treatments which the
textile materials undergo in manufacturing processes and in normal
use.
6.3 COLOUR AND CHEMICAL CONSTITUTION
Organic dyes and pigments, whether natural or synthetic, are very intense in
colour. The colour should be so intense that a little quantity of such material
is capable of coloration of large quantity of various substances such as
textiles, paper, leather, etc. If a large quantity of colorant is required for
coloration, the properties of the substrate may be adversely affected.
Graebe and Liebermann in 1867 undertook the first study of the
relationship between colour and chemical structure. They found that
reduction of some known dyes destroyed the colour instantly. They
concluded that the dyes are chemically unsaturated compounds.
Most of the organic compounds are complex unsaturated compounds
having certain substituent groups. It was from a study of compounds like
330
azobenzene and p-benzoquinone that led Witt (O.N. Witt, 1876) to formulate
his celebrated theory. Witt proposed that a dye contains a colour producing
chromogen, which is composed of a basic chromophore or colour bearing
group, to which can be attached a variety of subsidiary groups called
auxochromes or colour intensifiers, that lead to the production of colour.
Chromophores include carbon-carbon double bonds specially conjugated
systems having alternate single and double bond.
Witt also claimed that the auxochromes confer dyeing properties on the
molecule, but it is now established that colour and dyeing properties are not
directly related. However, Witt’s theory, in general, is still acceptable to
colourists.
Three years, later Nietzki stated that increasing the molecular weight of a
dye by the introduction of substituents such as methyl, ethyl, phenyl, ethoxy
or bromo, produced a bathochromic shift (i.e. shift of absorption peak
towards longer wavelength). Though Nietzki’s rule initially proved useful, its
utility decreased as many exceptions were subsequently discovered.
Armstrong proposed the quinoid theory in 1887, stating that only the
compounds, which can be written in a quinoid form, are coloured. The
theory soon proved to be erratic.
Gomberg first discovered the coloured free radical, triphenylmethane in
1900, which is devoid of keto, azo chromophores and auxochrome. Based
on the new chromphore, Baeyer proposed the theory of holochromy
whereby a colourless compound is rendered coloured on salt formation.
Halochromism is still used to denote a colour change of a dye on the
addition of acid or alkali.
Baeyer further proposed in 1907, the possibility of tautomerism to account
for the colour of dyes. For example, in Doebner’s violet there is a rapid
oscillation between the two tautomeric forms (6-1 and 6-2), the chlorine
atom flopping rapidly from one amino group to the other.
+
¯
H2N
+ Cl H2N NH2
NH2 Cl ¯
Ph Ph
(6-1) (6-2)
Hewitt and Mitchell (1907) first realised the importance of conjugation i.e.
presence of alternate single and double bonds. From a study of azo dyes,
they established Hewitt’s rule stating that the longer the conjugated chain,
the more bathochromic shift will be in the colour of the dye.
Dithey and Wizinger (1928) refined Witt’s theory and proposed that a dye
consists of an electron-releasing basic group, the auxochrome connected to
331
an electron-withdrawing acidic group by a system of conjugated double

bonds. The greater the neucleophilic and electrophilic character respectively
of the two groups and/or the longer the unsaturated chain joining them, the
greater is the resulting bathochromic shift.
When light absorption takes place in the visible range, the compound
attains a colour that is complementary to the light absorbed which is roughly
represented by the wavelength of maximum absorption (λmax). The
relationship between the light absorbed and colour perceived are shown in
Table 6.1 [3].
Table 6.1 The Relationship between Light Absorbed and Colour Perceived
of an Object
Wavelength of absorption (nm) Light absorbed Colour perceived
400-500 Blue Yellow

400-440 Violet Greenish yellow
460-500 Greenish blue Orange
400-620 Bluish green Red
480-520 Green Magenta
560-700 Orange Cyan
600-700 Red Bluish green
Certain colours require multiple absorption bands − green requires
absorption of red and blue-violet. This is difficult to achieve and the number
of green dyes is comparatively less. Black requires a combination of several
broad overlapping bands of similar extinction coefficients. The brown, olive
green and other dull colours also require bands covering the whole visible
spectrum, but of different extinction coefficients [4].
The early dye-chemist regarded the colour changes (by introduction of
auxochromes) from yellow through green to red as deepening of colour, the
shift was, therefore, termed as bathochromic and the change in reverse
direction as hypsochromic. In spectroscopy, these terms presently mean red
shift and blue shift respectively.
The organic colorants may be broadly classified into three groups [5].
Benzenoids are the most important group among synthetic colorants. These
include various aromatic compounds − in textile the most important
chromophores are azobenzene, triphenylmethane and anthraquinone (6-3,
6-4, 6-5 respectively). Benzenoids are also occasionally accompanied by
thio (>C=S), nitroso (-N=O) and many other groups.
Azo groups (-N=N-) are not available in nature. Azo groups incorporated
in benzenoids form the basis of majority of synthetic dyes. Approximately
70% of all dyes (belonging to various dye-classes) used in textile industries
are azo dyes.
332
H O
N=N C
O
(6-3) (6-4) (6-5)
Magenta and other triphenylmethane dyes were among the earliest syn-
thetic colouring matters and they still remain a large and important group.
This group includes diamino, triamino, aminohydroxy, hydroxy derivatives of
triphenylmethane and derivatives of diphenylnaphthylmethane. Dyes of the
triarylmethane class are usually red, violet, blue or green dyes. These are
characterised by high tinctorial power and brilliant hue but generally possess
only moderate fastness to light. This class includes basic, acid, direct,
mordant, solvent dyes and fluorescent pigments.
Anthraquinone dyes have important properties of chemical stability, light
fastness and brightness, which are difficult to attain with other structures.
However, anthraquinone dyes are at present on the decline, not due to any
shortcoming of these compounds as dyes, but chiefly because their
chemical synthesis is expensive. The process of anthraquinone production
is costly from a waste disposal point of view, waste products include strong
acid, chromium, vanadium and mercuric salts, plus a variety of ill-defined
organic and inorganic impurities, all of which have to be safely disposed of
without contaminating the environment.
The gradual replacement of the relatively weak anthraquinone, typically
with a molar extinction coefficient (ε) in the range 12,000 to 18,000 mol/(l
cm) by much stronger triphenodioxazine unit (8-19) with molar extinction
coefficient between 70,000 and 80,000 mol/(l cm), is now a well established
trend. All the major manufacturers now offer triphenodioxazine-based blues
as part of their product ranges [6].
Polyenes consist of non-benzenoid long conjugated double bond system,
which is the basis for many biological colorants. If such conjugated system
is large enough, it can absorb visible light and becomes coloured.
Carotenoids are typical non-cyclic natural colorants. An important member
of this group, β-carotene (6-6), the orange colorant present in carrots and
many other vegetables. This is used for coloration of cosmetics and food
products. When it is split into halves, a portion having a structure similar to
(6-7) is vitamin A1. A similar carotenoid crocein, which is the principal
colouring component of the naturally occurring yellow dye saffron, used for
food colouring. Rhodopsin, the visual pigment of eye, is similar to β-carotene
333
and vitamin A1. Carotenoids are responsible for various colours in bird
feathers.
Cyclic polyenes, the other type of non-benzenoid conjugated systems,
include porphyrins. The most important members belonging to this class are
α-chlorophyll (6-8) and heme, both similar in structure. While the green
coloured chlorophyll is responsible for photosynthesis of plants, red coloured
heme transports oxygen in blood. Both cyclic 18-member conjugated
2+ 3+
systems have a central metal ion, Mg in the former and Fe in the latter.
The synthetic pigments, blue and green phthalocyanines are also cyclic
polyenes like porphyrins, but they have additionally benzenoid groups, e.g.
copper phthalocyanine (6-9). Phthalocyanines, invariably copper or nickel
derivatives, have been employed alone to achieve bluish to greenish
turquoise shades, or in combination with lemon yellows for the production of
bright greens. The chromophore has been utilised in most of the dye-
classes, namely direct, acid, reactive and disperse dyes, and also in
pigments. In spite of their extremely high chromophoric strengths, they do
not appear particularly strong in colour on cotton and generally fail to build
up to very heavy shades. This is mostly due to moderate fixation efficiency
of these dyes, which in turn probably arises at least partly from the tendency
of the molecules to exist in highly aggregated forms. A patent from Dystar
describes the preparation and use of aluminium phthalocyanines as reactive
dyes for cellulose. These environmentally friendly dyes are claimed to have
very good light fastness, better build-up, especially at low temperature (40-
60°C) and good fixation efficiency [6].
Auxochromes are electron donor or acceptor substituent groups, which
shift light absorption within visible range. When the absorption is shifted to
longer wavelengths, it is known as bathochromic or red shifting. Shifting
towards shorter wavelength is known as hypsochromic or blue shifting.
Similarly, the increase and decrease in intensity are known as hyperchromic
and hypochromic respectively. Typical electron donors are primary,
secondary and tertiary amines, alkoxide, hydroxide and acetate groups.
Typical electron acceptors are nitrate, cyanide, alkyl sulphite, carboxylate,
nitrite, carbonate and CO groups as in anthraquinone (6-5) or in indigo (6-
10).
OH
(6-6) (6-7)
As various limitations of Witt's approach came to light, the resonance
theory was put forward. Adam and Rosenstein (1914) first proposed that it is
the oscillation of electrons, and not the oscillation of atoms, which produces
colour. Atomic vibrations give rise to the absorption of infrared radiation,
334
whereas the oscillation of electrons causes the absorption of ultra-violet or

visible radiation resulting in colour sensation.
N N
N-Mg-N N⋅⋅Cu⋅⋅N
N O N
CO CO
O C=C
O NH NH
O C20H39
(6-8) (6-9) (6-10)
Bury (1935) highlighted the relationship between resonance and colour of
a dye. He realised that it is only the electrons that move and not the atoms,
and such movement of electrons is a merely an example of resonance (i.e.
6-1 ↔ 6-2). The intense absorption of light, which characterises dyes, is due
to resonance in the molecule. The resonance is enhanced by the
auxochrome. The greater the number of limiting structures of similar energy,
the more bathochromic the dye will be.
It was proposed that π-bonding electrons involved in the second bond of
the double bonds are not localised but they belong to the whole conjugated
system of alternate single and double bond. One or more mobile π-electrons
of the system can move through the molecule. It is, therefore, possible to
write various electronic configurations of the molecule called canonical
forms or resonance hybrids. This does not imply any actual vibration or
oscillation among these forms, but merely signifies that the structure is an
intermediate one. When a donor-auxochrome is introduced in such
molecule, additional electrons are pumped into the conjugated system, while
an acceptor-auxochrome pumps electron out from the system.
Consequently, the structure becomes stable. The electrons can move more
readily along the molecule. The natural frequency of vibration is decreased
resulting in absorption at longer wavelengths. In other words, the absorption
range moves from ultra-violet to visible light, consequently simultaneous
hyperchromic and bathochromic shift.
Azobenzene may exist in five resonance forms (6-11 to 6-15), the
uncharged form (6-13) is the most stable. When two auxochromic groups
are attached to the azobenzene, the configuration (6-17) is more stable than
structures (6-11) to (6-15) as the charges are now firmly held on oxygen or
nitrogen atoms. The compound (6-16) is, therefore, of more intense colour
than azobenzene.
335
With the increase in stability of the alternating structures, its electrons may
be considered to move more readily along the chromophore. The natural
frequency of its vibration is decreased. Consequently, the absorption occurs
at longer wavelength. This is analogous to a violin string for which the longer
the string, the lower is the frequency, hence the longer is the wavelength of
the note it emits when plucked. This applies to adsorption as well as
emission of energy, because any oscillator absorbs energy most readily at
the wavelength of its natural frequency of vibration.
+
+ N-N -Ù N-N -Ù N=N
(6-11) (6-12) (6-13)
+ -
Ù N-N Ù N-N +
(6-14) (6-15)
O O
+
N N=N OH Ù N N-N OH
O -O
(6-16) (6-17)
As resonance theory cannot prove a completely satisfactory under-
standing of colour generation in organic molecules, finally molecular orbital
theory has been proposed. The electrons exist in various layers called shell
(named as principal quantum number, n = 1, 2,3 or any integer) around
atomic nucleus. The shells are further divided into various orbits.
The number of orbits in a shell is decided by the three factors:
1. Angular momentum quantum number, l = n - 1. Each l value repre-
sents a specific orbit named after the description of the hydrogen
spectrum such s for sharp (l = 0), p for principal (l = 1), d for diffuse (l
= 2), f for fundamental (l = 3) etc.
2. Magnetic quantum number, m = + l, + l - 1, + l - 2, ... 0, 1, 2, ..l
3. Spin quantum number, + ½ , - ½
When two atoms are close to each other, the respective atomic orbital
form various molecular orbital by overlap interactions. The molecular orbital
can accommodate exactly the same number of electrons as the atomic
orbital from which they are formed. Various research workers have studied
the formation of various molecular orbitals by linear and non-linear
combinations of the interacting atomic orbital. Molecular orbital techniques
without any approximation are possible at present. However, the necessity
of very complex and high level computation restricts its application to large
dye molecules. In a simplified approach, the molecular orbital can be
336
classified into low-energy bonding orbital, intermediate-energy non-bonding

orbital and high-energy anti-bonding orbital. When two atomic orbital interact
strongly by direct overlap and there is symmetry with respect to rotation
about the axis joining the two atoms, a sigma (σ) orbital forms resulting in a
σ bond. The sigma orbital will have less energy than the individual atomic
orbital from which it is formed, because some energy is utilised for bonding.
By absorption of energy, transition may occur from σ-bonding to σ* anti-
bonding state (σ Æ σ*). When overlapping occurs only for the outer region
of less electron density, the energy of bond is less than that in a σ bond.
Consequently, π orbital resulting π bonds are formed. A σ bond possesses
zero angular momentum around bond axis, whereas π orbital possesses
one unit of angular momentum. Again π-bonds can be excited into high
energy π* anti-bonding state (π Æ π*). There may also be transition from
non-bonding to anti-bonding state (n Æ σ* or n Æ π*). In a molecule, there
may be several numbers of each type of orbital of varying energy levels
formed by interaction of various pairs of atoms. For a molecule, the smallest
amount of energy absorbed is the energy required for transition from highest
occupied molecular orbital (HOMO) to lowest occupied molecular orbital
(LOMO). The most important transitions in respect of minimum absorption
resulting in generation of colour are (n Æ π*) and (π Æ π*).
All the early theories are qualitative in nature. Two modern qualitative
theories are Valence Bond (VB) theory and Molecular Orbital theory (MO).
While the former is based on the concept of bonding valence electron pairs
being localised between specific atoms in a molecule, the latter pictures
electrons as being distributed amongst a set of molecular orbitals of discrete
energies. The qualitative VB theory is very similar to the resonance theory
proposed by Bury. On the other hand, quantitative VB theory has never
been applied to dyestuff.
The PPP (Pariser-Parr-Pople) MO model [7] based on quantitative MO
theory is successfully used for predicting colour and tinctorial strength of
dyestuffs, particularly azo dyes. However, it deals with planer molecules
only – it does not take into account the effects due to π-electrons e.g.
hydrogen bonding and steric effects. Since most dyes are essentially planer,
this limitation is not a problem.
The PPP MO model calculates a quantity f called the oscillator strength. It
is directly proportional to the square of the transition dipole moment M, but
inversely proportional to the wavelength of the absorbed radiation, since νM,
the mean absorption frequency of the band is equal to 1/γM.
f = 4.0703×10 M νM
29 2
(6.1)
If transition dipole moment M is constant, the tinctorial strength should
decrease as λmax (wavelength of maximum absorption) increases. This is in
337
direct contrast to the empirical rule of thumb adopted by dyestuff chemists

that in a given series of dyes, the tinctorial strength increases as dyes
become more bathochromic − blue azo dyes should be stronger than red
azo dyes which in turn should be stronger than yellow azo dyes.
The oscillator strength f is directly proportional to absorption at λmax, i.e.
εmax.
f = 4.32×10 ∆ν½ εmax

9
(6.2)
Where ∆ν½ is the half-band width, i.e. the width of the absorption band in
cm-1, at ε = ½ ε max.
For qualitative colour predictions, VB theory is adequate for neutral azo
dyes and anthraquinone dyes. Where quantitative results, especially of
tinctorial strength and a thorough understanding of colour-structure
relationships are required, PPP MO model should be used.
6.4 COLOUR MEASUREMENT

As the dyes impart colour to the textile substrates, accurate colour
measurement is extremely necessary for quality control of dyeing processes
and dyed materials. A book has been written on the topic by the author [3].
Measurement may be made of dye solution or of dyed materials. Though
the latter should be more appropriate, the industry still prefers to measure
dye strength in solution state as the method is simple and straightforward.
When light of certain wavelengths are absorbed in preference to others,
the absorption is termed as selective. All coloured substances owe their
colour due to selective absorption in some portion of the spectrum.
Absorption of light by coloured solution is governed by two laws. Both are
applicable to the absorption of monochromatic light only.
The Lambert's law (more accurately Bouguer's law) states that the
fraction of light absorbed by a substance is independent of the intensity of
the light and, in other words, layers of equal thickness of the same
substance transmit the same fraction of incident light at a given wavelength
irrespective of its intensity.
The Beer's law refers to the effect of the concentration of the coloured
substance on the absorption of light and states that the absorption of light is
proportional to the number of absorbing molecules in its path, i.e. the
concentration of the absorbing solution. The two laws may be combined and
stated as follows (Eqn. 6-3):
- cL
I = I0e ε
338
I0
or log = εcL (6.3)
I
where I = intensity of transmitted light
I0 = intensity of incident light
ε = molar extinction coefficient (litre /mole/cm)
c = concentration of the absorbing solute (mole/litre)
L = path length or thickness of the absorbing layer, cm
I
Transmittance, T = = e -εcL
Io
or log 1/T = εcL = D (6.4)

Absorbance or optical density, D is an additive function, i.e. when objects
are in optical contact (no separate interface), the total absorbance can be
calculated by adding absorbance of individual objects. If light passes
successively through two or more absorbing layers, the total optical density
is the sum of those of the individual layers, i.e.
D = D1 + D2 + D3 ..... (6.5)
The transmittance, T, on the other hand, is the multiplication product of the
transmittance of the individuals, i.e.
T T T
T = 100 × 1 × 2 × 3 LL (6.6)
100 100 100
The optical density has a linear relation with concentration up to a certain
limit. The plot of c versus D is a straight line with a gradient of εl. However,
the laws are valid only for monochromatic radiation and for non-scattering
solution of very low concentration. The molar extinction coefficient ε is the
optical density of a solution of 1 cm thickness, containing 1 mole/litre
dissolved coloured substance. It is a measure of the probability that a
photon of correct wavelength striking the molecule will be absorbed; if the
5
probability is 100%, its value is 10 . The value for most of the dyes is around
4
10 − the highest found in any type of substance. The human eye can
-
readily see the colour of the dyes even when the amount is as small as 10
18
g or about 10,000 molecules [4].
Colour strength value is a numerical value related to the amount of
colorant in a solution. It is often used to calculate the difference in strength
(%) between two coloured solutions. The relative colour strength S of two
dye solutions may be given the Eqn (6.7):
D C
S = 100 × 2 1 (6.7)
D1C2
where C is the dye concentration.
339
Assuming equal concentration of the dyes (C1 = C2), the equation may be
simplified as Eqn. (6.8):
D2
S = 100 × (6.8)
D1
where subscripts 1 and 2 refer to the reference dye and dye under test
respectively.
The absorbance may be measured at a single wavelength (λmax) or
summed over all wavelengths at the interval of 10 or 20 nm within the visible
spectrum with or without weighting with visual functions ( x (λ ), y (λ ), z (λ ) )
before calculating the ratio. The method may be used to measure tinting
strength of the dyes by means of spectroscopic absorbance. It does not give
the colour strength when the dyes are applied to a textile substrate.
However, dye manufacturers and users prefer the test, because of its speed
and reproducibility.
A linear plot of c versus D does not necessarily indicate that the dye is
entirely mono-disperse in solution. It may be true in some cases, but such a
plot can also occur with highly aggregated dyes, in which case it indicates
that the aggregates are of uniform size over the range of concentrations
studied.
Nevertheless, most dyes appear to show non-linear beer’s law plots over
a range of highly concentrated solutions. Various experiments show that
probably all dyes associate in aqueous solution, to varying extent, according
to particular features in their molecular structures; the intermolecular
attraction is mainly due to Van der Waals’ forces. Dimers are probably
formed first and these grow by addition of further molecules (or dye ions) to
give lamellar micelles in which the dye molecules are stacked up like cards
in a pack. When the light is direct and monochromatic, a curvilinear Beer’s
law plot for a dye indicates progressive aggregation with rise in
concentration, and all such deviations from linearity are evidence of dye
association. In most such cases, the Beer’s law plot is concave to the
concentration axis and may be represented by the general equation as Eqn.
(6.9):
I0 εcL
log = (6.9)
I 1 + gC x
where g and x are empirical positive constants.
It is possible to measure the molecular weight M of the aggregate from the
extent of deviation ∆A of the optical density or absorbance A, from linearity,
in a Beer’s law plot as Eqn 6-10:
m m∆A
M= = (6.10)
1- α AP
340
where m is the molecular (or ionic) weight of the monomer, α is the

fraction of monomers, which are associated and P is the probability of
absorption of a photon by a monomer.
When light falls upon an object, a portion of it is always reflected. If the
object is not opaque, a portion of light transmits through the object. The
colorimetric property of an object is characterised by its reflectance and/or
its transmittance. The majority of the coloured objects encountered by us
are either opaque or translucent for which reflectance property is most
important. The light scattered back from opaque materials is called reflected
light. The perceived colour of a material is determined by the relative
amounts of light reflected throughout the visible range of light, i.e. 380-750
nm or for practical purposes 400-700 nm.
The process of reflection is quantified by reflectance (ρ) which is defined
as the ratio of the reflected radiant flux to incident radiant energy under
specified conditions of irradiation. Spectral reflectance is defined as shown
in Eqn. (6.11):
p
ρ(λ ) = λ (6.11)
p0λ
Where Pλ is the spectral concentration of the radiaA\nt power reflected by
the medium and P0λ is the spectral concentration of radiant power incident
on the medium.
Absolute reflectance is less reliable to measure. Hence, CIE (International
Commission on Illumination, Paris) has defined another term, spectral
reflectance factor Rλ, as the ratio of the light flux reflected from the sample
to the light flux reflected from a perfect isotropic reflecting diffuser identically
illuminated and viewed by the instrument at the wavelength λ. The
reflectance values are independent of the energy distribution of the
illuminant as long as the material is not fluorescent.
When a light beam is incident on a dyed or pigmented specimen, the
radiant energy interacts with colorant particles as well as molecules of the
medium carrying those particles, resulting in absorption and scattering of
light. In absorption process, the light energy is absorbed by the colorant and
converted to heat and other forms of energy. In scattering process, the
direction of the light beam is altered. If the light once scattered by the
colorant comes out of the medium, it is said to be single or independent
scattering. The mathematical modelling of single scattering phenomenon is
comparatively easy. The Raleigh’s theory and the Mie’s theory completely
account for the single scattering phenomenon.
In paint film or dyed textiles the colorants are closely packed. Therefore,
the light scattered by a single particle is re-scattered by many other particles
before the light emerges from the turbid media. Such phenomena, called
multiple or dependent scattering, are very complex to express
341
mathematically. Multiple scattering refers to scattered light from one particle

re-scattered by another particle. However, the dependent scattering refers to
the perturbation and twisting of the very scattering pattern itself because of
the presence of neighbouring particles. This is a more difficult problem and
cannot be solved very satisfactorily. Dependent scattering usually lowers the
scattering efficiency of a pigment. Though optical theories for densely
packed particulate systems are developed, those are too complex to be
suitable for application to industrial problems. Hence, alternate simpler
models are necessary for the purpose. Kubelka and Munk [7] dropped the
fluorescence phenomenon to reduce the complexity and proposed a two-flux
theory. Considering only absorption and scattering of light inside the media,
they assumed that the radiant flux inside the media could be resolved into
two fluxes, one going downward and other in the upward direction. If k and s
are the coefficients of absorption and scattering respectively and if the
material has infinite thickness (i.e. no background reflection), they deduced
that the reflectance, R∝ may be written as Eqn. (6.12):
1
2
R ∞ = 1 + (K/S) - [(K/S) + (K/S) 2 (6.12)
Where K and S are absorption and scattering coefficients of the reflecting
medium.
When solved for K/S, the equation takes the famous form of Kubelka and
Munk Equation as (6.13):
K (1 - R ∞ ) 2
F (R ∞ ) = = (6 − 13)
S 2R ∞
The function F(R∞) is known as Kubelka-Munk function. The equation is
valid for a single wavelength or monochromatic light and calculations are to
be made for the whole of visible range. The reflectance, R∞ is obtained
when the measurement is made at complete opacity. In textiles, the
condition is obtained by repeated folding of the fabric till the reflectance
becomes independent of the number of folds. In paints, the complete opacity
may be obtained by thick draw-down on a substrate. For simplicity, R∞ is
written as R, but it carries the same meaning. For deeply dyed shades,
Pineo correction may be necessary to eliminate the effect of surface
reflection by excluding minimum reflectance achievable in the deepest dyed
shade for all wavelengths from the actual reflectance.
The reflectance or transmittance measured by the instrument has no
direct relation with the concentration of the colorants. However, the Kubelka-
Munk function derived from the reflectance is directly related to colorant
concentration. It is called an additive function The theory assumes that the
ratio of absorption and scattering coefficients of the colorant is directly
proportional to its concentration and is additive in a mixture. If a mixture is
made with n number of colorants with concentrations Ci, the coefficients of
342
the resultant mixture may be calculated in two ways. For textile and other
applications where the quantity of the colorants is low and there is negligible
scattering by the colorants, the additive function of the mixture, F(R) is given
by the single constant formulation as shown in Eqn. (6.14):
n
F(R) = FS + Σ i=1
bici (6.14)
where FS is the additive function value of the substrate

bi is the specific additive function value of colorant i, i.e. [ F(R)i - FS ]/ci
ci is the concentration of colorant i
n is the number of colorants in the mixture
For paints and similar applications where both substrate and colorants
take part in scattering, the additive function of the mixture, F(R) given by the
two constant formulation as Eqn. (6.15):
K S + ∑ K i Ci
F(R) = (6.15)
S S + ∑ S i Ci
Where K and S represent the coefficients of absorption and scattering
respectively, and the subscripts have same meaning as above. These
formulae are widely used computer colorant formulation programs
commonly known as computer colour matching.
Colour strength value of opaque specimens on a spectrophotometer most
often involves calculation of K/S value at one or more wavelength intervals.
Accordingly relative colour strength is measured by ratio of K/S values of
two specimens at one wavelength (λmax) or summed over all wavelengths at
the interval of 10 or 20 nm within the visible spectrum with or without
weighting with visual functions ( x (λ ), y (λ ), z (λ ) ) before calculating the
ratio.
6.4.1 Measuring Instruments

Colour measuring instruments may be designed to measure physical
attributes (like intensity of light sources or reflectance/transmittance of
objects) or directly psychophysical attributes (i.e. some correlates of visual
perception). However, by interfacing with computer, physical analysis
instruments can provide psychophysical measures so quickly that a user
may hardly find any difference in the output. On the other hand,
psychophysical analysing instruments can provide only limited information.
That is why colorimeters, in spite of being highly economical, are gradually
being replaced by more versatile but costly spectrophotometers.
There are three types of colorimetric instruments in use − colorimeter,
spectrophotometer and spectroradiometer. Instruments with varying degree
of sophistication and specialisation are available in the market. While the
343
spectroradiometer measures in illuminant-mode, the other two generally

measure in object mode. The recent trend in instrumental process control
has resulted in use of on-line instruments. However the majority of the
colorimetric instruments till date is off-line and mostly used in laboratories.
Laboratory instruments should be highly accurate and standardised, while
on-line instruments should be rugged under varying environment and should
have good precision and firmness.
The instruments named colorimeters can be classified into two types −
visual and photoelectric. Again, visual colorimeters are of two types. The
earlier visual colorimeters are basically visual absorptionmeters or better to
be called colour comparators which compare colour of the sample, mostly
liquids, with that of standard and find a match of the two. Such instruments
are employed for chemical analysis, concentration determination or grading
based on colour. The other type is true colorimeter, which emphasises
visual equivalence or psychophysical estimation. The oldest and simplest
colour comparator is the Nessler tube, which was developed into Duboscq
colorimeter. This type of colorimeter can only compare the optical properties
of solutions of a particular colouring substance, but this is all that is required
in many colour-assessment tests.
Figure 6.1 shows the construction of the instrument. There are two vertical
cells which accommodate the reference and test solutions having the same
colour but of different concentrations. Two movable glass plungers can be
moved to vary the path lengths L1 and L2 of the absorbing solutions until the
colours in both fields in the eyepiece appear same. Applying Beer-Lambert
law, the concentration of the unknown solution can be determined by
multiplying concentration of the known solution with the ratio of path lengths.
According to the above law, when the colour of both solutions appear equal,
each of the light beam must have passed through the same number of
molecules. The number is directly related to the concentration of the solution
multiplied by the path length, i.e.
L2
C1 L1 = C2 L2 or C1 = C2 — (6.16)
L1
If the concentration C2 is known, we can easily calculate the other
concentration.
The accuracy of the measurement depends on the visual perception of the
observer. Hence in Hilger-Spekker absorptionmeter, visual assessment was
replaced by measurement with photoelectric cells. A calibrated light gate
was adjusted until the electrical output matches with that for test light. The
equality was assured when there is no deflection of the galvanometer.
True colorimeters define colours in terms of their own primaries. A
number of colorimeters were specially developed for colour vision research.
344
These were very elaborate, costly and highly specialised to serve one or a
limited number of purposes.
The earliest true colorimeter was Clerk Maxwell's colour box (1860),
consisting of a prism unit with adjustable slits in the appropriate parts of a
light path to control independently the amounts of red, green and blue light
beams viewed as a homogeneous colour in an optical viewing unit to match
the colour of the sample shown in the other half of the optical unit. The
relative aperture areas x, y and z are recorded as the amount of the three
primaries.
Eye
Eye piece
Mirror Mirror
Field
separator
Plungers
(glass)
L1
L2
Mirror Mirror
Lamp
Fig. 6.1 Duboscq Colorimeter
Lovibond colorimeter (1870-1880), is still a popular commercial visual

colorimeter even after 100 years of use and development [8, 9]. It is based
on subtractive colour mixing of coloured glass filters. There are 250
Lovibond glass filters for each of three primaries, namely red, yellow and
blue of very permanent nature. The filters are graduated in such a way that
two "1.0" glasses match a "2.0" glass plus a colourless glass. Equal value of
all three together give a grey series down to black. Putting suitable Lovibond
filters in the light path, nearly nine million colours of varying brightness can
be matched. In fact, the whole visible colour gamut can be covered except
highly saturated green area. This area now can be covered by using a cyan
illuminant in the matching field instead of normal north daylight light source.
The colour is assessed by visual matching of samples, such as surface
345
colour or transparent sample including liquid, keeping it in sample field and

the coloured filters on the path of illuminating light in the reference field.
Visual colorimeters are simple but slow and tedious in operation. To
increase the speed and reproducibility of measurement, photoelectric
colorimeters are developed which measure colours directly in colorimetric
quantities for one illuminant and observer (typically illuminant C and 2°
standard observer) with the help of broadband filters and photoelectric cells.
The principle of construction of a 3-filter photoelectric colorimeter is shown
in Figure 6.2. Light, reflected from the object, passes through the filters R,
G, B successively due to rotation of the filter-containing disc and is
measured separately by the photoelectric photon detectors. The results will
be misleading unless the three filters provide direct reading in terms of CIE
tristimulus values or similar standard specifications and represent three
response curves of CIE standard observer. It is almost impossible to obtain
such types of filters exactly, but the available filters may be adequate for
routine work. The method may be useless for metameric pairs, i.e. the
colours perceived indifferent under a particular light, but the reflectance
values at different wavelengths are non-equal. Lovibond automatic
colorimeter combines the simplicity of a visual system of nomenclature and
the speed and accuracy of photoelectric colorimeter.
Sample
Filters
G
R
B
Lamp
Detector
Fig. 6.2 Photoelectric Colorimeter
A spectrophotometer measures the spectral reflectance or transmission

factors of objects. It compares light leaving from the object with that incident
on it at each wavelength. The data are primarily related to the colour of the
object and are usually presented as curves in which percent reflectance or
transmittance are plotted against wavelength at regular intervals of 1 nm or
most commonly at intervals of 5 nm, 10 nm or 20 nm. The shape of the
spectrophotometric curves can give some indication of perceived colour by
comparison with those of known hues.
346
Light may travel in a single direction represented by a vector or in all

directions in a diffused manner. Most commonly during visual perception,
both illuminating and viewing lights are diffused. Such a condition is almost
impossible to imitate in colour measuring instruments. The geometry of
illuminating and viewing (or measuring) lights in such instruments can be of
two types (Figure 6.3), namely:
1. Bi-directional geometry
2. Diffuse geometry using integrated sphere
Lamp
Lamp Detector
Detector
Sample
00/450 (Bi-directional) 00/d (Diffuse)
Fig. 6.3 Geometry of Illumination and Viewing

In bi-directional geometry, the two directions may be 0° and 45° (for
reflectance measurement) or 0° and 180° (for transmission measurements).
The tolerance limit in all the above cases is ±5°. The reflectance geometry
may be again of two types 0°/ 45° or 45°/ 0°, the first angle being for
illumination while the second one is for viewing or measurement.
In diffuse geometry, either illumination or viewing should be in direction
normal to the sample (termed 0°, tolerance ±5°) and the remaining is dif-
fused, i.e. collected from all directions.
There has been considerable debate about the relative advantages of the
two geometries. The advantage of using diffuse radiation either in illumina-
ting or viewing the sample is that the variations in the surface texture (e.g. in
fabrics like corduroy, carpet, velvet, etc.) will be averaged out. In general,
bidirectional geometry is superior for measurement of colour and colour
differences with good correlation with the visual estimates. However for
colorant formulation (or colour matching) computation, the diffuse geometry
is preferred as it handles white specular light uniformly irrespective of glossy
or matte surface [10].
In a normal spectrophotometer to be used for non-fluorescent objects, the
illuminating light may pass through the monochromator and the
347
monochromatic light is directed to the object. Finally, the reflected or

transmitted light is measured by the detector as shown in Figure 6.4(a). The
bidirectional geometry has been considered in the figure, but diffuse
geometry may also be utilised. Monochromator is a device (either prism or
grating) for isolating a narrow portion of the spectrum by dispersing light into
its component wavelengths. The above geometry called Direct or Forward
Optics was very common in the earlier generation spectrophotometer, espe-
cially those used for transmission measurement.
Fluorescent materials absorb light at shorter wavelength and emit light of
longer wavelength due to fluorescence. The spectral reflectance factor of
such objects has two components − one due to reflectance only and the
other due to fluorescence only. For the measurement of true reflectance
Standard Light source

Light Monochromator
Monochromator
source
Detector
Detector
Sample Standard Sample
(a) (b)
Monochromator 1 Light source
Monochromator 2
Detector
Standard Sample
(c)
Fig. 6.4 Components of Different Types of Spectrophotometer

factor of these type objects, it will be correct to illuminate the object with
polychromatic light (i.e. light of multiple wavelengths) obtained directly from
the light source followed by passing through the monochromator and finally
to the detector as shown in Figure 6.4(b). This is known as Reverse Optics.
Nowadays most of the instruments are constructed with reverse optics using
integrated sphere. For non-florescent objects, both the instruments will give
the same result. The instruments with both types of optics are also available.
In such instruments, the geometry can be changed to either Direct or
348
Reverse mode. In further elaborately constructed instruments, two

Monochromators are used as shown in Figure 6.4(c). Instead of exposing to
lights of all wavelengths simultaneously, the first monochromator allows
monochromatic light to illuminate the object. The reflected light from fluores-
cent objects, may be of multiple wavelengths, which are analysed by the
second monochromator and are finally measured by the detector. The data
will be in matrix form, i.e. for each wavelength there may be reflection at
multiple wavelengths, which are measured separately. Such types of
instruments may be useful for advance researches in the colorimetry of
fluorescent colorants. The three types of instruments, shown in Figure 6.4,
consist of single beam of light source; the sample and the standard are x
illuminated alternately. However, double-beam instruments are also
available.
6.5 INSTRUMENTAL COLOUR SPECIFICATION

The colour of an object depends on the relative quantity of the light reflected
or transmitted at different wavelengths within the visible range (400-700
nm). Our sound sensation is analytical in the sense that we can detect
sounds of different musical instruments (of different frequencies) separately,
even if those are heard simultaneously. However, our colour sensation is not
analytical in nature. We cannot judge the existence of lights of different
wavelengths individually when those are mixed. We get the sensation from
cumulative effect. As this cumulative quantity can be matched by mixing
three primary lights, it is proved that our eyes have three type of colour-
detecting cones, the stimuli generated by them are mixed before reaching
the brain. Various other phenomena of colour have also lead to the
conclusion that our eyes have three types of cones only. Each object colour
is sensed by each type of cone separately and each type sends a stimulus
to the brain. Therefore, for each object colour, the brain receives three
separate stimuli. Keeping similarity with colour mixing experiment, we can
consider the three types of cones as red-sensitive r, green-sensitive g and
blue-sensitive b equivalent to the three additive primaries. The spectral
sensitivity of the three colour-detecting cones has been measured and
named as colour matching data r (λ ), g (λ ), b (λ ) (bar stands for statistical
average data of a number of colour normal observers) . To avoid negative
values, the data were subsequently transformed into more usable CIE
standard observer functions x (λ ), y (λ ), z (λ ).
The area under the functions multiplied by the reflectance at respective
wavelength signifies the amounts of three stimuli to be transmitted to the
349
brain for incidence of light having one unit of energy at each of visible
wavelength.
The three stimuli reaching our brain depends on the three sets of
parameters, namely:
1. Relative spectral energy distribution of the illuminating light source, Eλ,
which is being modified by
2. Reflectance characteristics of the opaque object, Rλ, the modified light
falls on our eyes and is sensed by the three types of colour-detecting
organs resulting in three stimuli depending on
3. Their spectral sensitivities represented by standard observer
functions.
An object colour can, therefore, be represented by three numbers (X, Y, Z)
called tristimulus values as shown in Eqn. (6.17), (6.18) and (6.19):
700
X=k∑ RλEλxλ (6.17)
λ=380
700
Y=k∑ RλEλyλ (6.18)
λ=380
700
Z=k∑ RλEλzλ (6.19)
λ=380
Objects are always seen in relation to their surrounding and not in terms of
the absolute level of reflected light. Therefore, CIE recommends that the
tristimulus values are to be specified as relative to the luminosity of a perfect
diffuser having reflectance of 1.0 at each wavelength.
K is a normalising constant and is calculated from the luminosity function
(Y) of a perfect reflectance diffuser. By definition, Y value for the perfect
diffuser is always 100.
Hence, k may be written as Eqn. (6.20).
700
k = 100/ ∑ Eλyλ (6.20)
λ=380
When the calculations are made for wavelength intervals of 10 or 20 nm,
the weights are so adjusted that the value of k is 1.
When two objects have identical (or very close) tristimulus values, they
will match under the particular illuminant. If the reflectance values (Rλ) are
also identical, the match persists under any illuminant, i.e. universal match.
Otherwise, the match may fail when the illuminant is changed and the pair of
objects is called metameric.
350
Chromaticity, an attribute of colour, is related with relative magnitudes of

the tristimulus values rather than with their absolute values. In order to
identify chromaticity independent of lightness, CIE proposed chromaticity
coordinates or trichromatic coefficients x, y and z as in Eqn. (6.21):
X Y Z
x= ,y= ,Z= (6.21)
X+Y+Z X+Y+Z X+Y+Z
As x + y + z = 1, only two chromaticity coordinates x and y have been
recommended by CIE to specify chromaticity.
However, none of the chromaticity coordinates is correlated with any
meaningful visual attribute of colour.
As only two variables are required to express chromaticity, it is possible to
plot the values on a two-dimensional graph called CIE chromaticity diagram.
When the chromaticity coordinates of spectral colours are plotted in such a
diagram, a horseshoe shaped curve is obtained.
Chromaticity diagram is of great help in finding colours generated by
additive colour mixing. If two lights are represented by two points on the
chromaticity diagram, any additive mixture of the two will correspond to a
point on the straight line joining the two points. Since the locus of spectral
colours is concave, all real colours must fall within the area bounded by the
spectrum locus and joining the ends.
Figure 6.5 shows the chromaticity diagram along with locations of different
spectral colours (i.e. monochromatic lights of different wavelengths). The
figure also shows the regions of locations of different surface colours viewed
Fig. 6.5 CIE 1931 Chromaticity Diagram and Locations of Object

Colours when Viewed under Daylight
351
under daylight. Approximately in the centre of the curve is the neutral point,
which represents the chromaticities of white, grey or blacks. The illuminant
C having chromaticity co-ordinates x = 0.310 and y = 0.317 also lies at the
centre of the curve (point C). The locations of other illuminants depend on
their colour temperatures. The chromaticity diagram is closed by a line
indicating the locations of non-spectral purple colours.
The colours of equal hue lie on a line between the neutral point and the
borderline of spectral colours and their saturation is indicated by the
distance from the neutral point. The further the colour is located from the
neutral point, the more saturated it is. When the line connecting the neutral
point and the test colour in the chromaticity diagram is extrapolated, the
wavelength of the spectral light at the point of intersection of the
extrapolated line with the horseshoe-shaped curve is known as dominant
wavelength of the test colour. The ratio of the length of line between the
neutral point and the test colour with the total length of the line is known as
excitation purity.
Lightness has to be indicated by an additional value. Since the colour mat-
ching function, y (λ ) is equal to the luminosity function of the eye, CIE Y
value is used as a measure of lightness, although their correlation is non-
linear. Y value can be plotted as a third coordinate vertically on the plane of
the chromaticity diagram. So the complete instrumental specification of a
colour may be expressed by Y, x, y values. Hardy [11] showed that Y, x, y is
superior to X, Y, Z for specification of colour appearance. Two objects of the
same hue but of different lightness may have different tristimulus values.
However, they will have identical chromaticity co-ordinates.
Chromaticity diagram is helpful for assessing the colour of illuminants and
light sources. The chromaticities of neutral objects follow the illuminant
exactly in x, y diagram. The chromaticities of coloured objects move with
change of illuminant in the same direction as those of the two illuminants,
but the shift is less in case of object colours.
CIE tristimulus values or chromaticity coordinates are not very convenient
for identifying colours of the objects, because these were designed for
colour stimuli of different modes. None of the values is directly correlated
with any visual attributes of colour. Only Y value has high correlation with
luminance and object lightness. The spacing of colours in chromaticity
diagram is not visually uniform. In other words, the relative size of
differences between colours in different portions of Y, x, y colour space does
not correspond to the sizes of the differences as seen or perceived by the
human eye.
A number of uniform colour scales, therefore, are developed which can
represent colours with equal visual spacing and are directly related to
meaningful attributes of colour appearance. The colour scales have been
formulated by linear or non-linear mathematical transformations of CIE
352
tristimulus values. Most of the uniform colour scales are based on opponent
colour theory, i.e. the chromaticity is represented by a red-green and a blue-
yellow attributes.
Chromaticity diagram shows only proportion of tristimulus values and not
their absolute values. Chromaticity coordinates can be compared only
among colours of equal luminance. In tristimulus colour space, the
chromaticity is independent of luminance or lightness. However, perceived
colour also depends on lightness values. Hence, in some of the uniform
colour scales, chromaticity has been linked with lightness values.
A number of uniform colour scales have been developed by different
colour scientists such as Judd Uniform Chromaticity Scale (1935),
MacAdam u, v diagram (1937), RUCS System (1939), Adam-Nickerson
Colour Scales (1950-52) widely known as ANLAB, Hunter L,a,b colour scale
(1958) and finally CIELUV and CIELAB Colour Spaces (1976) proposed by
International Committee on Illumination (CIE).
In 1976 CIE could not recommend a single colour space and a single
colour difference formula to satisfy all colour measuring industries. Colorant
industries were in favour of a formula similar to Adam-Nickerson (AN40)
formula as it was popular at that time. The CIELAB formula was acceptable,
as colour-difference values were about 1.1 times those produced by AN40
formula. On the other hand, television industries preferred a colour space
associated with a chromaticity diagram because of its simple way of
presentation of additive mixture, which also occur in television and other
display devices. The performance in representing perceptual colour
differences of both the formulae are comparable, the ratio of the maximum
to minimum values of ∆E (instrumental colour difference) corresponding to a
given perceptual difference being about 6:1 [12]. However, no simple
relation exists between the two colour scales.
Both CIELUV and CIELAB formulae are plotted on rectangular co-
ordinates. Lightness L* function is same for both colour spaces and is
represented by the Eqn. (6.22).
1/3
L* = 116(Y/Yn) – 16 if Y/Yn > 0.008856 (6.22)
Subscript n represents nominally white object colour stimulus given by a
perfect reflecting diffuser as reference surface illuminated by standard
illuminant D65 or A.
This function is a substitute for Munsell renotation function, which requires
the solution of a fifth-order polynomial to the measure of lightness. At low
values of lightness, the above function deviates appreciably from Munsell
renotation function and the formula is to be modified as Eqn. (6.23):
L* = 903.3(Y/Yn) if Y/Yn ≤ 0.008856 (6.23)

353
However, such low level of lightness is of little practical importance for

reflecting objects.
The chromaticities are expressed by u*-v* coordinates and a*-b*
coordinates for CIELUV and CIELAB colour scales respectively.
CIELUV Colour Space
/ /
Red-green attribute, u* = 13L*(u - un ) (6.24)
/ /
Yellow-blue attribute, v* = 13L*(v - vn ) (6.25)
/ /
where u = 4X/(X + 15Y + 3Z) and v = 9Y/(X + 15Y + 3Z).
CIELAB Colour Space
Red-green attribute, a* = 500[f(X/Xn) - f(Y/Yn)] (6.26)
Yellow-blue attribute, b* = 200[f(Y/Yn)-f(Z/Zn)] (6.27)
1/3
where f(A/An) = (A/An) or 7.787(A/An) + 16/116,
when A/An is greater or less/equal than 0.008856 respectively.
A = X, Y or Z, i.e. the above formulae are applicable for each of the three
tristimulus values. The tristimulus values for the two standard daylight
illuminants D65 and C for both 2° and 10° standard observer are as follows:
Illuminant/Observer Combination
D65/2° D65/10° C/2° C/10°
Xn 95.047 94.811 97.074 97.285
Yn 100.000 100.000 100.000 100.000
Zn 108.883 107.304 118.232 116.145
6.6 VISUAL COLOUR SPECIFICATION

Colour sensation is subjective, since it is generated within visual cortex.
Unlike the sensation of taste, smell or feeling, colour is not a characteristic
of objects, but of the light that enters our eyes from the objects. Objects are
visible or seen coloured only when light reaches our eyes after interacting
with those. The same object may be seen of different colours when
observed under varying lights. In the absence of light, all colours disappear.
The common attribution of colours as properties of objects is largely a
matter of memory and in most cases those refer to some form of sunlight.
Daylight is a mixture of direct sunlight and scattered component or skylight.
We say that snow is white, soot black, blood red, because under ordinary
condition of life, the objects appear to be of these hues. While specifying
colour, it is, therefore, essential, to mention the specific nature of illumination
and viewing.
Human visual perception can distinguish three aspects or attributes of
colour. While classifying coloured objects, the three attributes considered
may vary significantly from one system to another, but they are related by
354
one or another way to three of the following visual or psychophysical

attributes defined by CIE [13]:
Lightness
It is the brightness of an area judged relative to the brightness of a similarly
illuminated area that appears to be white or highly transmitting (adjectives −
light and dark).
Hue
It is the attribute, according to which a sample appears to be similar to one
or a mixture of two of the perceived colours red, green, yellow and blue. It
is the family name for a group of chromatic colours. Ostwald defined hue as
dominant wavelength [14], while psychologists stress that it should relate to
a visual appraisal of colours. Munsell colour order system divides hues into
five principal hues, namely red (R), yellow (Y), green (G), blue (B) and
purple (P) based on equal visual spacing.
Chromatic amount
It is the degree by which a sample differs from achromatic (i.e. hueless)
colour of same lightness. The traditional term for chromatic dimension is
saturation, but it may convey different meanings. Unless otherwise
specified, it denotes colourfulness (i.e. chromatic amount in proportion to
brightness) [15] or chromaticness, which increase with luminance/
illuminance.
Chroma is the colourfulness at a given illuminance level. Wright [16]
explained two different meanings of chroma. The American meaning is that
it is the attribute determining the degree of its difference from achromatic
colour most resembling to it. This is equivalent to Munsell chroma or DIN
saturation. British meaning is that the attribute is judged by the proportion of
pure chromatic colours in total sensation similar to NCS chromaticness.
CIE's definition of chroma is the colourfulness of an area judged in
proportion to the brightness of a similarly illuminated area that appears to be
white or highly transmitting (adjectives − strong and weak).
Hunt [17] proposed three terms to describe the chromatic amount, namely:
• Colourfulness i.e. total chromaticness
• Saturation i.e. chromaticness in proportion to brightness
• Perceived chroma i.e. colourfulness (of non-luminous related
colours) in relation to average brightness of its surrounding.
Colourfulness depends on the level of illumination and it is not usually
considered for any colour order system.
Wright [18] identified two sets of commonly used visual attributes:
Group A attributes are lightness, hue and chroma.
Group B attributes are whiteness, blackness and chromaticness.
355
According to Wright, group B attributes are more useful because it is most

easily understood and is more fundamental for observers to represent colour
appearance. However, they are less studied in psychometric (equal
perception) terms. The colours of outermost Munsell (group A) hue circle are
close to full colours, which is a term for group B attributes.
It is a difficult task to deal with ten million colours or more, which our eyes
can distinguish. We can feel the problem instantly, if we try to describe a
colour, particularly its variation from other colours from memory, or when we
try to describe a colour to some one at a distance via communication
channels. The problem was known from ancient days and several people
have tried to solve the problem in their own ways. Nevertheless, Nobel
laureate W. Ostwald, American artist A.H. Munsell and many others studied
the problem in detail. In colorant production and application industries,
colours are to be communicated, compared, recorded and formulated on a
regular basis. This necessitates systematic classification of colours. The
objects can be classified in various ways in terms of colour. The classifi-
cation may be based on visually or instrumentally assessed colour
parameters. Various colour order systems were developed originally based
on different visual attributes, but later supported and modified by
instrumental assessment. The colour order systems are mainly utilised for
the purpose of communication about colour over distance and time as well
as for analysis and definition of the aesthetic relations among various
colours [19]. The colour order systems have been discussed by the author
elsewhere [20].
A colour order system is any systematic and rational method of arranging
all possible colours or subsets by means of material samples selected so
that they represent all object colours. Once the colours are arranged
systematically, they are named in some descriptive terms and/or are
numbered [21].
Material based colour order systems are of three types [21]:
1. Colorant-mixture system
2. Colour-mixture system
3. Colour appearance system
The main emphasis of appearance-based systems is the visual uniform
spacing. The system thus allows easy interpolation between samples
represented and extrapolation of colours not illustrated in a given collection.
Collections of samples in the respective atlas generally represented in
pages of constant hue. Most popular appearance-based colour order system
is Munsell system.
Six popular Colour order systems are:
1. Munsell System [22]
2. OSA-UCS System [23]
3. Natural Colour System (NCS) [24]
356
4. Ostwald System [25, 26]

5. DIN Colour System [27]
6. Coloroid System [28]
In addition, there are a few less known and newly developed colour order
systems such as Swiss Colour Atlas 2541, Chevreul, Colourcurve,
Eurocolour system, Acoat system, Pope Colour System [29], etc. Most of
the above systems are defined by a set of aim points specified in the CIE
system.
6.6.1 Munsell Colour Order System

The Munsell colour order system has successfully bridged the gap between
art and science. This oldest and by far the most popular system [30], has
been extensively studied [31]. AIC (Association Internationale de la Couleur)
study group on Colour Order Systems prepared a computer-based
annotated bibliography containing about 400 entries out of which 115
references are on Munsell system [32]. Albert H. Munsell developed the
notation in 1905 and the atlas was realised in 1915 and commercialised in
1929.
Prior to 1943, the Munsell system was defined by the physical samples
composing the 1929 MBC colour chips and thus the basic specification of
the Munsell system was the spectral reflectance function of each colour
chip. The spacing of the chips was intensively studied by the colorimetry
committee of the Optical Society of America and in 1943 the CIE tristimulus
values of ideally spaced chips were published as the Munsell Renotation
system [33]. Obviously there are many important physical and psycho-
physical differences between the earlier reflectance based systems and the
present tristimulus based system [34].
The Munsell system is based on steps of equal visual perception. The
system describes all perceivable colours in terms of its three coordinates -
Munsell hue (H), Munsell value (V) and Munsell chroma (C). Munsell hue
is interval scale [35] ( i.e. equal numerical interval indicates equal perceived
difference of attribute), where as Munsell value and Munsell chroma are
ratio scales (i.e. interval scale having natural origin). The Munsell colour
space is shown in Figure 6.6 [36].
Munsell Hue
The first of three variables is Hue. The Hues (H) are represented along the
circumference of a circle. The circle is divided into five principal hues,
namely Red (R), yellow (Y), Green (G), Blue (B) and Purple (P). These are
further subdivided into five intermediate hues - YR, GY, BG, PB and RP.
Each of these portions is again subdivided into ten divisions giving a total of
357
100 hues. Hue can also be expressed in continuous scale numbering from
1 to 100 (shown under bracket in Fig. 6.6).
Hue
10/
10P (89)
10RP (01)
9/
10R (11)
10PB (75)
8/
Value
7/
6/
Chroma
10B (65) | | | | | 10YR (19)
5/
/2 /4 /6 /8 /10
4/
3/
10BG (57) 10Y (31)

2/
1/
10GY (41)
10G (49)
Fig. 6.6 Munsell Colour Scale
Munsell value (V)

This second variable is a measure similar to CIE lightness. It is represented
along the axis of the hue-circle vertically and is divided into ten equal steps.
White is at the top and black at the bottom.
Munsell chroma (C)
The third variable is represented by the distance from the centre (chroma =
0). It is the degree of departure of colour from an achromatic colour of equal
lightness.
The complete Munsell specification of a sample is expressed as H V/C
(e.g. 5R 4/8).
As Munsell system is based on polar coordinates, smaller perceptual dif-
ferences occur in the near-neutral grey region of colour space than in the
358
outermost saturated regions. Physical distance between the neighbouring

hue increases with increase in chroma, i.e. increase in distance from the
neutral axis.
The colour sensation as well as visual spacings of the Munsell samples
vary when the illuminant is changed [37, 38]. The Munsell colour system
is, therefore, meaningful only as a colour sensation system to be viewed
under a specific illuminant (mostly daylight).
The relationships between Munsell and CIE variables are very complex. In
CIE chromaticity diagram, lines of constant Munsell hue are curved and
location changes with change of Munsell Value. Munsell value (V) scale is
related to CIE luminance factor (Y) by complex fifth degree polynomial
equation called Judd's polynomial as Eqn. (6.28) [39]:
2 3 4 5
Y = 1.2219V - 0.23111V + 0.23951V - 0.021009V + 0.0008404V (6.2)
The equation is based on the use of magnesium oxide, assigned a value
of absolute reflectance of 1.026 for 45°/0° illumination and viewing.
Original Munsell book of colour has poor collection of high chroma
samples. SCOTDIC [40] is a textile version created by fusion of two quite
different systems − Standard Colour of Textile, Japan and Dictionnaire
Internationale de la Couleur, France. It has incorporated many bright
colours and the number of constant hue chart has been increased to 54.
The system has three versions − glossy (2,450 colours on polyester crepe
fabric), matt (2,020 colours on cotton poplin fabric) and yarn (890 colours on
woollen yarns). The system specifies six digit codes, two each for hue,
value and chroma successively. SCOTDIC notation for a particular colour
may be 026512, where hue is 02, value is 65 and the chroma is 12.
6.7 SOLUBILITY OF DYES

In most cases, water acts as medium for transporting dyes inside textile
fibres. Hence, solubility of dyes in water is very important for applicability on
textile materials. Solubilising groups also decide ionic nature of the dyes and
confer affinity for the particular textile fibre by ionic attractions.
The extent of solubility demanded for various dye classes may be
different, hence different solubilising groups are imparted in different classes
of dyes. Most of the dyes must be in soluble form during dyeing. The
solubility may be permanent or temporary. The solubilising groups present in
different dye classes are shown in Table 6.2 [2].
The pigments belong to a class of colorants which are completely
insoluble during dyeing or printing. Disperse dyes applicable on synthetic
fibres do not dissolve in the usual manner and are applied as dispersion.
However, completely hydrophobic disperse dyes have poor affinity for the
359
fibre and colour pick-up is very low. The suitable dyes are slightly soluble in
water and the dyeing probably proceeds from the very dilute solution
produced in pockets. Only a few nonionic water-attracting substituents such
as hydroxyl and amino groups can provide such limited solubility.
Table 6.2 Solubilising Groups in Different Dye Classes
Solubilising Group Dye Class
Permanent
-SO3Na, -COONa Direct, acid, mordant, 1:1 metal complex, reactive
dyes
- - Basic and modified basic dyes
-+NH2HCl , -NR3 Cl ,
+
-OH, -NH2, -SO2NH2 Disperse and 1:2 metal-complex dyes

Temporary
-OH Azoic (naphthol) colour
-C=O Vat dyes
- Solubilised vat dyes
-OSO3 Na+
NR2 Onium group in Phthalogen dyes (R= alkyl or Aryl)
-
-CHSC Cl
NR2
+
6.8 SUBSTANTIVITY AND REACTIVITY

The Society of Dyers and Colourists (UK) defines substantivity as the
attraction between a substrate and a dye or other substance under precise
conditions of test (or application) whereby the latter is selectivity extracted
from the application medium by the substrate.
Affinity is a measure of substantivity – it is the difference in Kcal/mole or
Joules/kg-mole between the chemical potential of the dye in its standard
state in the fibre and the corresponding chemical potential in the dyebath.
Briefly, affinity is derived from the ratio of dye in fibre and in dyebath under
exactly specified conditions of temperature, concentration of dye, material to
liquor ratio, concentration of ions in the solution.
The substantivity may be imparted to a dye by introducing various
chemical groups into it such as [2]:
1. Anionic groups like sulphonates (-SO3Na) or carboxalates (-COONa)
confer affinity to protein and polyamide fibres as in case of acid and
direct dyes.
360
2. Cationic groups confer affinity for protein and acrylic fibres. The group
may be an integral part of the molecule containing conjugated bonds
as in case of conventional basic dyes or may be separated from the
main molecule by a short alkyl chain as in case of modified basic
dyes, also known as pendant cationic dyes.
3. Polar groups such as hydroxyl and amino/substituted amino groups
confer affinity of disperse dyes for synthetic dyes.
4. A large number of benzene or other groups provide flatness or
planarity on the molecule thereby increasing substantivity as in case
of direct, vat and disperse dyes.
5. Conjugated double bonds i.e. alternate single and double bonds
increases substantivity of many dyes.
6. Presence of phenolic groups in certain positions on aromatic rings
enables the dye molecule be mordanted with a polyvalent metal like
chromium thereby allowing the dye molecule to be retained by the
fibre.
7. Quinone groups can be temporarily solubilised by reduction, thereby
acquiring affinity for cellulosic fibre.
8. A series of paraffinic groups can be incorporated into dye molecules to
improve the fastness to washing (in acid dyes), to dry heat (in
disperse dyes) or to light (modified basic dyes) in addition to increase
in substantivity.
The dyestuff may also react with the fibre thereby retained by them. The
reactive dyes contain various reactive groups, which are capable of forming
a covalent bond with the fibre thereby held by them.
6.9 FASTNESS REQUIREMENTS

The dyed materials have diversified use. Consequently, they are subjected
to treatment with several external agents under diversified conditions. The
resistance to such external agents is known as fastness properties.
Frequently a compromise must be reached between the cost of attaining a
particular colour of goods and the fastness properties of such goods.
The most important fastness properties are
1. Washing fastness
2. Light fastness
3. Rubbing fastness – wet and dry
4. Fastness to perspiration
5. Fastness to bleaching
6. Fastness to dry heat
The degrees of fastness are expressed numerically – 1 being the lowest
and 5 the highest (8 for light fastness). The fastness grading may be
361
intermediate between two full numbers and may be expressed as 2-3, 4-5 or
2.5, 4.5, etc. In most of the tests, the grading is decided by the difference in
colour of the material before and after the test. The contrast is compared
visually with the contrast represented by Grey Scale for assessing change in
colour (ISO 105−A02: 1993 or BS EN 20105−A02, 1995). Nine-step Grey
Scale (Figure 6.7(a)) consists of nine pairs of non-glossy neutral grey colour
chips (or swatches of grey cloth) placed on two sides of a black board which
illustrate the perceived colour differences corresponding to fastness ratings
5, 4-5, 4, 3-4, 3, 2-3, 2, 1-2, 1. The Y tristimulus value of the first member of
each pair shall be 12±1. The second member of each pair is increasingly
lighter for lower fastness grades. The colorimetric data of the Grey Scale
chips for assessing change of colour using 1964 10° standard observer
functions under the illuminant D65 is shown in Table 6.3.
Fig. 6.7(a) Grey Scale for Assessing Change of Colour

To use the scale, a piece of the original material and the tested specimen
of it are placed side by side in the same plane and the Grey Scale is placed
near-by. The surrounding field should be neutral grey. The illumination
should be 600 lux or more. The incident light should be at 45° and the
direction of viewing should be perpendicular to the plane of surfaces.
A nine-step Grey Scale (ISO 105−A03: 1993 or BS EN 20105−A03: 1995)
is also available for evaluating staining on adjacent fabrics (Figure 6.7(b)).
The Y tristimulus value of the first member (white) of each pair shall not be
less than 85. The colorimetric data of the Grey Scale for staining using 1964
10° standard observer functions under illuminant D65 is shown in Table 6.4.
Where there is a change of hue along with loss of colour, the change may
also be indicated. For example, the fastness ratings of 3R, 3B, 3Y or 3D
362
indicate that Grey Scale reading is 3 (all the cases) and hue has changed to
redder, bluer, yellower or duller respectively.
Fig. 6.7(b) Grey Scale for Evaluating Staining
The fastness of a dye is related to the depth of the shade. On exposure to

light, the number of dye molecules modified will depend largely on the
quality and intensity of exposure and is independent of the depth of shade.
Therefore, the proportion of decomposed molecules is much greater in pale
shade. The colour strength of dyes varies widely. Hence, no standardisation
is possible based on % shade or depth of dye. A range of standard depths in
18 hues, known as Standard Depths, has been prepared by The Society of
Dyers and Colourists, UK. The sample for fastness testing should be
matched in depth with 1/1 standards by comparing with standards of near-by
hue. Stronger depth standards (2/1 depth, twice strong in depth than 1/1
standard) and weaker depth standards like 1/3, 1/6, 1/12 and 1/25 are also
available.
6.9.1 Washing Fastness

The solubility and rate of desorption of dye from the textile materials in the
solution of soap or detergent under varying conditions of alkalinity
determines the washing fastness of a dyed material. Dyes, which exist in
insoluble form inside the fibre (e.g. vat dyes) as well as dye which, are
bonded with the fibre (e.g. reactive dyes) have in general better washing
fastness. Water-soluble dyes usually have lower washing fastness, but the
resistance to removal by soap varies greatly with the dye.
Washing conditions vary for various textile substrates and also depend on
the end-use of the dyed materials. Hence, a series of five washing test
methods (ISO 105 C01-C05, BS: 1006 C01-C05: 1978 [41] and IS: 678,
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3361, 764, 765 and 3417 - 1978 [42]) has been established to investigate
the fastness to washing of coloured textiles covering the range of washing
procedures from mild to severe. The apparatus and reagents may be as
follows:
1. Suitable laboratory machine consisting of a water bath with rotatable
(about 40±2 r.p.m) shaft radially supporting glass or stainless steel
containers of approximately 500 ml capacity. The bath temperature
should be thermostatically controlled at the specified temperature
±2°C. Suitable testing devices are Launderometer of AATCC, USA or
SASMIRA, India or wash wheel sponsored by SDC, UK.
Table 6.3 Colour-differences of the Grey Chips of Grey Scale for
Assessing Change of Colour
Pair for fastness grade Colour-difference in CIELAB units Tolerance

5 0 0.2
(4-5) 0.8 ±0.2
4 1.7 ±0.3
(3-4) 2.5 ±0.35
3 3.4 ±0.4
(2-3) 4.8 ±0.5
2 6.8 ±0.6
(1-2) 9.6 ±0.7
1 13.6 ±1.0
Table 6.4 Colour-differences of the Grey Chips of Grey Scale for
Assessing Staining
Pair for fastness grade Colour-difference in CIELAB Tolerance

units
5 0 0.2
(4-5) 2.3 ±0.3
4 4.5 ±0.3
(3-4) 6.8 ±0.4
3 9.0 ±0.5
(2-3) 12.8 ±0.7
2 18.1 ±1.0
(1-2) 26.6 ±1.5
1 36.2 ±2.0
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2. Soap containing not more than 5% moisture and of the following

specifications:
Free alkali – 3 g/kg (maximum) as sodium carbonate
Free alkali – 1 g/kg (maximum) as caustic soda
Total fatty matters - 850 g/kg (minimum)
Titre - 30°C (maximum)
Iodine value - 50 (maximum)
Fluorescent brightening agent – absent
3. Two undyed adjacent fabrics each measuring 10 cm x 4 cm, one
piece of the same fibre as the test material and the other of different
fibre choosing from blend considerations. For cotton/viscose test
materials, the second specimen should be of wool. For synthetic
fibres, it should be any natural fibre – cellulosic or protein. The
adjacent fabrics are used to check staining on the same fabric and
staining during cross dyeing of blended materials.
4. Grey Scales for assessing change in colour and staining.
The test specimen fabric of size 10 cm x 4 cm is placed between the two
adjacent fabrics and sewed along all four sides to form a composite
specimen. If the test specimen is yarn or fibre, a layer of parallel length of
yarn or a compressed sheet of fibre is to be placed inside the adjacent
fabrics.
The composite specimen is placed inside the container maintaining a
material to liquor ratio of 1:50 and treated as per the conditions mentioned in
Table 6.5 depending on the test procedure methods 1 to 5. Ten numbers of
non-corrodible stainless balls of approximately 0.6 cm diameter are also
incorporated in case of methods 4 and 5 only.
Table 6.5 Conditions for Testing of Colour Fastness to Washing
Washing fastness test 1 2 3 4 5

method number Æ
Temperature, °C ±2.0 40 50 60 95 95
Time, minutes 30 45 30 30 240
Soap(g/l) 5 5 5 5 5
Soda ash (g/l) - - 2 2 2
After treatment, the composite is rinsed twice in cold distilled water, then
with cold running tap water for 10 minutes and squeezed. The composite
specimen is opened out by removing stitches from all sides except one
shorter side. It is then dried at a temperature lower than 60°C. The change
in colour of the specimen and the staining of the adjacent fabrics are
assessed with the respective Grey Scales.
365
The method for assessing colour fastness to alkaline milling (BS 1006
E12: 1978) is very similar. For this test, a milling solution containing 50 g/l
soap and 10 g/l anhydrous sodium carbonate is prepared. Composite
specimen as above is taken inside the container and three times its own
mass of milling solution is added. 50 stainless steel balls are put into the
container and the machine is run for 120 minutes at 40±2°C. Sufficient
distilled water at 40±2°C is then added to give a M:L ratio of 1:100 and the
machine is run for an additional 10 min. The sample is washed, dried and
assessed for colourfastness as before. Wool serge fabric dyed with C.I. Acid
Blue 7 may be used as a test-control specimen.
6.9.2 Fastness to Laundering

The conditions maintained during domestic and commercial laundering are
quite varied and different from those recommended in washing fastness
tests. Hence, a number of laundering fastness tests have been
recommended (BS: 1006 C06: 1981) as shown in Table 6.6.
Table 6.6 Laundering Test Procedures
Test Temp. Liquor Available Sodium Steel balls
No. °C (ml) Cl (g/l) perborate (g/l) Single test Multiple test
A1 40 150 none None 0 10
A2 40 150 none 1 0 10
B1 50 150 none None 0 50
B2 50 150 none 1 0 50
C1 60 50 none None 25 50
C2 60 50 none 1 25 50
D1 70 50 none None 25 100
D2 70 50 none 1 25 100
D3 70 50 0.015 None 25 100
E1 95 50 none None 25 100
E2 95 50 none 1 25 100
A textile specimen in contact with specified adjacent fabrics (as
mentioned in washing fastness tests) is laundered, rinsed and dried under
appropriate conditions of temperature, alkalinity and bleaching agents.
Abrasive action is achieved with low liquor ratio and an appropriate number
of steel balls specified before. Two types of tests may be conducted, single
and multiple tests varying the time of treatment (30 and 40 minutes
respectively) and the extent of abrasion by using a different number of steel
balls.
An anionic detergent without optical brightener may be used, having
composition (proportion in % m/m ± 0.02%) as below:
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Linear alkylate sulphonate 14.0

Alcohol ethoxylate 2.3 (biodegradable nonionic)
Soap of high molecular mass 2.5
Sodium tripolyphosphate 48.0
Sodium silicate (SiO2:Na2O = 2:1) 9.7
Sodium sulphate 15.4
Carboxymethylcellulose (CMC) 0.25
Water 7.85
100.00
The treatment of the specimens (10 cm x 4 cm) sewed with adjacent
fabrics along one of the shorter edge is carried out with 4 g/l standard
detergent in suitable apparatus maintaining above conditions followed by
rinsing with 100 ml water at 40°C. The composite specimen is then treated
in 100 ml of 0.2 g/l acetic acid and rinsed with 100 ml distilled water – both
treatments are done for 1 minute at 30°C. The specimen is dried by
hanging in air at a temperature not exceeding 60°C, with the two part or
three parts in contact only at the line of stitching. The change in colour of the
specimen and the staining of the adjacent fabrics are assessed with the
Grey Scales.
6.9.3 Light Fastness

Most organic matters fade in light and the fading on exposure to light, is the
most complex of the reactions which dyes undergo on a fibre.
When light energy is absorbed, some of its molecules become unstable in
so-called excited state and may react with surrounding materials such as
oxygen in air or with the fibre itself, thereby loosing its colour. All the dyes
absorb light, but at any given moment, only a very small proportion of the
total dye decomposes, the rest realising its absorbed energy harmlessly as
heat [2]. In case of some dyes, once the specimen is removed from the light
source and placed under darkness, the colour is restored, at least in part.
This effect is called photochromism.
In most cases, oxidation is the major cause of the breakdown of the
colorant. However, it has been reported that sometimes reduction of the dye
may also takes place. This can arise when the substrate is more easily
oxidised than the dyestuff would be, or under anaerobic conditions when a
hydrogen donor is present. It has been long established that on protein-
based substrates, such as wool, reduction of the dye is usually more
favoured. In particular, electron-withdrawing substituents favour photo-
reductive pathways whilst electron-donating substituents promote photo-
oxidative routes. It has been shown that a single reaction order cannot be
assigned to fading mechanism [43].
367
Little is known of the course of reactions, except in azo dyes, the azo
linkages seem to be first attacked. The first products of the fading reactions
are often quinones, ranging in hue from colourless to brownish. Sometimes
severe loss of strength of the dyed fabric may occur on exposure to light as
in case of some yellow and orange vat dyes. A light fast dye may fade
quickly when mixed with certain dyes although they themselves may not
fade so quickly. The above two phenomena are called catalytic tendering
and catalytic fading respectively.
The light fastness of dyed materials is measured by exposing them to
daylight under glass or to an artificial illumination in an accelerated fading
lamp alongside a set of standard dyed materials. Essentially three light
sources are used for artificial light fastness testing namely mercury vapour,
carbon arc and xenon arc lamps, the last one has been accepted
internationally to be the light source for accelerated light fastness testing as
it most closely resembles daylight. Hereaus Industrietechnik first introduced
it in 1950s. An electric current is passed through an enclosed xenon vapour
under high pressure, causing ionisation. Xenotest series of instruments
manufactured earlier by W.C. Heraus AG and presently by Atlas employ a
xenon arc lamp as the light source. Such lamps have a spectral distribution
that is similar to that of daylight. The machine can be programmed to have a
specific relative humidity in the test chamber, specified periods of light (and
dark if desired) and sprays to simulate rain.
Currently the most common form of calibration for light fastness testing is
the blue wool scale. At the time of development of the light fastness
standards, wool was found to be the substrate that was least effected by
humidity. The scale consists of a set of eight woollen fabrics dyed with
different dyes numbered 1 to 8 in order of increasing fastness − 1 having
lowest light fastness and 8 having highest fastness. Light fastness of the
standard materials is such that the time of exposure required for their fading
is in geometric (GP) scale, i.e. each standard would take twice as long to
fade to a certain level as the one below it. However, marked deviations from
a geometric progression have been observed under xenon arc exposure.
Recently SDC has developed a set of pigment-printed light fastness
standards, which covers a geometric scale of levels 1 to 8 [43].
The dyes used for blue wool standards 1 to 8 are as follows:
Blue Wool Standard No. Dye used (C.I. No.)
1 C.I. Acid Blue 104
3 C.I. Acid Blue 83
5 C.I. Acid Blue 47
6 C.I. Acid Blue 23
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7 C.I. Solubilised Vat Blue 5

8 C.I. Solubilised Vat Blue 8
Blue wool standards developed and marketed in America are designated
as Standards L2 to L9. These are prepared by mixing various proportions of
wool dyed with C.I. Mordant Blue 1 (43830) and wool dyed with C.I.
Solubilised Vat Blue 8 (73801) so that each higher numbered standard is
approximately twice as fast as the preceding standard.
Before exposure to light, a portion of the specimen is to be covered with
opaque cardboard or other thin opaque material. In the absence of machine,
the sample should be placed in open air under sunlight, facing south in the
Northern Hemisphere and north in the Southern Hemisphere (BS: 1006
B01– 1078, IS: 686−1957). The samples should be inclined at an angle from
the horizon approximately equal to the latitude of the place where the
exposure is made. The samples should be covered with a transparent
window glass to protect from rain. There should be adequate ventilation of
air behind mounted specimens. The area should be non-polluted and dust-
A
C
E
Specimens
under test
Blue wool
standards
1-8
F
D
B
Fig. 6.8 Mounting of Specimens and Standards for Light Fastness
Testing
free. The sample rack should be firm and kept in a place so that no
surrounding shadow falls on it. The minimum permissible distance between
the glass and the specimen is 5 cm.
Accelerated fading may be carried out by exposure inside a well-ventilated
exposure chamber under controlled humidity conditions (BS: 1006 B02–
1078, IS: 2454–1967). The light source is a xenon arc lamp of correlated
colour temperature 5,500 K to 6,500 K. Appropriate light filters to reduce UV
light and heat filters to reduce infrared radiation may be placed between the
lamp and the samples under exposure. The light intensity variation over the
area covered by the specimens and standards shall not exceed ± 10 % of
369
the mean. A black panel thermometer should monitor the temperature inside
the chamber, which should not exceed 45° C.
When a number of samples are to be tested together, the arrangement of
samples, blue wool standards and covering cards are preferably to be as
shown in Figure 6.8. The card AB covers one-quarter of all the samples and
standards. The standards are inspected at intervals until an alteration of
shade in standard 3 is just perceived. At this stage the specimens, with
fastness not greater than 3, are assessed by comparing specimens and
standards 1-3. Otherwise, the card AB is then replaced in exactly the same
position as it was before. The exposure is continued until a change in
standard 4 is just perceived when a second opaque card CD is placed in
advance to card AB overlapping a portion of it. The exposure is continued
until standard 6 shows initial fading. At this stage the cover EF is placed
ahead of card CD overlapping a portion of it. The exposure is continued till
a contrast in standard 7 equal to Grey Scale rating 4 appears or the fading
of specimen equals to Grey Scale rating 3. The specimens and standards
will show three zones with the unexposed area at the left side. The zones of
specimens are compared with the standards and if the two degrees of fading
on the specimen do not correspond with the same standard, the fastness
would be the mean between the two.
6.9.4. Rubbing Fastness

A device called crockmeter is used for rubbing fastness test (BS 1006 X12:
1978, IS: 766−1956). It has a finger of 1.6 cm diameter which can move to
and fro in a straight 10 cm track on the specimen. The rubbing is carried out
by moving 10 times in 10 seconds with a downward force of 6 N. Undyed
unfinished cloth is cut into pieces of 5 x 5 sq. cm and placed flat on the
finger. Two pairs of specimens not less than 14 x 5 sq. cm are cut. One pair
is for the dry rubbing test while the other for the wet rubbing test. One
member of each pair has the long direction parallel to the warp direction, the
other parallel to the weft yarn. In wet rubbing test, the rubbing cloth is wetted
and squeezed until it contains its own weight of water. The staining of the
rubbing cloth is assessed by Grey Scale.
6.9.5 Perspiration Fastness

Unless dyes are selected carefully, those parts of the cloth or garment,
which come in contact with the body, where perspiration is heavy may suffer
local discoloration. Two artificial perspiration solutions (BS 1006 E04: 1978)
are prepared by dissolving in one litre of distilled water 0.5 g l-histidine
monohydrochloride monohydrate (C6H9O2N3HCl,H2O), 5.0 g sodium
nd
chloride, 2.5 g (2.2 g for the 2 solution) disodium orthophosphate
370
(Na2HPO4,2H2O) and pH is adjusted to 8 and 5.5 with 0.1 N NaOH and

0.1 N acetic acid for two solutions respectively.
Another recommendation (AATCC Test Method 15−1994) is to prepare
two solutions containing 0.25 g/l l-histidine monohydrochloride monohydrate
chloride, 1 g/l anhydrous disodium othophosphate (Na2HPO4) and 10 g/l
sodium chloride. The pH of the solutions are set to 4.3 ± 0.2 and 8.0 by
adding 1 g/l lactic acid (85%) and 4 g/l ammonium carbonate respectively.
The test with alkaline liquor may be necessary for special end-uses.
The material to be tested is placed between two undyed pieces, one of
which is of the same fibre and the other of a different fibre as in the case of
washing fastness test. The pieces are stitched on one side to make a
composite specimen and is wetted with two artificial perspiration solutions
separately maintaining M:L ratio of 1:50 for 30 minutes at room temperature,
after which the liquor is poured off. The specimens are then placed between
two glass plates pressed together with a force equivalent to 10 lb. (4.536 kg)
and allowed to stand in an oven at 37±2°C for 4 hours. For better control of
pressure during test, AATCC Perspiration Tester or other perspirometer may
be used.
The dyed sample and undyed cloths are then separated and they are
dried at a temperature not exceeding 60°C. The change of colour and
staining are then assessed with Grey Scales for each test.
Nowadays, certain eco-labelling organisations demand spit or saliva
fastness for baby-wears. The test method is similar. The saliva solution (DIN
53160-1964) is prepared by mixing 4.5 g sodium chloride, 0.3 g potassium
chloride, 0.3 g sodium sulphate, 0.4 g ammonium chloride, 0.2 g urea and
3 g lactic acid. The volume is made up to one litre and pH is adjusted to 2.5.
6.9.6 Fastness to Bleaching Agents

The test is intended for determining the resistance of the colour of textiles of
all kinds and in all forms to the action of bleaching agent in concentrations
normally used in commercial bleaching processes. In some fabrics coloured
threads are used and after making (i.e. weaving) of cloth, it may be
necessary to bleach the material as in case of handloom fabrics. The dyes
used for dyeing of such yarns should be fast to bleaching. Various bleaching
agents are used. Hence, alternate test methods are recommended.
1. Fastness to sodium hypochlorite (NaOCl) (BS: 1006 N01:1978) – the
test is carried out with sodium hypochlorite containing 2 g/l available
chlorine buffered at pH 11±0.2 with 10 g/l anhydrous sodium carbonate.
The specimen, 10 cm x 4 cm is dipped into the above solution in a
closed container with M:L ratio of 1:50 at a temperature of 20±2°C for
60 minutes. The specimen is thoroughly washed in cold water and then
stirred for 10 minutes in 5 g/l sodium bisulphite solution. The specimen
371
is dried at a temperature below 60°C. The change of colour of the

specimen is assessed with Grey Scale.
2. Fastness to peroxide (BS: 1006 N02: 1978) – the test is carried out with
a specimen sewed with two adjacent fabrics as in case of washing
fastness test. The composite specimen is kept inside a test tube by
rolling in the direction of the longer side and bleaching is carried out. A
reflux condenser is fitted with the test tube to reduce evaporation from
the bleaching bath during test. The bleaching conditions recommended
are shown in Table 6.7. After bleaching, the composite specimen is
removed and rinsed for 10 minutes in cold running tap water, squeezed
and dried by hanging in air. The change in colour of the specimen and
the staining of the adjacent fabrics are assessed with the Grey Scales.
3. Fastness to sodium chlorite – the test may be carried out in two ways.
For mild bleaching (BS: 1006 N03: 1978) 1 g/l sodium chlorite solution is
used and the pH is adjusted to 3.5 with acetic acid immediately before
the test. For testing under severe conditions (BS: 1006 N04: 1978), a
solution containing 2.5 g/l sodium chlorite solution, 0.1 g/l acid sodium
pyrophosphate is used. The pH is adjusted to 3.5 with formic acid
immediately before the test. The test is carried out exactly as above for
1 hour maintaining the temperature at 80±2° C.
Table 6.7 Test Conditions for Fastness to Hydrogen Peroxide
Starting bath per litre of Bath 1 Bath 2 Bath 3

distilled water
H2O2 (304g/l) , ml 5 20 20
Sodium silicate solution 5 5 5
(density 1.32), ml
Magnesium chloride, g 0.1 0.1 0.1
*
Initial pH, ±0.2 10.5 9.3 10
Temperature,°C ±0.2 90 50 70
Time in hours 1 2 2
M:L ratio 1:30 1:30 1:30
*
The pH should not fall below 9.
Bath 1 for natural and regenerated cellulose, Bath 2 for wool and
acetate, Bath 3 for silk.
6.9.7 Fastness to Dry Heat

This fastness (BS: 1006 P01: 1978) is to be regularly assessed for disperse
dyes on polyester, as these dyes are sublimable. Dyed or printed textile
specimen sewed with two adjacent fabrics, one of them usually polyester, is
heated by close contact with a medium that is heated to the required
372
temperature. Normally the heating device is equipped with two heated plates
with an electrical heating system, accurately controllable, that allows the
composite specimen to be set in a flat position under a pressure of 4±1 kPa
2 3 –1 –2
(kPa = kN/m = 10 kgm s ) at a preselected and uniformly distributed
temperature. The time of treatment is 30 seconds and the three
temperatures recommended are 150±2°, 180±2° and 210±2°C
When desired, the testing may be carried out at other temperature. After
the treatment, the composite specimen is left for 4 hours in air under
standard conditions, the temperature may be 20±2°C (27±2°C in tropical
countries) and relative humidity of 65±2%. The change of colour and
staining on adjacent fabric are then assessed with Grey Scale.
6.10 CLASSIFICATION OF DYES

Dyes are classified in two ways based on:
1. chemical constitution
2. dyeing properties
There is little correlation between the two methods. The members
constitutionally classified as azo dyes are found amongst several of the
classes based on application. The practical dyer will be concerned only with
the classification according to methods of application. The chemical classes
are more important for dye makers and researchers.
Globally thousands of dyes are being produced by various dyestuff
manufacturers. The industry is never static – new products are continually
being introduced and established ones are sometimes withdrawn. The
situation becomes complicated with frequent changes of the names of the
products. These difficulties were felt long back, and the need for a
systematic classification and recording resulting in a system called colour
index was developed by the Society of Dyers and Colourists, UK in 1924,
and supplement in 1928. In 1945, American Association of Textile Chemists
and Colourists (AATCC) collaborated and the publication is now being
jointly published in eight volumes [44]. The first four are original volumes
while the others are revisions and supplements.
Volumes 1 and 2 contain detailed classification of dyes and pigments
according to usage, while volume 3 shows classification according to
chemical constitution. Volume 4 contains, among other things, commercial
names of dyes and pigments and their respective C.I. (colour index)
designations. Two numbers namely C.I. generic number and C.I.
constitution number are allotted for each dye. For example, the C.I.
designations of two dyes may be C.I. Basic Violet 7 (48020) and C.I.
Disperse Blue 3 (61505). While the first portion is generic number, the
373
bracketed portion is constitution number. The generic name consists of dye

class according to usage (e.g. Direct, Acid, Basic, etc.), hue name (whether
yellow, orange, red, violet, blue, green, brown or black shade imparted by
the dye on the substrate, additionally white coloured pigment), an unique
number for each dye of a particular chemical structure. The dyes with
different chemical structures of a particular usage class of a particular hue
are allotted consecutive numbers. C.I. constitution number is based on
chemical structure of the colorant. A range of numbers is reserved for each
chemical class (e.g. for monoazo dyes C.I. constitution number 11,000-
19,999 and for disazo dyes 20,000 – 29,999) and a number is allotted for
the dyes of a particular chemical constitution. A dye may belong to a
number of usage class e.g. a vat dye may also be used as disperse dye
and may be included in both usage classes.
The volume 1 of Colour Index shows details of dyes under usage dye
classes namely acid, mordant, basic, disperse, natural dyes and pigments,
food and leather, while volume 2 shows details of dyes under other usage
dye classes namely direct, sulphur, vat (including solubilised), ingrain dyes,
azoic diazo and coupling components, oxidation bases, pigment, solvent
dyes, fluorescent brightening agents and developers. The supplement
volumes include revision, extension of above usage dye classes as well as
details of reactive dyes.
Volumes 1 and 2 provide following information on dyes of each C.I.
generic number:
1. Names of the manufacturers and commercial names
2. Application methods on various textile fibres or other substrates and
aftertreatments
3. Fastness properties
4. Dischargability
5. Solubility
6. Effect of metals
7. Textile usage
8. Non-textile usage, etc.
Volume 3 shows chemical aspects of dyes of each C.I. Constitution
Number namely chemical structure, name of the discoverers, brief
manufacturing process etc. The details under C.I. Constitution Number
13065 is shown below:
13065 C.I. Acid Yellow 36
Classical name: Metanil Yellow Discoverers:

Rumpff 1879,
SO3Na Hepp 1882
N=N NH
Metanilic acid Æ Diphenylamine
374
6.10.1 Classification According to Chemical Constitution

A number of chemical classes are reported in colour index (Volume 3). A
dye may have multiple chemical groups. Hence, a dye may belong to more
than one chemical class. The chemical classes are unlimited as because
dyes with newer chemical classes are constantly being developed. Some of
the chemical classes reported are:
/
1. Nitroso (R.NOH) 2 Nitro (R.NO2) 3. Monoazo (R.N=N.R )
4. Disazo, 5. Trisazo 6 Polyazo
7. Stilbene 8 Diphenyl methane 9 Triarylmethane
10 Anthraquinone 11. Xanthene 12. Acridine
13 Quinoline 14 Methine 15. Thiazole
16. Indamine 17 Indophenol 18 Azine
19. Oxazole 20 Thiazole 21. Sulphur
22. Lactone 23. Aminoquinone 24. Hydroxyketone
25. Indigoid 26. Phthalocyanine 27. Chlorotriazinyl
28. Vinyl sulphone
6.10.2 Classification According to Methods of Application

The dyes may be classified according to the methods of application or
dyers point of view as follows (Figure 6.9):
1. Direct dyes – these dyes have direct substantivity to cellulosic
materials and are also termed as substantive dyes. Chemically they
are sodium salt of sulphonic acid derivatives of organic aromatic
compounds and invariably contain one or more azo groups. They can
also be applied on protein fibres, namely wool and silk, but are not
commonly used because the rate of dye exhaustion is very slow.
2. Acid dyes (including metal-complex acid dyes) – they are mainly used
for protein and polyamide fibres and have no affinity for cellulosic
fibres. The term acid dye indicates that they are derived from organic
acids and not because they are acidic in nature. Chemically they are
sodium salts of sulphonic acid, occasionally carboxylic derivatives of
organic aromatic compounds and mostly contain one or more azo
groups. Chemically they are very similar to direct dyes. While the
direct dyes are coplaner and bigger in molecular size, the acid dyes
may or may not be coplaner and some of them are of low molecular
size and consequently have lower wash-fastness. They have more
solubilising groups than the direct dyes. If these dyes have two
/
hydroxyl groups or one hydroxyl and one carboxylic group in o-o
position with respect to azo group, the dye is capable of forming
complex with multivalent metal atom like chromium improving wash-
fastness. The complex may be formed during dyeing or during dye
manufacture. The latter, known as pre-metallised dyes, may be of two
375
types – 1:1 or 1:2 representing complex having one and two dye
molecules per metal atom respectively.
3. Basic or Cationic Dyes – they are usually hydrochlorides or other salts
of organic bases. As these dyes are cationic in nature, they are
termed as cationic dyes. They can be applied to protein fibres directly
and on cellulosic materials with the help of a mordant, which has
affinity for both the dye and fibre. However, the use of basic dyes on
wool or silk has declined significantly due to its poor light fastness.
The use on cellulosic materials has been discontinued, as several
superior dyes of other classes are available now. The invention of
acrylic fibres demanded a new class of dyes, as available dyes were
unsuitable. The conventional basic dyes can be applied and the light
fastness is better than that on wool and silk. The modified basic dyes
called pendant cationic dyes were developed by separating ionic
charges away from the chromophore. These dyes have superior light
fastness.
4. Mordant dyes – this group includes many natural and synthetic dyes,
the latter usually obtained from anthracene. They have no natural
affinity for textile fibres but are applied to cellulosic or protein fibres,
which have been mordanted previously with a metallic salt or natural
mordant. The acid mordant dyes are a special class of dyes applied to
wool or polyamide fibres as acid dyes, and subsequently mordanted to
improve wash-fastness. A sub-group, natural dyes are the oldest class
of dyes being used by human beings since ancient times. These dyes
are obtained from various natural sources like different portions of
plants (leaves, roots, and skins), insects, etc. These can be applied
with the help of a natural mordant along with several metallic salts.
The natural dyes were slowly being replaced by synthetic dyes due to
poor supply, poor colour build up and poor reproducibility of the
former. With world-wide consciousness about pollution and polluting
nature of many synthetic dyes, the use of natural dyes has been
revived again in recent years.
5. Azoic dyes – unlike azo dyes, they are not readymade dyes. Insoluble
azo pigments are formed inside the textile materials by treating textile
material with solubilised aromatic hydroxy compounds (naphthols)
followed by development (or coupling) with diazotised aromatic bases.
They are used to dye cheap shades of high wet-fastness on cellulosic
materials. They have been applied on protein fibres, but their
suitability is doubtful especially because of high alkaline conditions
maintained during dyeing.
6. Sulphur dyes – these dyes are complex organic compounds
containing sulphur. They are used to dye cheap shades of high wet-
376
fastness on cellulosic materials. The dyes, however, lack brightness

and the shade range is limited.
7. Vat dyes – as a dye class, it is characterised by highest all round
fastness properties, but are quite expensive. Vat dyes are insoluble in
water and are converted into water-soluble leuco compounds by the
action of caustic soda and sodium hydrosulphite. These solubilised
leuco compounds have high affinity for cellulosic materials and after
completion of dyeing, they are converted into insoluble form by
oxidation.
8. Solubilised vat dyes – they are water-soluble and can be applied
directly on cellulosic and protein fibres at low temperature. Chemically
they are sulphuric esters of vat dyes and are converted into parent vat
dyes by oxidation after completion of dyeing.
9. Reactive dyes – this most recent class of dye contains reactive
groups, which react with hydroxyl or amino groups of textile fibres
forming covalent bonds. These dyes are fast so long as the covalent
bonds are intact. As the fastness does not depend on the molecular
size of the dye, dyes of low molecular weight can be used which
usually provide brighter shades. These dyes were originally
developed for cellulosic materials, but special reactive dyes for wool
and nylon are also available. Depending on the reactive group, these
dyes are classified into a number of subgroups, namely cold-brand
(M-brand), Remazol (vinyl sulphone), high-exhaust (HE-brand), etc.
10. Disperse dyes – these dyes are finely divided organic compounds
with very slight aqueous solubility. They are suitable for hydrophobic
synthetic fibres namely polyester, acetate and polyamide.
11. Pigment colours – this class of colorant does not have affinity for
textile materials. They are applied with the help of a low-molecular
weight polymer called binder. The binder forms a transparent film on
the surface of the textile materials and forms cross-links with it. The
colorant molecules are entrapped inside the film. The fastness of such
colours will depend on the stability of the binder film. As the
application is not based on affinity, they can be applied on any textile
substrate including blends of different fibres and on inert fibres like
glass. The methods of application and fixation are quite different from
those of other dye-classes.
12. Mineral colours – these are again not readymade dyes, but insoluble
metallic oxides and hydroxides are precipitated inside textile fibres by
treating with soluble metallic salts followed by treatment with alkali. As
mineral compounds are used, the cost is very low. Moreover, the
inorganic pigments thus deposited, increase the weight of the material
and impart anti-fungal properties. Mineral colours are used for dyeing
police and military uniforms in India.
377
13. Oxidation colour – these colours are formed inside the textile
materials by oxidation of a group of aromatic amines and
aminophenols. Aniline black, a member of this group once used in
large quantities for cellulosic materials especially in printing, mainly
because of its low cost and brightness. With the introduction of various
synthetic dyes, their use has declined significantly.
14. Ingrain dyes – the name ingrain is used to describe a small group of
dyes, which cannot be included in the azoic and oxidation classes.
Alcian dyes, a member of this group, are water-soluble coloured
compounds, which are substantive to the fibre and are insolubilised by
removal of solubilising groups. The Phthalogen colours, on the other
hand, are built up inside the fibre.
Colouring Matters
Dyes Pigments
Vat Azoic Phthalocyanine Mineral
In-situ Developed Dyes

Readymade
Dyes
Azoic Oxidation Mineral
Ingrain Dyes
Water-soluble Water-insoluble
Vat Sulphur Disperse
Acid Reactive Solubilised vat

Direct Basic Optical
Brighteners
Fig. 6.9 Dyers’ Classification of Dyes

378
Suitability of various dye-classes for textile fibres may be summarised as

follows:
1. Cellulosic (cotton and viscose) – direct, azoic, sulphur, vat, solubilised
vat, reactive, ingrain, mineral, pigment, oxidation colours (limited use).
2. Cellulosic (jute) – most of the above classes, except those require
caustic alkali. Additionally acid and basic dyes.
3. Protein (wool, silk, nylon) – acid and selected direct dyes, basic dyes
(limited use).
4. Polyester, cellulose acetate and less commonly nylon – disperse
dyes.
5. Acrylic and modacrylic – conventional and modified basic dyes.
6.11 COMMERCIAL NAMES OF DYES

The commercial name of a dye usually consists of the following [2]:
1. A brand name which denotes the specific dye class of a particular
manufacturer, such as Sandolan, Cibacron, Dispersol, etc.
2. Hue or colour obtainable on the material after dyeing.
3. One or more suffix letters and figures indicating:
(i) Secondary hue or tone such as R, G, B for red, yellow and blue
respectively. The suffix G is for yellowness or greenness. These
suffixes may be numbered in order to compare the tone among
various similar dyes. One blue dye with suffix 2R will be more
redder than the blue dye with suffix R. The blue dye with suffix RR
will be more redder than R and leas redder than 2R respectively.
(ii) Some special qualities such as F for fine, FF for superfine, L or LL
for lightfast, N, W or K for IN, IW, IK class of vat dyes respectively.
(iii) Strength e.g. 250, 200 or 150% for a brand of increased dye
strength having less diluent as compared to normal brand of 100%
strength. Nearly all dyes are standardised by mixing with
colourless diluents, mostly common salt. The actual dye contained
in a commercial dye is most often less than 40%.
6.12 IDENTIFICATION OF DYES

Sometimes it is necessary to identify the dye-class from the samples of
dyed yarns and fabrics. There are several tests. The dyed materials are first
identified whether they are made of cellulosic, natural protein fibres or
synthetic fibres. Three separate sets of tests are carried out for the materials
made from cellulosic, natural protein and synthetic fibres [42].
379
6.12.1 Tests for Dyes on Cellulosic Fibres.

The material is first boiled three times with 1% hydrochloric acid and then
washed thoroughly. The following tests are carried out successively.
1. 0.5 g of the test specimen is successively treated with 50%

dimethylformamide, concentrated dimethylformamide and a mixture of
glacial acetic acid and rectified spirit (1:1) at boil for 3 to 4 minutes
with intermediate washing and squeezing – if no or partial stripping
occurs, the dye is reactive or ingrain dye (except azoics) (Group I).
Some basic dyes are also not stripped. The presence of phthalogen
blue is confirmed by boiling with little methyl pyrrolidone and cooled to
70°C. 1 to 2 ml of 10% sodium hydroxide and 2 to 4 mg sodium
hydrosulphite is added and boiled further. The colour does not reduce.
The spotting of specimen with concentrated sulphuric acid and nitric
acid shows bright green and violet colours respectively. The presence
of mineral khaki colour may be confirmed by boiling with 10%
hydrochloric acid when the colour is completely stripped and the
solution becomes green. The specimen may be burnt and the ash
may be tested for the presence of metallic chromium and iron.
2. If the dyes of group I are absent, the specimen is boiled for 1 to 2
minutes with 1% ammonium hydroxide solution. If the colour bleeds,
(i) The specimen is removed and a little bleached cotton fibre and 25
mg of sodium chloride are added and boiled for 2 minutes. The
solution is cooled and the cotton fibres are washed. If the fibres
are dyed significantly, the dye is direct.
(ii) If the cotton is left undyed or slightly stained, neutralise the
solution with acetic acid and add further 1 ml of 10% acetic acid.
Little undyed wool fibres are added and boil for one minute. If the
wool is dyed, then the dye is Acid.
3. If the specimen does not bleed (or if the bleed is negligible) in
ammonium hydroxide, a fresh sample is taken and 1 ml glacial acetic
acid and 3 to 5 ml of water are added and boiled. The specimen is
removed and 25 mg of mordanted cotton is added and boiled for 2
minutes. If the mordanted cotton is dyed, the dye is basic dye. The
presence of basic dye may be confirmed by treating the acidified
extract with a mixed solution containing 50 g/l tannic acid and 50 g/l
sodium acetate, when an insoluble precipitate forms.
4. If the above dyes are absent, a fresh sample is treated with 10 to 15
ml of 1% hydrochloric acid and boiled for one minute. This is repeated
once or twice. The acid solution is discarded. The treated sample is
neutralised and tested for direct dye. If the test is positive, the dye is
resin-treated direct dye.
380
5. If the dyes of Group I and II (direct, acid and basic) are absent, a fresh
test specimen is boiled for 1 to 2 minutes in a solution containing 10 to
30 mg of sodium hydrosulphite in 5 to 10 ml of water to which 4 to 6
drops of 44% sodium hydroxide are added. For sulphur, vat and
oxidation colours (aniline black) (Group III), the specimen gets
discoloured or the shade changes radically. The colour of the
specimen is restored on exposure to air or any oxidising agent.
(i) A fresh specimen is taken with 2 to 3 ml of water, 1 to 2 ml of 5%
soda ash solution, 500 mg of solid sodium sulphide and boiled for
2 minutes. The specimen is removed and 25 mg of sodium
chloride and a little bleached cotton are added to the treated
solution. The test specimen and white cotton are placed on filter
paper and oxidised. If the colour of the specimen is restored and
the white cotton is dyed to the original shade (except strength), the
dye is sulphur. The presence of sulphur dye may be confirmed by
boiling the specimen with stannous chloride in a test tube, the
mouth of which is covered with filter paper soaked with lead
acetate solution. Brown stains on the filter paper indicate the
presence of sulphur dye.
(ii) If the cotton in not dyed in the above solution, a fresh specimen is
taken in an evaporating dish and 2 to 3 ml of sulphuric acid is
added and is shake to extract the colour. The extract is poured in
a test tube and 25 ml of water is added and filtered. The filter
paper is washed with water and spotted with 10% sodium
hydroxide solution. If the spot turns red violet, the dye is oxidation
black (aniline black).
(iii) If sulphur dyes or oxidation blacks are absent, a fresh specimen is
boiled with sodium sulphoxylate-glycol solution containing few
drops of 44% sodium hydroxide solution. If the specimen is
discoloured or the shade is altered and the solution is yellow or
bluish red, the dye is vat. The original colour is restored by an
oxidising agent.
6. If the colour is destroyed with sodium hydrosulphite and sodium
hydroxide and is not restored by oxidation, the dye may be
aftertreated direct dye (Group IV) or azoic dyes.
(i) About 6 g test specimen is taken in a porcelain crucible and burnt
into ashes. 200 mg of flux and equal quantity of soda ash and
sodium nitrate are added and fused. If the fused mass is orange-
yellow colour when hot and permanent greenish yellow when cold,
the dye is direct dye after-treated with chromium salt.
(ii) If chromium is absent, the specimen ash is dissolved in a few
drops of concentrated nitric acid. 2 ml of water is added, boiled
and cooled. Blue colour on addition of 2 ml concentrated
381
ammonium hydroxide indicates the presence of direct dye treated

with copper salts.
(iii) If chromium or copper is absent, a fresh specimen is treated with
5% boiling sulphuric acid, cooled and 1% carbazol solution is
added drop by drop. Blue precipitate indicates the presence of
formaldehyde. The specimen is, therefore, formaldehyde treated
direct colour.
(iv) From the discoloured solution (with caustic soda and sodium
hydrosulphite), the specimen is removed and a little cotton
material is added and boiled for 2 minutes. A yellow colour, which
fluoresces strongly, indicates azoic dyes. These colours are also
bleached more slowly than vat or sulphur dyes.
7. If all the above tests are negative, a fresh specimen is boiled with 2 to
3 ml of pyridine for 2 to 3 times. If the colour bleeds with each wash,
the dyes are azoic colours. If the colour bleeds negligibly, the dye is
diazotised and developed.
8. If the test report is negative in all the above cases, or shows slower
and incomplete reactions, the colorant present is a pigment. In fact,
the pigment particles and the binder can be seen under a microscope
(Group V).
9. The effect of hypochlorite bleaching (pH 9) on various dye classes are
as follows:
Sulphur – usually bleached
Vat – in general not bleached, some bleach into brown or pale yellow
Direct and azoic – varies
Reactive – generally bleached, some are resistant
6.12.2 Tests for Dyes on Natural Protein Fibres

The dyed wool and silk may be subjected to the following tests for the
identification of dyes.
1. 0.5 g of the test specimen is successively treated with 50%

dimethylformamide, concentrated dimethylformamide and a mixture of
glacial acetic acid and rectified spirit (1:1) at boil for 3 to 4 minutes
with intermediate washing and squeezing – if no or partial stripping
occurs, the dye is reactive (Group I).
2. If the dyes of group I are absent, the specimen is warmed with 1 ml
glacial acetic acid and 5 ml water. If the extract is distinctly coloured,
the dye is basic (Group II). The confirmative test as described before
may be carried out.
3. If the dyes of group I and II are absent, a fresh specimen is treated
with 5 to 10 ml of 1% ammonium hydroxide. If the colour bleeds, a
382
little cotton along with little sodium chloride is added and boiled. If the
cotton is dyed, the dye is direct (Group III). Otherwise a little wool is
added and boiled. If the wool is dyed, the dye is acid (Group III).
4. About 6 g test specimen is taken in a porcelain crucible and burnt into
ashes. 200 mg of flux and an equal quantity of soda ash and sodium
nitrate are added and fused. The ash is stripped in 1% hot ammonium
hydroxide, cooled, acidified with hydrochloric acid and shaken with
ether. If the ether is coloured, the dye is metal-complex (Group IV),
otherwise the dye is mordant colour (Group IV).
5. If the above tests are negative, a fresh test specimen is boiled for 1 to
2 minutes in solution containing 10 to 30 mg of sodium hydrosulphite
in 5 to 10 ml of water to which 4 to 6 drops of 44% sodium hydroxide
are added. The specimen gets discoloured or the shade changes
radically. If the colour of the specimen restores on exposure to air or
any oxidising agent, the dye is vat (Group V). If the colour is
permanently destroyed, the dye if azoic (Group V).
6.12.3 Tests for Dyes on Synthetic Fibres

These tests are suitable for identification of dyes on synthetic fibres, namely
acetate, nylon, polyester, etc.
1. 0.5 g test specimen is boiled in 1% ammonium hydroxide solution for
1 minute. If the colour bleeds considerably, the specimen is discarded
and the solution is acidified with 30% acetic acid. 0.5 g of scoured
wool is added in the solution and warmed for 5 to 10 minutes at 80-
90°C. If the wool is dyed, the dye is acid dye.
2. If the bleeding in ammonium hydroxide solution is negligible, a fresh
test specimen is boiled with 5% acetic acid for 1 minute. If bleeding is
considerable, add a little scoured wool and warm for 4 to 5 minutes.
Staining of wool indicates the presence of basic or modified basic dye.
The presence of basic dye may be confirmed by treating the acidified
extract with a mixed solution of 50 g/l tannic acid and 50 g/l sodium
acetate, when an insoluble precipitate forms.
3. If there is no bleeding in acetic acid, a fresh specimen is boiled with
5% sodium hydroxide for 1 to 2 minutes. If considerable colour is
stripped, a little scoured cotton is added and is warmed for 5 to 10
minutes. Deep staining indicates the presence of direct dye. The
above extract is boiled with a little sodium sulphoxalate, if the colour is
permanently destroyed, the dye is confirmed to be dischargable direct
dye.
If cotton is not stained in the extract with sodium hydroxide, the dye
may be reactive.
383
4. A fresh specimen is boiled with glacial acetic acid for 5 minutes. If

some colour is stripped, little ether is added to the solution and
shaken. If the ether layer is coloured, the dye is disperse dye. A fresh
specimen is treated with hot liquid paraffin at 160°C for 5 minutes, if
colour is stripped, a little acetate fibre is added. Tinting of the acetate
fibre confirms the presence of disperse dye.
5. A fresh specimen is refluxed with diaoxane-water mixture (1:5) for 2 to
3 hours. If the extract is coloured, 10 ml of 20% sodium hydroxide and
10 to 15 mg sodium sulphoxalate are added in 20 ml extract. If the
colour is changed or destroyed permanently, the dye may be azoic or
diazotisable azo dye. If the colour restores on exposure to air or with
hydrogen peroxide solution, the dye is vat dye or sulphur dye. The
presence of sulphur dye may be confirmed by the stannous chloride
test described before. If the colour readily changes to brown and
restores to black on exposure to air, the colour may be aniline black,
which may be confirmed by warming a fresh specimen with
concentrated sulphuric acid and adding into cold water when a dull
green colour is produced.
If the colour of the specimen does not change, it may be chrome dye.
A fresh specimen is warmed with 16% hydrochloric acid for 1 to 2
minutes, cooled and added to pyridine-water mixture (57:43). If the
colour bleeds, little mordanted wool is added and warmed for 2 to 3
minutes. Staining of wool indicates that the dye is chrome dye.
6. 4 g of EDTA is dissolved in 100 g of glycerol and a fresh specimen is
heated in this mixture at 140°C. If the colour of the specimen changes
within 1 to 2 minutes, the dye may be 1:1 metal-complex dye and if
the colour changes slowly, say after 20 minutes, the dye may be 1:2
metal-complex dye.
6.13 THEORY OF DYEING
Dyeing process consists of four stages
1. Transport of the dye to the fibre surface

2. Adsorption of the dye on the fibre surface
3. Diffusion of dyes into the interior of the fibre
4. Fixation of the dye on the fibre
6.13.1 Transport of Dye to Fibre Surface

During dyeing, the first step is the transport of the dye to the surface of the
fibre. The most efficient way to bring fresh dye to the fibre surface is to stir,
to circulate or to agitate the dye bath or the fabric or to generate relative
384
motion of fabric and dyebath. In dyeing machines, therefore, agitation is

imparted either to the material (e.g. material moving machines such as
jigger or winch), to the liquor (e.g. liquor moving machine such as package
dyeing machine) or both (as in case of jet dyeing machine). The flow of the
dyebath carries fresh dye with it and tends to keep the dyebath
concentration uniform. In the absence of such relative motion, the dye
molecules can reach the fibre surface by a process called molecular jumping
or diffusion through stagnant liquid. This is a much slower process and the
resistance to transport is greater. In general, inadequate stirring or
circulation gives rise to nonuniformity in dyeing.
The portion of the fabric, which comes in contact with the dye solution first,
adsorbs dye from the solution and thereby depletes the solution of dye, and
those portions of the fabric which come in contact with the depleted solution
are starved of dye. For dyes of good levelling property, this initial
unlevelness can be eliminated by prolonged dyeing. It is probably better to
ensure that the rate of removal of dye from the dyebath by the fibre does not
exceed the capacity of the dyeing machines to provide dye solution, by
relative motion of dyebath and fibre. Dyes with high substantivity will
therefore show poor levelling properties.
6.13.2 Dye Adsorption at the Fibre Surface

Gibbs in 1928 [45] through his famous absorption equation defined the
relation between the surface tension of the solution and the difference in
concentration of the solute at the surface and in the bulk of the solution. The
solute tends to concentrate in the region of lower energy. If the surface
tension of the solvent is reduced by the solute, the solute molecules
concentrate at the surface, whereas if the surface tension is raised, the
solute moves away from the surface into bulk of the solution. In practice, it is
found that highly hydrated substances, e.g. some highly ionised inorganic
salts and amongst organic compounds, glycerol and sugars tend to increase
surface tension, therefore, they move away from the surface. Most of the
water-soluble organic compounds, including dyes, reduce the surface
tension of water. Therefore, they concentrate more at the interface than in
the body of the solution. The interface may be between the solution and air
or fibre. Fundamentally, dyeing starts at an interface – usually that between
an aqueous dyebath and polymer molecules in the accessible region of a
fibre.
The basis of all dyeing operations is the concentration of a dye at a solid
surface. This particular case of phenomenon called adsorption was known
for long time, but modern studies begin with Langmuir’s concept of gas
adsorption. Although the situation in dyeing is more complex than gas
385
absorption, the Langmuir equation can be applied to most dyeing processes

involving hydrophilic fibres.
Any adsorption is usually studied by plotting dye concentration in the
dyebath (Ds) and corresponding dye concentration in the fibre (Df) at
equilibrium in a graph known as adsorption isotherm. The most common
isotherm is Langmuir type (Figure 6.10(a)), which is obtained for most
dyeing processes involving hydrophilic fibres, where dyes interact strongly
with substrates. One can reasonably assume that solids have an internal
surface that can adsorb an amount Df of dye when the concentration in
solution is Ds and the total number of sites is such that the amount which
should theoretically be absorbed is Sf when the external concentration is
made enormously high. The number of unoccupied sites is Sf – Df. The rate
of adsorption r1 is proportional to the number of unoccupied sites available
to take up a dye molecule and to the frequency with dye molecules striking
these sites. The latter is proportional to the concentration of dye molecules
in solution and to the temperature, which is kept constant to obtain an
isotherm.
r1 = k1Ds(Sf – Df ) (6.29)
At this temperature some of the adsorbed dye molecules have kinetic
energy of vibration and occasionally acquire so much energy that they break
the bonds holding them to the fibre. The rate of this desorption process, r2,
at any instant, is proportional to the number of dye molecules adsorbed.
Consequently,
r2 = k2Df (6.30)
At equilibrium, the rate of adsorption, r1 is equal to the rate of desorption,
r2, so we get the relation as in the Eqn. (6.31).
(Sf – Df )Ds k2
 =  (6.31)
Df k1
Considering k1/k2 ,as k we get Df = kDs(Sf – Df )

kSfDs
or Df =  (6.32)
1+ kDs
Inverting the above as Eqn. (6.33),
1 1 1
 =  +  (6.33)
Df kSfDs Sf
The equation indicates that if the reciprocal of the amount absorbed is
plotted against the reciprocal of the concentration in solution, a straight line
386
is obtained with a slope of 1/kSf. k has the dimension of litres per mole, i.e. it
is a dilution, the inverse of a concentration, and differs from the partition
ratio (having dimensions of litres per mole), but is similar in that it represents
the volume of solution which will contain 1 mole of dye in equilibrium with
the solid when it is 50% saturated.
When dye interacts weakly (by hydrogen bonding or Van der Waals'
forces), Freundlich isotherm (Figure 6.10(b)) is obtained. He showed that for
these systems, the ratio of the amount of dye absorbed and the
concentration of the dye in solution is not constant. But if the concentration
of dye in solution is raised to a power N, the above ratio is constant at a
given temperature. The Freundlich isotherm, therefore, may be written as
Eqn. (6.34):
N
Df = K(Ds) (6.34)
N is a fraction, usually ca 0.5.
One objection is that, according to Freundlich equation, as the dye
concentration of the solution increases, dye adsorption should increase
without limit until the limiting solubility of dye is reached. In many cases with
readily soluble dyes, however, the curve of the amount of dye adsorbed
flattens off and approaches an obvious plateau, not predicted by the
equation. Besides, the equation itself does not seem to have a physical
significance – the mechanism of adsorption is not made clear.
The linear Nernst isotherm (Figure 6.10(c)) is obtained with disperse dyes
on hydrophobic fibres. It represents partitioning of dye between substrate
and dye liquor by solubility effects. This is the simplest possible model. Just
as a nonionic dye dissolves in organic solvents and can be said to have
affinity for them, so in dyeing the dye may dissolve in the fibre because of its
affinity for the latter, hence, the name solid solution model. Just as a
Sf
KSfDs Df = K(Ds)N
Df Df
Df = 
1 + KDs
Ds Ds
(a) (b)
Df Df = KDs
(K = slope)
Ds
(c)
Fig. 6.10 Dyeing Isotherms

387
disperse dye distributes itself between two layers of a pair of suitable

immiscible liquids (e.g. ethyl acetate and water), so the dye which is
adsorbed by a fibre can be thought of being dissolved in the solid phase and
distributed between the solid and liquid phases. With two immiscible liquids,
the equilibrium concentration in one liquid divided by the concentration in the
other is termed the distribution coefficient or partition ratio. Constant partition
ratios have been obtained for disperse dyes distributing themselves
between water and polyester and other synthetic fibres. For many disperse
dyes, the ratio is constant over a wide range of dye concentrations, often up
to the saturation solubility of the dye in water. It changes with temperature.
Smith [46] classified dyeing mechanism into four types:
1. Specific affinity of dye for fibre by hydrogen bonding, Van der Waals’
forces, or ionic interaction which may occur at specific sites, by
electrical effects or formation of covalent bonds.
2. Mechanical entrapment of dye within fibre.
3. Binders, which hold pigments in place on the fibre surface.
4. Simple distribution (dissolution) of dye between the substrate and dye
liquor (nonionic).
The Table 6.8 shows the dyeing mechanism and observed isotherms for
various fibre-dyestuff combinations [46].
Table 6.8 Dyeing Mechanism and Observed Isotherms for Various Dye-
Fibre Systems
Dye/Fibre Dyeing Mechanism Isotherm
Acid/wool
Langmuir
Acid/nylon Specific affinity
Basic/acrylic
Reactive/ cellulose
Direct /cellulose Freundlich
Disperse/ synthetic Simple distribution Nernst
Vat, sulphur, naphthol/cellulose Entrapment None*
Pigment/any fibre Binding None
*
two-step in which the exhaust phase is described by an isotherm
followed by a reaction phase not described by an isotherm.
6.13.3 Diffusion of Dye

In the next step, the dye starts penetrating or diffusing inside the fibre
through its accessible regions. The third step, diffusion obviously depends
388
on the physical or morphological structure of the fibre. Diffusion is a slow

process and is a rate-determining step.
Diffusion is the process by which matter is transported from one part of a
system to another because of molecular motion. This eventually leads to
equalisation of chemical potential and concentration throughout the system.
Textile fibres are heterogeneous substances. While diffusing into the
polymer molecules, the dye must follow a tortuous path in order to avoid the
impenetrable crystalline regions. In passing through the amorphous regions
of the substrate, the large dye molecules must weave their way through a
network of chains or along the surfaces of crystalline regions and may even
encounter voids. Because of these complications, most workers have
represented the polymer substrate by a model. Two simple models are pore
model and free volume model.
The natural fibres, namely cellulosic and protein fibres, have an
exceedingly large number of internal channels. The number of such
channels is immense, of the order of ten millions in the cross-section of a
cotton or wool fibre. Correspondingly, the fibres possess a large extent of
internal surfaces, i.e. the walls of the channels between the bundles of long-
2
chain molecules and the total surface is of the order of 100 m /g. This is
about one thousand times as large as the outer surface of the fibre.
When such fibre is placed in an aqueous dyebath, water penetrates the
pores very rapidly in a time measurable in seconds. Dye takes longer to
penetrate because the fibre pores exert restraining effect on relatively large
dye molecules. Within a short time, however, a large proportion of these
channels is swollen by water and the dye solution is in contact with the
internal surface of the fibre. This process is greatly assisted if the dye is
ionic and the fibre carries opposite charge. Strong affinity may also due to
hydrogen bonds between dye and fibre. Van der Waals' forces exerted by
long dye molecules also assist to align the dye molecules parallel to and in
contact with the molecular chains in the fibre walls. Because of the
constriction of the smaller pores, the concentration of the dye in the pore
increases promoting association of dyes into larger aggregates. However,
most of the pores are very small and water can penetrate only a small
proportion of the total internal space.
Water carries dyes while entering the channels and leaves back a portion
of it, while returning to the dyebath. By repeated in-out flow of water, the
quantity of adsorbed dyes on the internal surface increases. This theory is
known as pore theory and is valid for natural fibres. The model is somewhat
crude, in that it assumes that the dye molecule diffuses without hindrance
down the pore.
Most of the synthetic fibres have much less internal surface than the
natural fibres, but the dyes used on these fibres can penetrate between the
fibre molecules although water cannot always do so. When a low-molecular-
389
weight crystalline solid is heated, there is a change of state at the melting

point. The individual molecules separate spontaneously and the solid
changes to a free-flowing liquid. Polymer molecules cannot separate so
easily because their length inhibits the spontaneous molecular
disengagement, which characterises the melting of a simpler solid. Instead,
only segments of polymer molecule can separate as the temperature is
raised. The temperature at which this separation begins is well defined and
is called as glass transition temperature (Tg). On heating up a polymer, there
is an abrupt change in mechanical and other physical properties from those
of a glass-like substance to those of a rubber-like substance when the
temperature is exceeded. The abrupt change in properties permits the
experimental location of Tg. When the temperature is raised further, the
frequency of the change in the position of the polymer segment called
segmental jumps increases exponentially with increasing temperature. In
fibre, this leads to a rapid increase in volume creating voids.
The free volume is that volume in a liquid or solid not occupied by the
constituent atoms. In fact, it arises from the thermal motion of the atoms,
hence it increases with temperature. Below the glass transition temperature,
the polymer chains may be regarded as frozen into position and the only
motions they can undergo are thermal vibrations. When the glass transition
temperature is reached, sufficient energy is available for bond rotation in the
backbone of the polymer chains. An adequate free volume has been created
to provide a space large enough to accommodate the rotating polymer
segment. Once this segment has moved, the space it has vacated allows
another segment to move. The onset of segmental motion occurs over a
narrow temperature range, which includes glass transition temperature.
Further increases in free volume occur as the temperature is increased and
are related to the coefficient of thermal expansion. The free volume theory
assumes that there is a certain amount of unoccupied or free volume, which
is considered to be distributed in a random fashion so that fluctuations of the
size of a hole may occur. The ability of the chain segments to move relies on
there being sufficient free volume available for the segment to be
accommodated. To accommodate a molecule as large as a dye, presumably
a hole of a greater size must be available. The dye first adsorbs at the fibre
surface. This theory is known as free volume theory or segmental motion
theory.
The fundamental concepts of mass transfer are comparable with those of
heat conduction. Fick used the hypothesis that the rate of transfer of a
diffusant through a section of unit area is proportional to the concentration
gradient measured normal to the section expressed mathematically as Eqn.
(6.35).
δC
F = - D  (6.35)
390
δx
where F is the rate of transfer per unit area of section, C is the
concentration of the diffusing substance, x is the space co-ordinate
measured normal to the section and D is the diffusion coefficient. The term
δC/δx is, therefore, the concentration gradient. If F and C are both
expressed in the same unit (say grams or moles), then D is independent of
-1 2 -1
this unit and has dimensions of length2time , e.g. m s . The negative sign
arises because diffusion occurs in a direction opposite to that of an
increasing concentration. The Fick’s first law as above is applicable to
isotropic medium in which the diffusion properties at any point are same
relative to all directions. In an anisotropic medium, such as most crystals
and fibres, the diffusion properties depend on the direction in which they are
measured.
Fick’s second law of diffusion is of more fundamental consequence and
refers to non-steady state conditions, in that it describes the accumulation of
matter in a medium at a given point as a function of time. If the diffusion
coefficient is constant and independent of x, y, z directions, according to the
second law, we can write the Eqn. (6-36):
2 2 2
δC δC δC δC
= D  2 + 2 +  2 (6.36)
δt δx δy δz
For one-dimensional diffusion, say in x direction, the equation becomes

Eqn. (6.37):
δC δ2C
= D  (6.37)
δt δx2
In all fibres there exist regions of differing degrees of orders and disorders,
i.e. there exists a distribution of the degrees of lateral order, the extremes
being known as crystalline and amorphous (or non-crystalline) regions of the
fibre respectively. The crystalline regions provide strength and rigidity, whilst
the amorphous region provide flexibility and reactivity. The ratio of these two
regions has significant influence on the properties of a given fibre.
The degree of regularity of the polymer chains is reflected in two different,
but related forms of physical disorder, viz. orientation and crystallinity.
Orientation refers to the extent to which the molecular chains are
directionally correlated over the entire fibre. This is very high in some cases,
with the majority of the molecular chains lying with their axes within a few
degrees of the fibre axis. Information on the degree of crystallinity can be
obtained from the measurement of density of fibres, whilst birefringence
measurements can indicate orientation of the crystalline units. X-ray
diffraction techniques are now available, which provide information on
391
crystallinity, crystallite size and orientation and lateral order of the crystalline
units.
For natural fibres, crystallinity and orientation are inherent properties and
are for most practical purposes unalterable. For man-made fibres, the ratio
of crystalline and amorphous regions and the orientation can be controlled
to a large extent by conditions during fibre production, such as rate of
cooling of fibre melt, mechanical stress during cooling and the degree of
drawing or stretching applied on the final product. In extruded undrawn
filaments, the molecular chains may be packed together into crystallites, but
apart from orientation at the filament surface producing a skin effect, the
crystallites are in a state of random orientation. Subsequent stretching or
drawing orientates the crystallites along the fibre axis depending on the
extent of drawing. Marked structural changes may occur in the polymer
matrices of fibres when they are subjected to appropriate heat treatments,
whether for example, at 100°C in the presence of water or at 210°C using
dry heat.
Among cellulosic fibres, ramie and jute both have extremely high degrees
of orientation, whereas cotton has a much lower degree of orientation. Nylon
and polyester are highly crystalline fibres, polyvinylchloride and
polyacrylonitrile fibres have a low degree of crystallinity. The last two fibres,
however, exhibit a high degree of molecular orientation in the drawn state.
Both orientation and crystallinity strongly affect the kinetic and equilibria of
sorption of solvent and dye molecules by fibres. Dyeing can be hindered by
excessive crystallinity and so with the man-made fibres, is influenced by the
drawing and heat-setting history of the fibre. In some respects, the ability of
a given fibre to absorb water is a clearer indication of dye accessibility than
molecular orientation or crystallinity. Hydrophobic fibres cannot be dyed with
dyes of high aqueous solubility because the ionisation (and thus polar
behaviour) in water of the dyes produces adverse interactions with the fibre.
Apart from spatial hindrance, which is encountered with most ionic dyes
making penetration into these fibres difficult, electrical repulsion of anionic
dyes takes place owing to the high negative surface potentials exhibited by
hydrophobic fibres in contact with aqueous solutions.
6.13.4 Fixation of dyes

Fixation of dye in fibres is caused by any or more mechanism mentioned
below:
1. Ionic bonding, as in case of acid and basic dyes on protein fibres.
2. Covalent bonding as in case of reactive dyes.
3. Aggregation of dye molecules inside the textile fibres as in case of
direct dyes.
392
4. Insolubilisation of dye inside the fibre as in case of azoic, vat and

sulphur dyes.
5. Solubilisation of dye inside the fibre as in case of disperse dyes on
polyester.
Any discussion of the reactions between dyes and fibres must take into
account the various types of forces exerted by one molecule upon another
and a brief survey is, therefore, necessary. All originates in the movement of
electric charges. There may be two types of dye-substrate association.
Accordingly, all dyeing mechanisms can be divided into three groups:
1. Specific bond between dye and fibre owing to covalent bond,
hydrogen bonds or other directed bonds.
2. Non-specific attraction between dye and fibre owing to ion-exchange
or Van der Waals’ forces.
3. Absence of any interaction, dyes are only mechanically retained. This
may be due to insolubilisation of the dye inside the fibre or may be
due to self-association into possibly quite large molecular aggregates
following their entry into fibre. Aggregation is promoted by a high ratio
of molecular weight to ionic group as well as by increase in length of
the aromatic structure of the molecule, also by rise in concentration
and the presence of inorganic salts, e.g. common salt.
Van der Waals’ Forces
These forces are so named because they were first recognised by Van der
Waals in 1873. They can be broadly divided into two groups – polarisation or
electrostatic and dispersion forces.
The symmetric distribution of electrons around atoms is disturbed when
the atoms are chemically combined and may result in a permanent
unsymmetrical distribution of electric charge in the molecule, which therefore
has a permanent electric charge or dipole moment. Such non-symmetrical
organic molecules that are not hydrocarbons are called polar. The symmetry
of non-polar methane (CH4) molecule is disturbed when one, two or three of
its hydrogen atoms are replaced by halogen atoms. But the symmetry is
restored when all four hydrogen atoms are substituted by the same
substituent, as in case of CCl4 and the dipole moment is zero. Molecules
with dipole moments attract each other in two ways, viz. by permanent
dipoles and by induced dipoles as magnet attracts another or a piece of soft
iron by inducing magnetism therein. The polarisation Van der Waals’ forces
fall off with the sixth power of the distance between molecules.
Dispersion or London forces, named after F. London (1930), accounts for
the fact that non-polar molecules, e.g. CCl4 or argon, can attract one
another. The cloud of electrons is distributed spherically around a positive
nucleus. Though the electrons are continuously circulating, at an instant
they may be so distributed that there is a separation of positive and negative
393
charge and therefore a dipole moment. This moment then has a vector,
which is continually changing with the movement of electrons and the net
result is a zero vector. When two such atoms are close to one another, their
momentary dipoles interact and the motions of their electrons synchronise to
cause a continuing electrostatic attraction between them. The energy of the
system is lowered and a weak bond is established. The energy is
2 6
proportional to α /r where α is the polarisability of the molecules and r is
the separation. The α value is higher for higher volume of the molecule, so
that with increase in molecular size, the dispersion forces increase and
become more effective than polarisation forces. Dispersion forces are,
therefore, more important for dye-fibre systems as both molecules are large.
The very rapid fall-off of these forces with separation, and their increase with
increasing molecular weight, should clearly cause long dye molecules to
align as closely and as nearly parallel as possible with the long fibre
molecules as in the case of direct and vat dyes with cellulose or disperse
dyes with synthetic fibres. On decrease of intermolecular distance r, the
electron clouds of the molecules come close enough to begin to
interpenetrate and the attraction changes to a mutual repulsion [47].
Hydrophobic Bonding
The hydrophobic groups, especially alkyl chains, tend to associate together
and escape from aqueous environment. The effect is due to two
simultaneous causes – the Van der Waals' forces between the hydrocarbon
groups and the hydrogen bonds between water molecules. Each set of
forces causes respective assembly of molecules or groups to associate
together and to exclude the other. Hydrophobic bonds occur when both the
fibre and dye contain a considerable portion of purely hydrocarbon, aliphatic
or aromatic, as with some dyes applied on wool or most dyes applied on
polyester. It is strictly not a new type of bond or intermolecular force.
Hydrogen Bond
The very small size of the hydrogen ion or proton and its high polarising
power cause it under certain conditions to form bonds with two atoms
simultaneously. The hydrogen atom should be covalently bonded to one of
high electron affinity mostly N, O or F atom or sometimes Cl, S or C atom.
The hydrogen atom is, therefore, positively polarised and can attract a
second electro-negative atom. The most familiar example of the presence of
this bond is water, whose melting and boiling points are much higher than
would otherwise be expected. Most fibres and dyes contain groups, which
can form hydrogen bonds. Hydrogen bonds may form between the aromatic
nucleus of polyester fibre and hydroxyl groups of disperse dyes. The bond
may also form between cellulosic or protein fibres and various dyes. The
bond is relatively weak (2-10 kcal per mol) and, therefore, can readily be
394
formed and readily broken. The presence of a large number of this weak
bond may play a significant role in dyeing.
Ionic Bond
These bonds play an important part in dyeing fibres containing amino
groups, i.e. wool, silk, and nylon with anionic dyes. In the presence of water
or dilute acids the amino groups become protonated:
+ -
NH2CH2COOH Æ NH3 CH2COO (6.38)
Acid dyes, being anionic in solution, are attracted at the positive site of the
fibre. As the fibre forms zwitterion on ionisation, a negative charge is also
created on the fibre. This negative charge is responsible for attraction
towards basic dyes which forms cationic dye ions in solution. However,
basic dyes are now mostly applied on acrylic fibres which contain strong
acidic sites. Due to ionisation in acidic medium, negatively charged sites are
created in the fibre which attract cationic dye ions.
Ion-dipole Forces
While attracting those of opposite charge, ions in solution can exert
attraction upon any polar molecule, giving rise to so-called ion-dipole forces.
These forces are largely responsible for aqueous solubility of dyes. The
attraction between dipoles on the cellulose ether groups and ionic groups in
the dye molecules is also proposed.
Covalent Bond
When two participating atoms each contribute one electron to common
linkage, the electrons unite the atoms with a covalent bond of high energy
between about 20-200 kcal per mol. The bonds between reactive dyes and
fibre molecules are of this type; their high energy makes them difficult to
disrupt and they account for the high fastness of such dyes to water
treatments.
6.13.5 Equilibrium and Dyeing Rate

The word thermodynamics is usually applied only to reversible equilibrium
systems. Many dyeing processes, however, are essentially irreversible, at
least on a molecular state, in that they can be reversed only by another
drastic chemical reaction. Examples include the various forms of mordant
dyeing, the oxidation of leuco vat and sulphur dyes, the azoic coupling of
naphthols within the fibre, and the formation of covalent bonds between dye
and fibre in reactive dyeing. In these processes, only a forward reaction is to
be considered − there is no back-reaction whereby a reversible dynamic
equilibrium could be established. Therefore, affinities cannot be determined.
395
Time of half-dyeing (t½) is the time taken for a fibre to adsorb 50% of the
dye it would adsorb at equilibrium. It provides an indirect measure of rate of
diffusion and is useful for comparing the behaviour of dyes applied under
identical conditions. Because of the very gradual approach to equilibrium,
the time taken to reach equilibrium cannot be measured accurately.
However, equilibrium adsorption, Cα can be estimated readily by dyeing for
a prolonged period and t½ is then determined using a graph of exhaustion
versus time of dyeing at Ct = 0.5Cα (Figure 6.11). In certain cases, it is
preferable to plot exhaustion against log t since then the relevant portion
tends to be a straight line and a more accurate estimate of t½ can be
obtained.
C∝
C∝
%C % Ct = 
2
t½ Time
Fig.6.11 Exhaustion of Dyes (%C) with Time
In practice, the experimental conditions must be chosen with care. If the

conditions are such that the bulk of the dye is adsorbed on to the surface of
the fibres quickly (i.e. rapid strike of dyes) this will musk the effect of
diffusion into the fibre. The conditions should be so chosen that the dye-fibre
attraction is low and the final exhaustion is not very high (< 80%). The time
of half-dyeing is also very dependent on the amount of dye used.
During the initial period before the quantity of diffusant passing through a
sheet against time becomes linear, diffusant accumulates in the film under a
non-linear concentration gradient. This condition is known as the non-steady
state, since the amount of diffusant in the film is continuously increasing.
The same condition arises in normal dyeing process. If the contribution to
mass transfer through the ends of a filament or through the edges of a film is
considered negligible, the dye penetrates the empty filament or film along a
non-linear concentration gradient from both sides of the film or from the
surface of the filament. When the dye molecules reach the centre of the
material, the overall concentration gradient begins to decrease owing to
accumulation from both sides, until finally no measurable gradient exists.
396
The situation thus differs from steady state diffusion and the total amount of
diffusant taken up in time t can be determined by integrating Fick’s second
equation over the period t = 0 to t = t [ 47].
Until the diffusant penetrates into the center of the substrate, the latter can
be regarded as an infinitely thick slab of material into which diffusion is
occurring from one face. Vickerstaff described an approximation formula for
diffusion coefficient D, which gives satisfactory results in the initial stage of
uptake as in Eqn. (6.39).
Ct Dt
 =2  (6.39)
C∝ π
where Cα and Ct are the amount of diffusant accumulated at equilibrium

and after time t respectively.
A solution of Fick’s second equation given by Crank [48] is more suitable
to moderate and large times and is as in Eqn. (6.40):
∝
Ct 8 1 (2m+1) π²t
 =1-  exp -D  (6.40)
C∝ π² m=0 (2m+1)² l²
l is the film thickness and m is a positive integer. It is assumed that

diffusion coefficient D does not vary with diffusant concentration. The time of
half-dyeing, t½ can then be simply calculated to within an error of ±0.001%
by the formula as in Eqn. (6.41):
9
t½ 1 π² 1 π²
 =  ln  -   (6-41)
l² π²D 16 9 16
Since in the right-hand of Eq. (6-40) all values except D is known, the
value of Diffusion coefficient D is given by Eqn. (6.42):
l²
D = 0.04919 x  (6.42)
t½
The diffusion coefficient D can, therefore, be calculated if the time of half-
dyeing and the thickness or diameter of the film or fibre is known at a
concentration within the material corresponding to that at the time of half-
dyeing.
Hill [49] proposed a similar equation for diffusion into an infinitely long
cylinder of radius r or film of thickness l as in Eqn. (6.43):
397
Ct
 = 1 – 0.692(e –5.785β + 0.19 e –30.5β + 0.0775e –74.9β + ·····) (6.43)
C∝
where β = Dt/r² or Dt/l². If an arbitrary value is assigned to β then the ratio
Ct/C∝ can be calculated. For each value of β there is a specific value of the
above ratio. As the Hills equation is complicated, the solutions in the form of
tables [Table 20.1 of 47] or graphs are available. Since the value of r or l
and t are known, it is simply necessary to know Ct at time t and the
saturation equilibrium value C∝ to determine the diffusion coefficient D.
The rate of diffusion of a dye in a fibre increases with increase in dyeing
temperature. The effect of temperature on the rate of diffusion is given
numerically by the activation energy of diffusion (E) according to the
relationship shown in Eqn. (6.44):
-E/RT
DT = D0e
or log DT x 2.3 = - E/RT + constant (6.44)
Where DT is the observed diffusion coefficient at absolute temperature T,
D0 is a constant and R is gas constant. Hence, if the logarithm of the
observed diffusion coefficient is plotted against the reciprocal of T, a straight
line of slope E/R should be obtained, from which E can be calculated.
A corresponding measure, activation energy of dyeing, ED can be obtained
from the rate of dyeing measurement, i.e. by plotting log t½ against 1/T.
These values are not fundamental, but they provide a measure of the effect
of temperature on practical dyeing rate and may be used to calculate the
probable rate of dyeing at any temperature from the knowledge of the rate at
another temperature as shown in Eqn. (6.45).
2.3 R(log t/½ - log t//½)
ED = ————————— (6.45)
1 1
— - —
T1 T2
/ //
where t ½ and t ½ are the times of half-dyeing at absolute temperatures T1
and T2 respectively.
Thermal activation is only the first stage in the dyeing process. The driving
force in the transfer of dyes from solution to the fibre is the difference in free
energy between the two phases. In other words, the energy needed to
compress the dye molecules from their freedom of movement in the solution
to the restricted volume within the fibre (compression). This is more
conveniently expressed in the form of the chemical potential (µ) which is
defined as the difference in free energy between the two phases when a
very small quantity of dye is added to the solution, all other variables kept
constant. The standard potential is derived from the basic equation,
applicable to ideal solution, namely Eqn. (6-46):
398
µ = A + RT ln C (6.46)
Where A is a constant, which is a function of temperature and pressure
but is independent of the composition of the solute, and C is the molar
concentration.
When dyeing has proceeded to true equilibrium, the fibre will be
completely and uniformly penetrated and adsorption and desorption of dye
will be taking place at the same rate. The chemical potential is the same in
the fibre as in the solution and there is no net transfer of dye from one phase
to another. However, because the dye has greater affinity for the fibre than
for the external solution, the concentration [Df] of dye in the fibre is greater
than that [Ds] in the external solution. The affinity of a dye for a fibre (-∆µ°) is
derived as in Eqn. (6.47):
[Df]
-∆µ° = RT ln  (6.47)
[Ds]
Where µ° is the standard chemical potential, R is gas constant and T is
the absolute temperature. ∆µ° itself is not significant as ∆µ°/T.
In the simplest case, for disperse dyes applied on synthetic fibres from
aqueous dyebath, [Df]/ [Ds] is the partition coefficient, K. Thus the affinity is
determined by measuring the partition coefficient at that temperature using a
desorption technique.
The affinity is made up of two parts, viz. the heat of dyeing, ∆H° and the
entropy of dyeing, ∆S°, the relationship being Eqn. (6.48):
∆µ° = ∆H° - T∆S° (6.48)
If ∆H° is a constant, independent of temperature, ∆H°/T approaches zero
when T is very large. Hence, when the kinetic energy of the dye molecules
is very large, i.e. at very high temperatures, the dye-binding energy
represented by ∆H° becomes less significant and the entropy ∆S° then
dominates the situation and mainly determines the equilibrium states. The
change in entropy is a measure of that part of affinity, which is due to
probability, i.e. when the molecular motions are sufficiently random, the
equilibrium state is that which is most probable. As a summary, ∆H° controls
the equilibrium at very low temperatures, while ∆S° at very high
temperatures. At intermediate temperatures, there is a balance between
these two opposing forces of order and disorder.
The affinity of a dye is dependent on temperature. It decreases as the
temperature rises, i.e. the equilibrium shifts in favour of the external phase.
When -∆µ°/T is plotted against 1/T (T is the absolute temperature for a
particular affinity value), the slope of the straight line obtained gives -∆H°,
the heat of dyeing. It is a measure of the strength of the attraction between
399
the dye and the fibre. If the values for ∆µ° are available for two absolute
temperatures T1 and T2, it is more convenient to use the Eqn. (6.49):
∆µ1° ∆µ2° 1 1
∆H° =  -   - (6.49)
T1 T2 T1 T2
The values obtained are negative, which indicate that dyeing is an
exothermic process. The value of ∆H° represents the difference in heat
content between that needed to free one mole of dye from the solvent, and
that required to free the same quantity of adsorbed molecules from the
surface or from the interior of the solid by thermal agitation. It is thus the
heat of sorption, i.e. the increase in heat content (enthalpy) of the system
when the dye is sorbed. Large negative values of ∆H°, therefore, correspond
to high potential affinity. This high potential is not realised at ordinary
temperatures because of the change in entropy on sorption.
The change in entropy ∆S° represents (on a logarithmic scale) the ratio of
the probability (β1) of sorption to that of desorption (β2) as shown in Eqn.
(6.50).
β1
∆S° = Rlnβ1 - Rlnβ2 = Rln — (6.50)
β2
This entropy of sorption is the gain in entropy or randomness (disorder) of
the system when the dye is adsorped.
The world market for textile dyes was worth US$5.7 billion in 1997, but it
fell back by some 13% in 1998, and further declined by 10% in 1999. There
is now good evidence that the decline was starting to be reversed towards
the end of 1999 and it is predicted that growth between 2000 and 2005 will
be around 3% per annum. The market of dyes (according to study made in
1998) is dominated by the production of disperse dyes for polyester and
acetate (26.3%), and reactive dyes for cellulosic fibres, mostly cotton and
viscose (23.6%). There has been a decline in the use of direct (7.7%) and
vat dyes (16.8% including indigo and sulphur) for cotton. Cationic dyes
(7.0%) are mostly produced for acrylic, and acid dyes (18.6%) for nylon,
wool and silk. The nylon fibre has shown come back in recent years with the
popularity of microfibres in sportswear and leisurewear. The market of the
pigment industry follows a biennial cycle, where higher sales in one year
and lower sales in the following year. In 1999, the global pigment market
had a volume of 230,000 tons with expected growth by 6.4% per annum up
to 2004 [50].
400
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rd
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17. R.W.G. Hunt. 1978, Col. Res. Appl., 3, 79.
18. W.D. Wright. 1984, Col. Res. Appl., 9, 229.
19. A. Härd, and L. Sivik, (Colour reports F26 (1983) and F28 (1984). The
Forsius Symposium on Colour Order Systems and Environmental
Colour Design, Scandinavian Colour Institute, Stockholm.
20. A.K. Roy Choudhury. 1996, Rev. Prog. Coloration, 26, 54-62.
21. L.A. Graham, Ed. by G. Celikiz and R.G. Kuehni. 1986, Colour
Technology in the Textile Industry, (North Carolina, USA: AATCC) 135.
22. F.W. Billmeyer (Jr.), 1987, Col. Res. Appl. 12, 173-185.
23. D.L. MacAdam. 1974, J. Opt. Soc. Am., 64, 1691.
24. A. Härd, and L. Sivik. 1981, Col. Res. Appl., 6, 129-138.
25. Wilhelm Ostwald. 1915, Die farbenlehre , (Leizig, Germany: Unesma).
26. Wilhelm Ostwald, The Colour Primer (1916), translated by Faber Biren.
1969, (New York: Van Nostrand).
401
27. M. Richter. 1955, J. Opt. Soc. Am., 45, 223.

28. A. Nemcsics. 1987, Col. Res. Appl., 12, 135-146.
29. E. Heila. 1988, Col. Res. Appl., 13, 260-263.
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31. F.W. Billmeyer (Jr.), 1987, Col. Res. Appl. 12, 173-185.
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Beltsville, Md, 20705.
33. S.M. Newhall, D. Nickerson, and D.B. Judd.1943, J.Opt.Soc.Am., 33,
385.
34. R.S. Berns and F.W. Billmeyer. 1985, Col. Res. Appl., 10, 246-250.
35. A.R. Robertson. 1984, Col. Res. Appl., 9, 234-240.
36. M.R. Luo. 1986, New Colour Difference Formula for Surface Colours,
Ph.D Thesis, (Bradford, UK: University of Bradford).
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39. S.M. Newhall. 1940, J. Opt. Soc. Am., 30, 617-645.
40. Scotdic Colour Book, Kensaikan Ltd., Higashi-ku, Osaka 541, Japan.
41. Standard Methods for the Determination of the Colour Fastness of
th
Textiles and Leather, 4 Edn. 1978 (Bradford, UK: The Society of Dyers
and Colourists).
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nd
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Chapter
Dyeing Machines 7
7.1 INTRODUCTION
In textile production, the short length fibres or continuous filaments are spun
into yarn and then woven, knitted or bonded into fabric. The stage at which
coloration or dyeing is carried out depends on several factors, the fashion
and economics being most important. The merchants prefer to postpone the
decision of coloration as long as possible in order to cater for the dictates of
fashion and fabric dyeing facilitates this.
The coloration of textiles may be carried out at the following stages:
1. Mass pigmentation of polymer melt or solution

2. Dyeing of polymer gel
3. Fibre tow dyeing
4. Loose-stock or fibre dyeing
5. Dyeing of fibre top or sliver
6. Yarn dyeing
7. Fabric dyeing
8. Garment dyeing
Man-made fibres can be dyed at all the above stages, whereas only the
stages (4) to (8) are suitable for natural fibres.
The earliest stage at which synthetic filaments can be continuously dyed is
in the form of a water-swollen gel before stretching. Little has been
published about these processes because they form a part of the fibre
manufacturing process.
In volume terms, the major routes are gel, tow and loose-stock dyeing,
with yarn and fabric dyeing forming the next most important segments of the
industry. Dyeing textiles in the form of fabric or garment form offers the
processor maximum flexibility in responding quickly to changes in fashion
and market.
The selection of the coloration stage is decided by several factors such as:
403
(a) Economy.
(b) Availability of equipment
(c) Suitability of the stage for the particular fibre and end-product
The relative importance of different methods of coloration also depends on

market demand. The progress in gel-dyeing techniques has resulted in a
marked decline in yarn-dyeing capacity and some decline in loose-stock
dyeing. Continuous top dyeing has declined dramatically, mainly because of
cost. Batchwise tow-dyeing processes have at least held their share of the
market, with modest increase in certain European countries [1].
Mass coloration was a natural development following commercial
manufacture of man-made fibres. The addition of inorganic and organic
pigments to the polymer solution is a relatively simple means of colouring
the extruded filaments. The final product is characterised by the very high
level of colourfastness, with the pigment entrapped within the polymer. Mass
coloration is carried out in the fibre spinning machinery and as such no
special machine is required for the operation. This is truly not a dyeing
process.
Loose stock, top and tow can be dyed both batchwise as well as
continuously. The batchwise dyeing is carried out in circulating liquor
machines. The continuous dyeing unit is essentially the same for all physical
forms. This consists of a pad applicator for the dye solution (Section 7.4.5),
drying, fixation by steam or dry air, washing off and re-application of finish.
Clarke [1] summarised the features of various coloration routes as follows:
Gel dyeing
• Lowest cost of coloration
• Requirement of dyes of high quality
• Poor flexibility to trade demands,
• Inferior quality may be as compared to crude production,
• Requirement of larger lots per colour
Tow dyeing
• 10% less dye cost than gel dyeing, more flexibility of choice of dyes
• Moderate flexibility to trade demands
• Comparatively smaller lots per colour e.g. 2.5 tons
Fibre dyeing
• Lowest dye cost, maximum choice of dyes
• Smaller lots per colour
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Top dyeing
• Used for blended yarns
• Smaller lots per colour
Yarn dyeing
• Requirement of high-quality dyes
• Good flexibility
• Useful for patterned fabrics
• Additional winding costs
Fabric dyeing
• Maximum flexibility, rapid response to market
• Maximum levelness of dyeing to be ensured
The dyeing in fibre, yarn, fabric and garment form comes under the
purview of dyeing industries and specialised machines are required for the
purpose.
The basic requirements of a dyeing machine are [2]:
1. It should provide sufficient movement for the liquor to penetrate

uniformly into the textile materials.
2. The liquor movement should not be so vigorous that the material is
damaged, entangled or felted.
3. The material used for the construction must be stable during
prolonged boiling with acidic or alkaline solutions.
4. The heating arrangements of the machine should be able to maintain
uniform temperature throughout the liquor.
5. There should be provision for addition of concentrated dye solution in
such a way so that it is well diluted before it encounters the material.
6. All moving parts and attachments should be protected against the
corrosive action of steam and acidic fumes.
Other desirable features are:
1. The largest possible water inlet valves should be attached to the

machine, as considerable portion of the dyeing cycle is taken up for
filling and draining of liquor.
2. Closed steam pipes are preferred, rather than open ones, as the latter
increases liquor ratio during dyeing process. The same closed pipe
may be used for sending steam while heating, or cold water when
cooling is required.
405
3. Automatic temperature control devices may be attached for increasing

temperature at a pre-determined rate and a pre-determined maximum
temperature.
4. Enclosed machines are preferred, rather than open vessels, as in the
latter case steam or fumes may affect the surrounding atmosphere
and may cause loss of steam and/or volatile chemicals.
Uniform penetration and level dyeing depend upon both mechanical and
chemical factors. Level dyeing will not guaranteed by a perfect machine
unless proper precautions are taken with regard to addition of chemicals and
control of temperature. Of course, there should be adequate relative
movement of goods and liquor. Agitation is obtained either by moving the
goods through the liquor, or by forcing the liquor through the materials, or by
combination of both. Virtually no milling results when liquor is forced through
static woollen goods.
Dyeing machinery may be broadly classified into two types:
1. Batchwise dyeing machinery allowing processing in rope-form (e.g.

winches, jets, etc.) or in open width (e.g. jigger).
2. Continuous dyeing machinery aiming high production.
Continuous processing was traditionally restricted to long runs, usually

only possible for major processors. This limitation no longer applies, since
small padding units have been developed and units have been designed for
production in the range of 25 to 500 kg per hour. If such units are allied to
radio-frequency fixation and drying units (Section 7.8.3), a versatile
continuous dyeing unit of the appropriate size can be established with
significant savings in space. An important advantage of continuous
processing is that it can be a dry-to-dry operation – dry undyed material
enters at one end and dry coloured material leaves at the other.
Dyes may be applied relatively slowly in batchwise operations where the
prolonged contact between fabric and dye-liquor facilitates level dyeing.
Since the rate of dye transfer is slow, treatments even in rope-form provide
satisfactory results and thus batchwise processing is quite popular in dyeing
industries. Batchwise processes lend themselves more readily to the
treatment of relatively short lengths of fabric. Jiggers and winches are very
popular for this type of processing, among their most valuable features
being simplicity and easy operator access. For processing of synthetic
materials at high temperature, their pressurised versions were developed,
but these were never very popular. Batch machines like beam and jet dyeing
machines are especially developed for high temperature processing.
For the general transport of open-width fabric within the dyehouse, its
delivery to machines and removal from them, trucks holding the fabric in
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plaited form are used. However, the lying down will be inevitably somewhat
irregular with the possibility of creasing of the lower layers. The fabric may
also be transported in the form of wound rollers. These provide much more
compact carriage of fabric, but the full batches will be extremely heavy.
Tension-controlled take-up during batch making and controlled let-off at the
entry of machines are required.
During batch processing, the fabric changes direction in alternate
processes – the leading end becomes the tail end in the next. This is
normally of little practical significance, except that the job identification mark
is to be put on both ends. The inner layer of the batch is not accessible
unless the batch is unwound. For fully continuous processing it is necessary
to have some facility for delivering the last part of batch into a scray to allow
time for the tail end to be sewn to the leading end of the next batch or
threading fabric for production afterwards.
Though the fabric is produced and used in open width, the easiest method
of processing is in the form of a rope. Handling is easy, as is storage, and a
rope of fabric can be transported virtually any distance and in any direction
by passing it through circular guides. For rope form dyeing, the fabric is
converted to rope form at the entry of machine and the dyed fabric may be
retained in this condition for mechanical drying by centrifuge. For final drying
and further processing, the ropes are to be converted to full width and the
presence of twists may be a problem at this stage. The twists may be held
back by a beater, but it may be necessary to employ a detwister or scutcher.
The beater or detwister is used in conjunction with edge guiders, which grip
and position the selvedges of the opened fabric. Edge guiders are used at
the entry point of all open width machines for correct alignment of fabric.
The curved bars or curved roller expanders are placed before edge guiders
to minimise fabric creasing. The detwisting method is based on the fact that,
before entering the rope process, the fabric is flat. Thus, if it acquires
several twists in one direction at one position, there must be somewhere the
identical number of twists in the opposite direction. The fabric is drawn out
on a very long free run and on its return, is vigorously agitated by a rapidly
rotating beater. The twists resolve themselves, and the fabric is expanded to
full width by a series of driven scroll rollers. A modern beater-less type
detwister is available for delicate fabrics. The twists in the rope are detected
by feelers, and the rope is mechanically rotated as it passes through a
guide. Alternately, a wagon containing the fabric may be rotated for
detwisting.
Since considerable time is required for loading and unloading of materials
in batch-processing machines, it is common practice to perform a sequence
of processes (e.g. pre-treatments, rinsing, dyeing, rinsing and finishing) in
the same machine, simply by replacing one treatment liquor with the other.
On the other hand, for continuous dyeing machinery, each machine element
407
in the sequence performs a specific function. Continuous dyeing requires

the dye-liquor to be applied initially in a uniform manner throughout the
material, almost exclusively in open width by padding process, followed by
fixation in a subsequent stage.
Earlier all dyeing machines were made of wood. Earthen pots or
galvanised iron drums were also used in primitive methods of dyeing. The
dyes and chemicals are retained by these materials after dyeing affecting
successive dyeing processes. All dyeing machines are now made of
stainless steel, the normal type containing considerable amount of
chromium and nickel have the following composition:
Carbon ≤ 0.15%, Chromium ≤ 18%, Nickel ≤ 8%, Tungsten ≤ 0.5 to 1.0%.
Acid-resistant stainless steel containing Molybdenum is now widely used
for making dyeing machinery and has the following composition:
Carbon ≤ 0.07%, Chromium ≤ 18%, Nickel ≤ 8%, Molybdenum ≤ 2.5 to
4.0%.
Titanium possesses even greater resistance to chemical attack, especially
to oxidising agents. However, it is very costly and may be used in plants for
bleaching with sodium chlorite and for making impeller pumps for handling
corrosive chemicals.
The use of automation in the control of dyeing operation is now well
established. The principal benefit is the increase in productivity, reduction in
manual labour, reduction in dyeing time and fewer rejections and
reprocesses. The most important area for control is the dyeing cycle itself.
The operations, which can be controlled using level sensors and actuated
valves, are machine filling, rise of temperature, circulation of liquor or
material, flow reversal, holding time, cooling time and draining. The other
areas of control by automation are:
1. Weighting and recording of substrates.

2. Monitored weighing and controlled dispensing of dyes and chemicals.
3. Recipe storage and retrieval.
4. Computer colour formulation, colour correction or reformulation and
shade-wise sorting of lots to minimise rejection.
5. Inventory control and process management.
Automatic dispensing of dyes and chemicals directly to a particular

machine is a significant contribution to rapid response. The function of a
dispensing system is to provide precise colour and finishing recipes.
Benefits that then ensued are [3]:
1. Reduced waste of dyes, chemicals and water.

2. Quicker change over times (reduced dead time in each machine).
3. Improved control over shades.
408
4. Variable recipe procedures.

5. Exact records of consumption.
The automated machines are controlled and operated by means of a large

number of valves. The valves are usually activated by compressed air at
well-regulated and defined pressures. Compressed air may also be used for
sealing of vessel lids.
The historical steps in the development of control are as follows [4]:
1. The use of suitable activators – manually controlled functions can be

controlled by switches centralised on a control panel.
2. The use of a sequence controller to control a complete cycle.
3. The use of a logic system controller.
4. The control of various machines through a local area network by a
computer.
5. The use of microprocessor control in the individual dyeing machine.
7.2 DYEING OF LOOSE STOCK AND TOPS
Dyeing of loose cotton is expensive since the fibres are entangled during
dyeing and are torn in subsequent preparatory processes before spinning.
The effective stable length of the fibre decreases causing deterioration of
fibre quality. The natural oils and fats cannot be removed at this stage, as
their presence is necessary for better spinning. However, they offer
considerable resistance to the uniform dyeing of cotton. Waste linters in the
spinning cannot be reused as they are coloured.
However, considerable quantities of regenerated fibres, namely viscose,
are dyed in fibre form as these are blended with polyester in fibre form.
These fibres are obtained in much purer form and dyeing is easier than grey
cotton fibres. In case of synthetic fibres, the corresponding form is tow. For
dyeing, however, tow form is less preferred – it is converted to top or sliver
form before dyeing. The tops are made into balls or similar convenient
shape and packed inside package dyeing machine.
7.2.1 Batchwise Dyeing of Fibres

Dyeing of loose cotton does not always require special appliances. The
dyeing are frequently carried out in rectangular or cylindrical vats in which
material is turned by poles or forks. A rotating vertical shaft attached with
rakes may also be used. Every part of the lot is to be turned repeatedly and
the mass of the fibres is to be adequately opened to minimise matting.
Uneven dyeing caused by matting of the loose fibres is not noticeable after
carding and combing. Any unevenness of the shade is randomised during
409
the various processes in spinning. In loose fibre dyeing, the dye liquor
penetrates easily into the individual fibre. In yarn and fabric dyeing, the
penetration into individual fibres is obstructed by twist and weave
respectively.
However, circulation of dye liquor through a packed mass of fibre is more
convenient. Several machines are based on this principle. In earlier
machines (Rhode’s, Hussong’s, etc.), circulation was internal with creation
of vacuum or with the help of propeller or paddle. In next generation
machines, circulation was carried out with the help of external pumps. Two
such popular machines are of Longclose and Obermaier (Figures 7.1 and
7.2 respectively). Both contain a carrier for carrying the packed fibre and a
container for holding the dye liquor. However, Longclose carrier is of conical
shape with perforated base and cover, while that for Obermaier is a
cylindrical one with a central perforated pipe and perforated cylindrical
Fig. 7.1 Obermaier Cotton Dyeing Machine
Fig. 7.2 Longclose Cotton Dyeing Machine

410
surface. A gantry (light bridge-like overhead framework) and a travelling

hoist are necessary to lift the container in and out. Loose stock is packed as
uniformly as possible into the container in which it is retained by a lid, which
can be held down with a number of screw-threaded clamps. A flange at the
bottom of the carrier fits into seating of the container through which the dye
liquor is circulated by a centrifugal pump and the direction of flow can be
altered by a two-way valve. For Longclose machine, the flow is in the
vertical direction. The sides of the container slope inwards, so that as the
flow of the liquor pushes the mass upward, it becomes more compressed
and automatically closes up channels of least resistance to the passage of
the liquor.
In Obermaier machine, the flow is radial as the perforations are on the
side surface. For inside-out flow, the concentrated dye liquor emerging from
the central perforated tube comes into contact with a smaller amount of fibre
and weak exhausted dye liquor encounters a larger amount of fibre when it
leaves the carrier. The problem can be minimised by providing more time for
outside-in flow.
The capacity of these machines may be 100 lb. to ½ ton and the dyeing
time including washing may be about 3 hours. Having a spare carrier, which
is loaded with fibre while the other one is inside the container for dyeing, the
production can be increased.
Pegg’s machine is similar to Longclose, but the container is fixed with a
steam pipe for heating and twin propeller attached to a common shaft. The
design makes it possible to use short liquor with associated economy in use
of steam, water and chemicals.
In the above machines, dyeing can be carried out under atmospheric
pressure. However, the synthetic fibres are dyed at high temperature and
therefore, pressurised vessels are necessary. Nowadays, universal high
temperature high pressure dyeing plants are more popular as they can be
used for dyeing of any textile fibre in various physical forms, namely loose
fibre, tops, bobbins, cones and cheeses. The machines are also known as
H.T.H.P package dyeing machines.
International Wool Secretariat (IWS) has developed Lanapad R.F. (radio-
frequency) process [1] for dyeing wool in sliver form. Wool sliver is fed from
a conventional creel through a 0.5 metre wide horizontal padding mangle
and cuttled into a specially constructed insulated cart. The padding liquor
contains dye, wetting agent, thickener and a limited amount of urea. The
carts are passed into the R.F. heating chambers, where they are placed
between the upper and lower electrode plates. The fibres are heated
uniformly to 60ºC. After heating, the insulated carts are sealed to maintain
the temperature at 60ºC and left overnight. The process is completed by
washing-off in a conventional backwasher.
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7.2.2 Continuous Dyeing of Fibres and Tows

Owing to mechanical difficulties involved and non-availability of dyes, which
can be applied and fixed rapidly in satisfactory depths and provide sufficient
fastness properties, only fewer continuous dyeing machines for fibres and
yarns have been developed.
A method of continuous dyeing of gel filaments in the form of sliver from
dry-spun (i.e. by evaporation of dimethylformamide) or wet-spun
(precipitation from aqueous bath) acrylonitrile copolymer is reported [5].
After extrusion, acrylic filaments are given a wet treatment to remove the
solvent. The gel filaments are first washed at ≤ 70°C for 10 minutes,
squeezed and heat dried to residual moisture ≤ 10% and solvent ≤ 0.4%.
While the filaments are in the aqua-gel stage (water-coagulable) prior to
developing their final crystallinity and orientation, the accessibility of dye
sites in the polymer is excellent. Many modified basic dyes are suitable for
this process giving the opportunity of a full range of colours. Fastness to
light and wet treatments equals that of conventional dyeing. The application
conditions can be varied, but the temperature is maintained well below the
second order transition temperature, the dwell time is minimum and the dye
liquor is in constant circulation. Dyeing may be carried out continuously at
20-30ºC or at 60-80°C for 60 seconds in unstretched form.
The dyed tow is passed through several wash stations to remove excess
dye, after which it is subjected to normal drying and stretching. The
stretching of about 2.5-4.5 times may also be carried out in the dyebath at
60-80°C. The filaments are then subjected to dry-heat or steam fixation
followed by after-treatment, finishing and drying. The engineering behind the
application of colour at the aqua-gel stage is complex – it consists of several
successive baths with various attachments.
In spite of the disadvantage of prolonged times of fixation (15-60 minutes),
the pad-steam method has been widely adopted for dyeing of acrylic fibre
tow.
One popular machine developed by Fleissner used for dyeing viscose
staple in lap form consists of the following units [6]:
1. A hopper feeder and an opener to give a uniform lap of fibres.

2. A small capacity dyebath in which the lap is taken round under a wire
mesh cylinder completely immersed in the solution of dye (e.g. direct
dye and salt at 95°C). An internal propeller removes dye liquor from
inside the drum and feeds it back to the main dyebath. The liquor
flowing into the drum holding the fibre on its surface.
3. A squeeze mangle to which the lap is feed from the cylinder by a
conveyer belt.
412
4. Two suction drums through which a steam-air mixture is passed to

provide 2 minutes fixation period.
5. Final drums for drying and cooling.
The method, once popular for dyeing viscose staple yarn, was mostly
used for cheap tufted carpets. However, the use of direct dyes imposed a
limitation on wet fastness and the dyeing was restricted to pale colours for
carpeting.
Loose wool fibres can be continuously scoured and dyed in fibre-bowl
scouring machines. The first two bowls may be used for scouring, next two
for rinsing and the final bowl for applying milling acid dyes at pH 2.5-4 at 96-
99°C for 60-90 seconds.
A joint venture between Dawson International Ltd. and Smith Textile
Engineering Machinery Ltd. has resulted in a continuous dyeing machine
with dye fixation by R.F. energy called Fastran process. The equipment is
suitable for dyeing wool, acrylic and nylon fibres. The unit gives even dye
penetration throughout the mass with good fixation in minimum time and
good fibre quality after dyeing. The unit consists of a hopper feeder, a
conveyer to provide a uniform web to a dye padder consisting of two rollers
mounted one above the other and a horizontal spray-bar, which sprays dye
liquor or liquid dye on the web. The excess liquor is squeezed out by the
mangle due to the pneumatic pressure applied on the roller. The web
passes on a conveyer and then through a R.F. (27 MHz) unit with two 70 kW
generators. The fibres are heated to above 100ºC and dye fixation takes
place rapidly. When the fixation process is completed, the dyed fibre is
carried automatically to a conventional washing-off unit.
For worsted spinning, there has been a large demand for coloured
polyester and acrylic tows. Spin dyeing or mass coloration poses several
problems and tow dyeing may be advantageous. Considerable progress has
been made in the dyeing of polyester sliver and converter tow and fully
continuous dyeing equipment are supplied by three major European
manufacturers, i.e. Fleissner, Lima and Serracant [1].
The Serracant machine has proved popular for this purpose. Owing to
lower liquor ratio, high temperature of fixation and less thorough washing in
continuous process, a higher surface oligomer content is observed than that
associated with batchwise dyed polyester tow. Serracant Tunnel tow-dyeing
machine takes two tows and after applying the dye by padder, these are
passed through a tunnel. The tows are carried through the tunnel by a
heavy chain with horizontal spikes on each side, which support the tows. At
the entrance of the tunnel, two pairs of rollers are mounted on either side of
the chain. The tows pass between the rollers and then converge and lie on
the spikes. The arrangement is made to provide an effective seal so that
saturated steam, up to a temperature of 160°C, can be maintained inside
413
the tunnel. In fact, the first half of the 15-metres long tunnel is used for dye
fixation, while the second half is used for washing in three separate zones.
The production capacities in this machine may be up to 250 kg/h for
polyester or 300 kg/h for acrylic tow, the steam consumption is about 1
kg/kg tow.
7.3 YARN DYEING MACHINES

Yarn is dyed in hank form (i.e. endless bundle of specified length) or in the
form of packages, namely cones, cheeses or bobbins.
The first patent was issued to Obermaier for package dyeing around 1882,
whereas hank dyeing has a much longer history and probably dates back to
antiquity when yarn was simply suspended on wooden poles and turned by
hand. It is still preferred in the cottage sector as dyeing may be carried out
manually in an earthen pot or cemented tank. Hank form is very convenient
to handle and to transport. Many spinners are still equipped with hank-
reeling machines as the last operation in the spinning process. It is often
claimed that with certain products, a better quality is obtained by the hank
route. The products, normally hank dyed, are cotton doubled-yarn, hand-
knitting yarns in wool, nylon, acrylic and their blends, carpet yarns and
acrylic yarn for machine knitting.
The characteristic features of hank dyeing are [4]:
1. Hank dyed yarn has a fuller bulk and softer handle.

2. Yarn entanglement may occur.
3. Hank reeling and back-winding is costly and may generate waste.
4. Levelness may be inferior to package-dyed yarn.
5. Dyeing cost is less.
The advantages claimed for package dyeing over hank dyeing include the
following:
1. Elimination of hank reeling.

2. Waste is less.
3. Back winding is faster.
4. More controlled dyeing with better levelness and fastness.
5. Lower liquor ratio causing savings in water, effluent, energy, dyes and
chemicals.
6. Lesser floor space.
7. Less number of labour.
8. High temperature dyeing and rapid drying possible.
9. Larger control on the process makes automation easier.
414
Criticisms against package dyeing are increased cost of plant and the fear
that less bulk yarn may result. The latter fear can be minimised by
modification of the process or by changing the yarn specification. Currently,
yarns of many fibre types for a large range of end-uses can be package
dyed, namely:
1. Texturised yarns for both waving and knitting.

2. Sewing thread.
3. Singles cotton yarn.
4. Continuous filament yarn.
5. Wool or acrylic yarn for apparel and furnishing.
The features of package dyeing are:
1. Leaner yarn, but the yarn gives better fabric definition.

2. Faster back-winding and lesser waste.
3. Savings in space, energy, water, chemicals, etc.
4. Higher levelness and reproducibility.
7.3.1 Hank Dyeing Machines

For many centuries, hank dyeing is being carried out in primitive equipment
in which the yarn hanks are suspended on wooden poles in a rectangular
wooden vat. The sticks are moved from end to end of the vat to give some
degree of agitation and at the same time the hanks are turned manually to
dye the portion of hank in contact with the sticks. The system has been
gradually mechanised – wood has been replaced by metal like cast iron and
stainless steel.
The traditional Hussong hank dyeing machine is shown in Figure 7.3. It
consists of a frame (F) carrying sticks or poles on which hanks (H) are hung
P I
S
Fig. 7.3 Hussong Hank Dyeing Machine

415
and which can be lowered by a hoist on a gantry, into the rectangular vessel
containing the dye liquor. The liquor is circulated by means of a reversible
impeller (I), which is separated from the hanks by a separator and is located
at one side of the dye vessel. There is an adjustable weir at the bottom of
the impeller compartment, which regulates the volume of flow. A false
bottom (grid) (P) is provided at the bottom. The holes in the grid are
arranged in such a way that there are more holes at the remote end of the
impeller than adjacent to it to distribute the liquor flow uniformly. The
packing of the hanks should be denser at ends than in the middle as the
circulation is more powerful at the ends. The impeller can be rotated in
opposite directions alternately so that the direction of liquor circulation can
be reversed. The upward direction of circulation is maintained during greater
portion of the dyeing cycle. During this period, the hanks are pressed
against the perforated top of the pole frame, and the liquor by penetrating
through the hanks, is compelled to come into intimate contact with every
part of the hank. Heating is by open or closed steam pipes (S), which are
situated below the perforated false bottom. In modern machines, the yarn is
suspended from V-shaped sticks with perforations to prevent stick marking.
Even so, with some qualities, the yarn is turned on the sticks manually
halfway through the dyeing process.
In one-stick machine of the Hussong type, the direction of flow is mainly
up through the hanks, which causes the yarn to form a dense pack, which
impedes the liquor flow. This causes uneven dyeing especially with dyes of
high fastness and poor levelling properties. The use of a second stick at the
bottom of the hanks prevents the mass from being lifted by the flow and
allows a greater rate of flow to be used without severe entanglement. In
such machines, the distance between the sticks must be adjusted according
to the hank length, so that the yarn is not stretched tight during dyeing with
occurrence of consequent stick mark. A gap of about 4 cm is provided
between the bottom stick and the hank. For high-bulk yarns, allowance must
be made for the shrinkage to occur. Two-stick machines, capable of
operating at temperatures above 100°C, have also been developed. The
machine is capable of very high output depending on its size. The hank
carrier may have several racks accommodating a larger number of hanks.
This type of machine is made by several manufactures and is still widely
used for dyeing cotton hanks and in the carpet industry. A perpetual problem
of dyeing in this type of machine is that the hanks at the outside of the
carrier frame are often in direct contact with the sides of the dyebath. Due to
inadequate flow at the sides of the vessel, rapid rise in temperature is not
possible and poor levelness of dyeing may result.
The inlet and outlet of water should be beneath the false bottom so that
filling and emptying should cause minimum disturbance to the arrangement
of hanks. The liquor ratios in these machines are very high − generally
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around 1:30. Power consumption is low, the electric motor driving the
propellers, usually being 1-2 kW. The dye vessel must be free from rough
places or projections. The rectangular shape of the vessel does not facilitate
pressurised high temperature dyeing. A few machines have been adopted to
operate at 105-108°C for level dyeing of acrylic fibres with basic dyes.
An improvement on the conventional Hussong machine is the Pegg
Pulsator hank dyeing machine. The machine is more compact and is
claimed to provide an improved quality yarn. In the Pulsator, the hanks are
packed more closely so that upward flow is not needed to create a tight
mass of homogeneous density. The yarn is suspended from poles in the
usual manner, but is relatively tightly packed so that stainless steel end
plates are required to keep the mass together. In Pulsator mechanism, the
flow of liquor is automatically interrupted for 5 to 10 seconds every 2½
minutes, thereby giving a pulsating movement, which raises the hanks off
the sticks and prevents stick-marks [4]. There is no false bottom, the steam
pipe is placed in the small end section and the impeller shaft is horizontal.
The penetration is assisted by an automatically controlled unidirectional
pulsating flow. The flow is downward the whole time, so that the hanks
remain stationary and stretched at full length throughout the dyeing cycle,
resulting in better quality of yarn and less problem during winding. Upward
flow can also be used, if required. Due to its compact nature, the liquor ratio
in such a machine is much lower (1:10 as opposed to 1:20 in conventional
hank dyeing machine) with consequent savings in steam, water and
chemical costs. Machines ranging from 5 to 600 kg capacity are available
and machine coupling is possible.
The improved Pegg GSH hank dyeing machine is especially designed for
high-bulk acrylic and various types of hand-knitted yarns as it provides
better loftiness and acceptable uniformity of shade. A horizontal propeller
shaft circulates liquor in one direction only, up a narrow central
compartment, which forms part of the frame, and through the top hank poles
down through the hanks, returning to the propeller. The hanks are lifted
slightly off the poles to prevent stick-marks. This machine gives a gentle, but
uniform, liquor flow through the yarn pack, with minimum entanglement,
eliminates temperature differences through the pack and prevents glazing
and flattening of the yarn. The hank sticks are readily adjustable by means
of a central wheel on top of the frame allowing for a range of hank reel
lengths as well as giving the same liquor ratio for different hank lengths.
Dyeing time may be reduced because of better accessibility of the yarn to
the liquor. The circulation through hank poles allows quicker cooling of the
yarn when the dyeing is finished. This is beneficial for the synthetic fibres,
particularly the polyacrylonitriles.
In rotating-stick machines, the hanks are suspended from rods made of
porcelain or similar material having a smooth surface. These horizontal rods
417
are placed over rectangular vessel containing dye liquor. The rods may have
unidirectional or auto-reversal rotation. The suspended hanks may also be
provided with a reciprocating vertical motion. This type of machine is widely
used for dyeing cotton and rayon hanks.
In Clauder-Weldon machine, two parallel wheels are joined together by a
central axle. Replaceable poles, resting in slots of these wheels, one set
being near the centre and the other at the periphery, connect the wheels.
The hanks are placed on these two sets of poles. The entire assembly is
placed in a dye vessel keeping the wheels vertically. The assembly is slowly
rotated so that the hanks are alternately dipped into and removed from the
liquor. To prevent stick-marks, the poles are automatically given a partial
turning after each revolution of the wheels. The machine is not suitable for
vat and sulphur dyeing as the hanks are frequently exposed to the air during
dyeing [7].
Mezzera s.p.a, of Milan, Italy, developed a special hank dyeing machine,
model TMB (Figure 7.4) for dyeing of very delicate articles such as wool,
viscose, silk and finest cotton yarns including mercerised yarns. The
machine incorporates features that ensure preservation of yarn quality as
well as economy of production. The machine may have two to twenty
stainless steel supporting arms (A) on which the hanks (H) are placed. A
unique feature is that the hanks are never immersed in the dyeing liquor.
Each of the arms consists of a tube perforated on the upper side from which
liquor flows. Plates at the end of tube prevent the hanks from falling off the
A R
Fig. 7.4 Mezzera Model TMB Hank Dyeing Machine

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arms. A hank displacing rod (R) rotates about the perforated tube to lift and
move the hanks so that the point of suspension continuously changes,
thereby ensuring uniform dyeing of the whole hank. A timer adjusts the
interval between rotations of the rod according to the type of fibre and dye.
Liquor stops flowing while the rod rotates to avoid wool felting, silk fraying or
fibre entanglement. A three-speed pump sucks liquor from a specially
shaped vat to minimise the liquor ratio and distribute it through the arms.
The liquor then falls down into vat. In some other models, the rod is
eliminated and the perforated tube is half-rotated on either side at some
interval.
7.3.2 Package Dyeing Machines

Yarn is wound into suitable packages (e.g. cones, cheeses), mounted onto
perforated spindles and then dyeing is carried out by forcing liquor through
the package. Earlier the machines were known as pressure dyeing
machines, but the nomenclature is no longer recommended as it leads to
confusion with pressurised machines for high temperature. The first
package-dyeing machine was patented by Otto Obermaier in 1882. The
earlier machines were open to atmosphere with unidirectional flow (in to out)
of liquor through the package. Later better levelness was achieved by
enclosing the vessel and by frequently reversing the direction of the flow of
liquor. Virtually all modern package-dyeing machines are pressurised and
capable of operating at temperatures up to 135°C.
Hank reeling from ring bobbin is a comparatively expensive process, the
plant requires much space, and the yarn must be wound onto a bobbin,
cone, or pirn at a later stage. The second winding from hank after dyeing is
also slow and labour-intensive. On the other hand, a single yarn can be
wound directly from a cop or ring tube onto a cheese, dyed in this form and
then rewound with high-speed machine onto a cone. The spinner, before
delivery to the dyer, conveniently cones a doubled yarn. It is more
economical for the spinner to cone the yarn than to reel it into hanks.
For dyeing, the yarn is to be wound on perforated stainless steel cones or
cheese formers. The dyers prefer cheese-form, as they tend to give level
dyeing because of their uniform diameter. The success of package dyeing,
in terms of both levelness and yarn quality, is greatly influenced by the
degree of care taken in the preparation of the yarn packages. A wide range
of designs and materials are being used as supporting media for packages –
perforated cones, springs, rockets, plastic tubes and non-woven fabric
centres have all found favour. With most stainless steel formers, cost can be
a serious problem. Plastic formers are less expensive, but have a shorter life
and are heavily stained by certain dyes causing contamination. The
patented Tigges springs are used for high-bulk acrylic yarn, since they allow
419
a certain amount of shrinkage to occur in the package due to compression

of spring in both width and length. Texturised yarns are frequently wrapped
in stockinet for dyeing and are loaded into annular baskets of the type used
for loose stock, to prevent separation and breaking of filaments. The spiral-
spring type of cheese holder is covered with a sheet of porous paper to
manipulate during winding and makes the removal of unwound yarn easier.
The winding machine should yield soft cheeses so that there is limited
obstruction to the flow of liquor. There is poor penetration near the shoulders
of a cheese – with special attachments, it is possible to make softer winding
at these critical points.
All yarn packages for dyeing must provide:
1. Adequate stability during handling while putting in and taking out from
the machine spindle.
2. It should withstand the change in temperature of the flowing liquor and
pressure during reversal of flow.
3. All packages must accommodate a small amount of shrinkage in
some yarn and the effect of fibre swelling when wetted out.
4. The wound yarn should not be trapped, otherwise the back-winding off
the packages will be disturbed.
5. Fairly sufficient resistance to liquor flow at different temperature and
pressure − both within and between the packages. High porous area
will permit excessive flow causing relative starvation of its neighbours
on the same spindle. Packages of high resistance to flow will
inevitably suffer a shortage of liquor and get unevenly dyed.
Non-textured nylon or polyester filaments are relaxed before winding on

package formers, otherwise shrinkage during dyeing will cause damage to
the yarn and crush the package former. The winding onto radially
compressible formers is not very successful.
Cheeses may be wound on rigid formers (BS 2547/7:1979, ISO 3914) or
longitudinally compressible formers. The rigid formers are commonly 55 mm
in internal diameter, 170 mm long with holes commencing 16 mm from each
end. For in-house repeated use, they are made of stainless steel and have
indefinite life. For external work, the tubes are made from impregnated
paper or plastic and are generally for one dyeing operation. Compressible
formers are of similar size, but are made of stainless steel wire interlacing a
helix of coarser spring or of plastic extruded in a criss-cross pattern. These
formers are lengthways compressible up to 30% without appreciable
increase in diameter. Only a slight degree of radial compression is permitted
by the open structure. Stainless steel springs have long life. Plastic formers
are cheaper, but are susceptible to staining under adverse conditions.
During winding, linear speed should be constant in order to maintain uniform
420
tension in the yarn. Surface-driven systems are widely used for staple yarns.
Well-formed cheeses usually need sealing plates only at the top and bottom
of the spindle. The ends of adjacent cheeses should, when pressed firmly
together, form an adequate seal. Wherever possible, a cotton stockinette or
paper filter may be provided between the yarn and the former, which acts as
a filter. Recently bi-conical (BI-KO) polypropylene formers, reinforced with
glass-fibre are developed which may be interlocked to allow press-packing.
Cones facilitate back-winding of yarn after dyeing. It is generally 17 cm
/
long having half-angle of 4°20 and tapering down from 81 cm to 55 mm in
diameter (BS 2547/5:1978). Cone formers are also made from stainless
steel, plastic or impregnated paper. Cones are generally used for staple
fibre yarns as they stick together better under moderate tension than non-
textured filament yarns. Spun rayon yarns swell on wetting and are easier to
back-wind from cones than cheeses. When mounted on spindles, adjacent
cones are separated by circular plates to restrict liquor losses through the
base of each cone. Though the cone packages are wound with the external
yarn surface parallel to the cone formers, the liquor flow is not uniform as
with parallel-sided cheeses. The cones also do not accept lengthways
compression when mounted on spindles.
Cakes, the parallel-sided packages without centres, were earlier popular
for dyeing viscose filament yarn and recently revived for textured synthetic
filaments such as high-bulk acrylic yarns. After winding the yarn on former,
the latter is removed when the inner yarn collapses and the dyeing is carried
out in such relaxed condition to give greater stretch properties. The dyeing
in this form results in lower liquor ratio, rapid dyeing, rapid back winding with
less wastage.
Muffs are very soft, open wound packages, first winding stretch yarns onto
a frame and then after removal from frame, the yarn is allowed to shrink.
The packages are wound to give a honeycomb structure and lease strings
are inserted to preserve back winding. Muffs may be mounted on spindles
and compressed 50% or more in length.
Rockets are fairly large packages of staple yarns which could be used
directly on circular knitting machines. The winding is done on a conical base
mounted on a spindle. The packages are built vertically to a height of 25 cm
or more. These parallel-sided packages with conical top, fit one above
another and perform excellently during unwinding. However, the rockets are
fragile and are not amenable to centrifuging for removal of excess water
after dyeing.
Pack-dyeing refers to the dyeing of loose fibres, slubbing and continuous
tow when suitably packed in an annular basket or cage with perforated
sides. The same package dyeing machines used for cones, cheeses, etc.
can be used. The bottom of the cage is firmly held to the base of the vessel
and a top plate fitted to prevent the dye liquor from flowing over the
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substrate. The cage is lifted in and out of the vessel by an overhead crane.
When loading staple fibre, a bottom plate with lifting chains may be put in
the cage so that the fibre, after dyeing, can be lifted out and conveyed to the
hydro-extractor or dryer without lifting the cage. The fibres may be packed
into the cage manually or mechanically. The packing should be uniform. The
fibres are wetted and then compressed by screwing the top plate. The pack
density should be around 300 g/l for loose fibres or even 480 g/l in the case
of acrylic continuous tow. The insertion of twists during loading continuous
tow may be avoided by putting the cage on a slowly rotating turn-table while
the tow is run through a light nip, sprayed with hot water and mechanically
stamped to consolidate the pack. After dyeing, the tow is slowly unwound
while the cage is rotating in the opposite direction.
The cages can also be used for dyeing hanks, cakes or muffs of yarn, or
for dyeing terry towelling plaited in rope form.
A more recent innovation, bale dyeing [1], involves the fibres in the form
the original bale from the supplier of raw wool or cotton, or from the fibre
manufacturer. These bales are placed directly in a specially constructed
cage, which is designed to hold four bales. The cage is placed in a
conventional dye kier and dyeing is carried as usual. Following dyeing, the
bales are hydroextracted or vacuum-extracted to remove excess moisture.
The system is highly economical for a new installation, which processes a
limited product range. The stages of bell opening, dye-kier loading and final
packing stages are eliminated. It is claimed to give better yarn qualities, as
the handling of the fibre is least. The disadvantage is that new cages of
different dimensions are to be purchased as bale sizes vary widely. In some
cases, kier sizes of the dyeing machines may not accommodate bales. The
fibres of restricted fineness (denier i.e. weight of 9,000 metres of filament or
yarn in grams) can be processed in this way. Due to the higher density of
packing, exhaustion rates may be restricted to 1 to 1.5% per minute.
The basic configurations of package dyeing machines may be of the
following four types:
1. Rectangular dyeing machines, originally developed for hank dyeing,

but further improved to accommodate package frames. These are
usually horizontal spindle machines. Pegg GSH hank dyeing machine
has been improved by fitting it with larger pumps to accommodate
packages.
2. Horizontal spindle package dyeing machines, such as beam dyeing
machines. These side-loading machines are now obsolete.
3. Circular horizontal spindle machines, which are claimed to take 10%
higher load. However, such types of machines have little advantage
over vertical spindle machines.
422
4. Circular vertical spindle machines, which are probably the most

expensive, but also the most versatile type of machine.
A vertical spindle machine, popularly known as H.T.H.P. package dyeing

machine, is shown in Figure 7.5(a). The change from rectangular to circular
shape allows vessels to be more readily pressurised for dyeing above
100°C. Expansion
Space for
loading
Tank
carriers
Secondary
Pump
Circulation
Non-return Pump
Valve Drainage
Fig. 7.5(a) H.T.H.P Package Dyeing Machine

The pressure vessel is cylindrical with domed ends, the upper being the lid
or cover, which is securely locked by a series of bolts in older machines or
by a sliding ring or similar quick-locking device. The lid of a large-diameter
machine is heavy and is raised by a pneumatically or hydraulically operated
cylinder at the back of the machine. The machine capacity may vary from
100 kg to 1,000 kg. Machine diameters go up to just over 2 metres and the
vessel height is usually similar. The overall height of the machine is
increased by the pump, fitted immediately below the main vessel. The height
of the machine and the need to load it by an overhead travelling crane
necessitates either plenty of headroom or setting the machine in a pit below
the shop-floor level. Where the machines are mounted at ground level, a
raised platform with surrounding safety rail is required. A 5-ton hoist is
usually sufficient for a machine of 2-metre diameter.
The cheeses, cones or other packages are loaded onto the perforated
vertical spindles, which drop into seating in the package dyeing machine.
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The spindles are up to about 125 cm long and usually circular in cross-
section (7-cm diameter), although some have a Y cross-section to permit
easier longitudinal flow of dye liquor. Larger diameter spindles favour level
dyeing. The number of packages (cones/cheeses) per spindle is usually
around 8-10. The column is pressed down firmly by mechanical devices and
the end-cap is screwed on tightly to complete the seal. Packages of
hydrophilic fibres should be allowed time to wet out and swell before
pressure is applied. As some textured yarn packages tend to shrink when
wetted for the first time, it may be necessary to wet out the loaded packages
for 5 min, and then additional packages are put into each column to maintain
uniform permeability. Compressing the packages lengthways not only
provides a good seal but also tends to compact some areas of low density
and high permeability, thus providing more uniform liquor flow along the
column. Non-textured continuous-filament yarns are sometimes wound on
rigid formers, which either interlock or are fitted with spacers to provide a
seal against excessive liquor flow. Where high rates of liquor flow are
required, long spindles present problems of pressure drop along the column.
The spindles are screwed firmly into holes set in a frame called carrier with a
circular hollow base and a centre pillar with an eye at the top for lifting. At
the centre bottom of the carrier frame, is an inlet for dye liquor and this inlet
fits onto the pump discharge when the frame is lowered to the bottom of the
dye vessel. There may be separate carriers for cones/cheeses, tops and
loose stock as shown in Figure 7.5 (b).
Cones/cheeses Tops Loose

Fibres
Fig. 7.5 (b) Carriers for Package Dyeing
The cylindrical dyeing vessel is provided with a hinged lid, which when
closed, makes a pressure resisting seal. Before the lid is clamped down, the
carrier carrying the cones, cheeses, tops or loose fibres is lowered into
position, when it rests on a seating which is connected to the circulating
pump below. The liquor is forced through the perforated pipe on which the
packages are mounted. Under working conditions, the pressurised vessel
must be completely filled with dye liquor. An overflow pipe is connected from
424
the side of the vessel to the expansion tank so that extra water can be taken
out of the vessel to accommodate for the increase in volume, which
accompanies the rise in temperature. At the beginning the flow should
always be from outside to inside, and after a few minutes the intermittent
reversal may set into action.
The machine is connected with a circulating pump. When the vessel is
open to atmosphere, circulation is possible only from inside to outside, i.e.
the liquor moves from the interior of the carrier through yarn package and
comes into the vessel where from it returns back to the pump. The
circulation from outside to inside needs suction, which cannot be done
successfully by the circulation pump. The penetration will be obviously better
if the flow is reversed periodically. In order to have a two-way flow, the
vessel must be closed and capable of withstanding pressure of up to 20
lb./in². Development in package dyeing machine has resulted in
improvements in pump design and spindle geometry, with benefits of
circulation. The conventional machines have a flow rate of 30 to 45 litres per
kilogram per minute, with complete circulation every 30 seconds. The
machines with flow rate of 50 to 150 l/kg/min, with a complete circulation
every sixth second, are considered as rapid dyeing machines. These will
allow the temperature to rise at a rate of 8 to 16°C per minute, as compared
to 2 to 3°C per minute in conventional machines. The main pump is fitted to
the bottom of the vessel, usually as close to the centre as possible, in order
to minimise frictional losses in flow. The pumps in the earlier machines had
the problem of loosing efficiency at temperatures nearing boil due to
cavitation or formation of bubbles on the reverse side of the blade where the
pressure is low. The problem was minimised by placing the pump at the
base of machine so that maximum amount of liquor is just above the pump.
Secondly, the formation of bubbles can be prevented by making the whole
system pressurised.
In the ideal system, it can be shown [6] that
KPN π D
F= (7.1)
VT
where F = rate of flow of liquor per unit area
K = constant
P = pressure difference between inside and outside of the package
N = number of channels per unit cross-section
D = diameter of channels per unit cross-section
V = viscosity of liquor
T = wall thickness of the package
It is assumed that the package is stable. However, at high pumping
pressure, the yarns are flattened, thereby reducing the diameter of the
channels and consequently the rate of flow is reduced. A decrease in
viscosity of liquor on heating increases the rate of flow. Package
425
permeability varies tremendously with the type of yarn. For non-textured

yarns, the package permeability depends on the following factors:
1. Yarn or filament fineness – permeability increases with increasing

denier.
2. Yarn twist – low twist can adopt a flat rather than rounded shape, and
gives packages of low permeability.
3. Yarn traverse during winding – a low rate of traverse gives denser
package with low permeability.
4. Yarn tension during winding – higher tension during winding gives
denser and harder package with lower permeability.
5. Higher swelling of yarn reduces permeability.
6. With texturised yarns package, permeability is of a very higher order
and usually insensitive to denier, twist, etc.
Package densities are usually in the range of 0.25-0.5 kg/l for staple
yarns. The lower densities in this range allow adequate liquor flow and
uniform dyeing, whereas higher densities benefit in terms of machine
loading, productivity and economy due to low liquor ratio.
The pumps used are either axial flow or centrifugal type; the merits-
demerits have been summarised by Horn [8]. Axial pumps can be easily
reversed by simply reversing the motor, but the stop-start system fails on
frequent reversal. For efficient operation, the propeller of the axial pump
must be slightly smaller than the diameter of the surrounding tube. However,
such a narrow gap is susceptible to fouling with floating pieces of yarns, etc.
Centrifugal pumps revolve in one direction. The liquor is forced outwards
from the centre into pairs of ducts or ports and a four-way valve connecting
them is moved through an angle for reversal of flow. A reliable sealing
mechanism is required for distribution of dye-liquor at high temperature. The
pumps are now designed to combine the merits of both axial and centrifugal
pumps. The pump must produce sufficient pressure to overcome the
resistance to liquor flow and must have adequate capacity to maintain the
volume of flow. The difference in pressure inside the spindle and in the
dyebath may vary from 25 to 85 kPa [6].
The dyeing of synthetic fibre is carried out under pressure above 100°C.
For the purpose, a secondary pump, usually centrifugal type, is brought into
operation to create a high static pressure (about 275-310 kPa) in the dye
vessel at high temperature. A constant elevated pressure cannot be
maintained satisfactorily by the main pump alone. The pressure will vary
according to the density of the package, the speed of motor, etc. The
secondary pump maintains a constant static pressure by forcing dye liquor
from the expansion tank into the dye vessel. This pump is also used to add
dyes and auxiliaries to the dye bath.
426
Conventionally, for heating the liquor, high-pressure steam is passed

through horizontal coils located in the lower part of the vessel. A large
surface area is thus, available for heat exchange. The system is compact
and heat loss is minimised. Though accessibility is poor, the internal coils
are to be regularly checked for deposition of dyes and oligomers. Otherwise
crack marks may form. The coils are subjected to severe thermal and
mechanical shocks when steam is first applied in the cold bath or cold water
is first fed through the heated coils. Some machines have separate heating
and cooling coils.
In conventional package dyeing machines, the material to liquor ratio is
around 1:10 when fully loaded. In partially flooded state, the liquor covers all
the packages but does not fill the dome of the machines causing reduction
of the ratio even at 1:3. However, obviously only in-to-out flow through the
packages can be used and the packages must be sufficiently rigid to avoid
distortion.
Many package-dyeing machines are fitted with a small external pot
designed to take one package, which may be used as a sample package for
monitoring the progress of dyeing.
Package dyeing is costly when compared with other forms of dyeing and
much of this extra cost must be associated with transferring yarn from one
form to another which adds no intrinsic value to the end product. A study on
acrylic yarn showed that continuous tow dyeing is approximately 50%
cheaper than yarn dyeing. Efforts have been made to minimise package-
dyeing costs by maximising dye-lot size and pressure packing techniques.
The main advantages of all packages used for textured yarn is that they are
prepared on the texturing machine and, therefore, eliminate one winding
process for the dyer. Spun yarns have conventionally been delivered to the
package dyer on perforated cones ready for dyeing or on paper cones or
tubes, which should be rewound to give the correct packages for dyeing.
The former method is economical, but the dyers have little control on the
package densities produced. Moreover, cone form requires expensive
spacing devices and even with these, cones can slip on dyeing machine
spindles giving rise to channelling of liquor and uneven dyeing. The machine
load is less and flow properties are poor in cone form as compared to
parallel-sided packages. The principle advantage claimed for cone-dyeing
methods is that the dyeing package is prepared by the spinner and this
constitutes the delivery package to the fabric producer, thereby eliminating
two winding operations.
7.3.3 Warp Dyeing Machines

Sometimes warp yarns are dyed for weaving with weft as in the case of
denim fabrics. Warp yarns can be dyed in two forms – beam and rope form.
427
In beam dyeing machine, a set of about 9,000 metres (40-50 kgs) long
continuous warp yarns are wound parallel to each other on perforated beam,
usually 15 cm in diameter. Steel flanges are fitted at the precise width before
winding. The beam barrel is wrapped with non-absorbent, non-woven fabric
to form a good bed for the warp yarn, to permit diffusion from the
perforations in the beam barrel and to serve as a filter. The warp must be
provided with lease rods. A slight traverse motion is desirable in order to
provide a uniform build-up with adequate porosity. There is a marked
tendency of yarn for lengthways shrinkage producing high pressure on the
inner layers. The warp tension during winding is, therefore, to be carefully
controlled. Fibre swelling on wetting may cause sideways pressure and the
flanges should be capable to withstand such pressure. The thickness of the
beam depends on the count of yarn. The finer the yarn, thinner is the
package with greater density of winding and consequently, the resistance to
flow is greater. With coarser yarns, the winding density is lower and better is
the dyeability. For uniform winding density, automatic tension control
devices are to be employed during winding.
Warp beams are normally dyed in the vertical position. Usually four beams
are secured at the top of a carrier, the whole assembly is placed into the dye
vessel, and the dye liquor is forced through the beam mostly with in-to-out
flow.
Horizontal beam dyeing machines, such as Zittau beam dyeing machine,
are also available. It consists of a cylindrical vessel, similar to horizontal kier,
with a hinged lid at one end. The beam is carried on rails into the dye vessel
and when in position, the conical end of the beam makes a telescopic joint
with a suitable device by which the liquor can be forced in or out of the
beam.
As with other package dyeing machines, thorough after-treatments like
soaping is not possible. Warp beams are lightly scoured prior to dyeing.
Stripping, as required in the case of faulty dyeing, is not possible to carryout
evenly. Hence, uneven dyeing is usually covered by further dyeing in deeper
shades. The material to liquor ratio is about 1:7 to 1:10.
In rope form, a bundle of warp yarn (say 378 x 18,000 metres) is passed
through several dyeing compartments or units. In each unit, the yarns in
rope form are guided through the dyebath by immersed guide rollers
arranged in such a way that the warps pass up and down through the liquor.
Before leaving the unit, they pass through rubber squeezing rollers to aid
penetration and level dyeing. The first unit may contain wetting agent only,
followed by dye liquor in subsequent units followed by oxidation (if,
necessary), soaping, rinsing, etc. Because of short time of treatment, only
highly substantive dyes should be used and liquor of high concentration
should be continuously fed. For mixed shades, dyes of similar substantivity
should be used. Vat dyes can be conveniently dyed in this machine. For
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pale shades, the warps may be scoured and bleached separately in a kier
as these processes cannot be successfully carried out in the machine, as
the time of treatment is very short.
The rope of yarn may also be wound into a ball before and after dyeing. A
number of such balls (say 12) can be dyed at a time, depending on the size
of the dyeing machine. Such dyeing is popular in knitting trade (socks,
stockings, hosiery, etc.). The uniformity in dyeing from end to end depends
on the skill and judgement of the dyer in feeding pre-dissolved dye.
7.3.4 Continuous Dyeing of Yarns

Though the dyeing of texturised polyester is usually done in package form, a
novel process for combined continuous dyeing and false-twist texturising of
polyester or nylon filament is reported with a modified false-twist texturing
unit [5]. The unit has a padding trough for application of dye solution along
with a hydrotropic chemical such as an amide, alcohol, phenol or lactone
and a thickener. Hydroextraction and drying are critical because of the risk
of migration.
The traditional method of dyeing warps for denim using indigo has
declined because the equipment is capital-intensive and less versatile. The
best known continuous dyeing range is that of Kleinwefers consisting of
padding mangles, washing range and cylinder dryer and the sequence is:
Wetting Æ Rinsing Æ Indigo dye application Æ Rinsing Æ Softening Æ

Drying.
One bath pad-steam process, similar to fabric dyeing, can be used to dye
warps with sulphur dyes for denim. Figure 7.6 shows a pad-steam range for
the purpose in which the warp threads are first padded with sulphur dyes,
steamed, oxidised, dried on cylinder, sized and again dried on a second
cylinder range. The stages shown by numbers in the figure are: (1) padding,
(2) steaming, (3) water sealing,(4) rinsing, (5) oxidising, (6) rinsing, (7)
drying, (8) sizing, (9) drying.
1 2 3 4 5 6 7 8 9
Fig. 7.6 Pad-steam Dyeing of Cotton Warps with Sulphur Dyes

Another possibility of dyeing denim without indigo is the combined dyeing
with azoic colours (Rapidozol N dyes) and sizing. The stabilised azoic
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compositions may be applied in a single bath with sizes or best applied from
two separate baths as shown in Figure 7.7. The stages shown in the figure
by numbers are: (1) padding with azoic colours, (2) drying, (3) sizing and
development, (4) final drying, (5) cooling chamber, (6) beaming.
1 2 3 4 5 6
Fig. 7.7 Continuous Range for Two-bath Dyeing and Sizing of Cotton Warp
7.4 FABRIC DYEING MACHINES
Of all forms of cotton materials, the fabric is the one, which is dyed to a
much larger extent than in any other form. The fabrics are woven or knitted
in various machines in pieces of short length and these pieces are sewn
together to make a continuous length of fabric. The dyeing may be carried
out in rope form or in open width. The machines in which dyeing is carried
out in open width are jigger and padding mangles, where as in winch and jet
dyeing machines, dyeing is in rope form. The padding machines are used
for continuous dyeing, whereas most of the other machines are batch
machines, i.e. they handle a finite length of fabric at a time.
7.4.1 Jiggers
The jig or jigger is one of the oldest type of machine for dyeing woven
fabrics which must not be creased during dyeing, e.g. most taffetas, satins,
poplins, ducks and suiting. Jigs have been tried for certain types of knitted
fabrics, e.g. nylon shirting, but with limited success. This is most suitable for
materials in which the dyes do not exhaust well as the machine operates
with low volume of liquor (i.e. low material to liquor ratio of 1:5 to 1:6). In
machines of this type, the fabric is passed to-and-fro through the dye-liquor
from one batch roller to another.
In the simplest form (Figure 5.4), the jigger consists of a V-shaped trough
(100 to 150 gallon capacity) with two rollers called draw rollers fitted above
it. There is an additional roller, which may be placed on the fabric-wound
roller. The purpose of this roller is to squeeze out liquor from the fabric at the
end of the treatment. The rollers may be made of stainless steel or ebonite.
Fully immersed guide rollers are provided in the trough. The fabric in open-
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width is unwound from one of the draw rollers, passes into the liquor
contained in the trough with the help of guide rollers and wound on the other
draw roller. When the second roller is full, the direction of fabric movement is
reversed and the fabric is rewound on the first roller. The take-up roller is
positively driven by operating a lever to engage the clutch attached to the
roller to the central clutch, run by a motor. After complete winding of fabric
on the take-up roller, the clutch attached to it is disengaged by operating the
lever in the opposite direction. The central clutch is then engaged with the
clutch of the other roller from which the fabric is unwound and will now act
as take-up roller. This reversal of motion may be manual or automatic. In
modern jigs, the length of run is set after the first passage through the
machine and thereafter the direction of travel is reversed automatically. Both
take-up and let-off rollers are now driven, thereby reducing lengthways
tension on the fabric. The manufacturers have developed various devices
for driving the rollers to achieve fairly constant fabric speed (about 40-100
m/min.) at a moderate tension. Although many fabrics are adversely affected
by substantial warp-ways tension under hot wet condition, some fabrics,
particularly heavy cottons can withstand tension as high as 100 kg [6].
Most modern jiggers have rollers 1.8 or 2.0 metres long. On old jiggers,
roll lengths of 500 or 1,000 metres were customary, but modern ones can
accommodate rolls of up to 1 metre diameter, representing about
5,000 metres light-weight taffeta fabric. Old jigs with small rolls had relatively
small surface and liquor capacity of 200 litres. These were advantageous for
vat dyeing, as the chances of oxidation were less. The demand for high
capacity necessitates bigger diameter rolls with liquor capacity up to
750 litres. Jigs provide some degree of freedom to vary the depth of filling.
This gives scope to accommodate variations in fabric load to maintain
approximately the same liquor ratios.
When the whole fabric passes from one roller to the other, the passage is
called one end or turn. A number of ends are given during dyeing when the
fabric moves through the trough several times. The number of ends given
depends on several factors such as size of fabric batch or the time required
for one end (usually 10 to 15 minutes) and the depth of shade required.
On primitive jigs, the draw rollers are driven alternately, a weighted strap
being used to apply tension to the unwinding roll. As the rotational speed or
angular velocity of take-up roller is constant, the fabric starts at a low linear
speed, which increases as the diameter and circumference of the roll built-
up. For constant linear velocity, the applied tension should be low at the
beginning and high nearing completion of winding. At speed in excess of
around 110 m/min, on small diameter rolls, the dye liquor may be thrown out
of the rotating roll by centrifugal force. As the warp-ways tension is
considerable, lengthways extension may be as high as 5%. However, it
leads to lengthways shrinkage of the fabric in washing, lowering of warp
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crimp and reduction of fabric width. In the primitive jiggers, a brake

arrangement is provided. A leather strap is fixed at one end on the side of
the jigger and is loaded with a dead weight at its free end. The strap runs
over a pulley attached to the shaft of the let-off roller acting as a brake and
thus the tension and speed of the fabric are maintained constant. After
completion of a turn or end, the strap is lifted and placed on the other roller,
which now acts as let-off after reversal of the drive. In another type of jigger,
a steel strap passes over both the pulleys and with the help of a sliding
heavy weight, brake can be applied to the let-off roller. The modern jiggers
provide a variety of controls. For example, the direction of fabric movement
can be changed after a pre-set length and the number of ends and fabric
tension can be varied. The speed may be varied by a differential driving
mechanism so that the fabric passes through the dyebath at a uniform
speed irrespective of the varying diameter of the fabric roll. The jigger may
be provided with time switch to reverse the direction of fabric movement
automatically after each turn. The expanders may be provided to keep the
fabric free from creases.
For immersion of the complete length of fabric to be dyed in the jigger
trough, 4-5 metres of cheap end-fabric are sewn to each end of the roll. The
ends of the fabric are trimmed straight across the width and then tail ends
are sewn fitting the ends as close as possible to minimise overlapping. It is
essential that all the fabric in the roll should be of same width. The fabric
should be wound on roller with coincident selvedges, i.e. no part of selvedge
should come out of the roll, as that portion will be dyed differently. With vat
dyes, the portion will be quickly oxidised and pick up more colour in the next
turn. On most jiggers, one of the rollers can be traversed to a limited extent
to assist in straightening a roll. Some jiggers have the facility to traverse
over a small range automatically to minimise selvedge built-up on certain
varieties of fabric. For loading, the leading end of the fabric is threaded
under the two free-running rollers located at the bottom of the trough, pulled
upward and then wound around one draw roller. When winding is complete,
the trailing end is then secured around the second draw roller.
Heating is usually by low-pressure steam, through a pipe having
perforations at the lower side of the pipe. The pipe runs over the whole width
of the machine at the bottom of the trough. Close-coil heating may be used -
it is slower than direct steam injection, but offers better control of dyeing
temperature and liquor ratio. The temperature may be controlled by a
thermostat via a pneumatic valve on the steam line.
Dyeing of polyester fabrics at 130°C in jigger was tried, but met with
limited success. The jiggers are now supplied with top covers or hoods with
rubber-framed safety glass windows. The advantages are better
temperature control up to boil with minimum steam loss (energy requirement
may be reduced to 50%) and minimum exposure to air, that is advantageous
432
for vat and sulphur dyeing. Top covers should be provided with insulated
handles and steam exhaust valves. There should be provision for draining
out the liquor condensed on the sides and back of the machine.
Dyeing on the jigger may be regarded as a series of padding operations
followed by dwell periods on the roll, during which dye absorption and
diffusion take place. The factors controlling dyeing are [6]:
1. The amount of liquor held in the interstices of the fabric.

2. The exhaustion of the liquor in time between successive immersions.
3. The degree of interchange of exhausted dye-liquor with fresh dye-
liquor during each immersion.
7.4.2 Winches
The winch or beck dyeing machine is the oldest form of piece dyeing
machine. The construction is comparatively simple and therefore
economical to purchase and operate. It is suitable for practically all types of
fabric, especially lightweights, which can normally withstand creasing when
in rope form such as woollen and silk fabric, loosely woven cotton and
synthetic fabrics, circular and warp knitted fabrics. The winch imposes much
less lengthways tension as compared to the jigger, hence it is suitable for
delicate fabrics which are damaged under high tension. Scouring efficiency
is high due to greater mechanical action caused by constant reformation of
lengthways folds. Many fabric varieties, such as tubular knitted fabrics are,
therefore, successively scoured and dyed in these machines. Crimps are
developed due to the greater mechanical action combined with low tension.
Winch dyeing results in thicker fabric with fuller handle, more fabric cover
and better crease recovery.
Old winches were made of wood, but nowadays are made of high-quality
stainless steel (AISI type 316 or equivalent) with welded joints, ground and
polished. The shape and size of the vessel and reel vary considerably
depending on the type of fabric to be processed. Most of the winch
machines are about 2.5 metres in length and 0.5 metre (single rope) to 4.5
metres (40 ropes) in width. Most winches are fitted with an overflow duct at
the back so that rinsing can be carried out in liquor flow from front to back.
In winch machines, a number (1 to 40) of endless ropes or loops of fabrics
of equal length (about 50 to 100 m) are loaded with much of their length
immersed in folded form inside the dyebath. Pegs separate individual ropes
from each other. The upper portion of each rope runs over two reels
mounted over the dyebath. One 15 cm diameter reel called fly roller or
jockey (J) is at the front and a much larger driven reel called winch reel (W)
is at the back for pulling the ropes round. The winch reel not only controls
the rate of movement of the fabric rope, but also the configuration of the
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rope in the dyebath. The reel does not grip the fabric positively, but by the
weight of the wet fabric and the friction between the reel and fabric.
Originally, wooden-slatted reels were used, but they had limited lives and
they were difficult to clean. Nowadays stainless reels with corrugated and
broken surface for increased frictional forces are used. The said reels may
be wound with polyester or polypropylene tape at a narrow angle across the
reel. Tape-covered reels retain a much greater degree of friction even at
high temperature. However, dye contamination may occur from lot to lot
through the tapes unless sufficient precautions are taken.
Winches are of two types:
1. Deep-draught winches,
2. Shallow-draught winches. L J
W
Deep-draught winches [Figure 7.8(a)]
usually have circular or slightly elliptical
reels (W) with diameter ranging
between 20 and 50 cm. It pulls the P
fabric and lifts it out of the dyebath and
over the jockey reel. On leaving the
winch reel, the fabric falls straight into
the dyebath with very little plaiting S
action.
For woollen and heavy cotton fabrics D
a deep-draught vessel with a sloping
back is preferred. The depth enables Fig. 7.8(a) Deep-draught Winch
long length of the bulk fabric to be
accommodated and the sloping back enables piled-up fabric to be pushed
easily towards the front of the machine. The dye liquor is usually 1 metre
deep and the comparatively small surface area minimises steam loss when
dyeing at high temperature and oxidation of vat dyes during dyeing.
As the fabric falls into the liquor from the winch at the back of the machine,
it tends to bunch up and lie in a heap for a short time. This creates creasing
problems for man-made thermoplastic fibres. To overcome this, a long
shallow machine with a larger elliptical winch has been designed. Shallow-
draught winches [Figure 7.8(b)] handle lighter fabric better and have
elliptical winches of about 2 metres circumference and 2:1 axis ratio.
Elliptical winches (W) provide more mechanical action and a plaiting action
as the fabric falls into the dyebath – the material is folded in wide layers
which are free from random creases as it falls into the dye liquor. The size of
plait increases with reel size. The larger the reel, lesser is the mechanical
action and is advantageous for delicate fabrics. Reels with adjustable cross-
section are also available.
434
L
J
P G
S
D
Fig. 7.8(b) Shallow-draught Winch
The dyeing of filament viscose, acetate and nylon fabrics require shallow-
draught winches to minimise creasing. The depth of liquor is reduced (to
about 75 cm) to decrese pilling pressure and the bottom of the machine is
flattened. There is no great weight of water pressing on the fabric to make
creases permanent.
The winch reel is driven from one side of the machine through a V-belt
system permitting a variation in reel speed between 40 to 80 m/min,
depending on the nature of material to be dyed. The greater the speed or
movement of the fabric, higher will be uniformity of dyeing. However,
woollen fabrics are felted and delicate fabrics are damaged when run under
high speed and a slow speed is preferred.
The jockey or fly roller (J) acts as a guide roller. It is mounted at the front
of the machine in free-running bearings, and is rotated by the pull of the
fabric. Mostly they are circular in cross-section, but for providing higher
mechanical action on the fabric, sometimes the cross-section is made
polygonal. The roller removes some of the surplus spent dye liquor from the
fabric. In some winch machines, a pair of rollers is provided which exert a
mild squeezing action on the fabric. For dyeing delicate fabrics, it is
advisable to fit the jockey near the winch reel.
Many shallow-draught winches are fitted with an adjustable horizontal bar,
called mid-feather or gate (G) halfway back in the winch, and usually located
about 15 cm below the top of the liquor. The bulk of the plaited fabric is kept
submerged at the back of the dyebath. The fabric slowly rises to touch the
gate, which prevents bulk of the material from moving forward. From the
gate onwards, the fabric moves nearly in a horizontal sweep in creaseless
condition up to the jockey. The formation of permanent lengthways creases
is thus avoided.
When a number of ropes are dyed simultaneously, a peg rail, fitted with
numerous horizontal pegs, is provided in front (and little below) of the
jockey. The rail runs the full width of the machine and is located about 20 cm
above the top of liquor. The pegs are usually 12 cm apart and act as
435
separators for the ropes − the ropes pass between the pegs to avoid
entanglement. The pegs may be fixed or they may rotate with the movement
of the fabric, minimising tension and chafing. The pegging of the rail controls
the fabric distribution widthways in the dyebath.
One feature of winch dyeing machine is that a perforated sheet (P) of
stainless steel is fitted vertically across the full width of the machine and
about 30 cm away from the front wall of the machine. The separate
chamber, thus formed, is the addition chamber where the concentrated
solutions of dyes and auxiliaries are added and stirred thoroughly to make
uniform dilute solutions before they enter the actual dyebath. The box also
provides a house for the water inlet pipe, outlet (D) and open horizontal
steam pipe (S), as liquor can easily diffuse into and out of the dyebath with
minimum disturbance to the fabric ropes at the bottom of the vessel.
Medium capacity winch machines are provided with a single drain valve
operated by a lift rod (L), while large capacity machines have two 12-cm
outlets, one at each side of the addition chamber. Direct steam injection into
the dyebath is usually carried out by means of a perforated pipe mounted
horizontally at the front and near the bottom of the addition chamber. This
simple arrangement results in rapid heating and vigorous agitation − steam
bubbles are forced into the liquor at high pressure. Excessive noise may
result if the bubbles condense very quickly and collapse with a bang while
starting with cold water. If the vibration is very high, it may be necessary to
alter the steam pressure, the location of the pipe or the size of the holes in
the steam pipe. For very wide winches, two steam pipes may be provided –
one providing steam for half of the width, while the second, having no
perforation in the first half, provides steam for the second half of the width.
Some swallow-draught winches have no separate addition chamber – the
dyes and chemicals are added by means of a perforated pipe across the
width. Heating is made by a heat exchanger provided below the machine.
Circular knitted fabrics are dyed in tubular form and slit lengthways after
dyeing. Warp-knits have the tendency to curl at the edges, hence these are
chain-stitched to join opposite edges along the length so that they are dyed
in tubular form. When dyeing of tubular fabric is carried out in winches, air
bubbles are collected inside the tube from immediately below the jockey roll,
through the peg rail and down towards the dye-liquor. This causes inflating
the fabric tube and dispersing lengthways creasing. However, creases are
again formed in different positions, as the fabric passes over the jockey roll.
The bubble is continually pushed back along the rope by the jockey roll. The
origin of air inside the tube is probably due to air entrapped in interstices of
the fabric, or air induced into the fabric as it passes over the reel or plunged
back into the dyebath. Sometimes air is blown manually by the workers. It is
observed that ballooning is highest at the temperature of 70−80°C and
diminishes appreciably above 90°C.
436
Most winch machines are now totally enclosed, but some interlocking
device to open a vent to allow the steam to escape before the front is
opened, is essential. The steam loss is thus minimised and a good
uniformity of temperature is maintained. To provide good accessibility to
front and back, toughened glass doors are fitted to lift vertically.
For loading, the leading end of each rope is taken and thrown over the
winch reel, drawn forward and tied to the peg rail. The winch reel is started
and it draws the fabric in. Twisting of fabric during loading should be
avoided. Two ends of each rope are tied by knot. While unloading, the knots
in all the ropes are opened, one end resting over the peg rail. The other end
is thrown over the unloading reel mounted high above the front of the winch.
In winch, the material to liquor ratio is usually around 1:25. For better-
designed machines, it is around 1:15, while for small winches it may be as
high as 1:40. When the fabric is lifted from the dyebath, the liquor starts to
drain back by gravity, assisted by the mild squeezing actions of the jockey
and winch reel. This downward movement of liquor plays an important role
in dye migration and levelling. Normally, the concentration of dye in this
drained liquor is appreciably less than that in the dyebath. As the fabric is
plunged back into the dyebath, it immediately acquires additional dye liquor,
which stays closely associated with the part of the fabric, as it travels to the
front. The rate of dyeing is controlled by the number of fabric cycles in a
given time. There is no appreciable movement of the ropes in the dyebath.
Otherwise, entanglements may result. However, considerable movement of
liquor in the dyebath is apparent from the fact that the dye diffuses very
quickly throughout the dyebath as soon as it is added in the addition
chamber.
The winch dyeing machine does not give very efficient movement of the
fabric through the liquor as a large portion of it is always lying at the bottom
of the dyebath. Moreover, the fabric is irregularly piled and uneven dyeing
may occur unless suitable dyes and levelling agents are used. Due to high
liquor ratio, dye exhaustion is poor and considerable amount of dye remains
in the bath after dyeing, especially in case of low substantive dyes.
A fault with winch machines is the tendency for the temperature to vary in
different parts of the dyebath, which may cause variation in colour depth of
different ropes, especially with temperature-sensitive dyes. The variation of
temperature can be minimised by circulating the liquor through an external
calorifier. There is also loss of heat, particularly for the open type, due to
large surface area of the machine. The fabric also carries away heat during
its passage to air and cools the liquor when it re-enters into the bath.
In winch, the fabrics are processed in short lengths, necessitating
trimming and sewing before loading and locating and breaking of joints
before unloading. Attempts have been made to dye continuous lengths of
rope by spiralling the fabric very slowly across the width of the winch. The
437
problem is to arrange a method of feeding back across the winch. A sloping

transporter trough or tube filled with dye liquor is often employed. The major
difficulty of such a system is, however, lack of flexibility with different fabric
types.
British silk dyers developed a system in 1964 later known as Spiraloda or
Autoloda, as shown in Figure 7.9 [6]. In this system, the leading end of the
rope (T) is attached to a loading arm (L), which is advanced slowly by a
chain drive (C) at one side of the winch (W) and guide roller (G). The time
taken by the arm to complete a cycle is about 1 minute and if the winch reel
speed is 70 m/min, the loop length is about 70 metres. The system enables
the dyer to select the most convenient loop length for the machine. The peg
rail is replaced by a continuous helix roll (S), which is rotated away from the
leading end at one revolution for each revolution of the loading arm, in order
to maintain equilibrium in the dyebath. The pitch of the helix determines the
spacing of the rope and interchangeable spiral rollers of different pitch are
available for fabrics of varying bulk. Sometimes it is preferred to use every
alternate spiral curve in the spiral roller, and accordingly, the rate of
revolution of this roller is doubled. Apart from the savings in time for loading
and unloading, less sewing and less fabric wastage, the Autoloda technique
enables the dyer to select the most convenient loop length for the machine.
Due to uniform spacing, higher machine loading with lower liquor ratio is
possible and this type of device will be widely used in future.
L
G
S
C
F
Fig. 7.9 Fabric Movement in Autoloda Spiral Dyeing Machine
Until 1960s, the machines used for dyeing fabrics in batches were the
winch, jigger and beam. When polyester was first introduced as a textile
material, conventional pressure-free winch beck equipped with a hood was
mainly used for dyeing using carriers. Soon it became evident that dyeing
above 100°C would be necessary to eliminate the use of carriers and
438
accelerate the diffusion of the dyes for cutting down dyeing time. This
prompted machine manufacturers to construct high temperature or high-
pressure modifications of the existing winch dyeing machines. The dyebath
is essentially a normal winch dyeing machine and a kier, on a track, which
can be pushed into position so that the dyebath is totally enclosed, in a
pressure-resisting container. Although many HT machine constructions were
in the market, there was no ideal dyeing machine for circular knitted
polyester texturised goods. It was originally expected that the HT winch beck
would fill this gap, but its drawbacks were soon obvious. The deficiencies
are:
1. Formation of running creases during dyeing may not be removable

even by stentering.
2. Considerable longitudinal tension exercised on the goods resulting in
elongation and deformation.
3. Rapid heating and cooling promoting deformation.
4. Dimensional stability not ensured even if the material is heat-set
before dyeing.
5. Long liquor ratio hampering economy of dyeing.
6. Risks of entanglement of fabric ropes.
7. Difficulty in maintaining uniform temperature throughout the dyebath.
Burlington HT winch beck was fitted with a pump for circulating the dye
liquor. This enabled good levelling-out of temperature within the dyeing
system, hence higher heating-up and cooling-down rates could be
maintained. Some manufacturers made additional use of this liquor
circulation by spraying dye liquor continuously against the circulating ropes.
This resulted in improved guiding and plaiting of the goods.
7.4.3 Jet Dyeing Machines

It was impossible to solve the all problems of polyester dyeing by mere
modification of HT winch beck. It was increasingly felt that dyeing time was
too long in these machines.
All the disadvantages of HT winch becks had been overcome by the jet
dyeing machine, based on a Venturi tube in which the circular movement of
the liquor carries the fabric round with it in a totally enclosed tubular
chamber, annular in shape. The Venturi tube is a constriction in the annular
passage through which the flow rate of the liquor must be increased, thus
causing suction, which imparts movement of the fabric. In all true jet dyeing
machines, the fabric rope is threaded through a ring or Venturi, to which the
processing liquor is supplied. The jet of liquor issuing from the ring serves
both to transport the fabric and to bring the liquor into intimate contact with
439
it. The primary flow is given by a centrifugal pump, but it is usual to

incorporate a few inclined steam jets also to boost the movement of both
fabric and liquor. The first jet dyeing machine was commercialised by
Gaston County Dyeing Machine Co. in Atlantic City in 1961. This American-
designed machine was novel, in that it used a high-speed jet of dye-liquor to
transport the fabric from the front to the back of the machine at a speed of
400 m/min. It was essentially a pressure-withstanding cylindrical vessel with
up to 6 separate tubular chambers arranged side by side, each (Figure 7.10)
containing one endless rope. The jet (J) plaited the fabric at the back of the
machine, and from it slid down to the bottom of the vessel and then started
to rise. When lifted from the top of the pile, the fabric passes round driven
metering rollers, which control the rate at which the fabric enters the jet tube.
The rollers are smooth and are driven not to provide positive lift of the fabric,
but to apply a very small tension prior to the jet. Originally three metering
rolls, also called lifter roller (L), were provided, but these were soon found
excessive and the number was reduced to one. The roll also assists in
removing some of the partially exhausted dye-liquor from the fabric before
the jet saturates it with fresh liquor. Since the pressure vessel is not full of
liquor, it is described as partially flooded machine and has the advantage
that the liquor ratio can be varied between 1:6 and 1:15. The dye liquor is
withdrawn from the bottom of the machine by a powerful pump (P) and
V
Fig. 7.10 Gaston County Horizontal Jet Dyeing Machine

440
passed through a vertical heat-exchanger (H) before being injected at the

top of the machine through the jet (J) via a jet throttle valve (V). The liquor
level is kept low and dye additions are made via a small secondary pump.
The vessel is pressurised by compressed air. The material is loaded through
a small port (R) by means of a tape already threaded inside the machine.
While unloading, the tape is tied to the trailing end of the dyed piece so that
the machine is always threaded up. If the operator forgets to attach the tape
or a seam is broken during dyeing, rethreading is extremely painstaking.
Most jets of this type have two or three tubes mounted side by side within
the same pressure vessel, but machines with up to ten tubes have been
made. When dyeing double jersey fabric, weighting 600 g/m, loads of up to
150 kg per tube can be accommodated, the entire rope circulating in about
1 minute. Lightweight fabrics usually require a smaller diameter jet and
each machine is supplied with a range of jets of different sizes – nowadays
adjustable jets are also available. The jet should be accurately positioned,
otherwise a spiral motion may be imparted to the liquor flow causing fabric
twisting and creasing. It is beneficial to have two-way flow – in case fabric
entanglement in the jet, the flow may be reversed to force back the fabric to
clear the entanglement.
Jet dyeing machine has the following advantages over HT winch beck:
1. Dyeing at 125°C causes much rapid dyeing with better penetration,

exhaustion and levelness, less dye at the surface resulting in quicker
washing with marginally better fastness properties.
2. Lower material to liquor ratio provided savings in energy and faster
heating and cooling.
3. Less lengthways tension and slightly greater fullness of handle.
4. Vigorous circulation of liquor and material causing quicker dyeing.
5. Frequent movement of fabric minimises creasing problem.
1. High capital investment and maintenance costs.

2. Limited accessibility to the material when the machine is running, the
fabric is loaded and unloaded through a small port.
3. Internal cleaning is difficult as the machine is completely enclosed.
4. Any roughness inside the machine causing snagging of the fabric is
difficult to locate.
5. Vigorous movement of the liquor may create severe foaming. The
chemicals having tendency to create foam should be avoided and
defoaming agents may be added in the machine before dyeing.
Foaming problem can be avoided by using fully flooded jet dyeing
machines.
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6. The force of the jet may be damaging for delicate fabrics.

7. The width of the bottom compartment is designed to accommodate
the widest fabric likely to be dyed in the machine, lightweight narrow
fabrics may not fill up the available space uniformly and may get
entangled.
8. Most machines are fitted with one or more port holes with illumination,
but except when producing pale dyeing, the fabric movement is
difficult to perceive.
9. Sampling of dyed fabric during dyeing is difficult. A remote-control
cigar-cutter may be fitted near the port, the fabric movement may be
stopped when a joint is near the port, the cutter is advanced, a sample
is removed and is withdrawn through a pressure lock.
Probably the single most important factor in the success of jet machine is
its versatility. Versatility in dyeing machine means:
1. Ability to dye many different types of fabric.

2. Processing of a wide ranges of batch sizes.
3. Suitable for various dye-fibre systems.
4. Suitable for various processing stages, e.g. preparation, dyeing and
after-treatments.
In first generation jet dyeing machines, longitudinal creases are formed

when the fabric is lifted from the dyebath. To minimise creasing and damage
to the delicate material, a new type called fully flooded jet dyeing machine
has been developed in which the fabric remains completely immersed
throughout the dyeing cycle. Foaming problem is thus avoided. The partially
flooded systems have been virtually replaced by fully flooded designs, often
referred to as soft-flow machines. In order to reduce tension, the dye vessel
is either horizontal or only slightly inclined. Whilst the liquor is circulated by a
pump an extra motion is imparted to the fabric by an accelerator, there is
usually a driven reel to assist movement. A good control on the fabric speed
is provided by the driven circular reel; any jamming of the fabric increases
the load on the driving motor and this can be used to initiate an alarm. The
circular reel creates much less strain in the fabric than the conventional
winch reel with its elliptical cross-section.
In these machines, the transportation tube is filled with the dye-liquor
using an overflow system and both liquor and fabric flow along the tube
under gravity. The reduced speed of the fabric (100-200 m/min as compared
to 250-400 m/min) and consequently gentler action on the fabric, led to this
type of fabric movement system being called soft-flow. As the transportation
tube is filled by overflow, only a low pressure is to be exerted by the pump,
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hence a less powerful pump (e.g. 5 kW) is required. In HT models, a

secondary pump is usually available to generate adequate internal pressure.
Several designs of fully flooded machines are being commercialised. The
Vald Henriksen machine is most compact – semicircular horizontal tubes are
placed one above the other. Thies Jet Stream has a very long vertical and
comparatively narrower storage compartment. It is economical in floor
space, but is a tall machine requiring either a deep pit or a gantry to permit
loading and unloading. The Pegg machine is similar, but has a much wider
and smaller compartment. The machine designed by Then has a lower
height convenient to operate, but occupies much more floor space (Figure
7.11).
F T
S R
J
E
A C P D
H
M
Fig. 7.11 Thenjet Dyeing Machine
The fabric passes through a high-speed jet (J) feeding fresh dye-liquor to
the fabric and is carried along a tube (T) to the entrance of a much wider
section chamber used as a storage compartment (S). In this section both
liquor and fabric move very slowly until reaching the end when the fabric is
drawn off through a narrow tube and is fed to the jet. By regulating the flow
of liquor through the storage compartment, the speed of the fabric in this
critical area can be controlled. The dye liquor is drawn off from both the
ends of the storage compartment and passed through a heat-exchanger (H)
by the main pump (M) before being fed back to the jet. Heat exchangers
should be regularly cleaned (mechanically or with caustic soda and sodium
hydrosulphite) as dyes and oligomers are deposited on the heated surface
causing slough off.
Other components of the machine shown in the Figure 7.11 are:
F = fabric entry.
A = jet controlling valve.
C = connection for counter current flow.
E = addition or expansion tank.
D = secondary pump for dyebath.
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O = overflow pipe.
P = dyebath discharge.
R = overflow rinsing.
Fully flooded machines are particularly good at minimising creasing in

delicate fabrics, but are difficult to operate. The control on fabric in the
storage compartment is limited. Lightweight fabrics cover a small portion of
the compartment creating possibilities for entanglement. The material to
liquor ratio is 1:15 onwards.
Due to ever-increasing fuel costs, there is continuous demand for low-
energy processing machines. In 1975, reel-jet dyeing machines operating at
liquor ratios down to 1:5 have been developed. The oil crisis of 1974
initiated a search for improved machinery designs requiring less than half
the quantity of water, chemicals and energy that were necessary in the fully
flooded and earliest partially immersed types. This enabled rapid increase in
temperature thereby enabling quicker dyeing by rapid dyeing process. The
use of less dye-liquor not only gives savings in water consumption, heat and
effluent disposal, but also of dyes and chemicals. However, creasing
problem may be enhanced, when very low liquor ratio is persuaded.
The essential lay-out of the reel jet machine is similar to the Gaston
Country Jet (Figure 7.10), at the front the fabric is lifted by a driven roller and
fed across the top of the machine to the jet. Fabric movement in this type
machine is primarily by the lifting reel supplemented by the jet, whereas in
Gaston Country Jet, the metering rolls provide a restraining action. High
running speed up to 400 m/min is employed – this is particularly useful for
removal of excess surface dye. Both atmospheric and pressurised models
are produced, the former is advantageous for application of reactive dyes on
knitted cotton fabrics. The dye-liquor is withdrawn from the bottom and
pumped through a heat exchanger to the jet. As the volume of liquor is low,
pumping pressure and power consumption are low. Multiple units may be
combined sharing a common liquor flow and lifting roller system.
Rectangular-shaped jets are used in some machines encouraging opening
out of the fabric rope.
The recent developments in jets have the following objectives:
1. Minimising liquor usage
2. Minimum fabric distortion, pilling and creasing
3. Improving rinse efficiency
In Longclose supersoft Hitech machine, a double winch system is used to

transport the material in a low-lift, non-slip, tension-free manner, while
allowing liquor treatment to be achieved with reduced pressure and
improved surface quality. A special system has been used to minimise time
and water consumption during rinsing.
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In Apollan Twin Soft Flow of Sclavos, two distinctly separate jet nozzles
are used in tandem, which allow higher fabric speeds at very low liquor
velocities, guaranteeing tangle-free operation. An elbow-plaiting system
places the fabric folds precisely on top of one another in such a way that all
available storage space is occupied, while a liquor-bypass system protects
more delicate fabrics from crush creasing. Originally applied to crease-prone
woven fabrics, this technology is also applicable to knitted fabrics of suitable
construction. The advent of ultra-light micro-fibres require ultra-high speed
(above 600 m/min) fabric dyeing machine that allow relaxation to occur
within an extended storage zone, so avoiding rope marking and crowfoot
creasing.
Then airflow and Thies Luft-roto are circular type machines. The fabric
transport is by winch and high-speed airflow, thereby reducing liquor ratio,
higher fabric speeds and freedom from creasing.
Longclose Ventura Rapide and Hisaka CUT FL machines are capable of
fabric running speeds in excess of 600 m/min being achieved on ultra-light
qualities and at M:L ratios 1:4 onwards. These are especially suitable for
microfibres, which are allowed to relax within an extended storage zone.
Early in the 1970s, the machinery makers in Japan and Western Europe
began to introduce overflow and partially immersion jets. These took
advantage of supporting influence of almost complete immersion of delicate
fabrics, but avoided the vigorous turbulence of the constricting Venturi. The
rope of fabric is lifted briefly from the dyebath by a driven circular reel and
then carried along a transportation tube by means of a relatively gentle flow
of liquor. The principle is available in both atmospheric and high temperature
pressurised machines. In most jet machines the transportation tube is filled
with liquor and fabric/liquor movement along the tube depends on gravity.
The transportation tube is usually outside and above the main vessel except
in ATYC Rapidsuau machine.
In all jet dyeing machines the fabric rope passes through two main
phases:
1. The active phase, in which the fabric moves at high speed, passing
through the jet at vigorous pick up of fresh dye-liquor, about 2% of the
total time, the material is in active phase,
2. The passive phase, in which the fabric moves slowly around the
system until it is feed back to the jet.
The majority of dye absorption from liquor occurs during active phase and
the diffusion of dye from solution takes place during the passive phase. In
passive phase, the fabric is folded, although the precise conditions depend
on the fibre, the fabric thickness and the sharpness of creasing.
The fabric ropes should circulate in about one minute and correspondingly
the length of rope should be 300-400 metres. This is satisfactory for heavy
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fabrics, but is uneconomical for lightweight fabric, which is dyed in parallel

with flyer system, i.e. additional lengths of fabrics are attached to the main
rope as flyers. Parallel ropes of equal initial lengths, are not very useful as
they contract or extend differently.
While passing through the jets, longitudinal creases are formed, but are
usually eliminated as the fabric balloons out after jet. Jet of too small
diameter gives excessive lengthways creasing, while too large a jet gives
poor fabric movement relative to the liquor.
With constant settings on the machine, fabric speed increases
considerably as the temperature is raised, e.g. from 100 m/min at 40°C to
150 m/min at 110°C. This increase is due to reduction in viscosity of dye
liquor with increase in temperature and its effect on pump efficiency and
resistance to flow.
With most high temperature jets, internal accessibility is extremely difficult.
Earlier such machines were supplied as an integral pressure vessel, but
later supplied in flanged sections so providing greatly improved access.
Jet dyeing is now quite a mature technology. A large number of machine
manufacturers have introduced jet dyeing machines with various advanced
facilities. One fundamentally new innovation is the use of air, either in
addition to or instead of water, as the motive force in driving the fabric rope
(Airflow AFS, Then). A few other innovative additions to the machine are [9]:
1. Automatic controlled variable jets, e.g. Vario Jet and Thies

2. Self-cleaning filters
3. Auto untangling device
4. Spray system for efficient cleaning
5. Semi-automated salt dissolving and dosing system
7.4.4 Beam Dyeing Machines

In beam dyeing, a length of fabric is wound on a perforated carrier and
processed in a cylindrical autoclave. The system is fully enclosed and is
normally pressurised to provide processing at temperatures up to 130°C
(40 Mpa, 4 atm.). Pressure beams came into use in late 1950s in order to
dye lightweight, delicate warp-knitted nylon and acetate fabrics and later for
dyeing of polyester fabrics at high temperature. Many of these fabrics, when
dyed in a winch machine, suffered creasing and occasionally mechanical
damage, whereas when dyed on the beam dyeing machine, the dyed fabric
was comparatively smooth but somewhat thinner and slightly glazed.
Lightweight woven fabrics containing filament yarns and some polyester-
cellulosic blended fabrics are also dyed on the beam. Without doubt, beam
dyeing is well suited for dyeing texturised woven and knitted polyester
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goods. The circulating system, as well as high volume of liquor used, results
in good penetration in such materials.
The first generation beam dyeing machines consist of a roll of fabric
wound round a perforated beam into which dye liquor is forced from inside
to outside, the whole being immersed horizontally in an open dye tank. This
simple machine permits only one-way liquor flow and dyeing below 90°C.
These open-bath dyeing machines were soon replaced by pressure vessels
of circular cross-section with complex pumping circuit to permit two-way
flow. Though more expensive and difficult to maintain, the high temperature
models are versatile and they provide much better dyeing. The earlier top-
loaded machines are now largely superseded by front-opening machines
(Figure 7.12).
O C
A
I
D
V M S
Fig. 7.12 Fabric Beam Dyeing Machine
A beam dyeing machine, 2 metres long and 1 metre diameter, has a liquor
capacity of 3,000 litres and about 200 kg knitted fabric. A machine having a
length of 4 metres and diameter of 1.6 metres may accommodate 700 kg of
20 denier warp knitted fabric or up to 1,500 kg of thicker fabric. The lowest
M:L ratio is 1:7.5, but usually the ratio is 1:12 or 1:15.
The pressure vessels (V) are about 200 cm in internal diameter and
2 metres (for woven) to 4.5 metres (for wide warp-knits) in length. The
fabric (B) to be dyed is wound on perforated beams (B) and loaded from the
front. The front door (D) is fitted with a rubber seal and the door is securely
locked by a series of bolts on older machines or a ring-locking device for
speedy locking and unlocking. Two rails, running the full length of the
vessel, are mounted at the sides about a quarter of the way above the
bottom. These rails support the weight of the roll and accompanying cradle
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during dyeing. At the centre of the back of the machine is the inlet (I) for
feeding dye-liquor into the perforated beam. Below the cylindrical vessel is
the outlet for the dye-liquor to the main pump (M) via heat exchanger (H).
The main pump is to handle a large quantity of water rather than to produce
a high pressure – the small-capacity secondary pump (S) largely produces
the pressure. The main pump is fitted as close as possible to the entry point
at the back of the vessel. Although two-way liquor circulation is used, in-to-
out flow through the roll of the fabric is greatly preferred. Out-to-in flow tends
to compress the fabric causing flattening and glazing the fabric, particularly
the inner layers, with the danger of water marking. Nearly all machines are
fitted with automatic flow reversal controls via control panel (C). The period
of flow in each direction being set independently, but the in-to-out flow
predominates.
During dyeing, a small quantity of liquor leaves the vessel and passes
through a overflow pipe (O), fitted with a cold-water condenser into the
addition or expansion tank (A) alongside the main vessel. This open tank is
also used for adding dissolved dyes and chemicals. From the bottom of the
tank, liquor is fed by a small-capacity high-pressure secondary pump (S)
back into the main system. As the temperature of the liquor in the system is
raised, the level of the liquor in the addition tank rises.
The making of a good beam is an essential prerequisite for uniform
dyeing. The perforated beam must be sufficiently robust to withstand the
weight of the full roll of wet fabric. Apart from 20 cm at each end which is
smooth, the beam has several thousand holes, usually about 5 mm in
diameter. One end of the beam is closed, the other is to closely fit into the
inlet pipe at the back of the machine. In order to accommodate fabrics of
less than the maximum width, excess holes at both ends of the beam are
blanked off by securely bolted flexible stainless steel sheet collars. The
overlap of the sheet with the fabric should be carefully controlled and usually
about 3-5 cm. Before winding the fabric to be dyed, the beam is wrapped
with a few layers of woven or non-woven cotton fabric, which provides a
good bed for the fabric to be dyed without disturbing diffusion of dye-liquor.
The fabric to be dyed should be dimensionally stable during dyeing − it
should not appreciably extend causing channelling of liquor or shrink
building high pressure on the wound layers of fabric. The fabric should be
heat-set or hot scoured before beaming. Successive lengths of fabrics are
stitched together keeping minimum overlap. For winding, the beam is
usually surface-driven and mounted on a pair of parallel rubber-covered
rollers, rotating at constant speed. Alternately, a tension-controlled centre-
wind take-up drive may be used. In the feeding line, scroll rollers, uncurlers
and a short pin-stenter may be incorporated for better control of fabric width
and tension, but such type of beam winder will be very expensive. The
tension during winding should be kept at minimum for better stability of the
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beam. After completion of winding, a short length of cotton or polypropylene

net, slightly wider than the fabric to be dyed, is wrapped around the roll for
additional stability and to protect it from soiling. Solid flanges may be fitted
on each side of the roll to prevent flow from the sides, but their effectiveness
is doubtful.
After careful loading of the beam, the door (D) is securely locked and
safety devices are checked, the drain valve is closed and the outlet valve for
overflow pipe is opened. The pump is started on in-to-out flow when water
flows through the outlet valve to the addition tank. The flow is reversed
every few minutes. A de-aeratic agent is added into the tank and the
secondary pump starts pressurising the system. All trapped air is to be
removed at this stage, which may otherwise cause undyed patches. The
normal scouring and dyeing then follows. Scouring performance of
pressurised beams is poor and only soluble contamination is removed.
Before discharging the spent liquor, complete depressurisation is done by
stopping the secondary pump, lowering temperature below 85°C and
opening air inlet valve.
As liquor is being circulated through a stationary batch of fabric, this form
of processing is inherently liable to non-uniformly in dyeing, because of the
higher rate of flow of liquor per unit area near the centre of the beam and the
danger of channelling through the more porous regions of the batch.
Uniform winding of the batch of fabric is, therefore, crucial. Probably the only
way to learn the maximum practicable loading of the beam for a given
quality of fabric and class of dyes is by practical experience. The uniformity
can be promoted by higher rate of flow, which is constrained by the pump
capacity and fabric porosity. The dyeing faults, which commonly occur in
beam dyed materials, are:
1. Gross unevenness near the edge mostly due to slack winding.
2. Uneven or light patches due to air bubbles.
3. Variation near the edge on inside layers due to misjudged overlap of
the steel collar.
4. The inside layers are relatively more deeply dyed than the outside
layers. As the dye-liquor passes through the roll, the concentration of
dye diminishes especially in case of high-affinity dyes. To prevent
noticeable inside-outside depth difference, not more than 2% dye
should be absorbed on each passage through the fabric roll at the
initial stage of dyeing. This is achieved by controlling the temperature
and pH and using proper levelling agents.
Dye exhaustion is followed by diffusion inside the fabric and migration into
dyebath. The chances of dye migration are poor in beam dyeing process –
an unevenly dyed beam is difficult to rectify unless easy-migrating dyes are
used.
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With the limitation on dye exhaustion per cycle, it is desirable to increase

the rate of flow of liquor through the fabric, which depends on the following
factors:
1. Permeability of the fabric
2. Number of layers of the fabric
3. Pump characteristics
4. Viscosity of the liquor
Specific information regarding the rate of flow through the beam is difficult
to acquire. The pressure/flow characteristics of pumps indicate complete
dye liquor circulation within 35-45 seconds, corresponding to around 20 l/kg
(goods)/min. It is reported [6] that the time taken for dye to pass from the
addition tank through the secondary pump, main pump, roll of fabric and out
through the overflow is about 5 minutes at 40°C. If pump efficiency is
constant, liquor circulation is doubled at 100°C due to reduction of the
viscosity of water. At 120°C, the liquor flow is 2½ times that at 40°C, i.e.
around 2 minutes for a complete cycle, corresponding to about 5 l/kg/min.
Most fabric beam dyeing is carried out using liquor cycle times ranging from
45 seconds to 3 min, but obviously, there is a wide variation in rates of flow.
The fabrics must be suitably pre-treated before they can be dyed on HT
beam dyeing machine. The main demand is development of bulk, which
may be obtained by treating in a tumbler. However, the method remains
unpopular for several reasons. Hence, pre-treatment involves scouring with
development of bulk. Pre-setting the goods to final width is necessary for
satisfactory stability during dyeing. The beam dyeing produces excellent
hydrofixation. As good dimensional stability is achieved after dyeing,
subsequent setting may be omitted. However, additional pre-treatment is
more costly than dyeing untreated goods in jet dyers, as is often practised.
Hence, jet dyeing machines are nowadays more widespread than beam
dyeing machines.
A definite disadvantage of beam dyeing which has been more acute these
days probably due to general switchover to tandem texturising, is related
with the increased appearance of oligomers or low-molecular-weight
polymers. These impurities come on the fabric surface after dyeing. While
the oligomers hardly affect the appearance of the goods in rope-form
treatments, a wound package on the beam acts as a good filter. Apart from
producing oligomer dust, which can be a more or less pronounced nuisance,
oligomers may settle on the goods.
7.4.5 Padding Mangles

The padding mangle (Figure 7.13) is perhaps the most familiar and universal
of all textile dyeing and finishing machinery. It gained popularity for
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application of dyes and chemicals in continuous and semi-continuous dyeing

and finishing processes. The continuous dyeing process is advantageous
when a large quantity of fabric is to be dyed in a single shade. The uniform
application of dye-liquor to the fabric is the most critical part of a continuous
dyeing process and satisfactory performance of the padding mangle is
absolutely essential for success of such processes.
The padding process is suitable for applying dyes and chemicals having
low or no affinity for the fibre. Low-substantive naphthols, reactive,
solubilised vat dyes, vat dyes by pigment padding or vat acid process,
phthalogen blue, aniline black, mineral khaki, etc. can be applied by padding
process, as the original dyes have little or no affinity for the textile materials.
If the dyes used in the padding mangle have high affinity, their concentration
in the trough decreases with time, resulting in tailing effect. The effect can
be minimised by using feeding liquor having higher concentration than the
solution initially fed to the trough. The padding mangle is not a complete
dyeing machine by itself – other machines are necessary for fixation of dyes
in the padded fabric.
The padding operation consists of two steps. Firstly, the fabric, usually
woven, is immersed in the dye-liquor to achieve thorough impregnation, and
secondly, the fabric is passed between two rollers to squeeze out air and to
force dye-liquor inside the material, the excess liquor being sent back along
the fabric. The former step is known as dip, while the contact between the
squeeze rollers as well as passing between the rollers is known as nip. For
one dip and one nip padding process, the fabric is immersed in the trough
once and passed through the nip once. For dyeing most fabrics at speeds of
up to 50 m/min, single-dip and single squeeze are sufficient. For higher
speed (say 120 m/min) or for heavy fabrics, double dip and double squeeze
process using a three-bowl padding mangle is preferred. The liquor retained
in the fabric after padding is expressed by weight as percent of the weight of
dry fabric and is known as % pick-up or % expression. Thus, 80%
expression means the fabric weight is increased by 80% of dry weight after
padding. The expression less than 60% is difficult to obtain in padding
mangle. An increased pressure at the nip results in a lower percentage
expression, but at the same time, the penetration inside the fabric is better.
The fabric is subsequently passed through various machines for fixation and
post-fixation processes. The padding mangle is also termed as dye pads or
padders. The expression mangle is often confined to less critical machines
for squeezing water from fabric, usually prior to dyeing.
Mangle width for textile applications may be as high as 4−5 metres, but
widths of 1.7−2 metres are more common for continuous dyeing of woven
fabrics. Most of the padding bowl mangles have a steel mandrel covered
with about 15-mm deep hard rubber with a comparatively soft rubber surface
having softness of 55-70° shore hardness. The softer the rubber, the more
451
readily it deforms under pressure providing a greater area of contact, and

thereby reduces pick-up of fairly open fabrics. However, such rollers are
also more readily damaged, especially at the selvedges and a compromise
must be established. The physical strains may cause unevenness,
particularly for wider padders, and regrinding may be needed from time to
time.
The mangles should be equal in diameter, usually 30−40 cm, but larger
diameter rollers are also used for high-speed running. With larger diameter
rollers, the revolution per minute for a given fabric speed and the deflection
under pressure are less, but they require larger bearings and heavier
foundation. Depending on the pressure applied, higher diameter rollers have
a larger area of contact between two rollers. For padding of dyes, a
minimum contact distance of 1 cm is desirable. In old mangles, one of the
rollers is rubber-covered while the other one, the driving roller is made of
stainless steel, brass or ebonite. However, such types of mangle may give
face to back difference on the fabric. Now both rollers of the mangle are of
similar hardness.
The chemical composition of the rubber surface should be chosen
carefully so that it is unaffected by the liquor containing dyes and textile
auxiliaries. For cross-linking finishing, it should be impervious to
formaldehyde condensates. Immediately after a run, the rollers should be
washed thoroughly to avoid hardening or fixing of dyes and chemicals on
the rubber surface.
In most of the two-bowl padding mangles, the lower bowl is in fixed
bearings and the upper bowl is separated by about 2 cm, when the mangle
is not operating. The bearings of the top roller are mounted on arms pivoted
at the side of the mangle and actuated by pneumatic cylinders attached to
each side of the machine. Just before padding operation, the upper roller is
moved to press against the lower roller by pneumatic pressure created by a
small compressor. The pressure is applied to the mandrel at the end of the
roller, the maximum pressure being about 400 Newton per cm (50 kg/cm) of
bowl width or about 10 tonnes across the total width, 5 tonnes at each end.
In the three-bowl padding mangle, the centre bowl is in fixed bearings and
the two outer rollers are pressed against the centre. When the mangle is not
operating, the top rollers should be detached from the fixed rollers, i.e. in
open position. The roller in fixed bearings is driven from one side of the
machine, the drive system depends on the maximum speed of the mangle,
which may vary from 25 to 120 m/min. The sides of the padding mangle
must be robust in order to withstand the forces applied. Applying pressure
to the ends of a roller causes some deflection of the roller providing lower
pressures (consequently higher pick-up) in the middle of the pad and higher
pressures (and lower pick-up) at the sides. The deflection can be measured
by using the Shirley Bowl Deflection Indicator. To counteract the effect of
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bowl deflection, the surface of one or both bowls may be tapered slightly
towards each end.
The problem of bowl deflection can also be tackled by using a special
mangle bowl, such as swimming roll mangle of Küsters. The roll has a
stationary mandrel, around which the roller shell rotates in bearings. The
space between the mandrel and the shell is divided by pressure seals into
two compartments. The smaller compartment, pressurised by oil, is always
towards the nip. Oil is constantly pumped into the compartment, some
passing the seals and circulating back to the reservoir. When oil pressure in
the compartment is increased, the surface pressure at the middle of the roll
is raised and thereby the deflection of the mandrel is compensated. By
2
controlling internal oil pressure (maximum 500 kPa or 71 lbf/in ) and
hydraulic pressure at the ends of the mandrel, the configuration of the bowl
can be adjusted to have a uniform linear pressure at the surface. The
swimming rolls may be used in pairs or in combination with another
conventional roller. Artos stabilised roller system consists of three
components and the load is applied at the tube shaft at the centre. Although
the inner shaft deflects under pressure, the force is transmitted to the outer
sleeve via the inner sleeve covering only the middle section of the roller.
To minimise oxidation of rubber, the rollers should be covered during
storage and protected from sunlight, moisture, excessive heat or cold. After
prolonged storage, the oxidised surface is to be ground for better results.
The pressure should be applied only when the rollers are running and they
should be cleaned thoroughly after use.
Situated below or at the front of the squeeze rollers is the padding box or
trough, having a free-running roller at bottom which guides the fabric
through the trough. The box may be V-shaped, deep immersion type or
shallow type (shown in Figures 7.13 (a) as (I), (II) and (III) respectively)
having a width slightly more than maximum width of the fabric to be
processed. The volume of the pad-box should be as small as practicable
//
(about 2 gallons for a two-bowl padding mangle with 60 bowl width) so that
the wastage of dye-liquor is minimum at the end of the run. It is made small
in order to avoid tailing effect, a problem arises from preferential pick-up of
dye or water by the fabric, resulting in variation in composition of the liquor
as the run continues. Dye-liquor may be fed to the trough manually or with
the help of a pump through a perforated pipe running across the back of the
box. The perforations are pointed down and are away from the fabric. A
constant level of dye-liquor in the box can be maintained with the help of a
float switch. For a very wide fabric, a liquor circulation system is often
recommended, but the advantage is questionable. A drain plug is fitted at
the bottom of the box for rapid draining at the end of run. The interior of the
pad box should be smooth and easy to clean. Usually impregnation is done
at room temperature. However, some pad boxes are fitted with an external
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heating jacket for circulation of hot water or oil. Hot impregnation may be
required to achieve rapid and uniform wetting-out and high pick-up of dyes.
When two pad boxes are fitted in tandem, the second is kept at a slightly
higher level so that the liquor overflows from the second to the first.
The mangles may be arranged as vertically opposed in ascending or
descending order or as horizontally opposed position. The said three
arrangements with Artos 2-bowl padder are shown in Figure 7.13 (a) as (1),
(2) and (3) respectively. For three-bowl padders, all three may be inclined
with a steady central bowl, while the top and bottom bowls press themselves
against the central steady bowl with the action of levers and pneumatic
pressure. There may also be a combination of ascending and horizontal
with two-dip (same or different bath)-two-nip (4) or descending and
horizontal with one-dip-two-nip (5) arrangements as shown in Figure 7.13
(b). The ascending-bowl gives better observation of the nip, while in
descending-bowl system, the fabric path does not change much. With
horizontally opposed mangle, the fabric rises vertically from the padding box
directly to the nip and straight through a dryer mounted above the nip. This
arrangement is widely used for Thermosol dyeing process for polyester and
its blends. In three-bowl arrangement, maximum impregnation occurs at the
first dip-squeeze and maximum uniformity at the second squeeze.
After impregnation and before entering the nip, it is necessary to take the
fabric over a free-running smooth roller. The rollers should be positioned so
(2)
(1)
(3)
(I) (II) (III)
Fig. 7.13(a) Two Bowl Padding Mangles with Varying Troughs and Bowl
Arrangements
(4) (5)
Fig. 7.13(b) Three-Bowl Padding Mangles with Varying Bowl

Arrangements.
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that the fabric path leaving the pad box is nearly vertical and on leaving the
rollers, the fabric enters straight to the nip. Nip guards covering both the
entry zone and the sides may be fitted. On leaving the nip, the fabric should
leave both rollers simultaneously, otherwise face-back differences may
appear. The number of rollers following padding should be less so that the
squeezed wet fabric has fewer points of contact.
Dry fabric is fed from plaited form to the pad bath after skying. An end
piece is to be attached to the tail end if run from a large roll. Alternately, the
fabric may be run through an accumulator or scray, which will continue to
deliver to the padding mangle. The fabric must be dry but readily absorbent,
as the immersion time in mangle is very short (about 0.5 seconds). It should
also be free from loose impurities, waxes, oils, etc. Polyester-cellulosic
blended fabrics are to be heat-set before padding. These fabrics, which are
slow in wetting-out may have to be treated with a rewetting agent
beforehand. The fabric must be flat and crease-free. The knitted fabrics
require low lengthways tension and the presence of scroll rollers and edge
uncurlers. The fabric must be centred accurately on the padding mangle and
run under moderate lengthways tension. Excessive tension gives poor
absorbency and low liquor pick-up.
In order to reduce the volume of dyebath and to stop draining back of the
liquor after preferential absorption, troughless mangles such as Fibe
padding mangles (Benninger Engineering Co.) have been developed. In
such machines (Figure 7.14), two sets of horizontally opposed mangles are
placed one above the other so that each of the four bowls makes contacts
with two others and there are four nips. These bowls are provided with to-
and-fro as well as up-and-down motions and no separate trough is used.
Fig. 7.14 Fibe Troughless Padding Mangle

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The geometry of the rollers provides some space between the four rollers
where the liquor is held. Two stainless steel plates covered with rubbers
//
sheets about 3 thick on inner sides are fixed at the ends of the rollers to
prevent the padding liquor licking through the ends. A perforated pipe
(shown above the guide rollers in the figure), entering the liquor space
through one of the steel end plates feeds the pad liquor. The liquor is fed at
the same rate at which the liquor is taken up by the fabric during padding
and is circulated by a centrifugal pump. Only about 2½ gallons of liquor will
//
be held in the space in 36 width machine.
The fabric enters between the nip of the topmost rollers, which are under
considerable pressure. The high pressure removes much of adsorbed air
from the fabric so that it is wetted very quickly. It then passes over a guide
roller inside the dyebath and horizontally through a nip. It passes round
guide rollers outside and re-enters the dyebath through the nip of two
bottom rollers. The fabric then passes round a guide roller in the dyebath
and goes out horizontally through the nip of two vertical rollers.
However, the wedge nip, as it is sometimes called, is restricted to padding
lightweight fabrics. The thicker fabrics suffer from liquor seepage at the
selvedges, difficulties in wetting-out in such short time, and the continuous
expulsion of air may cause frothing. The setting of end plates has to be
adjusted very accurately. The wedge nip is normally used as the second
stage in combination with the conventional dip-squeeze unit.
The presence of occluded air in the fabric structure prevents ready
absorption of dye liquor during padding process. It was observed that a roll
of fabric when put under vacuum is readily saturated with dye liquor. Farmer
Norton designed a machine for continuous vacuum impregnation. The fabric
is carried on a rubber belt underneath a perforated rotary screen, in the first
half of which suction is applied to the fabric, while in the second half, dye
liquor is fed at atmospheric pressure. The fabric is then passed to a mangle
to remove excess liquor, which may be rejected or re-circulated. Good
impregnation may be achieved even on loom-state fabric containing sizes.
However, such a machine is not commercially popular as adequate
impregnation may be achieved on most of the fabrics in conventional
padding mangle by two-dip-two-nip process. Moreover, very high
penetration in thick fabric necessitates increased quantity of dye liquor to
obtain a given depth of dyeing.
For conservation of energy, lower liquor retention during padding is
necessary. The relatively high liquor retention from normal padding
techniques is expensive in terms of energy requirements, because drying is
one of the most expensive stages of a dyeing process. Furthermore,
migration is a more serious problem when the fabric contains excess water
and the use of migration inhibitor increases the cost. To minimise liquor
retention, pad-transfer technique has been suggested, in which the padded
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and squeezed fabric encounters dry fabric. Owing to the initial over-
saturation, however, the amount of liquor remaining is still typical of that
achieved by a good conventional system.
In three-bowl loop-transfer technique (Figure 7.15), the fabric is not
directly dipped into the trough. Instead, a loop of fabric dipped into the
trough encounters the dry fabric while passing through a nip. The pick-up of
liquor at the transferring loop can be controlled by varying both squeezing
pressure (between bowl 1 and 2) and transferring pressure (between bowl 2
and 3) independently. A study on dyeing terry towel fabric with reactive dyes
[5] showed liquor retention values below 25% could be achieved, but 35-
40% was necessary to ensure level dyeing. Reproducibility and levelness
are better at higher transfer pressure. Fixation values for fabric dyed by
either loop-transfer or conventional padding showed close agreement.
1 2 3
Dry fabric
Loop
Trough
Fig. 7.15 Loop-transfer System with three-bowl Padding Mangle
The methods designed for low pick-up values in the range of 5-40% region
are of considerable interest for the application of finishing agents. The use of
a coated fabric with a spongy surface as a backing fabric or endless
conveyor backing to give more effective squeezing of heavy fabrics in
continuous dyeing and finishing.
7.4.6 Semi-continuous and Continuous Dyeing Methods

Continuous dyeing is aimed at maximum productivity, but considerations of
resource conservation and environment protection are now overtaken in
importance. Conservation measures include the recovery of heat, water,
chemicals from waste process liquor, lower liquor retention in padding, slick
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rollers and loop transfer methods of application and more efficient

hydroextraction to achieve minimum cost of drying.
The semi-continuous methods are also popular, the alternate sequences
are:
1. Pad Æ cold batch Æ wash

2. Pad Æ preheating Æ hot batch Æ wash
3. Pad Æ dry Æ jigger development
The three sequences are shown in Figure 7.16.
Pad Cold batch Wash
IR heater
Steam-filled
Pad Hot batch Wash
Pad Dry Jigger
Fig. 7.16 Three Semi-continuous Sequences of Fabric Dyeing
In cold-batch process, the fabric is padded with the dye and necessary
auxiliaries, and is batched on a roll. The rolls are subsequently stored for
2−24 hours depending on the time required for fixation. Covering the rolls
with polyethylene sheets during storage is advantageous. During storage,
the rolls are to be rotated slowly to prevent drainage of padding liquor. The
method is very popular for application of cold-brand as well as Remazol
brand of reactive dyes.
Pad-hot batch system was first developed in Sweden in 1954 for
application of direct dyes on cellulosic materials and acid dyes on nylon and
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then extended for application of metal-complex dyes to warp-knitted nylon

automobile fabrics. The method may also be used for application of hot-
brand or Remazol brand of reactive dyes. The fabric is padded with the dye
and then preheated with IR (infrared) heater for only a couple of seconds
before the fabric is wound on a large roll. The roll is kept in an atmosphere
of saturated steam in a cottage or chamber for several hours for dye fixation
to take place. The roll is slowly rotated during the period to prevent the liquor
from settling. The heat input should be carefully regulated to raise the
temperature of the wet fabric to near 100°C without drying and without
excessive condensation. Very few dyers achieved this objective
successively and consistently and now it is rarely used for coloration.
In another popular sequence, the fabric is padded with finely dispersed
non-substantive dyes, dried and then the fabric roll is transferred to a jigger
where the development or fixation is carried out, followed by washing.
The most common sequence for continuous dyeing is padding followed by
drying, steaming and washing in continuous machines. In many cases, an
additional padding step is necessary between drying and steaming for
application of fixation chemicals just before steaming. Therefore, the most
popular sequence for continuous dyeing, as shown in Figure 7.17, is:
Pad Æ dry Æ pad Æ steam Æ wash
Pad Dry Pad Steam Wash
Fig. 7.17 Continuous Pad-steam Range for Fabric Dyeing
The classical pad-steam route was developed by Dupont for the

production of military uniforms with vat dyes, and was later adopted for other
dye classes. It is still the major method used by continuous dyers to apply
vat, reactive and sulphur dyes on cellulose in a fully continuous process.
However, the dramatic growth in the leisure and sportswear sector has had
an impact on the industry. Frequent fashion changes have led to a
requirement for more rapid response and lower stock inventories, which in
turn have resulted in a dramatic reduction in lot size. The reduction in lot
sizes forced continuous dyers to develop other methods apart from pad-
steam. Some of the alternate routes rely on different ways of generating
heat energy.
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Pad-dry-bake method is well established for dichlorotriazine (DCT) and

monochlorotriazine (MCT) reactive dyes and currently for bifunctional MCT
reactive dyes. However, the use of urea in the process results in obnoxious
fumes in the factory.
Investigations were made to introduce a simpler method of heat fixation
dyeing. In Ecosteam method, introduced by Brückner in early 1980s, the
fabric remains wet (instead of dried), condition known as warm wet dwell,
before fixation. However, the method has not produced any major impact in
the market. In the absence of urea, poor colour is obtained. On the other
hand, urea can be avoided with DCT reactive dyes if a certain degree of
humidity can be maintained around the fibre whilst fixation takes place. In
the Econtrol process, recently developed jointly by Monforts and BASF, the
relative humidity content in the dryer is carefully controlled. It is
demonstrated that in the hot flue drying, the minimum drying cost is
achieved with humidity content of 10-20 vol%. In Econtrol Thermex machine
(Monforts), humidity is injected into the hot flue at the impulse of the
computer, which would monitor and control the humidity level (about 20−25
vol% relative humidity). The machine is not very effective for less reactive
MCT dyes.
Continuous roller steamers are used for fixation of different classes of
dyes on cellulosic and blended materials in continuous dyeing processes.
The fabric is subjected to a treatment with saturated steam at 100°C while
the uniform distribution of dye in the fabric is undisturbed. The fabric in
open width is taken around alternate rollers in top and bottom horizontal
banks as in hot-flue dryer. The top rollers are driven, commonly by chains
but increasingly by a series of hydraulic motors, and the bottom rollers are
free wheels. The rollers must be accurately aligned to avoid the formation of
any lengthways creases. The roof is heated by steam to avoid
condensation. The main supply of steam is around 90 kPa feeding directly
into a water pump at the bottom of the machine and is controlled by a
thermostat. Thermostat settings of 105−108°C are customary, implying a
small amount of superheat and slight heat loss by the fabric. The water
rapidly raises to the boil and helps to maintain equilibrium at the steamer.
The fabric enters the steamer through a narrow slot, which is heated to
prevent droplets of condensation and against a slight counter-current of
steam to minimise the inflow of air with the fabric. The presence of air, as
little as 10−20% in the steam, is said to reduce the evaporation temperature
to 97−94°C respectively, affecting dye fixation significantly. The heat transfer
rate to the fabric is also reduced. Steam, being less dense, displaces air
downwards and air venting is effected mainly through steam traps. However,
some venting from the roof is desirable to remove air-steam mixture. When
leaving the steamer the fabric passes through an exit leg, often feeding
directly into a cold-water seal.
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For the diffusion of reduced vat and sulphur dyes, steaming time of 20−60
seconds is usually allowed and capacities are of the order 30−60 metres of
fabric. For steaming of vat dyed materials, the steam vapour must be dry
and saturated at 100°C, i.e. with minimum superheat. But the practical figure
will be 102−104°C. The steamer should be completely free of air during
steaming. The wet exit leg must be kept cool by a constant cold water feed,
otherwise, it will act as a dyebath.
Economical continuous dyeing ranges are designed for the processing of
short lengths (500−1,000 metres) in order to provide versatility of response
to fashion colour changes. One such machine, Kleinwefers Universa-colour
pad-steam range, consists of a two-roll padder with economy trough, special
wet-on-wet chemical applicator, a small horizontal steamer with water lock
for rinsing or acid development and a compact rinsing, neutralising, oxidising
and soaping compartment. In most of the conventional steamers, there are
two sets of rollers at the top and bottom of the machine and the fabric mostly
moves in vertical direction. On the other hand, in horizontal steamer, the two
sets of rollers are in vertical direction and the fabric mostly moves
horizontally.
Another advanced steamer is loop or festoon steamer, such as Stork HS II
steamer. This atmospheric (pressure-less) steamer is suitable for all types of
steaming with saturated steam at 100°C and superheated steam up to
185°C, especially for the printed materials. The fabric in-feed and low-
tension plaiting system makes the steamer suitable for all qualities, even
extremely sensitive knitted materials. The loops of fabric are rested on rods
and the rods are carried forward by a chain. The loops are formed under the
influence of the fabric’s own weight without any additional tension. The
tension of the fabric can be reduced by about 50% by reducing loop length
down by almost one half. At regular intervals, a rod on the transport chain is
brought up from the bottom of the steamer. The rod picks up the fabric web
with which it hangs free. The chain and the rod run vertically again, so that
the fabric which follows can form a free loop. The transport rod is finally
positioned on the rails in order to be moved to the back of the steamer. The
rod rotates slowly and continuously so that the fabric is not marked. In the
meantime, a new rod arrives from the back of the steamer in order to form a
new loop. One side of the fabric is untouched by any mechanical part,
which is advantageous for printed materials.
In case of synthetic fibres, especially with polyester, the steaming step
may be replaced by a hot-air treatment, commonly known as Thermosoling,
introduced in 1950s. The process has changed a little and depends on heat
treating the polyester at a temperature of 200−220°C with disperse dyes.
After uniform application of dyes by padding, it is crucial to dry the fabric
without permitting migration of dyes. Conventional drying methods apply
heat to the surface of the wet fabric, producing a rise in temperature leading
461
to evaporation of water from the surface and transportation of water from

inside the fabric to the surface until the fabric is dry. The movement of water
causes migration of dyes and other substantive solutes to the surface. As
below 30% liquor pick-up the migration is negligible, the padded material
with liquor pick-up above 50% is to be dried quickly to bring the pick-up at or
below 30%. Where the chances of migration are too high, as in the case of
disperse dyes on polyester, an infrared (IR) preheater is mounted above the
padding mangle. The fabric emerging from the nip and without touching any
roller is subjected to a powerful blast of radiant heat for a few seconds. The
temperature of the wet fabric raises quickly around 100°C when there is
rapid loss of moisture from fabric surface. The IR heat must be equally
balanced on both sides of the fabric to prevent migration. The IR preheaters,
having length of 1.5−3 metres and temperature around 800°C, may be
heated electrically or by gas. The heat output is very high and difficult to
control. An IR radiation of about 3 µm wavelength is required as it is
preferentially absorbed by the textile materials. The IR preheater is
preferably aligned vertically and warm air is blown in and travels upwards
along with moisture of the fabric.
The Thermosol technique for dyeing fabrics containing polyester consists
of five steps, as follows:
1. Padding the dye-liquor onto the fabric.
2. Pre-drying with IR preheater to prevent migration.
3. Final drying on steam-heated cylinders.
4. Fixing the colour by a treatment at 200−220°C normally for 30−60
seconds.
5. Washing.
The fixation may be carried out on a variety of machines capable of
heating the fabric uniformly to about 210°C, the variation across the width
should not exceed ± 3.5°C.
Originally, pin stenters were used for thermofixation. However, long
stenters with eight or more chambers are necessary. This involves a very
long pin chain, much space and very high capital and maintenance cost.
The pins and pin-plates introduce variation in heating at the selvedges.
Hot-flue units are widely used in Western Europe, the fabric being led
vertically round a series of top and bottom parallel rollers mounted in an
oven. Air is circulated around heat exchanger at the bottom. The top rollers
are driven (nowadays by hydraulic drive) while the bottom are free running
and are at a distance less than 125 cm from the top. Large diameter rollers
(18 cm) are used to avoid fabric creasing. Due to smooth surface of the
rollers, there is significant amount of fabric slippage and a fair amount of
lengthways tension must be maintained. The lengthways tension in the
fabric causes it to stretch slightly. In many machines, the drive to the top
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rollers is divided into two or more sections, the speed of the rollers in each
section being controlled by the position of a compensating roller immediately
preceding the section. The fabric enters and exits through narrow slots. At
the entry, the fabric is subjected to a blast of hot air to raise the temperature
of the fabric quickly. It is important that the fabric is fully dried and hot when
it enters the machine. The heating may be made by passing air through a
heat exchanger filled with oil or may be heated with burnt gas. The rate of
heat transfer is not as good as that in stenter and the heat transfer from
roller to fabric plays an important role. The fabric selvedges tend to heat up
more quickly than the body of fabric. The inner surface of the oven should
be well-insulated [6]. There is no control of the width of fabric. In order to
compensate the widthways shrinkage, Monforts Thermosoling unit consists
of a hot-flue unit to provide dye fixation followed immediately by a short pin
stenter.
Hot flue units require 30−90 seconds for dye fixation, but much of this time
is utilised for raising the temperature of fabric. Contact heating by cylinders
provides much rapid heat transfer, hence the time required may be as low
as 20 seconds. Cylinder thermosoling units are used in USA. The cylinders
of about 60-cm diameter are mounted in banks and heated internally by gas
firing. The fabric tends to have a polished appearance.
Fleissner perforated suction drum range contains 4−8 perforated drums of
100-140 cm diameter. By fitting an exhaust fan to the drum axis, air is drawn
through the fabric as it moves with the rotating drum, ensuring good contact
of the fabric with the drum. The air is heated by a hot-oil or gas-fired heat
exchanger and recirculated. The air flow through the unused arc of the drum
is being restricted by internal baffles. The rate of heat transfer is
exceptionally good, as benefits of contact heating as well as passing air
through the fabric in alternate sequence, are combined rather than blowing
air on the fabric surface as in stenter. On leaving the heated chambers, the
fabric passes round a cooling cylinder, normally filled with cold water. The
dye fixation time is around 15−20 seconds with a six-drum machine running
at a speed of 60 m/min. The range may be fitted in tandem with a padding
mangle and preheating unit and others are supplied with a pin stenter. At the
end of the run, circulation and expulsion of air should be continued for
several minutes to remove the dye leaving the fabric and circulating with hot
air.
7.4.7 Continuous Washing Ranges

As discussed earlier, in batch dyeing machines washing after dyeing is
carried out in the same machine after changing the treatment liquor. In
continuous dyeing machine, each unit performs a specific job and a
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continuous open width washing range is necessary for removal of dyes and
chemicals after dyeing.
Washing is necessary not only after dyeing and printing but also after
scouring, bleaching, etc. Just about 30 years ago, the major fibre being wet
processed was 100% cotton, as polyester was not widely available and it
was often prepared in rope form. The rope washing at that time was a spiral
rope washer. Such rope washing was refined into Tensitrol washer, which is
still in use. With the introduction of polyester and the use of wider fabric, the
rope processing was almost impossible to carry out without the problem of
creasing. Open-width washing machines gradually replaced rope washers.
Some of the merits of rope washers are:
1. Independent of width up to a certain limit.
2. Easy movement of fabric over long distances.
3. Higher running speeds.
4. Less storage space.
5. Less floor-space for the washer.
6. Less capital and maintenance costs.
7. Less tension on the fabric.
8. Better relaxation of fabric resulting in better handle.
9. Savings of water, time, etc.
The demerits of rope washing are:
1. Unsuitable for fabric of all types and weights.
2. Additional opening stage after washing.
3. Fabric structure prone to distortion or creasing.
4. Light fabrics prone to tangling and knotting.
5. Difficulty of loading compartments equally.
Open-width compartments may be of four types:
1. Tight-strand washers, i.e. vertical and horizontal washer, which are
most popular.
2. Drum washers, i.e. suction or sieve drum washers and possibly a
spray.
3. Spray or jet washers, i.e. washers using jets of liquor but not drums.
4. Slack or relaxation washers, i.e. conveyors or storage chambers.
Continuous open width washers probably started as a single-dip saturator

and quickly evolved into a multi-dip box in which the fabric passes
alternately between the top and bottom rollers (in tight-strand machines)
with the latter being immersed in washing liquor. The top rollers are driven
usually by chains or V-belts in a bank of five or six, which make up a
compartment or unit. The bottom rollers are free wheels. Both the top and
bottom rollers should be of largest practicable diameter, e.g. 12−13 cm and
distance between them should be kept to a minimum to reduce fabric
464
creasing or curling. In the era of cheap energy, these open vertical boxes
dominated the market. Each rinse box in the range was flooded with plenty
of fresh hot water. As energy availability decreased and cost increased in
the 1970s, tremendous interest developed in decreasing energy cost for
continuous washing. Counter-flow lines were added to existing ranges,
partitions were added between the bottom rollers inside the box to increase
the counter-flow effect and makeshift tops were attached to the open boxes
to reduce heat loss.
The standard range consists of a series of compartments, separated by
mangle nips which draw the fabric through the machine and to limit the carry
forward of liquor, which determines the washing efficiency. The
effectiveness of washing also depends on the number of units in the range
and on the efficiency of impurity interchange between fabric and wash
water. The use of water may be minimised by feeding fresh water at the last
chamber which flows to the last but one chamber and so on, i.e. the flow of
water is opposite to the flow of fabric. Each successive immersion of the
fabric is in cleaner liquor, whereas the liquor becomes increasingly
contaminated as it approaches the discharge point close to the fabric
entrance.
The fabric path in the washing compartment is vertical between the upper
and lower rows of guide rollers, with only the lower ones submerged. More
recent designs have a horizontal fabric path with enhanced counter-flow of
water (Figure 7.18), whilst the use of spray techniques (as opposed to fabric
Fig. 7.18 Horizontal Washer

465
being immersed in water) has the benefit of reducing the amount of wash
liquor substantially. The spray techniques give better mechanical push
through of the liquors into the fabric. When a compact machine is required,
double threading or lacing may be employed, in which case additional free-
wheeling top and bottom rollers are fitted between each set of top and
bottom rollers as in Benninger Becoflex washing compartment (Figure 7.19).
This arrangement effectively doubles both the fabric capacity per washing
unit, the number of immersions and the effective time of washing for a given
speed. However, the arrangement is complicated, the threading is difficult
and accessibility is reduced. In Convi-Tex C (Babcock, Germany) spray
lines with flat section jets are used in place of nips between compartments.
The jets run on recirculated or heated fresh liquor. Nip unit is retained at exit
of the washing zone. It is based on modular system − several compartments
(as per requirement) are joined together to form a long self-contained and
steam-tight assembly without intermediate nip units.
Fig. 7.19 Double-laced Enclosed Washer with Internal Nips
Several techniques are adopted by the machine manufacturers for

promotion of fabric-liquor interchange and for providing mechanical action
on the fabric, such as:
1. Fluted or wavy bottom rollers, which not only agitate the wash liquor in
the box, but also tend to force liquor through the fabric.
2. Passing the fabric between corrugated formers, which distort the
liquor movement, e.g. Gaston County Agitator.
3. Passing the fabric round a 30−cm diameter perforated cylinder
immersed in wash liquor as in Kuster Vibrotex machine. The axle of
the cylinder is vibrated and it causes vigorous radial oscillations in the
wash box. Such a type of machine is intended for fairly open-
structured fabrics, especially knitted fabrics.
4. Passing the fabric round a perforated drum containing an inner fluted
roll or a roll fitted with baffles, independently controlled. The rotation of
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the inner roll induces a pulsating action on the fabric. The outer roll is
free rotating and is taken round by the fabric.
7.5 GARMENTS AND FOOTWEAR DYEING
Conventionally, fabric is dyed in piece form, which are subsequently cut to

shape and made up into clothing. However, a significant section of dyeing
and finishing industry is involved in dyeing in the form of garments, footwear,
etc., especially made of knitted fabrics. The dyeing machines are developed
to handle hundreds of individual articles of different shapes and sizes rather
than fabrics of definite lengths.
Paddle wheels and laundry wheels are the two types of machines used in
garment dyeing. Sweaters and socks are dyed in paddle machines for many
years. Paddle machines are available as overhead and side paddle wheel
types. The gentle action of side paddle makes it ideal for dyeing delicate
garments such as wool or acrylic knitwear. The disadvantages of such
machines are high liquor to material ratio (usually 50:1, minimum 25:1), high
consumption of water and energy, high labour costs and unlevel dyeing. A
fixed amount of material loading is necessary for good circulation of goods.
Modified side paddle machines with paddles of variable speed and length,
and perforated paddles are also available.
The first rotary or centrifuging garment dyeing machine was installed in
1969 by Neil and Spencer in London. The modern rotary drum garment
dyeing machines have advantages of low liquor to material ratio (8-15:1),
high versatility, less labour, level dyeing, easy sampling, easy loading and
unloading, automatic control of dyeing cycle and hydro-extraction. The
disadvantages of rotary machines are their high initial costs and
maintenance costs.
The traditional and commonest machine in general use is Gorrie or oval-
type side paddle machine (Figure 7.20). The machine is oval shaped in
horizontal plane with an annular dye vessel (V) round a central island (I)
formed by a perforated sheet separating the goods from the water space
within the island. The dye liquor along with goods is circulated round the
annulus by a large multi-bladed paddle (P) located on one of the straight
sides of the machine. The central island may be used for discharging the
liquor away from the garments and for addition of dyes and chemicals.
Garments may be dyed loose or in open-mesh bags of polyester or
polypropylene. Two heating pipes are fitted at the bottom with holes so
arranged that the live steam lifts the garments to keep them in circulation.
Compressed air may be employed if closed steam coils are used. The
machine may be open or totally enclosed with a hood, which may be lifted
for loading and unloading.
467
Fig. 7.20 Schematic Top View of Side Paddle Machine
The machine capacity usually ranges from 1,000 to 5,000 litre liquor with
lowest liquor ratio of 25:1. The paddle wheel on a 2,500-litre machine is
about 1.5 m in diameter with the axis mounted above the highest water
level. The paddle rotates at about 5-10 r.p.m., each of the five blades
penetrating to about half the depth of the liquor, and each blade being
slightly swept back primarily to minimise the risk of catching garments or
bags carrying garments on it. The paddle induces considerable turbulence
into the circulating liquor.
At the end of processing, the garments are fully impregnated with water
and they must be lifted out in this state and transferred to the centrifuges to
remove most of the water. Unloading from a side-paddle machine is
strenuous. After cooling and rinsing the goods, the paddle wheel is set in
motion and the operator standing on a platform grabs and lifts the garments
or bags as they float past. No satisfactory alternate method has been found.
Side-paddle machines are simple in principle and cheap. They can be used
for scouring, bleaching, dyeing and finishing of garments.
Gridflow paddle machine (Freeman Taylor Machine Ltd.) is totally
enclosed and it incorporates perforated paddle blades. Footwear is
generally packed in mesh bags for dyeing, and the holes in the blades
cause a current of dye liquor to pass through the bag during the period of
contact.
Overhead-paddle machine (Figure 7.21) consists of a dye vessel with a
semi-circular bottom and a four-bladed full-width paddle mounted at the top
and back of the machine. The blade dips about 10 cm into the dye liquor
and pushes the garments and liquor down. The machine relies not only on
the paddle for circulation, but also on the curved sides of the tank deflecting
the flow imparted by live steam emerging from the heating pipes. These
machines are cheap but more difficult to unload and suffer from the
disadvantage that the circulation of the goods practically ceases if the steam
has to be turned off. Sometimes compressed air or an air-intake Venturi
468
tube is connected. Overhead-paddle machines are used for dyeing

stockings (in bags), felts for hat, etc.
Fig. 7.21 Schematic Side View of Overhead Paddle Machine

In rotary-drum machine (Figure 7.22), the goods are placed in a perforated
horizontal cylinder (P) rotating slowly (5 to 15 r.p.m. depending on the size
of the drum) inside a vat of slightly greater size (V) having a door (D) at the
top and partially filled with dye liquor. The internal cylinder is divided into
separate quadrants (Q1, Q2, Q3, Q4), thus ensuring that the goods move with
the rotation of the drum and each quadrant has its own sliding cover (C). It is
customary to mount two drums side-by-side on the same revolving shaft. A
standard size machine may have the following specifications:
Drum diameter: 116 cm
Drum width: 80 cm
Liquor capacity: 1800 L
Maximum load: 90 kg
M:L ratio: 1:20
D
C P
C
Q2 Q1
Q3 Q4
C
V
Fig. 7.22 Rotary Drum Dyeing Machine

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Rotary drum machines are used for dyeing small garments, especially
stockings and hoses. The garments may be placed in open mesh non-
absorbent bags randomly or after folding flat. The mechanical action in the
machine is very gentle. The rotary drum is cheap, compact and simple to
operate. Silk hosiery is frequently dyed in such machines, but the internal
surface must be polished to the highest degree of smoothness. A reversing
mechanism causes the drum to make a certain number of rotations in one
direction and an equal number in the C other. High temperature rotary dyeing
machines and machines with programmable automatic controller are also
available.
The tumblers are similar but front-loading machines. The goods are
loaded into a perforated drum, which rotates about a horizontal shaft at the
back of the machine. The drum may be divided into three or four pockets or
fitted with buffles to lift the goods, which are usually contained in bags. The
height of dye-liquor in the drum may be varied over a wide range and the
M:L ratio may be kept as low as 1:8. The speed of rotation is variable,
usually in the range of 10-30 r.p.m. The tumbler machine may be used for
denim washing and scouring of garments and particularly for milling of
woollen garments. The speed of rotation has a marked effect on the rate of
milling. A hot-air blowing system may be incorporated, as used in tumbler
dryer, thus providing a complete dry-to-dry sequence in the same machine.
The differences in mechanical action between tumbler and paddle machine
results in significantly different products. Tumbling promotes shrinkage and
bulk in crimped nylon.
With the introduction of textured polyester yarns into knitted garments,
dyeing became necessary to be carried out at 120-125°C and pressurised
garment dyeing machines, such as Pegg Toroid machine, have been
developed. The principle is to induce a circular flow in a vertical plane
around the machine. The load of garments is placed on a removable
perforated false bottom, which may be lifted for unloading using an
overhead hoist. The pump collects the liquor from the bottom of the vessel
and impinges upon a spreader plate, which deflects the flow round the sides
of the cylindrical outer vessel. It then flows over the top of the annular cage,
containing the goods, from which the pump withdraws the liquor through a
central perforated pipe. A swirling action is imparted to the dyebath, which
keeps the goods in constant movement.
Static machines work on the principle of circulating the liquor through a
stationary pack of garments and have been developed for dyeing fine
hosiery, with the advantage of preventing damage to the delicate fabrics,
often containing elastomeric (e.g. Spandex) fibre. The hosiery may be
presented in polypropylene bags or on trays.
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7.6 FOAM DYEING MACHINES

The conservation of water and energy is assuming importance day by day.
Sandoz (presently Clariant) developed Sancowad method in 1971 to
investigate the possibility of dyeing in liquor ratios of the order of 1.5 to 1, by
converting water phase into microfoam. The foams used for textile dyeing
and finishing are invariably generated from a dispersion of air in the
aqueous dyeing or finishing liquor.
The machine (Figure 7.23) was originally developed for solvent dyeing.
The goods are placed in a rotating drum (D), which is rotated by a motor
(M). The dye liquor is made up in the mixing tank (T). The drum is set in
motion. The dye liquor is pumped via valve (V) and pump (P) and is sprayed
onto the rotating load with the help of a sprayer (S) to give a pick-up of
about 100% on the weight of dry goods. The dye liquor contains:
1. x% of dye
2. 20 to 40 g/l of foaming agent
3. Other assistants required for the specific dye-class
4. Required amount of water to have a M:L ratio of 1:1.5 to 1
The composition of the foaming agent is not revealed, but sodium salt of
lauryl sulphuric ester of an ethylene oxide condensate and
nonylphenylpentadecaglycol ether are quoted as possible foaming agents.
In addition, a foam stabiliser is required.
D
S
T
V
P
Fig. 7.23 Sancowad Dyeing Machine

When the whole of the liquor has been discharged through the spray into
the drum, the rotation is continued at cold for 15 minutes during which the
foam bearing the dye is distributed uniformly throughout the charge. After 15
minutes, the temperature is raised to 100°C or at the temperature required
471
for the particular dye-class, either with steam or hot air or both, and the
machine is allowed to run at the temperature for 30-45 minutes during which
fixation takes place. The cycle may be programmed to carry out any desired
sequence of operations such as dyeing, rinsing, finishing, centrifuging and
drying. As the necessary amount of water is significantly lower than in
conventional processes, the Sancowad technique resulted in substantial
savings, in both water consumption and the energy required for heating.
The Sancowad foam-dyeing principle has been extended from batchwise
to continuous dyeing systems and this approach to the saving of water and
energy has proved appropriate for the dyeing of pile fabrics and carpets.
7.6.1 Continuous Application of Foam

The technology for continuous application of foam differs from the
Sancowad technique, in that the foam is generated by mechanical action
prior to application. The foam application techniques permit liquor to be
applied at the pickup values of 25-35% for cotton and 10-20% for synthetics.
In foam generator or foam mixer, compressed air is driven through a
closed system into the liquor, which is foamed forcibly by the pressure. From
the moment the foam exits from the mixing head, the pressure gradually
declines and by the time it flows from the outlet pipe, it has a fine cell
structure. The foam generator manufactured by BIP (UK) is based on a
nozzle system. All generators are fitted with elaborate setting and control
devices, which enable foams of constant composition. Every foam
application system requires foam of a particular quality. Some other makers
of commercial foam generators are Hansa-werke, Mohr, Weserland
(Germany), Mondo-mix (Holland) and Oakes (USA).
The continuous methods have following steps:
1. Foam generation.
2. Foam application to the substrate.
3. Foam distribution with simultaneous drainage and diffusion of the
liquid into the substrate.
4. Foam collapse and release of active substance.
5. Fixation of the active substance.
The various methods of continuous application of foams are [10]:
1. Horizontal padding machine [Figure 7.24(a)] may be used for
application of foam on both sides of the fabric, which may be set with
a slit opening. The wetting power and the rate of foam decay have to
be closely attuned to the substrate. The air from the drained foam
dilutes the remaining supply of foam in the nip, which may make
constant dosage problematic. The method is suitable only for open-
structured fabrics and non-woven fabrics.
472
2. In Valchem process [Figure 7.24(b)], the foam is spread on the

substrate with a coating blade, the dosage is controlled by the gap
between the blade and substrate. The foam is then broken down by
the pressure from a pair of squeeze rollers. The fabric should have
even absorption capacity and should run under constant speed during
application.
3. The second method of Valchem/United Merchants and Manufacturer,
USA [Figure 7.24(c)] also employs a blade for direct foam coating.
Instead of a pair of squeeze rollers, a suction nozzle is placed
underneath the fabric, which draws the foam down. Besides breaking
down the foam, the arrangement improves penetration.
4. The FFT process developed by Gaston County and Union Carbide,
USA [Figure 7.24(d)] utilises a slot nozzle, which drives foam upwards
against the fabric. Relatively unstable foams are used which break
down as soon as they touch the substrate and wet it out rapidly. The
wetting out of fabric and the collapse of foam occur at the nozzle
surface within milliseconds. Penetration is assisted as the foam is
driven under slight pressure. Two slot nozzles may be placed on both
sides of the fabric.
5. In the Hoechst method [Figure 7.24(e)], the foam is deposited on the
fabric through a chamber-like slot. A suction element, placed below
the fabric and aligned with the nozzle, draws the foam through the
fabric.
(a) (b) (c) (d) (e)
Fig. 7.24 Various Methods of Continuous Application of Foam

6. Foam may also be applied by a rotary screen printing machine. The
Mitter (Germany) foam applicator was designed for carpet printing with
a triangular screen and a doctor roller. Stork (Holland) developed RSF
foam applicator in which a specially designed slit doctor presses the
foam through a cylindrical screen. As it is a virtually closed foam
transfer system of low foam content, foams of low stability and of any
desired viscosity can be used.
7. In Monforts’ (Germany) Vacu Foam applicator, a doctor blade applies
foam onto an endless rubber belt, which meets the fabric at the point
of contact with a vacuum cylinder. The rubber belt seals the cylinder,
473
creating high vacuum, which draws the foam forcibly into the fabric, on
which the bubbles expand, break and the foam collapses.
7.7 SPACE DYEING MACHINES
Space dyeing concerns section-wise dyeing or printing of fabric or yarn and

tow in order to achieve fancy effect after fabric manufacturing. The effect
obtained is localised application of dyes, i.e. effect similar to that obtained in
printing, but by dyeing methods. Though during space dyeing, colours are
applied at regular intervals, the effects obtained after fabric manufacture are
abstract and random. Thus, the style obtained cannot be imitated by printing
directly on the fabric. Space dyeing is the collective term for a variety of
methods [11].
The working methods can be divided into several groups, such as space
dyeing methods of:
• Knitted fabrics and deknitting
• Warp yarns
• Hanks of yarn
• Wound yarn packages
• Knitwear, woven fabrics, tufted material and non-woven
The term printing has been used here frequently, but it is actually localised
application of dyes and not printing with any conventional printing machine.
7.7.1 Knit-deknit method

In knit-deknit method (USA), the yarn is knitted, padded with pale colour and
printed wet-on-wet. After printing, the goods are passed through an ager,
where they are steamed for 3-10 minutes in saturated steam. This is
followed by rinsing, washing, finishing and drying. The material is then
deknitted, reeled, wound on bobbins or section beamed and run into tufting
machine.
7.7.2 Space Dyeing of Warp

In Laing method (Edger Pickering Ltd., UK) [Figure 7.25(a)], about 500
threads running parallel to each other are padded and printed. Two rollers of
different sizes are used, the lower roller is smaller and dips into the colour
trough. Colour paste is transferred only when the relief patterns of the upper
and lower rollers meet. Multicolour effects can be obtained by arranging
several print rollers in series.
Stalwart method (Stalwart Dyeing Co., UK) [Figure 7.25(b)] is similar to
the Laing method. The difference is that smooth rollers are used instead of
rollers engraved with a relief pattern. The upper roller is pressed on the
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lower roller for transfer of colour and then lifted. Monitoring of the movement
of upper roller is automatic, either electronic or mechanical.
Martin process (Martin Proc. Int. S.A., Belgium) is similar to Stalwart’s, but
several independently controlled rollers are used instead of a single roller
over the full width of the yarn.
In Zaza printing (Antonis Zanolo, Italy) and also in Vigoureux printing
[Figure 7.25(c)], the yarn sheets are passed between an engraved roller and
a felt-covered roller supplied with colour paste from the trough directly or by
means of a rubber roller. The colour is transferred to the yarn whenever the
raised parts of the engraving press the yarn on to the felt roller.
In Eastern Colour Dyeing Method (Daito Sangyo Co. Ltd., Japan) [Figure
7.25(d)], yarn is reeled off from bobbins, passed by the side of centrifuges
supplied with dye liquor from above, sprayed, dried briefly and wound
(a) Laing (b) Stalwart (c) Zaza/Vigoureux (d) Eastern Colour Yarn
Dyeing
(e) H-W-D (f) Astro-Dye (g) Polychromatic Dyeing
Fig. 7.25 Various Space Dyeing Methods

immediately. Three centrifuges are arranged on top of each other and up to
three shades can be applied on the yarn. Fixation is then affected by
steaming.
475
The Superba method (Ets. Superba, France) is similar to the above, but
the colour is sprayed in vertical direction and eight threads are sprayed
simultaneously.
In OPI method (Omnium de Prospective Industrielle S.A., France), the
desired space-dye effect is produced by the to-and-fro movement of a jet-
bar (eight jets) transverse to the running direction of eight yarn threads. Up
to three jet bars can be used, depending on the required pattern. The
traverse movement is monitored electronically. The excess dye liquor is
removed, or the material is dehydrated, by compressed air with a specially
developed jet acting individually on each thread.
Unitika-Mixy method (Unitika Ltd., Japan) is similar to the above methods.
The colour is applied by jets on the reeled off yarn running at high speed.
The yarn is dried and rewound on a bobbin.
7.7.3 Space Dyeing of Hanks

Timmer hank yarn printing machine (J. Timmer, Germany) consists of four
pairs of small rolls running through the colour troughs and two counter-rolls.
Printing is effected in four phases. In every phase, one quarter of the total
circumference of the hanks is printed. Movement in longitudinal hank
direction is automatic. The hanks are moved in transverse direction and
stopped automatically for colour application. The machine is suitable for a
definite hank length.
In VH-Syn-O-Flow method (Vald Henriksen A/S, Denmark), the hanks are
rolled up in moderate density around a stainless steel drum fitted with slits.
Coloration is effected automatically with all 60 dye-liquors at the same time,
in 30 to 90 seconds, through the drum slits. The total quantity of wool yarn
dyed in one operation is 5 to 7.5 kg.
Multispace dyer machine (Callebaut-De Blicquy S.A., Belgium) is
developed for continuous dyeing and steaming of yarn in hanks. For
coloration, the yarn hanks are placed in series transverse to the direction of
the movement of the conveyor carrying the hanks. The conveyor runs under
a series of 40 jets placed side by side and transverse to the conveyor when
colour is sprayed on the hanks. A group of 10 jets with variable sequence
sprays colour liquors, hence four colour liquors may be applied
simultaneously. After spraying, the conveyor passes through a steamer
when the colorants are fixed. The speed of the conveyor can be varied
between 0.9 to 3 m/min.
Hussong-Walker-Davis (H-W-D) method (Hussong-Walker-Davis Co.,
USA) [Figure 7.25(e)] is a mechanised version of Ombré dyeing or shadow
dyeing. The hanks are suspended from several arms, which can be turned
around their longitudinal axis. The hanks are sprayed from both sides and
from inside by means of spray tubes rigidly fixed parallel to the arms, using
476
hot dye liquor. The excess liquor runs down the hanks and is recollected
and pumped back to the spray tubes until the dye is exhausted. The height
of the arms can be adjusted, so that spray tubes can cover a fairly large
area of the lower part of the hanks. The position of the arm determines the
length of hank to be dyed. After the first shade is applied, the hanks are
moved by a definite length around its circumference. The second liquor is
applied. This can be repeated until the hanks are completely dyed.
7.7.4 Space Dyeing on Wound Packages

Astro-Dye method (Astra-Dye-Works, USA) [Figure 7.25(f)] enables
spraying of dye solutions in yarn bobbins to obtain coloration up to four
shades. The spray arrangement consists of four bars arranged at equal
distance around the yarn bobbin. Each bar houses four injection syringes or
nozzles, placed on top of each other. Each of these 16 syringes may contain
any of the four dyestuff solutions. The yarn must not be soiled and all
bobbins must be equally tightly wound. The dyes must have good solubility
and a rapid wetting agent must be used. The dye liquor should be accurately
metered depending on the type of fibre and method used.
7.7.5 Space Dyeing of Tufted Carpets, Knitted and Woven Fabrics

In Küster continuous carpet dyeing machine, the liquor is taken off a carrier
roller by means of a doctor blade and transferred in full width to the surface
of the goods. A modification of this process, TAK space dyeing method
(TAG, Germany) utilises a special doctor blade, which applies the dye liquor
in the form of individual thin streams running through narrow channels. By
moving the doctor blade to-and-fro at the transfer roll, wavy lines are
produced on the running carpet material. However, this is prevented by
means of a chain band, which distributes the streams irregularly in the form
of drops over the entire material. The irregular application of drops in
different colours on pre-dyed material produces a number of mixed colours
and overlapping designs. The standard TAK model has two colour
applicators.
Polychromatic method (James Farmer Norton, UK) [Figure 7.25(g)] can be
used to produce a wide variety of patterns in many shades on tufted carpets,
woven and knitted fabrics and non-wovens, even on warp threads. Two or
three sets of jets apply the dye liquor to the goods passing below the jets.
The individual jets can be connected with dye liquors of different colours by
means of a special dyestuff supply tube. A sheet called mirror is placed at
an angle below the jets. The angle is so adjusted that the liquor stream
coming from one or two series of jets reaches the goods only after running
down the slanted sheet, ensuring partial mixing of the dye liquors. Lateral to-
and-fro movement of the rows of jets produces changes in patterns and
477
colour mixtures. After applying a constant amount of liquor, which must be

fixed beforehand by a suitable choice of jet size, the goods are passed
through a padder, when the final pattern is obtained. The goods are then
steamed continuously, washed and dried.
7.8 WATER EXTRACTION OR DRYING
The drying operations are carried out in order to remove water from textile
materials that have been thoroughly wetted in the dyeing process. When a
textile material is withdrawn from dyebath, it may retain three or four times
its own weight of water, the ratio may fall to two or less if the material is
allowed to drain briefly. The objective of drying processes is to reduce the
water content from a value probably well in excess of 100% to a value close
to the normal air-dry figure, which for cotton fibres is typically 6−7%. Drying
may be achieved by keeping the material completely exposed to open air.
However, the process is extremely slow and cannot be followed in industry.
In industry, the last stage of drying must be carried out by evaporation, but
thermal drying is inevitably an energy-intensive process and costly. Hence,
water extraction is carried out in two stages: firstly, mechanical removal of
extraneous water followed by the application of heat to complete the
process. Mechanical means are maximised for better economy.
7.8.1 Mechanical Drying Processes

The small amount of moisture associated with textile materials at normal
levels of atmospheric humidity is bound very strongly to the fibre. Increasing
the humidity increases the moisture content, but the water is held
progressively less strongly until eventually a stage is reached beyond which
further uptake is due to unbound water in capillaries and voids in the fabric
structure. Mechanical drying under practical conditions can remove only
unbound water and that too only partially. Mechanical processes can reduce
water retention to a value of 30-45% for cotton.
The three mechanical drying methods commonly employed for textile
materials are:
• Centrifuging
• Mangling
• Suction drying
Under the best conditions, all three methods achieve a similar level of
performance and the lowest water retention normally attainable is about
45% for cotton. Depending upon conditions, the actual retention may be
much higher and the choice of method depends on various factors.
478
Centrifuging
L
Centrifuge hydroextraction (Figure
7.26) is the natural choice for drying
materials in batch form, such as
loose fibres, hanks or packages of
yarn, fabrics processed in small
batches in rope form and garments.
The machine consists of two P
concentric cylindrical vessels (O and
P), the inside one (P) has a
perforated periphery and may be O
rotated at high speed. The wetted D
materials are placed inside the inner
perforated vessel. When the inner
vessel is set into motion, the water
molecules from the materials are Fig. 7.26 Centrifuge Hydroextractor
forced to move away from the centre
due to centrifugal force and are removed through the perforations to the
drain (D). As the machine runs, the extracted water is accumulated at the
bottom. The machine is stopped when the quantity of extracted water is
almost negligible. If the goods are free to move, they will be compressed
into a narrow band against the basket wall, but all the water removed must
pass through the outer layer.
The significant variables in this process are the centrifugal acceleration
and the duration. The acceleration is determined by the rate of rotation and
is proportional to the radius.
The centrifugal force, g acting on a body in a spinning hydro-extractor is
proportional to the weight of the body, the diameter of the hydro-extractor
basket and the square of the number of revolutions per minute.
2 -6
g = 5.6 x N x D x 10 (7.2)
Where N and D are the r.p.m. and diameter (cm) of the basket
respectively.
A basket having 120 cm diameter rotating at 1440 r.p.m. will produce g
value of 1,392, which will reduce down the moisture content of acrylic yarns
and tops down to 6-8%, and of wool down to about 27%.
A centrifuge or hydro-extractor especially suitable for yarns in hank form
may have a basket diameter of just above one metre and a depth of about
735 mm. The basket is made of galvanised steel. The top of the machine
has a hinged and a balanced safety cover (L) with a sight glass. The cover
is operated pneumatically and interlocked so that it cannot be raised while
the basket is moving. The basket is mounted on a central spindle carried by
479
ball and roller bearings. The electric motor (0.45 kW) is built round the
spindle, eliminating the need for belt drives or coupling, as in conventional
centrifuge. The machine is heavy (about 2.5 tonnes) and a strong floor or a
thick foundation block is recommended [6].
Centrifuges for fabric are very similar to those used for yarn, but are
usually larger in diameter (150 cm) and revolve at a much lower speed.
There is a tendency to form irremovable creases on fine delicate fabrics
after centrifuging. For sensitive fabrics, extraction for 10 minutes at 350
r.p.m. in 150 cm basket, or at 400 r.p.m. in a 120 cm diameter basket, is
recommended [6].
Unlike the other two mechanical drying processes, centrifuging is a
batchwise process. The materials should be uniformly loaded throughout the
basket – the fabric is run from a driven pulley via a pot eye, the basket being
rotated very slowly by hand.
Mangling
This is a most important continuous method of removing water from fabrics
in open width or in rope form. Squeeze mangles are structurally similar to
padding mangles, but in the former, nip uniformity is less critical. The prime
requirement for padding mangles for applying dyes and finishes is
uniformity, whereas in mangling the efficiency of squeeze is of paramount
importance. In squeeze mangles, more pressure may be applied resulting in
more water removal. However, it is still necessary to have one relatively soft
bowl in the nip, providing a cushion effect to protect the fabric from damage
in the event of creasing.
The factors determining the quantity of water retained by the fabric after
mangling are:
1. Pressure applied to the fabric, expressed by the load applied to the
ends of the rollers, divided by the length of roller i.e. kg/cm. The nip
2
pressure, in kg/cm , is simply the nip loading in kg/cm divided by the
nip width in cm. An increase in pressure reduces water retention, but
the reduction diminishes exponentially depending on the
compressibility of the fabric. Usually 20 kg/cm is a low pressure and
little benefit is achieved by exceeding pressure above 55 kg/cm.
Modern bowls, primarily by nature of their hardness, achieve nip
2
pressures of the order of 100 kg/cm from applied loading of
60-80 kg/cm and this represents a good level for efficient water
removal.
2. Hardness of the bowl. Harder bowl results in higher pressure, lower
water retention and less deformation. Wooden mangles are now
replaced by stainless steel, ebonite, wood fibre and rubber-covered
materials.
480
3. Temperature of treatment water. Water of higher temperature gives

poor retention due to lower viscosity, causing it to flow back more
rapidly from the nip. Water retention is also reduced due to swelling of
fibre at high temperature. Water retention for a particular fabric was
found [6] to be 71% at 5°C and 58% at 65°C.
4. Higher fabric speed increases the amount of water retained by the
fabric, but not to a marked extent. Fabric speed, up to 90 m/min, has
little effect. For doubling the speed, the water retention of cotton
increases only by 3%, viscose 3½ % and nylon 1% [6].
5. Bowl diameter has little effect unless both bowls are of 10 cm or less.
Smaller diameter bowls have less area of contact and produce higher
pressure, but the difference between 50 cm and 15 cm diameter bowls
is only 3% in favour of the latter [6].
6. Differences in fibre and fabric structure can influence water retention.
The lightweight and open-structured fabrics can retain more water
than heavier tightly woven fabrics. Inside the nip, the fabric structure
effectively holds the bowls apart with all the voids filled with water. The
structures that are more open have a greater proportion of void
volume, hence leave the nip with a higher retention. This is similar to
sucking action of some bowl fillings. The centrifuging and suction
drying are less influenced by fabric structure and may be superior to
mangling for lightweight, open structured fabrics.
Most mangle bowls are loaded at the ends, which produce some
deflection and lower pressure at the middle of the bowl. This may be
counteracted by tapering one or both bowls so that the rolls are slightly
thicker in the middle than at the ends.
Although a rubber-covered roller may be used, it is now universal practice
to use harder so-called filled bowls running against metal bowl for open-
width fabrics. For fabrics in rope form, somewhat more resilience is
desirable. Filled mangle bowls are made from a variety of materials. Modern
bowl fillings commonly consist of discs cut from sheets of impregnated
synthetic fibres, mounted on bowl shaft and held with pressure between the
end cheeks. An important development is the introduction of Roberto bowls
having super-resilient filling composed of micro-porous fibre-embedded
rubber. These fillings achieve extra water removal by a blotting or sucking
action at the exit of the nip [12]. The effectiveness of the super-resilient
bowls has been ascribed to three factors:
1. The relative softness of the bowl enables the surface to deform,
thereby facilitating higher liquor expression.
2. The porous structure absorbs liquor from the fabric. This liquor is
expressed as the covering enters the nip again.
3. Immediately after the nip, the bowls rapidly regain their original shape
due to decrease in pressure, and the porous structure absorbs liquor
481
from the fabric surface. The liquor absorbed by the bowl on the exit
side of the nip is expressed at the next entrance.
All mangle bowls, especially bowls with porous structure, should be
washed thoroughly after use. The washing for 5-10 minutes with water hose
under pressure is recommended. Bleach liquors and solvent should not be
used.
One consequence of this form of bowl construction is a greater
susceptibility to lengthways bending under load, since only the metal shaft
contributes to rigidity. Although the loss of rigidity may not be a serious
problem in squeeze mangles, it is desirable to have bowls of larger
diameter, permitting a larger diameter shaft. For mangles wider than 2.5
metres (face length), some form of level pressure loading system may be
required.
Unlike other mechanical drying processes, mangling is a water-limiting
operation. Water retention after mangling is virtually the same, irrespective
of the water content of the fabric before mangling. On second nipping
without rewetting or dipping, the water retention decreases very little, say
about 1% [13]. The mangles are devices providing simultaneous water
removal and fabric transport. Hence, the mangle nips are almost the
inevitable choice for inter-stage driving device in machines like washing
ranges.
Suction Drying M
Many fabrics, such as filament woven S
fabrics, are badly creased during
centrifuging or mangling. Water F P
extraction from such fabrics can be
safely carried out in open width by
passing over a suction hydroextractor
(Figure 7.27), which is often located in
front of a stenter or cylinder dryer.
The slot (S) is cut along the top of a
horizontal cylinder of about 20 cm
diameter, coupled at the bottom to a
large-diameter pipe leading to a gauze
filter (F) (to trap any loose yarn), a D
water separator (D) and a vacuum
pump (P). The machine draws the air Fig. 7.27 Suction Hydroextractor
through the fabric into the slot, the
inrushing air sweeping out extraneous water from the fabric. Obviously air
leakage is to be minimised and the lengths of the slot at either side of the
fabric are covered with rubber or plastic sleeves or masks (M). The fabric
482
must be centred before passing over the slot and then round a pair of draw
rollers.
Water is removed in the form of droplets driven from the fabric by the air
flowing into the vacuum system. Some evaporation may take place, but
within the fabric, the removal is almost wholly mechanical. The rate of
removal is so rapid that a 2-3 mm wide slot may give satisfactory suction
drying at a speed of 60 m/min with contact time of 2-3 microseconds. Except
for very dense fabrics, a vacuum of 40 kPa is adequate.
The important variables in suction drying are the vacuum achieved, the
fabric speed and the slot width. When the vacuum pump runs at a fixed rate,
the vacuum achieved will depend on the slot width and the density of the
fabric.
At constant vacuum, the slot width alone has a very little effect on water
retention. With a given slot-width, retention does not change much when the
fabric speed is increased. Investigation showed that most of the water
removal occurs in regions close to the slot edges, the central region
contributing very little, although it does influence the airflow into the vacuum
chamber. For highest possible vacuum, the slot should be narrow. Multiple
slots may be advantageous. The achievement of adequate level of vacuum
is the main practical problem in suction drying. Open structured fabrics lower
vacuum, thereby obstructing easy water removal.
Suction drying requires a separate mechanism for fabric transport, and the
power requirement of the vacuum pump is more than double of that required
for mangles. Nevertheless, suction process is less severe and has a useful
role in mechanical drying.
Each of the mechanical pre-drying systems has its merits and demerits.
Hydroextractors are by their nature batch dryers only, while the other
methods are continuous. The mangle is considerably cheaper, but the
suction slot is capable of lower water retention rates over a range of fabric
types and it can be used to recover excess chemicals padded onto the
fabric. In terms of performance, a centrifuge falls between mangles and
suction slots. Nevertheless, because of the tendency to form creases,
hydroextractors are mostly used to de-water loose stocks.
7.8.2 Thermal Drying

Thermal drying is the second stage of drying following mechanical water-
extraction processes. Some form of thermal drying is necessary to bring the
textile materials to an air-dry condition. Thermal drying is an age-old
phenomenon. It is a very energy-intensive process as a considerable part of
energy applied is dissipated into the surrounding. The energy loss can be
minimised by better insulation. Different drying processes show different
483
levels of heat loss and different machines of a given type may vary from one
to another.
Cylinder and Conveyor Dryers
Contact heating is probably the simplest and cheapest method for final
drying of fabric and is widely used for woven fabrics. Cylinder dryers have
good thermal efficiency and give an excellent, smooth, lustrous finish to
acetate taffetas, together with a crisp handle without any pin or clip marks in
the selvedges. The effect is very similar to ironing. The finish is useful for
certain varieties of fabrics, but unsuitable when a surface effect or a full
handle is required.
The fabric is passed round a series of cylinders filled with steam under
pressure, typically at a surface temperature of 160°C. There are still
machines having thin-walled cylinders using steam only at a pressure of 70
kPa, but most machines operate with 210 kPa and some even take up
pressure as high as 600 kPa. High pressure machines have fewer cylinders.
The cylinders are staggered in banks to provide maximum contact with the
fabric. In 32-cylinder machines, the banks usually run horizontally, but in
smaller machines the banks are in vertical sets. The cylinders are driven
from a common drive on one side of the machine. The hollow shaft contains
the steam supply to the vessel and a condensate removal pipe, which
should extend down to within 5 mm of the bottom of the cylinder.
Each cylinder must be fitted with a safety valve and anti-vacuum valve to
permit air to enter when the steam in the cylinder cools and condenses, and
when the machine is no longer in use. Thermostatic air vent units should be
fitted to the exhaust side of the machine in order to expel air from the
cylinder when the steam is turned on. On approaching the operating
temperature, the vents close automatically.
The rate of drying on cylinders is measured by the weight of water
evaporated per hour per unit area of contact between cylinder and fabric.
The parameter permits reliable comparison between machines comprising
different number of cylinders of different sizes. The cylinder temperature
largely influences the drying rate, but tension and fabric structure have
marked effects.
The main limitation of a conventional cylinder dryer is that there is no
control of fabric width and a final finish is often given on stenter to ensure
consistent and specific width of the final fabric.
The conveyor dryer is used for drying loose fibres. In the earliest types of
machine, the fibre on a moving brattice is transported through a heated
chamber. In modern perforated-drum dryers, circulating fans create suction
to hold the fibre on the drum surface. Such machines can be used to dry
loose fibre, tow or top, and this type of dryer is often incorporated into
continuous processing lines.
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Stenters
Stenters are the most expensive and most important machines in a dye-
house and finishing works. However, the stenter is the only drying machine
that provides adjustment and control of fabric width during drying. In addition
to drying, stenter performs several other functions, namely:
• Heat-setting of fabrics made of synthetic fibres and blends.

• Application and fixation of several finishing agents.
• To impart particular mechanical finish affecting appearance and feel,
commonly known as stenter finish.
The fabric is held at the edges by two endless chains, which convey it
through a stove in which hot air is blown at the fabric. After emerging from
the stove, the fabric is disengaged from the chains and either wound into a
roll or plaited into a truck. The chains return back to the fabric entry point.
The modern stenters are usually made of 3 to 5 compartments, each about
3 metres wide. Different temperatures are maintained at each compartment.
The stenters are of two types – pin stenter or clip stenter, depending on
the means of holding the fabric onto the chains.
The more common pin stenters have pins about 5 mm long, mounted in
two rows, about 3-4 pins/cm, along the base plate. The pins are thicker near
the base to prevent direct contact of the fabric with the hot base plate.
In clip stenters, the clips are in two sections, upper and lower; the upper
being in either in opened or in closed position. At the entry point of the
fabric, the upper jaw descends and grips the edge of the fabric. At the
delivery point, the jaw opens and releases the fabric. Clip stenter requires a
specific edge, preferably selvedge, to grip and is usually confined to woven
fabrics. Clip stenters leave no pin marks in the sevedges, but customers
accept pinholes in the selvedges associated with pin stenters.
The speed of stenter ranges from 10 m/min for heavyweight to 100 m/min
for lightweight fabrics. The actual speed also depends on the particular
operation (drying, heat-setting, weft-stretching or finishing) being carried out.
The higher the speed, the more vital is the need for a good entry system to
ensure that the fabric is properly centred and the edges fed onto the pins at
the correct speed.
For many fabrics, good dimensional stability to washing is demanded.
Lengthways stresses and strains acquired during processing require
compensating in the form of feeding fabric slightly more rapidly than the
speed of the stenter chains. For synthetics and blends, the overfeed is
allowed during the heat-setting stage. The amount of overfeed is often a
matter of skilled judgement. In some machines, the amount of overfeed may
be increased up to 20%, but 5% is more frequent. Although the surface
485
speed of the main feed roller may be set 5% faster than the stenter chain,
the fabric speed at entry to the chain may be less due to slippage.
Excessive overfeed means less final length and in extreme cases, cockling
at the selvedges.
Near the end of the machine, the fabric is lifted off the pins by a driven
take-off roller and then often passes round a pair of draw rollers, which
deliver, either to an overhead plaiting mechanism, or to a take-up roll
attached to the stenter, or on a driven A-frame.
A variety of methods are used to heat the air circulating in stenters via the
heat-exchanger, namely:
1. High-pressure steam from boiler, but this will provide a maximum air
temperature of 165°C – adequate for drying and curing, but
inadequate for heat-setting and thermo-fixation of dyes.
2. A thermo-stable oil called thermic fluid is heated to a temperature
above 250°C. A separate thermic fluid boiler is the best choice, but the
provision of a separate boiler and other accessories increases the
capital and maintenance costs.
3. Separate oil burners discharging into one side of the heat-exchanger
of each compartment, but the arrangement may cause oil spots and
soot due to incomplete combustion.
4. Burnt gas fumes may be fed directly into the stenter chamber. To
avoid any build-up of unburned gas in the stenter, the exhaust fans
must be operating for 30−60 seconds before the gas supply is turned
on. Indirect firing through a heat exchanger can be used for gas, but
the additional capital cost, together with lower thermal efficiency (only
about 60% against direct firing), are major disadvantages.
5. Stenters may be built with electrical heating, but the electrical energy
requirement and the operating cost will be very high.
Hot air is forced into pairs of tapered ducts extending across the width of
the fabric and discharged on it. In some stenters, the ducts have nozzles
running the full width to provide uniform air distribution onto the fabric. Some
other designs have circular nozzles arranged to strike the fabric surface at
an angle. It is most important, particularly during heat-setting prior to
dyeing, that hot-air distribution is uniform across the full width of the fabric.
A reasonable balance of air distribution is to be maintained between top
and bottom ducts. During drying, slightly more air is forced into the bottom
ducts to support some of the weight of fabric, and also because the bottom
of the fabric is wetter than the top. This helps to prevent excessive sagging
particularly in knitted fabrics. But it should not be overdone, otherwise the
fabric may be lifted off the pins.
486
The hot air, after being forced against the fabric surface, makes its way
between the ducts to the sides of the stenter where it is collected by a fan
and recirculated. At the top of the compartment is a damper that regulates
the rate at which exhaust gases, including steam, are removed into an
exhaust duct.
In some stenters, e.g. model FS-600 developed by Primatex (Mumbai,
India), the exhaust duct has been dispensed with. The initial air medium is
turned into superheated steam made of water vapour evaporated from the
fabric. Excess water vapour is allowed to escape through the entry and the
exit slits. The pressure inside the chamber is slightly high preventing the
entry of any fresh air. Due to high heat content of superheated steam, the
drying efficiency is enhanced claiming 35% savings in energy and 40%
increase in production speed. The actual production per minute of
conventional and FS–600 stenter claimed by the company is shown in Table
7.1.
Table 7.1 Comparative Production in m/min of Conventional (a) and

FS-600 (b) Stenters
3-Chamber 4-chamber
(a) (b) (a) (b)
Shirting,10 m/kg
Dry heat-set 38 75 50 100
Pad, dry, set 24 45 32 60
Finishing 40 60 52 80
Drying 50 72 68 96
Suiting, 4 m/kg
Dry heat-set 24 45 32 60
Drying 19 27 26 36
Resin finish 16 22 20 28
Stenters with several special features are available in the market. A few
are mentioned below.
In Brückner’s (Germany) split-flow model, separate flow of air is provided
to the upper and lower nozzles using separate fans causing optimum and
extremely even distribution of air at the nozzles and gentle impingement on
the fabric. In the event of a standstill, the bypass flap opens so as to prevent
nozzle marks on the fabric. Brückner have fully automated the process
sequence with their Process Visualisation System (PVS). Energy savings up
to 30% are achieved via Brückner heat recovery and exhaust air purification
systems.
FS-21 model of Morrison (USA) utilises a unique elliptical nozzle, which
provides higher air discharge efficiency and superior heat transfer rate due
487
to more direct air impingement on the fabric. The non-turbulent flow

provided by the unique fan and smooth running chains make FS-21 one of
the quickest finishing range with very low noise level.
Babco-Star of Babcock (Germany) utilises Star-Jet nozzle system for
optimum temperature and high production.
KM-16 multilayer stenter of Krantz (Germany) provides gentle fabric-
friendly drying. Outstanding results are due to the gentle air-delivery to both
sides alternately. Less floor area, but more height is required. Only one
operator is required as fabric entry and exit are at the same side.
Top-air multilayer stenter of Effedue (Italy) is suitable for all types of
fabrics.
Float Dryers
The float dryers are drying chambers in which the fabric moves in a floating
condition without guide rollers. This is most suitable for drying of printed
goods. It can be used in tandem with stenters for increased drying capacity
and avoiding sizes or resin sticking on clips or pins. The fabric is fed from
the mangle through an adjustable swivel while a crease opener fixed on
both sides straightens the creased fabric. Aerodynamically balanced air jet
system eliminates colour migration and ensures even drying.
7.8.3 Radiation Drying

IR radiation derived from electrical or gas-fired heating elements can be
used for fabric drying, mostly as a supplement to cylinder or stenter drying,
or to provide rapid pre-drying. However, the source temperature of IR
generator is much higher than that of cylinders or of air in stenter. Sufficient
protection against overheating of fabrics is to be taken if the fabric stops for
any reason. The efficiency of IR heating depends on the efficiency with
which the fabric absorbs the incident radiation. In general, the process
efficiency is comparable to that of a well-run stenter.
Recently the radio frequency or dielectric energy and microwave are being
used for drying of textiles industrially. Dielectric heating has a low frequency
but high field strength and microwave heating has high frequency but low
field strength. The advantages of these forms of heating are:
1. The interior of the fabric is heated at the same rate as the surface, so
that the migration of dyes or resins towards the surface during drying
is lowest.
2. Drying times are considerably reduced.
Some molecules called dipoles, or molecules having dielectric moments,

notably water, have structures in which the positive and negative charges
488
are separated by a small finite distance and they exist in a position of

minimum stress in an electrical field. A dielectric is the electrically non-
conducting medium between the two electrodes in an electric capacitor.
When the field is reversed, this position is reversed. In case of high
frequency these reversals take place several million times a second.
Typically electromagnetic fields in use are 13 and 27 MHz radio frequency
and 896 and 2,450 MHz microwave frequency [13]. The effect of this rapid
dipole oscillation is to generate heat within the molecule itself, which in the
case of water leads to evaporation. The textile materials have symmetric
molecules, which means there is little generation of heat in the substrate. Of
course, the temperature will rise to that of evaporating water, because of
intimate contact. The amount of heat generated is related to the amount of
water present, so that the wettest portions heat up more than those with low
moisture content. The amount of heat generated decreases, as water is lost
during drying. In conventional drying, water from the surface is dried and
more water from inside is brought to the surface by capillary action.
Dielectric method generates heat wherever water is, irrespective of
whether bound (imbibed) or unbound. A limited number of frequencies are
permitted and most dielectric heaters for textile drying use 27.12 MHz.
Dielectric machines have a conveyor belt moving slowly through a
rectangular tunnel in which an electromagnetic field is applied. A 50 kW
machine will evaporate 70 kg of water per hour giving an output of 150 kg of
cotton (moisture content from 48% to 8%) or 400 kg of acrylic yarn (18% to
3%) [14].
In case of microwave, the energy will flow at the same rate irrespective of
whether or not there is material in the oven to be heated. The control of the
rate of energy flow is achieved by varying the voltage of the magnet.
In case of radio frequency (RF) heater, the power can be drawn from the
generator only when the material is present. In other words, the material
being heated is an essential electric component of the circuit and as the
parameters, which affect the electrical characteristics, vary so does the
power being drawn from the generator.
The power, P damped into the material is given as:
P = 2π.f.ε0.εR .E
// 2
(7.3)
Where f = frequency, hertz
ε0 = permissivity of free space (constant)
εR// = loss factor which increases with increase in moisture content
and temperature
E = electric field, volts/metre
The permissivity constant depends on dielectric constant, K, of the
medium, which is the ratio of the capacity of the capacitor using the medium
489
between the electrodes to the capacity of the capacitor when there is a

vacuum between the electrodes. The dielectric constant of vacuum,
insulating materials like textiles and water are 1, 2-8 and 80 respectively.
For package dyeing, the majority of water is to be removed mechanically
before applying the dielectric heater. Centrifuging or suction hydroextraction
based on carousel principle may be carried. Radiation drying by radio
frequency or microwave heating is rarely employed for fabrics. An economic
limitation is that the efficiency of conversion from electrical to heat energy is
only about 60%.
7.8.4 Drying of Fibres and Yarns

Fibres, hanks and packages of yarn cannot be dried by any continuous
method. Preliminary water extraction may be carried out in the
hydroextractor and final drying needs special arrangements. Loose fibres
are normally dried by passing through a conveyor dryer, which is a hot
chamber inside which the fibres are carried slowly by a metallic conveyor
and are discharged out after drying. Presently, RF dryers are being widely
used for fibre drying as the process is clean and damage of the fibre is much
less.
The yarns, both in hank form and in package form, are first hydroextracted
in a centrifuge. The hanks may then be transferred to a pole dryer where the
hanks are placed on small metallic rods called poles that are being carried
forward inside a hot chamber by two parallel moving chains. The poles are
released at the delivery end. The hanks are detached and the poles are
brought back to the feeding end manually or automatically. The yarn
packages may be dried by keeping in a warm chamber, but it may take 24
hours or more for complete drying. Dryers are now developed for handling
the complete load whilst still on the carrier frame. The vessel is of similar
diameter to the largest dyeing machine and the carrier frame is lowered to fit
onto a central boss. The kier is closed and securely locked and compressed
2
air is introduced to give a pressure of 480 kPa (70 lbf/in ). The blower motor
is started and hot air is forced through the package, first out-to-in and then
in-to-out. Water vapour is condensed in the condenser unit.
Some 30 years ago, most dyes and auxiliaries were manually weighted
and dissolved in tubs and were added to the dyeing or printing machines
directly. Nowadays, most of the modern dyehouse prefer automatic dosing
or dispensing systems involving measurement of dyes and chemicals (by
weight or volume), mixing or dissolving and transportation of the mixture to
the dyeing machines. A list of supplier of dispensing equipment is given by
Hickman [15]. The elements common to all dosing operations are:
1. PCs, PLCs (programmable logic controller) and control signals
(analogue or digital)
490
2. Electronic weighting systems

3. Kinetic pumps, particularly centrifugal types
4. Solid handling devices
5. Level indicator and control
6. Flow-meters
7. Volumetric or gravimetric dosing.
REFERENCES
1. G. Clarke. 1982, A Practical Introduction to Fibre and Tow Coloration

(Bradford, UK: SDC).
2. E.R. Trotman. 1984, Dyeing and Chemical Technology of Textile
th
Fibres, 6 Edn (London, UK: Charles Griffin).
3. B.C. Burdett and A.J. King. 1999, Rev. Prog. Coloration, 29, 29-36.
4. J. Park. 1981, A Practical Introduction to Yarn Dyeing, (Bradford, UK:
SDC).
5. J. Shore. 1979, Rev. Prog. Coloration, 10, 33-50.
6. C. Duckworth (Ed.). 1983, Engineering in Textile Coloration (Bradford,
UK: SDC).
7. V.A. Shenai. 1980, Technology of dyeing, Vol. VI, (Mumbai, India:
Sevak).
8. Horn. 1965, JSDC, 81, 262.
9. M. White. 1998, Rev. Prog. Coloration, 28, 80-94.
10. Colour Chronicle. 1983, April/June issue (Mumbai, India: Sandoz).
11. Bayer Farben Revue. 1976, No. 26 (Leverkusen: Bayer).
12. G.W. Madaras, G.J.Parish and J. Shore. 1993, Batchwise Dyeing of
Woven Cellulosic Fabrics, a Practical Guide (Bradford, UK: SDC).
13. International Dyer. 1980, June 27, p 470.
14. Moss. 1959, J.Text. Inst., 50, 654.
Chapter
Dyeing of Cellulosic Fibres 8
It has been estimated that between 1990 and 2000 the percentage of textile
raw materials derived from cotton fell from 48.7 to 42.2%, whilst the share of
synthetic fibres rose from 39 to 48.3%. The production of cotton was
predicted to rise marginally from about 20.0 million tons in 1990 to
approximately 21.4 million tons in 2000. Production of polyester is expected
to rise even faster and to equal that of cotton by 2005. The increasing use of
aesthetically pleasing synthetic fibres, such as polyester micro-fibres, will
continue to make inroads into sectors that have traditionally been dominated
by cotton.
Unlike some other classes of dye, the production of reactive dyes for
cellulose is to increase more rapidly than the production of cotton itself. This
is because they continue to gain market share at the expense of other types,
such as azoic colours. Reactive dyes are also used for the coloration of wool
and polyamide, but the annual consumption at these outlet at around 2,000
tons is dwarfed by the quantities used in cotton dyeing, approximately
120, 000 tons [1].
8.1 FIBRE STRUCTURE

The fibre structure of cellulosic materials has been discussed in Chapter 1.
The most important natural cellulosic fibre, cotton, has remarkable affinity for
various dye-classes. It is dyed with a very large number of dyes using
various machines and methods, depending on the availability, fastness
requirements and cost permitted. The other natural cellulosic fibres, namely
jute, flax, ramie and hemp (bast fibres) have significant quantities of non-
cellulosic materials. They can be dyed with most of the dyes suitable for
cotton provided caustic alkalinity is low or absent. In addition, they can be
dyed with some other dye-classes, which are not applicable on cotton. The
second most important cellulosic fibre, man-made viscose fibre is a cheaper
substitute for cotton and is now widely used in the textile industry especially
for blending with polyester. All dye-classes, which are suitable for cotton,
can be applied on viscose, provided the alkalinity is low. As the fibre is
492
man-made, it is much cleaner than cotton and is dyed mostly in fibre form so
that it can be blended with other fibres. The dyeing may be carried out
during fibre manufacture (i.e. dope dyeing) or in package dyeing machine.
In all cellulosic fibres, there are regions of differing degrees of molecular
order and disorder resulting, at each extreme, in crystalline and amorphous
regions respectively. Cotton is made up of structural bundles called fibrils,
which are made up from the close packing of identical smallest highly
ordered units called unit cell. The sequential repeat of unit cells forms the
underlying structure of the crystalline region, which is the central core of
each fibril, the less ordered material being confined to the fibril fringes.
Accessibility and reactivity are, therefore, explained in terms of a system of
interconnecting voids bounded by fibrillar surfaces. As chemical reactions
take place at the surfaces of fibrils, an essential aspect of all coloration and
finishing treatments of cotton is the access to fibrillar surfaces. The
association and distribution of the fibrillar material within the surrounding
voids are important factors that determine the chemical reactivity of cotton.
The crystalline regions provide strength and rigidity, whereas the
amorphous regions are associated with flexibility, sorption and reactivity.
The dyes and chemicals are first adsorbed on the fibre surface and then
they diffuse within the disordered or accessible region of the fibre. The
crystalline regions are inaccessible. The relative proportion and distribution
of the crystalline and amorphous regions determine the dyeing behaviour of
the fibre. The differences in fibre structure may occur in molecular, fibrillar or
in morphological level due to varying conditions of growth of cotton or due to
variations in manufacture of viscose. Wetting, swelling, steaming and drying
processes may also modify the structures. The dyeing properties of cotton
also vary with fibre diameter or fineness − finer the fibre, faster is the rate of
dyeing. The diameter may vary by as much as 5:1. Depending on the source
of origin, the fibre weight per cm, i.e. linear density may vary by 3:1.
The heterogeneous nature of cotton and viscose, particularly in a radial
direction, affects the rates of diffusion of dyes and can lead to ring dyeing in
case of cotton or skin-core difference in viscose.
Depending on the growth of the secondary wall, a cotton fibre may be
mature, immature or dead. The distinction may be made by swelling in alkali
and by observing the extent of swelling under a microscope. During
spinning, the immature and dead fibres roll up into knots and tangles known
as neps. Some direct dyes dye neps to the same depth as a normal fibre,
but most dyes dye to a paler depth. The depth on immature and dead fibres
lowers further during washing processes. Even for optical reasons, the thin-
walled fibres appear paler. In many commercially dyed fabrics, the neps are
readily apparent as lighter specks [2].
493
8.2 DYE-CLASSES
In the dyeing of non-cellulosic fibres, a single class of dyes predominates on
the substrate concerned, for example, acid dyes on nylon or wool, basic
dyes on acrylics, disperse dyes on polyester and cellulose acetate. This is
not the case for cellulose because:
1. Wide use of cotton since the beginning of civilisation resulted in

search for newer and newer dyes.
2. The high stability of cotton fibre under prolonged aqueous treatments
in the presence of acids, alkalis and various chemicals, even at high
temperature, made the use of various dye-classes viable.
3. The complementary nature of the classes of dyes used.
4. No single dye class fulfils all requirements; each has its own merits
and demerits.
A variety of fabrics are made from cellulosic fibres for numerous end uses
and at all price levels. Some fabrics may require high fastness, as those for
common apparel, military uniform, work-wear and furnishing fabrics. For
bedspreads, curtains and various other fabrics, washing fastness
requirement may not be very high and cheaper dyes may be used for the
purpose.
From ancient times, cotton is being dyed with natural colouring matters
(and later with bright basic dyes) after mordanting. The problems faced at
that time were inadequate fastness, limited colour range and poor
reproducibility. Congo Red discovered in 1884 was the first dye, which had
good substantivity for cotton and provided a level shade on unmordanted
cotton easily. A number of dyes having similar properties were soon
developed and because of direct affinity for cotton, such dyes were termed
as substantive dyes or direct cotton colour and later simply as direct dyes.
Many early members of this class had limited fastness. After-treatment of a
few direct dyes (by diazotisation and development or by applying dye-fixing
agent), improves washing fastness and copper-complex direct dyes have
improved wash and light fastness.
At the beginning of the last century, other dye classes, namely vat, sulphur
and azoic with better fastness properties replaced direct dyes for dyeing of
cellulosic materials except for the cheaper varieties. Though sulphur dyes
were discovered before direct dyes, as a class it has never achieved
popularity. C.I. Sulphur Black 1, the only sulphur dye, is still popular and is
the best selling individual dye for textile coloration till today. Other sulphur
dyes, giving shades like dull yellow, orange, brown, blue and green colours,
are used in small quantities for cheaper varieties with better fastness than
direct dyes. With the introduction of viscose fibres in 1930s, the demand for
494
direct dyes had increased, as these dyes are cheap, simple to apply and do
not require strong alkaline conditions as for the other dye classes.
Initially azoic colours like Para Red were made from coupling of diazotised
amines with β-naphthol and they had poor substantivity and poor fastness
properties on cotton. The practical applicability of azoic colours started with
the invention of more substantive Naphthol AS series in 1912. A broad
range of shades on cellulosic materials is now available in this class having
a broader colour gamut, excellent brightness, improved build-up and
fastness properties.
The plant extract, indigo, a natural vat dye was in use from ancient days.
Though synthetic indigo was available by the turn of the century, the real
forerunner for vat dyes is Indanthrone Blue developed in 1901. Soon other
anthraquinone vat dyes came in the market covering the whole shade range
having wash and light fastness properties not hitherto attainable with other
dye classes. The difficulty in dissolving these dyes, especially in printing and
the non-applicability on wool and silk fibres, due to high alkalinity required
during dyeing, resulted in development of indigosol dyes. These dyes are
water-soluble leuco sulphuric esters derived from indigo and a few
anthraquinoid vat dyes.
Vat dyes dominated the market at that time, but the deficiencies were the
lack of shades like bright greenish-yellow, turquoise or greenish blue, scarlet
or reds. Reactive dyes developed by ICI in 1950s fulfilled the gap and soon
a large variety of reactive dyes were commercialised due to bright shades
combined with high wet fastness and simplicity of application procedures.
Greater economy is assured by shorter liquor ratios and lower consumption
of chemicals. This resulted in modification of processes and equipment
(winch, jigger, jet and finally to pad-batch), all of which favoured the growth
of reactive dyes at the expense of azoic and vat dyes.
The dye classes applicable on cellulosic materials may be classified into
four groups [3]:
1. Dyes directly substantive to the fibre

(i) Direct dyes
(ii) Reactive dyes
or made substantive by the use of mordants
(i) Basic dyes
(ii) Natural dyes
2. Dyes applicable by solubilisation
(i) Vat dyes and solubilised vat dyes
(ii) Sulphur dyes
3. Colorants formed in situ
(i) Aniline black
(ii) Insoluble azo colours
495
(iii) Mineral colours

(iv) Solubilised pigments mostly phthalocyanine
4. Colorants applicable with external agent
(i) Resin bonded pigment
Among the dye-classes mentioned above, basic dyes and aniline black
are no longer used for cellulosic materials, especially on cotton. Natural
dyes also have very limited use for the purpose.
The world market share of major dye classes for cellulosic and all fibres
estimated in mid-1980s are shown in Table 8.1.
Table 8.1 World Market Share of Major Dye Classes Estimated by Park
[4] and Sumitomo (showed under bracket) [5]
Dye Class Cellulosics (%) All Fibres (%)
Sulphur 29 (34) 18
Direct 27.4 (27) 17
Vat 19.4 (17) 12
Reactive 9.7 (12) 6
Azoic 8.1 (10) 6
Pigments 6.4 4
Acid x 16.5
Basic x 4
Disperse x 16.5
8.3 DIRECT DYES
Although Perkin synthesised the first synthetic dye, Mauve, thirty years
earlier, the discovery of first fibre-substantive direct dye, Congo Red in
1884, actually initiated the period of major growth and establishment of the
synthetic dyestuff industry. The name direct cotton colour (D.C.C.) or simply,
direct dye, was derived from the fact that it was the first synthetic dyes,
which had inherent substantivity for cotton. Earlier, cotton usually had to be
mordanted with either natural mordants or their synthetic replacements,
before application of dyes. The most attractive feature of direct dyes is the
essential simplicity of the dyeing process and lower cost for achieving high
depth of shades. Direct dyes represent an extensive range of products
which are easy to apply and very economical. In 1977, the production of
direct dyes in the United States was 30.7 million pounds, out of total
production of synthetic dyes of 264 million pounds [6]. While a major portion
of the production of direct dyes goes to the textile industry, approximately
25% of the production of the dyes go for coloration of paper, leather and
496
other uses. Direct dyes are water-soluble and can be applied to cotton and
other cellulosic fibres such as viscose, linen, jute, hemp and ramie.
Direct dyes have varying fastness to washing, light, perspiration and other
wet fastness properties, and varying staining properties on wool, silk,
polyester and acrylic fibres. Most direct dyes have limited wet fastness in
medium to full shades unless they are after-treated, but some are better
than others. Resin finishing after dyeing produces a notable improvement in
wet fastness, especially on regenerated cellulosic fibres. The light fastness
varies from very poor (rating 1) to outstanding (rating 8).
Direct dyes are used in low-priced viscose or blended curtain fabrics,
furnishings and carpets. Cheap cotton apparels, casual wear and
bedspreads, low-quality discharge-printed materials, which are not washed
frequently, are dyed with direct dyes.
Direct dyes are sold under various brand names such as Solar, Pyrazol
(Clariant), Incomine (Indochem), Sirius, Sirius Supra (Bayer), Chlorantine,
Cuprantine, Solophenyl (Ciba), etc.
8.3.1 Chemistry
At least 70% of all direct dyes listed in Colour Index are unmetallised azo
compounds. In contrast to other dye-classes, the great majority of them are
disazo (about 50%) or polyazo (about 33%) types, the former predominating
in the brighter yellow to blue sector and the latter in the duller greens,
browns, greys and blacks. The copper complex direct dyes derived from the
above two types are mostly duller violets, navy blues and blacks. Stilbene
and thiazole direct dyes, the non-azo chromogens in the yellow to red
sector, also bear certain similarities to the above two types. The
phthalocyanine and more recently, dioxazine chromogens are utilised for
producing bright blue direct dyes of high light fastness [7]. The example of a
disazo direct dye is C.I. Direct Blue 130 (8-1).
An important group of direct dyes is derived from stilbene such as C.I.
Direct Yellow 19 (8-2). Some important yellow, orange and brown direct
CH3O OC2H5 OH SO3Na
H2N -N=N- -N=N- CH N=N OH
CH N=N OH
SO3Na SO3Na SO3Na

(8-1) (8-2)
497
dyes are based on stilbene. Primuline is the first of the thiazole direct dye.
/ /
A limited number of o,o -dihydroxy or o- methoxy-o -hydroxy dyes can be
complexed with copper (prior metallisation or aftertreatment) which has
slightly better wash and light fastness. The best-known example is C.I.
Direct Blue 76 (8-3), a greenish blue copper complex derived from C.I.
/
Direct Blue 1 (same as 8-3 with methoxy and hydroxyl groups in o and o
positions respectively) by metallisation with cuprammonium sulphate in the
presence of an alkanolamine.
+ Cu
II CuII +
NH3 O O O O NH3
–
O3S SO3–
-N=N- -N=N-
SO3Na (8-3) SO3Na
Some extremely light fast highly bright blue and bluish green dyes are
derived from phthalocyanine, e.g. C.I. Direct Blue 86. Direct dyes, based on
sulphonated copper phthalocyanine derivatives, provide bright turquoise
blue shades of excellent light fastness, but wet fastness is poor unless resin
finished. They have poor absorption properties so that deep dyeing is
virtually unobtainable. Dyeing should be carried out at a temperature as high
as 95°C.
The triphenodioxazine ring system is the basis of some important blue
direct dyes such as C.I. Direct Blue 106.
The recent pronouncement that azo dyes in general could be
carcinogenic, rather than the very few members of the class actually
demonstrated to be so in animal tests, is likely to tarnish the image of direct
dyes disproportionately [8]. The oldest direct dye, Congo Red (8-4) was
synthesised from benzidine by Böttiger in 1884, but now it is universally
recognised as carcinogen. In spite of the efforts to find replacements for the
benzidine-derived products, the developments in the chemistry of direct
dyes have been few. Many important disazo direct dyes based on benzidine
NH2 NH2
-N=N- -N=N-
SO3Na NaO3S
(8-4)
498
are withdrawn from manufacture because of the carcinogenicity (cancer

producing) of benzidine and some of its derivatives. The most toxic ones are
found among the disazo and cationic classes. Non-benzidine direct dyes
derived from less hazardous diamine derivatives have replaced those
prohibited − but those are costly and have much poorer built-up properties
than the corresponding benzidine derivatives.
An intensive search was undertaken into alternatives produced from less
/
hazardous intermediates, new diamines namely 4,4 -diaminobenzanilide,
/ / /
4,4 -diamino-diphenyl-benzaldehyde, 4,4 -diaminodiphenyl ether, 4,4 -
diaminodiphenylsulphone and 1,5-diaminonaphthalenes. Another novel
/
intermediate synthesised for the purpose is 7-amino-3-(4 -
aminophenyl)quinoline (8-5) that has been used to prepare various disazo
and trisazo derivatives. Unfortunately, the dyes produced were deficient in
tinctorial power and light fastness.
For non-carcinogenic azo dyes, the intermediates used should be non-
mutagenic in nature and low potential genotoxicity of the metabolites
resulting from the reductive cleavage of the azo linkage. The replacement of
/ /
benzidine by 5-5 -diamino-2-2 -bipyridine (8-6) in four well-known
carcinogenic azo structures showed that the derived dyes are much less
genotoxic than their older analogues made from benzidine [8]. The presence
of bulky alkoxy groups was useful in lowering the mutagenicity of certain
analogues of C.I. Direct Black 17.
N
H2N
N
N
NH2
NH2
(8-6)
(8-5)
One of the most significant breakthroughs in the field of direct dyes had
been the introduction of Indosol SF dyes by Sandoz (now Clariant), the
special direct dyes, which respond to special after-treatments to give
exceptionally high wet fastness. The aim is to employ a much cheaper and
simpler process of dyeing, together with a suitable after-treatment fixation to
provide a dyeing of high fastness, capable of competing with reactive dyes,
which are more expensive. The original range of Indosol dyes comprised of
twelve members, all copper complexes, selected from the existing Solar
range of dyes for good light fastness when aftertreated with the preferred
agents. The copper plays a role in fixation and is responsible for making the
shades dull. The original range of Indosol SF dyes was strong in the blue
499
and grey sectors, but somewhat deficient in the yellow to violet series. Novel
reactive yellow and red dyes were later introduced to supplement the range.
Three different after-treatments may be employed, i.e. Indosol E-50,
Indosol EF and Indosol CR, the choice depends on the depth and fastness
requirements. All are polycationic in nature with suitable co-ordination
groups. With Indosol EF, a further bond is formed between the agent and
cellulose similar to that in reactive dyeing. Indosol CR gives a high degree of
fastness as well as easy-care properties due to incorporated resin. Indosol
E-50 and EF can be applied at long liquor ratios, i.e. by batchwise methods,
or continuously, while Indosol CR can only be applied by padding.
The patent literature relating to Indosol CR, revealed that it is a mixture of
three components, namely [8]:
(a) A polybasic condensate of diethylenetriamine and an amide, such as

cyanamide, dicyandiamide, guanidine or biguanidine.
(b) An N-methylol pre-condensate of the dicyandiamide-formaldehyde
type.
(c) A latent acid catalyst, such as lactic acid.
The polybasic condensate (a) was later marketed alone as Indosol E-50
for the exhaust aftertreatment of Indosol dyeing, for improvement of fastness
only.
Compared to conventional reactive dyes, savings in time, labour,
chemicals, water and effluent treatment can be achieved with Indosol dyes.
However, the shade range is restricted and bright shades are difficult to
achieve. Indosol dyes can be used with particular advantage over reactive
dyes to dye the cellulosic portion of polyester/cotton blends. The dyeing of
Indosol dyes and disperse dyes is a single step process as both can be
fixed under identical conditions of pH and temperature. Restricted shade
range is a problem, but Indosol dyes are very suitable for production of full
navy, brown and burgundy shades.
Direct dyes are soluble in water. Chemically, they are sodium salt of azo
dyes with sulphonic or carboxylic groups (sulphoxalates or carboxalates
respectively). When dissolved in water, they ionise into dye anions and
sodium ion:
− +
DSO3Na Æ DSO3 + Na (8.1)
Dyes often exist in aqueous solution as aggregates of several ions or
molecules rather than as individual molecules. Aggregation number (the
average number of molecules or ions per aggregates) of direct dyes may be
measured. However, the number varies for different methods of
measurements. There is general agreement that such solutions contain a
mixture of aggregates of various sizes in dynamic equilibrium. The
500
aggregation increases with increasing concentration of added electrolyte or

of the dye itself and decreases with increasing temperature. The
aggregation tendency of a direct dye depends on its chemical structure.
Under given condition of temperature and electrolyte concentration, C.I.
Direct Orange 26 is much more aggregated than C.I. Direct Yellow 12. Both
are disulphonated disazo dyes, but presumably the two phenolic groups,
and especially the urea residue in the former dye, provides much greater
scope for intermolecular hydrogen bonding than the etherified phenolic
groups in the latter. C.I. Direct Red 28 is highly aggregated because the
protonated amino groups and sulphonate anions are on opposite sides of
the molecule and two neighbouring molecules can thus attract each other.
C.I. Direct Blue 1 is considerably less aggregated as because the above two
oppositely charged groups satisfy each other due to their presence in close
proximity. The dye anion has also net negative charge of two because of
two remaining sulphonic groups.
During storage, some of the dyes are dissociated into free acid form,
which are sparingly soluble in water. It is, therefore, customary to add little
soda ash during dissolving and/or during dyeing so that the free acid form is
converted into sodium salt.
Direct dyes are closely related chemically to acid dyes, the main
difference being in the number of solubilising groups, the groups that form
hydrogen bonds, often in the size of the molecules and the number of azo
groups. As the number of solubilising groups in a direct dye increases, it
begins to assume the properties of an acid dye. Because of steric effects,
acid dyes usually have less capacity for forming hydrogen bonds than direct
dyes.
For example, an acid dye (8-8) called Acilan Ponceau 6R (Bayer), C.I.
Acid Red 41 is chemically similar to a direct dye called Direct Fast Red BT
(Bayer) (8-7), except that the former has three additional sulphonate groups
and one additional hydroxyl group [9]. Even C.I. Acid Red 88 is very similar
OH SO3Na
NaO3S N=N
N=N
NaO3S
(8-7) (8-8) SO3Na

SO3Na
501
in chemical structure with the said direct dye with only an additional hydroxyl
group in the same position as in (8-7).
The decomposition of a minor portion of the dye may occur, if the dyeing
with direct dyes is unduly prolonged, especially at or above boil. The rate of
decomposition is more rapid in the dyebath phase than on fibre, and the
onset of decomposition may be observed as a change in colour of the
exhaust liquor. The decomposition is mostly due to the reduction of the azo
linkages. Dyes with exposed azo groups free from electron-withdrawing o-
substituents (e.g. C.I. Direct Yellow 12 and C.I. Direct Green 33), azo
groups with protonated o-aminoazo groups (C.I. Direct Red 28) and
diphenylurea type dyes (C.I. Direct Orange 26) are most reduction-sensitive.
/
Azo groups with o,o –substituents, especially sulphonate groups are quite
resistant to reduction, while copper-complex dyes are fully protected and
they show excellent stability at high temperature conditions.
Viscose has reducing nature under alkaline dyeing conditions and
buffering to pH 6 with ammonium sulphate confers a stabilising influence
when dyes of low-stability are to be used on viscose. A mild oxidant like
sodium m-nitrobenzenesulphonate or more effective strong oxidant
potassium chlorate or dichromate, may be used. Sodium perborate may be
used, but not with copper-complex dyes [7].
Simultaneous dyeing and finishing is possible with direct dyes because
they do not need alkali additions like other dye-classes used for cellulosics.
Cotton fabric can be padded with direct dyes, N-methylol reactant and
ammonium chloride as catalyst, dried and cured at 160°C.
Direct dyes vary considerably in their ability to cover dead or immature
cotton, but by careful selection, a sufficient range can be found suitable for
this purpose.
The principal parameters affecting adsorption of direct dyes by cellulose
from aqueous dyebath are temperature, time of dyeing, liquor ratio, solubility
of the individual dye, salt controllability and to a lesser degree, by the
presence of auxiliary agents. Nonionic agents tend to inhibit the formation of
large aggregates and thereby stabilise concentrated solution of direct dyes.
However, the absorption of the dye by cellulose may decrease.
8.3.2 Substantivity
The relationship between the chemical structure of a direct dye and its
substantivity for cellulose is an intriguing complex one that has never been
comprehensively explained [8].
Most commercial direct dyes conform to the general type, R1-N=N-X-N=N-
R2, where R1 and R2 are benzene or naphthalene derivatives which may
/
contain further azo linkages, while X is derived from pp -benzidine,
diphenylamine, stilbene, diphenylurea or naphthalene in which the two azo
502
groups are attached in the 1:4 or 2:6 positions [10]. Because of this
arrangement, the direct dye molecules are greatly extended in one direction.
Meyer, in 1928, suggested that if a dye possesses a long, chain-like
molecule, it can lie close to the cellulose molecule and the residual valency
forces will thus be more effective in holding the two together. Nearly all
known direct dyes can be formulated as extended linear molecules and
deviations from linearity are generally accompanied by a loss in
substantivity. J-acid (6-amino-1-naphthol-3-sulphonic acid) is only amino
naphthol that gives linear azo dyes and is the basis for many direct (and
reactive) dyes for cotton. If aniline is first coupled to J-acid and then to H-
acid, the product (8-9) is linear and substantive. However, if aniline is first
coupled to H-acid and then to J-acid, the dye (8-10) is not linear and has
poor substantivity. The number and type of polar groups and the molecular
weight are the same in both dyes. However, a weakness of the theory is that
the dye (8-10) can also be drawn linear, if the azo groups are arranged in
the cis form, though the trans form is more stable.
N NH2
N
NaO3S N HO
OH
NaO3S N
OH
N N
SO3Na
N
SO3Na
N
NaO3S OH
NH2
SO3Na
(8-9) (8-10)
Hodgson proposed coplanarity hypothesis suggesting that the various
benzene and naphthalene nuclei in a direct dye must be capable of lying in
/
one plane. He showed that none of the dyes derived from 2:2 benzidine
/
derivatives (e.g. 8-11) is substantive, because the substituents in the 2:2
503
position prevent the free rotation of the two nuclei about the common bond
thereby making them non-coplanar.
Schirm suggested that a direct dye, in addition to being linear, must
contain a long conjugated chain of double bonds. An increasing number of
conjugated double bonds is accompanied by increasing substantivity due to
increasing residual valency forces at the ends of the chain. He concluded
that a chain containing at least eight double bonds is necessary for
substantivity. It seems likely that Scrim’s conjugation theory is another way
of expressing Hodgson’s coplanarity theory. Substantive dyes contain
conjugated chains implies that the aromatic nuclei are coplanar.
A much more clearly defined mechanism, which includes most of the
earlier theories, was suggested by Valkó and Eistert and later supported by
many others, according to which the link between the fibre and dye is
formed by hydrogen bonds. A hydrogen atom can act as an acceptor of
electrons, particularly when it is directly attached to nitrogen or oxygen. The
azo nitrogen atom and hydroxylic or ether oxygen atom can act as electron
donors.
Valkó suggested hydrogen bonds might form between amine and amide
groups of dyes and cellulose as shown in (8-12). Rose (1935) confirmed that
the direct dyes could assume a linear form containing hydrogen bond-
forming groups placed at intervals of 10.3 Å. He concluded that at least two
hydrogen bonds between fibre and dye are needed for substantivity and
fixation is more stable the further the bonds are spaced.
Cellulose Cellulose
H-O H O
CH2 CH2 H
H O
H2N NH2 N C N
(8-11) (8-12)
Direct dyes are made soluble by introduction of sulphonic acid groups or

more rarely, carboxylic groups. These groups confer negative charge on the
dye molecule. Since cellulose in water is itself negatively charged, this leads
to an electrical repulsion between the fibre and dye. An increase in the
number of solubilising groups in a molecule, therefore, must reduce its
substantivity. From a study of this problem, Schirm concluded that a polarity
produced by sulphonic acid groups across the molecule at right angles to its
length and distributed uniformly along is favourable to substantivity.
The following structural properties, therefore, govern substantivity of direct
dyes for cellulosic fibres:
504
• Elongated linear molecular structure with few side chains.

• Several aromatic rings, which are arranged in one plane, i.e. the dye
molecules are coplanar.
• Presence of hydrogen-bonding groups such as –OH, -NH2.
• Presence of a limited number of solubilising groups such as –SO3Na, -
COONa.
Favourable, but not essential, conditions are:
• The presence of a conjugated system of double bonds, which by
resonance promotes coplanarity of the molecule and probably favours
hydrogen bond formation by the groups at the ends of the conjugated
chain.
• Widely spaced hydrogen bond-forming groups, spaced at a distance
corresponding as nearly as possible to the cellulose unit length of
10.3 Å or some multiple of this distance.
• The presence of minimum number of solubilising groups necessary for
solubility.
• The deposition of the solubilising groups along one side of the dye
molecule and of hydrogen bonding groups along the other side.
The relationship between molecular weight and wet fastness for direct
dyes on cotton is more tenuous than those for acid dyes on wool due to the
additional contributions in the former case of steric and hydrogen-bonding
effects.
The absorbed Congo Red has been pictured by Vickerstaff as (8-13)
based on the above concept.
Cellulose
OH 10.3 Å OH
H H
NH NH
-N=N- -N=N-
SO3- (8-13) SO3-

The colour of a dye is due to the oscillation of electrons along the
conjugated chain of bonds running through the molecule. These electrons
can be excited by plane polarised light which has an electrical oscillation
parallel to the length of the dye molecule, but not by light with its electrical
vector at right angles to this. In other words, the parallel oriented dye
molecules will have different absorption coefficients towards plane polarised
505
light, according to whether the plane of polarisation is parallel or at right

angles to the length of the molecules (K1 and K2 respectively), the
absorption being greater in the latter case. The ratio of these two absorption
coefficients (K1/K2) is known as dichroic constant. If the dye molecules are
perfectly oriented parallel to the fibre axis, the constant will have a value of
infinity, while for random distribution of the dye molecules, the value will be
1.0. Values between these limits can be attributed either to imperfect
orientation of the dye on a perfectly ordered substrate, or to an imperfectly
oriented substrate, the arrangement of which is completely reproduced by
the dye. Morton observed a dichroic effect when highly stretched viscose
was dyed and examined through a polarising device. The fibres appear to
absorb more or less light as the polaroid is rotated. An interesting
observation is that for the fibres dyed with azoic dyes the plane of maximum
absorption of light is rotated through 90° as compared with direct dyes. The
azoic dye molecules must, therefore, be arranged with conjugated chains at
right angles to the cellulose micelles, which is supported by the fact that in
these dyes, the amide group is the only substantive group and the complete
dye is attached to the fibre by one end only (Figure 8.1). From the
observations, it may be concluded that the direct dye molecules are
adsorbed along the celloboise chains.
Direct dye
Azoic dye
Fig. 8.1 Direction of Electronic Oscillation (↔) of Absorbed Direct

and Azoic Molecules Relative to Cellulose Surface
It had also long been observed that the non-substantive acid dyes usually
give molecularly dispersed solutions, whereas the substantive direct dyes
give solutions containing aggregates. The effect of salt in promoting dye
adsorption was attributed to its action in aggregating the dye and so bringing
the solution to that degree of dispersion most favourable for dyeing. The
view has now lost favour, but still claims some adherents. Although many
direct dyes are highly aggregated at room temperature, the degree of
aggregation at the normal dyeing temperature of 90-100°C is very small and
a large portion of dye exists in the monomolecular state at this temperature.
Furthermore, the pores in cellulose do not permit the entry into the fibre of
aggregates containing more than two or three molecules. This is, however,
not a serious problem if the dye aggregates are assumed to be in a state of
506
mobile equilibrium. The single molecules may enter the fibre and there they
re-form aggregates to an extent dependant on the space available. Valkó
suggested that the presence of aggregation in direct dyes is of no
importance in itself but merely indicates the associating tendency of the dye.
The forces, which lead to aggregation in solution, are the same as those,
which attract the dye to the fibres.
The earlier proposals of hydrogen bond formation have now been
disputed. There is evidence that the hydroxyl groups, which were assumed
to participate in hydrogen bond formation, are firmly attached to a layer of
water molecules, which would cause interference. The experimental
confirmation of the fact has been made [11] by measurement of monolayer
of surface-active diazo dyes on water containing cellubiose. There is also
the possibility of a weak acid-base reaction between the hydroxyl groups of
the cellulose and the amino groups in the dye molecule. More recently,
emphasis has been directed towards the behaviour of the dye molecule
within the fibre.
The absorption of light passing through a phase is proportional to the
number of molecules situated within its path. It is possible to calculate the
degree of aggregation of the molecules by the shape of the plot of
absorbance against concentration.
There is significant evidence that dye molecules exist in a higher state of
aggregation in the fibre than in solution. The dye enters in a state of low
aggregation, and when in the fibre, becomes more aggregated and thus is
entrapped inside the fibre. The existence of aggregates in the fibres has
been confirmed by electron microscopy. Flat orientation of the dye
molecules in relation to the surface of the fibre suggests that Van der Waals'
forces probably play a significant role. The attachment of the dye to the fibre
may also be assisted by hydrophobic interaction. There is no complete
satisfactory explanation for all aspects of cellulosic dyeing with direct dyes.
The adsorption isotherm obtained with most direct dyes corresponds with
Freundlish equilibrium, indicating unlimited opportunity for hydrogen bonding
and Van der Waals' forces to bind the dye. The available surface for
attachment is unlimited. As the accessible areas become crowded, the more
inaccessible ones are occupied.
Important factors affecting the absorption of direct dyes by cellulosic fibres
include the time and temperature of dyeing, liquor ratio, salt concentration,
and the solubility and aggregation behaviour of individual dyes. The
production of level and well penetrated dyeing is favoured by an increase in
the time of dyeing. Strike and penetration into fibre are temperature-
dependent and are accelerated by an increase in temperature. Dyeing
above the boil shortens the dyeing period, enhances levelling and produces
fully penetrated dyeing. An increase in the temperature of dyeing raises the
rate of dye absorption, but decreases the equilibrium exhaustion. For a fixed
507
dyeing time, there is an optimum temperature at which dye exhaustion is at

a maximum (Table 8.2). However, at this temperature migration may not be
as good as at the boil.
Table 8.2 The Temperature of Maximum Exhaustion of Different Direct
Dyes [12]
Name of the Dye (C.I. Direct ....) Temperature of Maximum Exhaustion
Yellow 12 40-60°C
Yellow 6 100°C
Red 37 60°C
Violet 7 20-60°C
Violet 22 40-60°C
Blue 2 60-80°C
Blue 26 100°C
Direct dyes are almost invariably applied from a neutral solution. Addition
of acid may alter the shade. Mild alkali has a retarding effect upon the rate
of absorption. A small amount of soda ash is added either to counteract
hardness in water or in a few cases, to improve the solubility of certain dyes,
which decompose into less soluble free sulphonic acid form during storage.
Many direct dyes tend to decompose during dyeing at or above boil,
probably due to reduction of azo linkages. It frequently occurs when viscose
fibres are dyed under alkaline conditions, since these can exert a reducing
action. This may be prevented by careful selection of dyes and control of
dyebath pH using a buffer like ammonium sulphate. Some direct dyes will
withstand high temperature dyeing of polyester-cellulosic blends by
maintaining pH at 6 with ammonium sulphate. Dyebath exhaustion is highly
dependent on liquor ratio, hence the depth will vary largely among various
methods of dyeing with varying liquor ratio. For better reproducibility, the
liquor ratio in subsequent batches should be kept constant. For economising
in dyestuff consumption, dyeing is to be carried out in short liquor ratio.
The addition of electrolytes to the dye liquor tends to promote exhaustion
of direct dyes, although the effect varies considerably with different
dyestuffs. Cellulosic fibres assume a negative charge when immersed in
-
water. Thus, the similarly charged (negative) direct dye ions (DSO3 ) are
repelled by the fibre. Electrolytes reduce or extinguish the charge on the
fibre, thus facilitating the approach of the dye ion to within the distance at
which hydrogen bonding or Van der Waals’ forces can become effective.
The more electronegative charges are on the dye, the greater will be the
repulsion exercised by the fibre, i.e. the effectiveness of electrolytes in
promoting exhaustion will vary with the number of sulphonic groups in the
molecule. For example, C.I. Direct Yellow 12 has two sulphonic groups and
the cellulose is dyed deeply by the dye without addition of electrolyte. On the
508
other hand, C.I. Direct Blue 1 with four sulphonic groups in the molecule
only stains the cellulose until an electrolyte is added.
In the light of the new ideas on π-π interactions in solution, it is possible to
further clarify why some direct dyes (e.g. C.I. Direct Red 23, disulphonic) are
substantive to the fibre in the presence of only a little electrolyte (0-10 g/l)
whereas others (e.g. C.I. Direct Red 75, tetrasulphonic) require a relatively
large salt addition (80-100 g/l) to achieve reasonable dye uptake. Clearly
disulphonic low-salt dye is more hydrophobic in character than the
tetrasulphonic high-salt dye; in the case of the former dye, there also exists
increased possibility for π-π interactions both in solution and in the fibre
[13]. So-called Yoshida forces have been evoked to explain direct dye-
cellulosic fibre substantivity. Yoshida proposes direct hydrogen bonding of
the substrate with the extended π-electron system of the direct dye
molecule. If π-π interactions are considered in the wider context of
electrostatic interactions, then the existence of π-facial hydrogen bonds in
direct dyed cotton appears very likely. Hydrogen bonds form part of a
hierarchy of electrostatic bonds varying from strong to weak; intermediate
strength is shown by hydrogen bonds such as C-H···O and π-facial bonds for
the direct dye-cellulose system [14].
8.3.3 Classification
It was previously thought that dyes exhibiting similar times of half-dyeing
(i.e. same rate of dyeing) would have similar dyeing characteristics and
would therefore be the preferred choice for mixtures. This view was
subsequently proved incorrect. A detailed study by an SDC (Society of
Dyers and Colourists, UK) committee showed that the four important
parameters in defining the dyeing properties and compatibility of direct dyes
are:
1. Migration or levelling power
2. Salt controllability
3. Influence of temperature on exhaustion
4. Influence of liquor ratio on exhaustion
The SDC committee recommended that direct dyes might be classified
into three categories, such as:
• Class A: Dyes that are self-levelling, i.e. dyes of good migration and
levelling properties. Dyes will level even in the presence of a
considerable amount of salt.
• Class B: Dyes with poor levelling properties, but level dyeing can be
obtained by regulating salt addition. These are described as salt-
controllable.
509
• Class C: Dyes that are not self-levelling and are highly sensitive to
salts. They exhaust well in the absence of salt. The exhaustion of
these dyes is controlled by the rate of rise of temperature of the
dyebath. These are described as temperature-controllable.
Less salt is required for class C dyes for good exhaustion than for Class A
and Class B dyes. Extreme care should be taken in making salt addition with
dyes in Class C and caution should be exercised for Class B too. It is a good
practice to start with a small addition of salt, possibly 2.5% on the weight of
material and to double the amounts in subsequent additions until all the salt
has been added. The total amount of salt will depend on the dye selected,
the depth of shade, liquor ratio, and will vary from 5-25% or more (o.w.m.).
In exhaust dyeing, the ABC classification is widely used to select dyes for
mixtures. When more than one dye is necessary to match a shade, it is
undesirable to mix members of different classes. The selection of
compatible dyes for jig dyeing and padding is best carried out by simple dip
or strike tests. Fabric samples are dyed briefly in dyebath containing a
mixture of dyes (2 minutes), removed from the dyebath, replaced by fresh
samples and this procedure is repeated several times. The dyed patterns
are mounted in series and are assessed visually for change of hue and
depth. A marked change of colour indicates incompatibility. There is a
limited number of direct dyes which have a slow rate of adsorption and a
high rate of migration, and these are most useful for shade corrections when
the additions are to be made at high temperature. Examples of such dyes
are [12]:
C.I. Direct Yellows 6, 11, 37 and 50
C.I. Direct Reds 80, 81 and 83
C.I. Direct Orange 34
C.I. Direct Blue 106
C.I. Direct Green 27
The direct dyes do not possess good fastness to washing nor to other wet
processes. The light fastness ranges from poor to moderate, but many are
quite good.
8.3.4 Application Methods

For Class A dyes, the dyestuff is pasted with cold water, if necessary with an
anionic or nonionic wetting agent. Sufficient boiling water is then added with
constant stirring to bring it into solution. It is then added to the dyebath
containing a large volume of cold water through a strainer. Soft water is
preferred, but is not essential. However, some dyes are precipitated by hard
water and this can be prevented by adding a sequestering agent such as
sodium hexametaphosphate (but not with metal-complex direct dye) or 1-3%
510
(o.w.m.) (0.5-2 g/l) of soda ash. Common salt amounting 5%, 10% or 20%
(o.w.m.) for pale, medium or heavy shades respectively (or about 10-15 g/l),
is then added to the liquor. Pastel hues are preferably dyed without addition
of salt.
Wet cellulosic material, scoured and optionally bleached, is then entered
into the dyebath containing dye at 40-50°C. Alternately, the material is first
run in water in the dyebath and then dye and salt solutions are successively
added. The liquor is then heated slowly and the temperature is raised to boil
over a period of 30-40 minutes, after which dyeing is continued for 45-60
minutes. If the dye distribution is not uniform throughout the fabric, further
boiling may be carried out. Improved yields can be achieved when applying
full depths by cooling to 80°C at the end of the period at boil, adding a
further 5 g/l salt and rising to the boil again. The exhaust dye liquor is
drained. The material is washed with cold water, hot water and lightly
soaped (optionally).
For Class B dyes, the method is similar to the above, but the salt is not
added at the beginning. It is added only when the temperature is near boil
and the addition may be continued after the boiling is reached. The most
preferred method will be addition through drip feed. The levelling agents
may be added to reduce the sensitivity to salt.
For Class C dyes, again the dyeing should commence at low temperature
without salt. The temperature is raised very slowly to the boil. Electrolytes
required to complete exhaustion should be added in portions after boiling is
reached. There is often a narrow temperature range for each Class C dye
over which exhaustion is rapid. The temperature rise is to be controlled
cautiously during this range.
Many direct dyes are suitable for combined scouring and dyeing process
employing soda ash and a nonionic detergent. Dyes with amide groups
should be avoided.
Combined peroxide bleaching and dyeing can be carried out with selected
direct dyes. The materials should be thoroughly prepared. Soda ash is
preferred to caustic soda and organic stabiliser to sodium silicate.
Direct dyes are much less suitable for continuous application than for
batchwise dyeing. Tailing is a serious problem in continuous dyeing and
prolonged diffusion is necessary in pad-batch or pad-steam methods [8].
Pad-roll process at 80-100°C is the most suitable semi-continuous method
of dyeing cellulosic fabrics with direct dyes.
8.3.5 After-treatments of Dyed Materials

The lack of wet-fastness of direct dyes may be undesirable for the materials,
which are expected to withstand washing. Many methods are used to
increase the molecular weight of the dye, after it has been adsorbed by the
511
fibre, to render less soluble in water and, therefore, more fast to wet
treatments. The methods may be classified as:
1. Diazotisation of the dye and coupling with coupling components

2. Coupling of dye with diazotised amines
3. Treatment with formaldehyde
4. Treatment with metal salts
5. Treatment with cationic fixing agents or synthetic resins
Diazotisation and coupling
Direct dyes containing amino groups are applied in the normal way, washed
off and treated in a bath containing sodium nitrate and hydrochloric acid,
suitably buffered. The material is then rinsed and passed into a bath
containing dissolved coupling component. Such compounds, usually
referred to as developers, are phenolic compounds like resorcinol, m-
phenylene diamine and β-naphthol, and are dissolved in sodium hydroxide.
The treatment in developer solution is carried out for 15-20 minutes and
then washed off. The hue of the developed dye is usually quite different from
that of the original. A few direct dyes, which can be diazotised and
developed, are:
C.I. Direct Yellows 64 and 65

C.I. Direct Reds 127, 136 and 155
C.I. Direct Blues 2 and 20
C.I. Direct Green 52
The improvement in fastness rating may be of the order of 1-2 units.

Coupling with Diazotised Amine
The cellulosic material is dyed with a direct dye containing an amino or
hydroxyl group (C.I. Direct Brown 152) and then the dyed material is treated
with a solution of diazotised base, usually paranitroaniline. Virtually a new
dye is produced in situ in the fibre.
Treatment with Formaldehyde
Azo direct dyes, with two hydroxyl or two amino groups adjacent in one of
the end components, are capable of forming complexes with formaldehyde,
forming less water-soluble products. The exact reaction has not been
established, but there can be little doubt that the dye molecules are linked
together by the formation of methylene bridges as shown in Eqn. (8.2). The
dyed material is rinsed and run in a liquor containing 2 to 3% (o.w.m.)
formaldehyde (40% solution) and 1% acetic acid (30%) at 70-80°C for 30
512
R R R R
CH2
+ H.CHO + H2O (8.2)
H2N NH2 H2N NH2 H2N NH2 H2N NH2
minutes. The improvement is of the order of 1 in the scale of the ISO wash
test.
Treatment with Metal Salts
/ /
A few direct dyes having o-o hydroxy azo, o- hydroxy-o -carboxy azo or
salicylic groups can be complexed with metal salts for improvement of
The washing fastness of materials dyed with suitable dyes can be
improved by immersing the dyed material in a solution containing 1 to 3%
(o.w.m.) potassium or sodium dichromate and 1-2% (o.w.m.) acetic acid
(30%) for 20-30 minutes at 60-80°C. For improving fastness of light as well
as washing, the treatment may be made with 1-2% (o.w.m.) sodium
dichromate, 1-2% (o.w.m.) copper sulphate and 2-4% (o.w.m.) acetic acid
(30%) as above. The disadvantages of copper complex types are that the
complexes are sensitive to acids or sequestering (e.g. histidine in
perspiration) and discharge printing is either impossible or extremely
difficult.
A number of dye manufacturers have come out separate brands of direct
dyes which can be aftertreated with copper salts e.g. Coprantine,
Neocupran (Ciba), Cuprophenyl (Geigy), Cuprafix (Clariant).
Cationic Fixing Agents
Most of these products are cationic surfactants, which unite with the dye
anion producing a new substance of greater molecular complexity and less
water-solubility with better wash fastness. However, most of these
compounds tend to lower light fastness of the dyed materials and alter the
shade. The complexes may also be broken down by surface-active anions,
which compete with the dye anions for the cationic sites of the agent. The
agent may thus be removed and wash fastness is lowered down to the
original. Some of the cationic dye fixing agents are Sapamine W (8-14),
Fixanol C (8-15), Matexil FC-PN (8-16), etc.
C17H35CONH(CH2)2  N+  (C2H5)3Cl – +
C16H33  N Br –
(8-14) (8-15)
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The details of their application to direct dyeing can be found in

manufacturer’s literature. The method of application is usually to treat the
dyed materials with 1-3% (o.w.m.) fixing agent at 70°C for a period of 15-20
minutes. The quantity of fixing agent depends on the depth of the shade and
on the concentration of the product. A small amount of formic or acetic acid
is often necessary to bring the cationic product in solution.
The earlier dye-fixing agents are based on alkyl pyridinium halides. The
literature shows that many amines, quaternary ammonium, phosphonium
and tertiary sulphonium compound can be used as a dye-fixing agent. A
number of synthetic resin compounds are also used. Many patents on resin-
fixing agents for direct dyes (e.g. Fibrofix) are based on dicyandiamide and
its reaction products with formaldehyde yielding products having a cross-
linked three-dimensional structure such as (8-17).
R R
/
R R
/ + –
+ –
-[NH2–CH2–NH-C=N-CH2 -]n nCl
N ↔ N + Br
R// Br R// NH
CN
(8-16) (8-17)
This type of compound also forms complexes with many metals such as
copper, chromium, etc. However, formaldehyde is a suspected human
carcinogen and the products, based on formaldehyde are not eco-friendly.
Many similar compounds, such as condensates of formaldehyde and
melamine, polyamines and cyanuric chloride, chloroalkanes and
polyethylene imine have been developed as dye-fixing agents. Fibrofix
(Courtauds) is based on cyanamide and formaldehyde. Lyofix SB (Ciba) is
based on melamine-formaldehyde. Neocupran Salt D is Lyofix SB plus
copper sulphate. Interaction of the dye fixing agents relies on the weak
electrostatic bonding. Hence, the complex may not be very stable while
washing with soap or anionic detergents.
Long-chain polyamines showed consistently better wet fastness than
dicyandiamide-formaldehyde adducts. Fastness performance varied with the
number of sulpho groups, hydrogen-bonding sites and their positions in the
dye molecule and the active agent content of the fixing agent [15].
8.3.6 Stripping of Direct Dyes

Unless after-treated, the stripping of direct dyes from dyed fabric is quite
easy. Less fast direct dyes may be largely removed by boiling in detergent
solutions. The colour can usually be destroyed by boiling with 5% (o.w.m.)
sodium hydrosulphite and 4% (o.w.m.) caustic soda at 90°C for 30 minutes,
514
by overnight treatment at cold with sodium hypochlorite solution (1.5-2 g/l

available chlorine), or at boil with 1-2% (o.w.m.) sodium chlorite at pH 3-4.
When the dyed material is after-treated with a cationic dye fixing agent,
the latter is to be removed first. This is in order to release the dye and
because the agent would act as a mordant for the anionic dye to be used
subsequently for redyeing, causing rapid uneven dyeing. The stripping of the
cationic agent is done by boiling for 30 minutes with 2% (o.w.m.) formic acid.
Copper must be removed before treating the fabric with hypochlorite, since it
catalyses the attack on cellulose. For copper after-treated material, the
treatment is to be made with 1-3 g/l EDTA, an anionic detergent and 1 g/l
soda ash.
8.4 REACTIVE DYES
Reactive dyes are the youngest and most important dye-class for cellulosic
materials. Worldwide consumption of reactive dyes for cellulosic materials in
mid-1980s was about 10-12% [4, 5], whereas in Japan alone it represented
about 40% of total dye consumption. The reactive dyes offer a wide range of
dyes with varying shades, fastness, costs with high brilliancy, easy
applicability and reproducibility. However, good preparation of the material is
a prerequisite. The colour yield and brilliancy of shades are enhanced
significantly by mercerisation. The dyes are unstable to hypochlorites.
Hence, bleaching with hypochlorites may create problem during subsequent
dyeing with reactive dyes.
Unlike other dye-classes, as much as 50% of the total cost of a reactive
dyeing process must be attributed to the washing off stages to remove
unfixed or hydrolysed dye and treatment of the resulting effluent. This
aspect of the process should be recognised as a major limitation that
prevents reactive dyes from achieving the degree of success that was
predicted for them at the time of discovery. Certain other deficiencies are
associated with the limited stability of specific types of dye-fibre bond to
various conditions of treatment of the dyed fibres.
Unlike vat dyes, most of the reactive dyes are not fast to chlorine
bleaching. The fabric containing reactive-dyed threads cannot be post-
bleached. However, it is proved that certain structural features, in particular
the presence of a sulphonic or carboxylic group ortho to the nitrogen of the
diazo component and a similar group in ortho or para to the hydroxyl group
of the coupling component, conferred good chlorine fastness. The
dissociated form of the dye undergoes degradation, hence the pKa of the
dye is thus an important determinant of chlorine fastness (−NH−N= ↔
−N−−N= + H+) [1]. The introduction of more powerful cleansing agents has
imposed additional demands on dye manufacturers. The dye should
515
withstand prolonged multi-machine washing in the presence of activated

oxygen bleach-containing detergents.
Reactive dyes comprise a chromophore and a reactive group. They differ
fundamentally from other dye-classes in the fact they chemically react with
the textile fibre forming covalent bonds. The conventional dyes, on the other
hand, owe their wet fastness because of physical association, non-specific
chemical bonding (e.g. hydrogen bond) or insolubilisation inside the fibre.
There is no clear borderline between physical and chemical interactions
between molecules. Van der Waals' forces and hydrophobic bonding are
usually considered physical processes, whereas hydrogen bonding and
coulombic attraction of ions can be considered as physical or chemical
phenomena. On the other hand, the formation of covalent bond is definitely
a chemical process.
Chemically cellulose behaves as a polyhydric alcohol and most
commercial reactive dyes react with it only under alkaline condition. There is
substantial evidence to show that the adsorption of sodium hydroxide by
cellulose follows an ionic mechanism, the cellulose behaving as a weak
acid, which dissociates into sodium cellulosate. Under neutral conditions
reactive dyes adsorb and diffuse inside the fibre, but do not react with it as
the concentration of cellulosate ion is extremely low. Addition of alkali
increases ionic concentration and promote reaction to occur between the
dye and fibre.
While soda ash (98% anhydrous sodium carbonate) remains the most
widely used alkali for reactive dyeing, sodium bicarbonate, sodium silicate,
caustic soda and various phosphates are also important. Sodium
bicarbonate should be dissolved at cold. In recent years, liquid buffer
systems and liquid alkali products such as Alkaflo (Tanatex) have been
introduced for automatic dosing and metering systems.
The reactive dyes are compounds having suitable groups capable of
forming covalent bonds between a carbon atom of the dye ion and oxygen,
nitrogen, sulphur atom of a hydroxy, an amino or a mercapto (R.SH derived
from thio-alcohol) group respectively, of the substrate. This definition
excludes mordant and 1:1 metal-complex dyes, which may form covalent
bonds between the metal ion and the nucleophilic groups of the protein
fibres. These dyes were in use for long time, but the covalent nature of their
interactions with fibre was known only after mid-1950s, when reactive dyes
were invented. The differentiation between covalent and metal-ligand bond
is difficult.
The reactive dye is held by the fibre so long as the covalent bond is intact.
The bonds are generally stable under domestic and industrial wet
treatments and are fast to repeated washing. For conventional dyes, the
molecular size of the dye plays an important role in determining fastness
properties − bigger molecular sizes are preferred for better wash fastness.
516
However, this necessitates incorporation of several groups, resulting in

absorption at different wavelengths of visible light. The absorption band is
therefore broader, hampering purity of colours produced by these dyes.
Reactive dyes have no such limitation. The fastness largely depends on the
strength of the covalent bonds formed allowing flexibility of the molecular
size. They are valued for their brilliance and variety of hue, exceptional
application versatility and high wet fastness profiles. Such properties place
dyes of this class at the quality end of the market. They are used for the
dyeing and printing of cellulose, and to a lesser extent for polyamide fibres.
The growth rate of reactive dye consumption is 3.9% per annum world-wide
(3% in the EEC), which is four times the growth rate of other dyes for
cellulosic fibres.
It took 100 years of dye chemistry to produce reactive dyes following
Perkin’s discovery of the first synthetic dye, Mauvein or Mauve in 1856. This
obvious and uncomplicated principle went unnoticed for so long. The reason
for this neglect is that most dye chemists believed cellulose to be relatively
inert. More attention for developing reactive dyes was for wool fibre, which is
more chemically active, though the need and potentiality of the change of
technology was not so great as in case of cellulosic fibres. Industrially
successful reactive dye technology began in the field of wool dyeing around
1930 with the introduction of chloroacetylamino (ClCH2CONH-) and sulpho-
β-chloroethyleneimide (-SO2NHCH2CH2Cl) groups. The related compounds
became important some 20 years later for developing reactive dyes for
cellulose.
The most important event in the history of reactive dyes was the
introduction of reactive dyes for cellulose by ICI in 1954. Rattee and
Stephan of ICI claimed that, when water-soluble dyes containing a
SO3H
H Cl
N O
N N N
HO3S Cl
NH N
(8-18)
dichlorotriazine (DCT) group is applied to cellulose from a neutral bath and

then increasing the pH value, a covalent bond is formed between a triazine
517
carbon atom and an oxygen atom of a cellulose hydroxyl group. An example

of such dye is C.I. Reactive Orange 1 (8-18).
Immediately after introduction of Procion dyes, all major dyestuff
manufacturers began investigation for newer reactive dyes. The variations
made may be summarised as follows:
1. Replacement of s-triazine by other reactive groups.
2. Variation of the chromophore.
3. Replacement of one of the chlorine atoms by a non-labile atom or
group such as amino.
4. Replacement of one or both of the chlorine atoms by other labile
atoms or groups.
5. Replacement of =NR by other bridging groups.
CIBA manufactured monochlorotriazine dyes (MCT) or

aminochlorotriazine, which can be applied on cellulose at higher
temperature and pH. CIBA named the dyes as Cibacron dyes, while the
same dyes were introduced by ICI in the name of Procion H (H for hot), both
in 1957. Later Ciba introduced monofluorotriazine (MFT) dyes in the name
of Cibacron F. Hoechst introduced Remalan dyes based on vinylsulphone
(VS) for wool in 1949, claimed to be suitable for cellulose too. However, they
introduced Remazol reactive dyes exclusive for cellulose containing
sulphuric acid ester of β-hydroxyethylsulphone in 1958. In subsequent
years, various dyestuff manufacturers introduced further reactive groups.
Though reactive dyes were originally developed for wool, the commercial
exploitation of reactive dyes for wool started after introduction of Lanasol
(Ciba) dyes based on α-bromoacrylamide (-NHCO-C(Br)=CH2) by Ciba.
These dyes as well as difluorochloropyrimidine dyes e.g. Drimalan (Clariant)
and Verofix (Bayer) dyes, have high fixation ratio.
8.4.1 Components of Reactive Dyes

The different structural components of a reactive dye are:
1. A chromogen responsible for the colour.
2. Solubilising groups responsible for the solubility of the dye
3. Reactive group, which forms covalent bond with the substrate.
4. An optional bridging link between the reactive group and the
chromophoric system.
The variation in chromophore is necessary for the following reasons:
1. In order to provide various shades to cover the maximum possible

colour gamut.
2. The reactivity of the dye is affected by the chromophore.
518
3. The chromophore affects substantivity and diffusion coefficient, which

in turn determine fixation efficiency and washing off properties of
reactive dyes.
When a greater portion of the reactive dye is adsorbed on the cellulose, it

is more likely that the dye will react with the cellulose rather than with water,
the process of fixation will, therefore, be more efficient. It is possible to
produce reactive dyes of high affinity by using a chromophore similar to that
of a direct dye. However, this is not a practicable method for securing a
higher degree of fixation. Any portion of hydrolysed dye retained inside the
fibre will have relatively poor fastness as compared to chemically bound
dye. If the chromophore is highly substantive, the hydrolysed dye will be
difficult to remove during washing and fastness will be less than that of
chemically bound dye. Dyes with a high association tendency reduce the
rate of hydrolysis and frequently improve fixation owing to high substantivity.
However, undesirable dimers may form. For this reason, dye structures of
relatively low affinity are used for manufacture of reactive dyes for cellulose.
Consequently, the reactive dyes have a moderate rate of diffusion, high
brightness due to simpler structure, very attractive levelling and penetration
properties before reaction occurs. However, some affinity is essential in
order to ensure adsorption by the fibre prior to chemical reaction with it,
especially in case of long-liquor batch processes. Reactive dyes of low
reactivity normally require larger molecules in order to provide sufficient
substantivity to the substrate at high temperature of dyeing.
Therefore, the substantivity is to be tailored according to the purpose for
which the dye is intended to be used. The attachment of a reactive system
may alter substantivity, which is increased more by arylaminochlorotriazinyl
group and less by dichlorotriazine group. The similar effect is shown by
dichloroquinoxaline groups, but not by chloropyrimidinyl, β-chlorpropionyl or
β-sulphato-sulphoethyl groups.
On principle, the chromogen of a reactive dye may belong to any chemical
class, provided it has necessary substantivity for the fibre. Metal-free simple
monoazo dyes are used for yellow, orange and red reactive dyes.
Cupriferous mono and disazo dyes are used for rubine, violet and navy
dyes. Bright blue dyes are derived from 1-amino-4-arylaminoanthraquinone-
2-sulphonic acid and phthalocyanine and black dyes from disazo dyes.
The gradual replacement of the relatively weak anthraquinone
chromophore, typically with a molar extinction coefficient, εmax in the range
12,000 to 18,000 mole/(l cm) by the much stronger triphenodioxazine unit
having εmax between 70,000 and 85,000 mole/(l cm) is now a well
established trend. All of the major manufacturers now offer
triphenodioxazine-based blues, an example is (8-19). Several new products
utilising disazo chromophores with J-acid have recently been introduced into
519
Cl
O N
H2N-
N O
-NHCO- -SO2CH=CH2
Cl
(8-19)
shade areas previously dominated by much weaker monoazo systems.
Bayer has patented and commercialised, a reactive dye based on this type
of chromophore (8-20, R = reactive group). This product is very bright
yellowish-red; unlike many disazo products, it is not dull. Additionally, it is a
very strong chromophore with an extinction coefficient of about 50,000
mole/(l cm).
Although disazo derivatives have traditionally been widely employed for
the production of dull shades, such as browns and navies, several other new
disazo products have also appeared. For example, some of Cibacron LS are
based upon strong disazo chromophores in which the naphthol coupling
component of the bright red (8-20) is replaced by a conventional para-
coupling amine [16]. Trisazo dyes are well known in direct dyeing. They
found little application in reactive dyes, probably due to poor levelling and
migration properties. However, a couple of them have recently been
marketed.
HO3S
N
N
H
N O
HO3S
N
HO3S R
(8-20)
Phthalocyanines, invariably copper or nickel derivatives, are almost
universally employed in reactive dyes, either alone to achieve bluish or
greenish turquoise shades or in combination with lemon yellows for the
production of bright greens. In spite of their extremely high chromophoric
strengths, they do not appear particularly strong on cotton and generally fail
to build up to very heavy shades. This is because of modest fixation
efficiency, which in turn probably arises from the tendency of the molecules
to exist in highly aggregated forms. DyStar proposes to use aluminium
520
phthalocyanines for preparation of reactive dyes for cellulose. In contrast to

nickel and copper derivatives, these are environmentally safe and also
provide brilliant green to turquoise shades. Other benefits are very good
light fastness, better strength and build-up on the fabric, especially at low
temperatures (40-60°C) and good fixation efficiency.
Reactive dyes for cellulose and protein fibres require 1 to 3, in a few cases
4, sulphonic acid groups. The reactive dyes for nylon require no special
solubilising group as in case of disperse dyes, because the reactive groups
themselves provide sufficient substantivity for the substrate at the dyeing
temperature.
The bridge link is mostly required for chemical synthesis purpose. It
influences the properties of reactive dyes such as:
1. Reactivity of the system – dissociation of imino bridge (-NH- Æ -N-)

reduces reactivity by several powers of ten. This may occasionally
reduce substantivity and degree of fixation.
2. The length and flexibility of the bridge affect the degree of fixation.
3. The stability of the dye-fibre bond as well as the link between the
chromogen and reactive group may be broken under adverse
condition [17].
Among the groups that have been disclosed in patents as alternative to

=NR for linking chromophore to the chlorotriazinyl reactive group are: −O−,
−S−, −SO2NH−, aliphatic or aromatic chains, e.g. −NHCO·C6H4·NH−,
−N(alkyl)·CO− groups. Though variation of the linking group is known to
affect various properties, for various reasons little use has been made of this
in commercial reactive dyes, the overwhelming majority of which have =NH
as linking group. Firstly, several of the alternative bridges, particularly the
–O− and –S−, are considerably less stable towards alkaline hydrolysis than
=NH. The use of aliphatic or aromatic chains as linking groups tends to
lower water-solubility of the dye, usually without conferring any advantage in
other directions. Due to ease of synthesis, stability towards hydrolysis and
minimum interference with solubility, the =NR, and particularly the =NH
group appears to be advantageous. Its wide use in commercial
chlorotriazine dyes is, therefore not surprising [16].
8.4.2 Reactive groups

Giles [17] classified reactive groups into five categories depending on the
mechanism of reaction with the substrate such as:
1. Nucleophilic substitution.
2. Nucleophilic addition.
521
3. Multiple addition-elimination reactions.

4. Fixation under acidic conditions.
5. Dyes forming disulphide bonds.
More recently other classes of reactive dyes have been developed which
provide much higher degrees of fixation than the conventional reactive dyes.
These high fixation reactive dyes contain multiple (mostly two) reactive
groups attached to each dye molecules. The reactive groups may be
identical or different and accordingly the dyes are known as homofunctional
or heterofunctional reactive dyes.
Nucleophilic Substitution
The most important member of this group is chlorotriazines obtained by
reaction of dye chromogens having NH2 groups with cyanuric chloride. The
latter is based on 1,3,5 triazine or s-triazine (s = symmetrical) ring, which is
made up of three carbon and three sulphur atoms in alternate positions with
three chlorine atoms on carbon atoms. Cyanuric chloride, a white solid
having a melting point of 146°C and possessing a pungent odour of mouse
excrement, is a low cost and highly reactive substance. One, two or three of
its chlorine atoms can be replaced with any nucleophilic reagent. Several
such replacement reactions, especially those occurring with amines, are
capable of being carried out stepwise, so that, according to the conditions,
mono-, di-, or tri-condensation products may be obtained.
When cyanuric chloride is reacted with a dyebase (D.NH2), highly reactive
DCT dyes, Procion MX (ICI, now Zeneca) and Basilen M (BASF) dyes are
obtained. When it is reacted with a colourless amine (8.3), less reactive
MCT dyes, e.g. Cibacron and Procion H, Cibacron Pront (-OR instead of –
NHR) are obtained. Although the usual procedure of making MCT dyes is to
react cyanuric chloride first with colourless amine, before reacting with
dyebase.
Under favourable conditions nucleophilic groups of the substrate (e.g. -OH
groups of cellulose or –NH2 groups of protein fibres) react with the chlorine
atoms on the heterocyclic ring by nucleophilic addition-elimination or
substitution mechanism. The functional group of the textile fibre is first
added to the dye molecule and then an ion (usually chlorine) is eliminated.
The overall reactions for DCT and MCT dyes are shown in (8.4) and (8.5)
respectively. The reaction (8.4) occurs at around 20°C when one or both
chlorine atoms of DCT dyes may be replaced by cellulose. The reaction
(8.5) of MCT dyes occurs at high temperature, around 70°C. The by-product
of both the reactions is hydrochloric acid (HCl). Hence, the rate of forward
reactions can be increased by addition of alkali. In other words, the
reactions are base-catalysed. Before addition of alkali, the majority of the
dye originally put into the dyebath is adsorbed by the action of the
exhausting agent, common salt and is diffused into the fibres. Hence, the
522
dye mostly reacts with cellulose. A portion, however, reacts with water in the
dyebath and is deactivated. This hydrolysed dye, which is simply the original
reactive dye with its labile atom or group replaced by hydroxyl, usually has
very similar diffusion and adsorption properties compared to the original.
After diffusion into the fibre, it is distributed between the fibre and dyebath in
a manner similar to the original distribution of reactive dye in neutral
solution. This hydrolysed or loose dye must be removed by a final washing
process in order to produce dyed material of high wet fastness.
Cl O.Cell.
(8.4)
N N Cell.OH N N
D.NH Cl D.NH Cl
N N
(8.3) R.NH2
Cl O.Cell.
(8.5)
Cell.OH
N N N N
D.NH NHR D.NH NHR
N N
The other members of this group are:
1. 2,4,5 trihalogen-pyrimidine, e.g. Reactone (Geigy), Drimerene
(Clariant) (8-21a), Drimarene K, Drimalan F (Clariant), Verofix,
Levafix E-A (Bayer) (8-21b).
X1
Cl (8-21a) X1 = X2 = Cl
N (8-21b) X1 = X2 = F
D.NH X2 (8-21c) X1 = CH3 , X2 = SO2CH3
N
2. 2-methylsulphonyl-4-methyl-5-chloro-pyrimidine, e.g. Levafix P
(Bayer) (8-21c).
3. 3,6-dichloropyrazine, e.g. Solidazol (CFM) (8-22).
4. 2,3-dichloroquinoxaline, e.g. Levafix E (Bayer), Cavalite (8-23).
5. 2-chlorobenzthiazole, e.g. Reatex (Fran) (8-24).
6. 4,5-dichloropyridazone, e.g. Primazin P (BASF) (8-25).
523
In most of the above reactive systems, the nucleofugal-leaving group is a

chlorine atom, but there can be other groups like fluorine, alkyl sulphones,
sulphonic acid groups or quaternary ammonium groups.
D.NHCO
Cl D.NHCO N
Cl
Cl N N Cl
N
(8-22)
(8-23)
N Cl
D.NHCO S D -NHCO-(CH2)2 Cl
N
Cl
N O
(8-24) (8-25)
Nucleophilic addition
Reactive dyes, based upon chlorotriazines or chloropyrimidines, are
acylating dyes that become attached to fibres by the process of nucleophilic
substitution, thus forming compounds with cellulose possessing some of the
properties of esters (R-CH–O.alkyl). Another type of reactive dyes is
conceivable with which the dye-fibre compound is formed by nucleophilic
addition rather than substitution and has the properties of an ether (R.O=C-
O.alkyl) rather than those of an ester. An ether type of linkage is formed
between azo compound and cellulose, either by direct reaction of the
sulphuric ester or by desaturation and subsequent addition. However, in the
absence of a suitable activating group, such reactions proceed far too slowly
to be of any practical use. Various electron-attracting groups have been
used to provide such activation, one of the most common being sulphonyl.
By interposing such a group between a chromophore and the olefinic group,
as in vinylsulphone (VS) dyes, the double bond becomes sufficiently
polarised for nucleophilic addition. The reaction proceeds readily under mild
alkaline conditions with alcohols (R.OH) including cellulose, the group –OR
becomes attached to the β-carbon atom.
It is not necessary that the vinylsulphonyl system is to be present as such
in the dye molecule. The activation, which facilitates addition of cellulose,
also enables the corresponding β-sulphatoethylsulphonyl or similar
precursor to undergo desaturation very easily under mild alkaline conditions
in the dyebath (8.6), although it is not absolutely certain that this mechanism
is involved in dyeing.
524
DSO2CH2CH2·O·SO3Na Æ DSO2·CH=CH2 Æ DSO2CH2CH2·O·Cell. (8.6)

In nucleophilic substitution reaction, the functional group participates in the
addition as well as in the elimination step, while in Eqn. (8.6), the first β-
elimination step is independent of the substrate. Therefore, with the latter
class of dyes, it is possible to optimise the rate of formation of the true
reactive compound at constant dyebath pH by varying the concentration and
type of buffer. This may be of particular significance in obtaining level
dyeing. The degree of fixation also depends on the type and concentration
of buffer.
The product of hydrolysis, a 2-hydroxyethylsulphone, is generally much
less substantive than the reactive dye itself and can be easily washed off
after dyeing. In case of halotriazines, the hydrolysed species are only
marginally less substantive than the corresponding dyes and prolonged
washing off is necessary.
Ever since the Remazol dyes were introduced in the 1950s, the dyeing of
dischargeable ground for subsequent discharge printing has been a
preferred outlet for them. Largely they have ousted the earlier favourites for
this application, namely the direct dyes. No other range of reactive dyes
offers such a wide choice of dischargeable products, i.e. dyes, which can be
made colourless by the action of a reducing agent at high temperature.
Various reactive groups present in commercial reactive dyes, which
undergo similar chemical addition reactions, are listed below:
Groups yielding vinylsulphone can be represented as:
–SO2CH2–CH2–X
X = -OSO3H, Remazol and Remalan (Hoechst) dyes
X = -N(CH3)CH2–CH2–SO3H, Hostalan (Hoechst) dyes
+ -
X = -N(NH3 )CH2–CH2–SO3 , Remazolan (Hoechst) dyes
Groups yielding acrylamide groups can be represented as:

-NH-CO-CH2–CH2-X
X = -OSO3H or X = -Cl, Primazin (BASF) dyes
Epoxy (8-26), its precursor 2-chloro-1-hydroxylethyl (8-27), aziridine (8-28)

and 2-chloro-ethyl-1-amino (8-29) groups present in Procinyl (ICI) dyes also
undergo nucleophilic addition reactions.
CH2 CH CH2 CH2
CH2 CH CH2 OH Cl N NH CH2 CH CH2 Cl
CH2
O
(8-26) (8-27) (8-28) (8-29)
525
Several addition-elimination Steps

There are dyes, which react via several addition and elimination steps with
the functional group of the substrate. Lanasol (Ciba) dyes having
α-chloroacrylamide group belong to this group. Other five possible groups
present in such dyes are shown in (8-30).
-NH-CO-CH-CH2 -NH-CO-C=CH2 -CH-CH2 -CH-CH2 -SO2-CH=CHCl

Br Br Br -CF2-CF2 -CF -CF2
(8-30)
Parton [18] described in details the chemistry of halopyrimidine reactive
dyes. The dyes are less reactive, but more expensive than triazine dyes.
The also have higher acidic and alkaline stability, but lesser oxidative
stability. The different brands of Drimerene reactive dyes developed by
Sandoz (presently Clariant) and the respective reactants used for the
formation of reactive groups (like trichloroazine in case of Procion dyes) are
as follows:
1. Drimerene X (1958) − tetrachloropyrimidine (TCPI).
2. Drimerene K (1970) − 5-chloro-2,4,6-trifluropyrimidine (FCP).
3. Drimerene XN (1985) − monochlorotriazine (MCT) dyes.
4. Drimerene CL (1995) − FCP + vinylsulphone (VS).
5. Drimerene HF (2000) − trifluropyrimidine (TFP) + VS.
The last two brands are heterobifunctional dyes described latter in this
section. The characteristics of dyes formed with TFP are:
• Good fastness properties.
• High fixation.
• Good wash-off.
• Good solubility.
• No AOX.
• Expensive, but cost effective.
Acid-fixable Reactive Dyes
Most of the reactive dyes are applied on cellulosic materials under alkaline
conditions. Long-standing ambition to combine dyeing and finishing,
especially resin finishing, resulted in development of reactive dyes which
can be fixed under acidic conditions. One such type of dye is Calcobond
(Cyanamid) dyes marketed by American Cyanamid Company in 1965. They
contain N-methylol groups obtained by reacting dyes containing melamine
groups (1,3,5-triaminotriazine) with formaldehyde (8-31).
526
Calcobond dyes are stated to react with cellulose only under the combined
effect of catalyst and dry heat. All acid-type catalysts fix the dyes, but
because of overall compatibility and effectiveness, ammonium chloride is
preferred. These dyes are stated not to undergo hydrolysis in aqueous
solution and to have low substantivity towards cellulose. Calcobond dyes
are suited for use with disperse dyes in dyeing of polyester-cotton blends,
and in simultaneous dyeing and resin finishing processes. A disadvantage is
that cotton loses about 50% of its tensile strength during fixation of these
dyes at high temperature.
NH-CH2OH
N N
D.NH NH-CH2OH
N
(8-31)
In 1973, workers of Stanford Research institute in conjunction with

Burlington industries, observed that phosphoric acids react with alcohols to
give phosphonate monoesters and this can be utilised for reactive dyes as
shown in Equation (8.7).
Dye-PO3H2 + Cell-OH Æ Dye-PO2H-O-Cell + H2O (8.7)
Much detailed study by ICI resulted in the introduction of Procion T (ICI)
dyes in 1977. These dyes can be applied to the cellulose under mild acidic
conditions (pH 5−6) and are also sold as liquids. They are also sold as
admixture with disperse (Dispersol, ICI) dyes under the Procilene trademark
for application on polyester/cotton blends by single-stage process. In two
stage process with alkali-fixable conventional reactive dyes, disperse dyes
are subjected to destruction by hot base. Moreover, the phosphonate ester
dye-fibre bond is exceptionally stable to chemical agents like strong acid or
base and does not suffer easy cleavage under mild alkaline and acidic
conditions as do the vinylsulphone and triazine dyes respectively. The
mechanism of fixation of phosphonic acids to cellulose is particularly
interesting and requires a second agent, which in practice, is dicyandiamide.
The fixation is carried out at 180-200°C in the presence of an acid donor
such as ammonium dihydrogen phosphate. The reaction is shown in
Equation (8.8).
O HN-CN O NH2
Dye-P-OH + H2N-C=NH + Cell·OH Dye-P-O·Cell + HN-C=O (8.8)
OH OH H2N-C=NH
527
These dyes are sold as solutions of ammonium salts. They underwent

dissociation at high temperature liberating free phosphonic acids.
Although offering some significant benefits, phosphoric acid dyes suffer
from several drawbacks. Very high temperature, typically about 210-220°C
is required for their fixation. The treatment, at such high temperature under
acidic condition, may cause tendering of cotton, a defect less obvious for
polyester/cotton blends. Dye migration during drying prior to thermo-fixation
may be encountered, especially in case of heavy fabrics. The dyes were
withdrawn in 1987, essentially for economic reasons after introduction of
new and more cost-effective products and processes for dyeing
polyester/cotton blends [19].
Dyes Forming Disulphide Bonds
Thiosulphate dyes containing one or more –S·SO3H groups, irrespective of
their mode of attachment to the chromophore, belong to this class. Some of
the usual types are:
1. Dyes having –S·SO3H groups directly substituted in aromatic nuclei,
e.g. Dykolite (Southern Dyestuff Corporation) and Hydrosol (Cassella).
2. Dyes having –S·SO3H groups attached to the aromatic nuclei through
an alkyl group, usually -CH3 – e.g. Inthion dyes (Hoechst).
3. Dyes having substituent -SO2·NH·CH2 CH2–S·SO3H, often known as
Bunte Salt dyes.
It seems certain that, as far as cellulosic fibres are concerned, fixation of
these dyes does not involve covalent bond formation with the fibre but the
formation of an insoluble disulphide bond (polycondensation). In case of
wool, however, the fibre to some extent, is involved in fixation.
The reaction between Bunte Salt dyes and cystine proceeds by initial
− −
attack of the dye (D·S·SO3 ) on cysteine (F·S ) formed in small quantity by
the action of water on cystine.
− − −
D·S·SO3 + F·S ↔ D·S·S·F + SO3 (8.9)
The asymmetrical disulphide largely disproportionates to form the
symmetrical disulphides.
2D·S·S·F Æ D·S·S·D + F·S·S·F (8.10)
These dyes, therefore, are borderline cases with respect to the definition
of reactive dye [17].
Neutral Fixation Reactive Dyes
The observation that alkali was not essential for fixation of nicotinotriazines
to take place was exploited in 1984 by Nippon Kayaku. A full range of
bis(aminonicotino-triazine) dyes was introduced, an example being
528
Kayacelon React Red CN-3B (C.I. Reactive Red 221), the nicotino analogue
of Procion H-E3B (C.I. Reactive Red 120) [20]. Exhaust dyeing is
recommended from a neutral dyebath at temperatures above boil, conditions
that render these dyes suitable for single-bath dyeing with disperse dyes.
The diffusion problem with such large molecules can be minimised by
dyeing at 130°C. The behaviour of these dyes is similar to their H-E
analogoues in terms of hue, fastness and dye-fibre bond stability. They have
slightly higher reactivity than VS or chlorodifluoropyrimidine dyes, but are
less reactive than DCT and dichloroquinoxaline systems [21].
High Fixation Reactive Dye
The most obvious deficiency in the conventional reactive dyes lies in the fact
that their dyeing efficiency always stands well below 100% because of
incomplete fixation on the fibre. Usually the efficiency is not more than 70%
even in printing application, the remainder undergoes hydrolysis instead of
reaction with the fibre. The removal of 30% or more unfixed dye during
soaping is troublesome and time-consuming, whereas the application
procedures of reactive dyes are quite simple.
The acid fixable Calcobond (American Cyanamid) and Basazol dyes
(BASF) are claimed to give high degrees of fixation. The former type has
been discussed earlier. Basazol dyes are intended for application on
cellulosic and other fibres in conjunction with polyfunctional fixing agents.
The dyes must contain nucleophilic groups such as primary or secondary
amino groups, sulphonamido, hydroxy or mercapto groups, etc. in
heterocyclic ring systems. Among polyfunctional fixing agents, best colour
yield is obtained with 1,3,5 triacylhexahydro-s-triazine in which acyl groups
contain carbon-carbon double bonds. Such compounds are very effective
because the three substituents are very mobile. It is assumed that the three
reactive groups can react with equal probability with the substrate, the dye
and water. Basazol dyes are primarily used in textile printing. Neither they
nor the fixing agent possesses any appreciable substantivity towards
cellulose. These developments by no means provide more than a partial
solution to the problem. The above two classes have their own limitations.
Calcobond dyes result in loss of strength of cotton during fixation at high
temperature. Basazol process requires an additional fixing agent and their
process of application is quite different from other reactive dyes.
In theory, it would be possible to achieve high fixation by using dyes
having groups capable of reacting with cellulose without substantial
hydrolysis. For example, acryloylamino groups suffer very little, if any
hydrolysis occurs in the dyebath. Unfortunately, such groups, although
satisfactory for wool, are insufficiently reactive for cellulose.
The other possibility is to use dyes containing more than one reactive
system. A dye molecule with only one reactive group may react either with
529
cellulose or with water; but once it has reacted with the latter, its reactivity is
completely lost and it is then incapable of reacting with the former. In case of
dyes having more than one reactive group, the part of the dye which has
reacted with water is still capable of further reaction with cellulose. An
exception to this may occur if the hydrolysis of the first reactive group
markedly deactivates those still remaining unhydrolysed, but this is unlikely
to happen unless the two labile atoms or groups are in close proximity and
conjugated to each other as in the case of DCT dyes. Although the presence
of two or more reactive groups in a dye usually favours high-fixation
properties, only carefully selected dyes of this type are technologically
suitable, because other properties, such as substantivity and diffusibility, are
also determining factors. In spite of higher probability of reaction with the
fibre, a small amount of dye will always be completely hydrolysed and has to
be removed from the fibre by washing off. To simplify rinsing, the
substantivity of the dye must be kept as low as is consistent with satisfactory
dyeing properties.
Patents have been filled covering reactive dyes with three and four
reactive groups, but no range of commercial dyes based on three or more
reactive groups has resulted. The concept of exploiting the advantages that
accrue from the presence of two reactive groups was first utilised by ICI in
1968. The first bifunctional dyes, however, lack in substantivity for cellulose
and their use was confined to printing and continuous dyeing. For dyeing
purpose, suitable chromophore is to be selected for high affinity. This has
resulted in the development of very successful Procion H-E range of
products (8-32) by ICI in late 1960s. The Cibacron LS (low salt) range of
dyes is based largely, but not exclusively, upon bis-monofluorotriazines and
has similar structure.
The other approaches to build bifunctionality into known chromophores
are as (8-33), (8-34) and (8-35). In (8-32) and (8-33) A and E represents
residues of diazo and coupling components respectively. In (8-34) C is non-
azo chromophore, e.g. triphenodioxazine.
MCT-HN-A-N=N-E-NH-MCT MCT-HN-A-N=N-E-N=N-A-NH-MCT
(8-32) (8-33)
Cl
N
Monoazo-NR N
N
MCT-HN-C-NH-MCT NR—X
2
X = bridging group
(8-34) (8-35)
530
The idea behind these approaches was to produce a range of high-

temperature dyes for exhaust dyeing, with substantially increased
substantivity, exhaustion and fixation values compared with corresponding
products carrying only one triazine reactive group. Unlike the
sulphatoethylsulphonyl group, the chlorotriazine reactive group readily lends
itself to substantivity enhancement. Increased substantivity and application
at high temperature result in good levelling properties and the presence of
two reactive groups and high exhaustion values favour a high degree of
fixation for these dyes. However, the removal of unfixed dye at the washing
stage may not be easy due to higher substantivity built into such dyes.
By providing an ideal profile (substantivity, final exhaustion and rate of
fixation) and cloning the model profile, it is possible to develop a range of
dyes (e.g. Procion H-EXL dyes) having very similar performance and least
sensitivity to small processing variables when used in mixture – fundamental
to Right-First-Time production performance. A Reactive Dye Compatibility
Matrix (RCM) can be formed by measuring the following parameters of
individual dye:
1. Substantivity (S).
2. Final exhaustion (E).
3. Migration index (MI), (influenced by temperature, diffusion and
mobility).
4. Level dyeing factor (LDF = S/E x MI), i.e. influence of migration phase
on reactive dye system.
5. Index of reactivity (T50), i.e. time to achieve 50% of final fixation.
The comparison of the RCM of the individual dyes will provide a measure
of the compatibility of dyes when they are used in combination. Dyes with
similar substantivities, similar and high MI values (>90%), similar and high
LDF values (>70%) and similar T50, will, when used in admixture, exhaust,
migrate and react as a single dye. These combinations will provide level
dyeing. They offer high shade reproducibility, as they are insensitive to the
small but expected variations in liquor ratio, electrolyte concentration,
fixation pH, time and temperature and will support the key measurements of
performance of the dyehouse: Right-First-Time production. The eXceL scour
process, based on low foaming surfactant and powerful sequestering agent,
can save time up to 2 hours by avoiding lengthy post-scouring rinses before
filling for dyeing. Further, time saving is achieved by salt-at-start procedure
instead of adding salts in instalments during dyeing. Cold rinsing stages
after dyeing and after soaping are eliminated. Hot rinse immediately after
dyeing, maintains open state of interstices of cellulose and prevents freezing
of structure, causing lock-in unfixed dye within the fibre. During this stage,
an alkaline pH will maintain the negative state of cellulose, which will repel
the negatively charged dye hydrolysate, thereby assisting the diffusion-out
531
process. Procion H-EXL dyes, which have excellent diffusion properties and
are insensitive to alkaline hydrolysis, allow the benefit to be fully utilised.
The combined saving from optimised preparation, dyeing and rinsing
processes now make the 5-hour dyeing cycle for cellulosic fibres achievable
[22].
A variety of mixed or hetero-bifunctional dyes was disclosed in the patent
literature by ICI as early as 1959. However, Sumitomo (Japan) was the first
company to develop and launch a range of mixed bifunctional dyes in the
name of Sumifix Supra dyes in 1980s. These dyes, exemplified by the
structure (8-36), contain a MCT (low reactivity) group and a
sulphatoethylsulphonyl (medium reactivity) group. The triazine ring furnishes
not only one of the reactive groups, but a ready means of attaching the VS
precursor. Some patents recommend mixed fluorotriazine and
sulphatoethylsulphonyl groups.
Cl
NaSO3 N
OH NH N
—N=N N
NH— —SO2C2H4OSO3Na
NaO3S SO3Na
(8-36)
Sumifix Supra dyes are designed primarily for exhaust dyeing, with the
triazinyl group being used to enhance the substantivity (30-60%) of this type
of dye. Such medium substantivity product (also termed as Reactive M-E
dyes by many manufacturers at present) favour level dyeing through good
primary exhaustion in the presence of inorganic salts and two reactive
groups lead to high fixation. Due to the presence of MCT group, these dyes
may also be applied by pad-batch method with a batching time of more than
12 hours.
Mixed bifunctional dyes offer a number of distinct advantages over mono-
or homo bi-functional dyes. Two reactive groups of different reactivity result
in less temperature-sensitivity of the dye so that the dye can be applied over
a wide range of temperature (50-80°C), and shade reproducibility is thus
improved. They show minimum sensitivity to inorganic salts, alkali and liquor
ratio. In fixation process, VS group is operative at low temperature and less
reactive MCT group at high temperature. Sumifix Supra dyes are expected
to show intermediate fastness properties, i.e. less sensitivity to acid and to
alkali than MCT and VS dyes respectively. Compared to DCT,
dichloroquinoxaline, difluorochloropyrimidine dyes such as Levafix P-A and
532
E-A (Bayer), Drimerene R and K (Clariant), mixed functional dyes show

superior fastness to acid hydrolysis and peroxide washing, and slightly more
over MCT and monofluorotriazine (MFT) dyes. On the other hand, mixed
bifunctional dyes show some weakness to alkaline treatments due to the
presence of sulphatoethylsulphonyl groups, but less so than products solely
fixed by this means. These dyes have better wash-off properties as
compared to pure triazine or pyrimidine dyes of equal substantivity [19].
Early in 1988, Ciba-Geigy launched its Cibacron C range of mixed
bifunctionals based on a new aliphatic vinylsulphone system and either a
monofluorotriazine bridging group or an arylvinylsulphone function. They are
designed mainly for pad application (pad-batch, pad-steam, pad-dry-pad-
steam, and pad-thermofix) and are characterised by outstanding bath-
stability, medium to low affinity, good build-up, easy wash-off and high
fixation. These dyes are costlier than Sumufix Supra dyes. But Cibacron C
dyes combine the possibility of stable liquid brands, rapid and high fixation,
easy wash-off and are a step towards more environmentally acceptable
reactive dyes. Cibacron FN dyes have similar chemical structure applicable
by exhaust system claimed to have very high fixation rates.
Most dye manufacturers now market at least one range of
heterobifunctional reactive dyes. The most commonly encountered
combinations include vinylsulphone with monofluorotriazine, vinylsulphone
with 2,4-difluoropyrimidine, vinylsulphone with 2,4-difluoro-5-chloro-
pyrimidine, 2,4 difluoropyrimidine with monofluotriazine and 4-fluoro-5-
chloropyrimidine with monohalotriazine [1].
The introduction of more than two functional groups can theoretically give
more fixation values, but in practice this approach can be counterproductive
owing to the fact that the additional groups can have lower migration,
leading to lower fixation, especially at heavier depths, and poor build-up.
Nevertheless, some commercially successful dyes of this type are now
available, the notable being the trifunctional derivatives Cibacron Red C-2G
and Remazol Red BS. The former possesses three reactive groups (VS,
aliphatic VS and MFT) per single unit of chromophore and thus represents
an expensive route of higher fixation. In the second case, two similar,
economic, reactive dye units are linked together via a reactive chlorotriazinyl
bridge and thus the dye contains two units of chromophore and three
reactive groups.
A detailed study of representative members of Procion H-E dyes, as well
as other potentially crosslinking reactive systems (dichlorotriazine,
chloromethoxytriazine, dichloroquinoxaline, trichloropyrimidine and
chlorodifluoropyrimidine) provided convincing evidence of the extent of
crosslinking that could take place. The degree of crosslinking was non-
existent or relatively insignificant for cold pad-batch process, but thermal
533
fixation by pad-dry-steam method resulted in a much higher proportion of

crosslinked dye molecules [23].
Controlled enzymatic degradation of cotton fabric batchwise dyed at 60°C
with heterobifunctional Sumifix supra dyes yielded interesting results [24]:
1. About 80% of the vinylsulphone groups had reacted with the cellulose.
2. About 50% of the chlorotriazine groups had not reacted with cellulose
and only half of these had hydrolysed to OH groups.
3. A considerable proportion of the dye molecules had formed crosslinks
by reacting via both mechanisms.
Informative studies of the relationships between dye structure and

substantivity [25] and between dye structure and levelling properties [26] are
available. The interaction between these dyeing properties and the
controlling parameters in exhaust dyeing with reactive dyes, such as applied
concentration, pH, temperature and electrolyte addition, is the key to
achieving successful and reproducible dyeing.
A valuable classification of reactive dyes based on application properties
has been formulated [27] as follows:
1. Alkali-controllable reactive dyes are characterised by low neutral
exhaustion and because of high reactivity, alkali is to be carefully
added to achieve level dyeing. Their optimum temperatures of fixation
are between 40°C and 60°C. DCT, chlorodifluoropyrimidine,
dichloroquinoxaline or VS reactive systems belong to this group.
2. Salt-controllable reactive dyes exhibit high neutral exhaustion and salt
addition is to be made very carefully to achieve level dyeing. The dyes
in this group show optimal fixation at a temperature between 80°C and
boil. Low-reactivity systems such as trichloropyrimidine, MCT and H-E
dyes belong to this group. Monofluorotriazine dyes in Cibacron F
range, are highly substantive and should be regarded as salt-
controllable, but they are sufficiently reactive for fixation at 60°C or
lower.
3. Temperature-controllable reactive dyes are represented by dyes that
react with cellulose at temperatures above boil in the absence of
alkali, although they can be applied as salt-controllable dyes under
alkaline conditions between 80°C and boil. The dyes are self-levelling
and no auxiliary products are required to facilitate levelling. Good
results can be obtained by controlling the rate of temperature rise. At
present only Kayacelon React (Nippon Kayaku) range of bis(amino-
nicotinotriazine) dyes belong to this group.
In 1992, ICI changed into Zeneca and later (1996) merged with BASF.
Bayer and Hoechst merged in 1995 to form a new company called DyStar
534
and BASF merged with it in 2000 to become the world's largest dyestuff
manufacturing company. It shares about 30% of global production of
reactive dyes. The reactive dyes currently marketed by DyStar are [28]:
1. Procion XL+
2. Remazol
3. Levafix C-A
The earliest monoflurotriazinyl (MFT) dyes were marketed in 1978 as

Cibacron F (Ciba) dyes. MFT and VS reactive groups have similar reactivity.
Thus mixed bifunctional dyes developed from them enable both groups to
be applied at optimum temperature thereby maximising fixation yield. The
concept of matched reactivity has been refined with the new Levafix C-A
range of dyes.
8.4.3 Reactivity
The relative advantages of different reactive groups require a consideration
of their value in dye synthesis, dye-fibre bond stability, application methods
and its reactivity. Whatever the nature of the reactive system might be, it is
rarely completely insulated electronically from the chromophore to which it is
attached. The type of chromophore and the substituents present in it,
therefore, always affect the reactivity. Consequently, the reactivities of any
particular series of reactive dyes are spread over a range. Although different
series possess different average reactivities, a considerable overlap exists
between one series and another. The average reactivities of various reactive
dye sub-classes (monofunctional) under appropriate fixing conditions of pH,
temperature and time may be ranked in order of increasing reactivity as
follows [29]:
1. Primazin (acryloylamino, BASF)
2. Drimarene (Clariant), Reactone (Geigy) (chloropyrimidine)
3. Cibacron (MCT, Ciba)
4. Procion H (MCT, ICI)
5. Remazol (vinylsulphone, Hoechst)
6. Cavalite (various, Dupont)
7. Levafix E (dichloroquinoxaline, Bayer)
8. Procion MX (ICI), Basilen M (BASF) (DCT)
Dichlorotriazinyl dyes are considerably more reactive than all other types
of commercial available reactive dyes. The difference in reactivity is of
practical importance because, in the first place, it determines the stability of
dye solutions especially in the presence of alkali. In jigger dyeing,
appreciable hydrolysis of highly reactive dyes causes tailing effect as the
time required for transferring the fabric from one roll to the other is high.
535
The high reactivity shown by the dichloro-s-triazinyl group arises from the
presence of three ideally situated heteronitrogen atoms in the s-triazine ring,
most of the other reactive systems in use having not more than two such
nitrogen atoms.
In general, the reactivity of Remazol dyes lies between the reactivity of
DCT and MCT dyes but, as with other series, there is a variation among
individual members of the range. Many of the Remazol dyes can be applied
to cotton at 20-30°C in the presence of sodium hydroxide. However, the
usual procedure is to dye at 60°C with soda ash.
8.4.4 Bond Stability

The materials dyed with reactive dyes generally have excellent wet fastness
when they are properly soaped. Even dyed materials which have been
washed thoroughly may show a reduction in wash fastness because of the
cleavage of dye-fibre bonds in course of storage, distribution and use.
Various causes are acid hydrolysis by atmospheric acid gases (e.g. carbon
dioxide, sulphur dioxide, nitrogen oxides gases), oxidative decomposition by
oxidising agents in washing such as chlorine in tap water, sodium
percarbonate, sodium perborate in detergents and thermal decomposition
by heat during ironing. The stability of reactive dyes carrying various
reactive groups on dyed cellulose is shown in Table 8.3 [5].
Table 8.3 Stability of Dye-fibre Bonds of Reactive Dyed Materials
Conditions
Reactive groups 1 2a 2b 3 4
Monochlorotriazine M S M M M
Monofluorotriazine M S M M M
Trichloropyrimidine S S M S U
Difluoromonochloropyrimidine M S M M U
Dichloroquinoxaline U S M U U
Sulphatoethylsulphone S S U S S
S = Stable 1 = acid, pH 3−4, 2a = alkali, pH 9−10
M = Moderate 2b = alkali, pH 13−14
U = Unstable 3 = dry heat, 180°C,
4 = peroxy bleaching
Generally substitution type reactive dyes are stable to alkali, but are
unstable to acid with varying degree. On the other hand, addition type
reactive dyes are stable to strong acid, but not to strong alkali.
The resistance to acid hydrolysis is least for MCT followed by DCT,
trichloropyrimidine and dichloropyrimidine. Sulphatoethylsulphone dyes
536
show negligible acid hydrolysis. Again the dyes having –O- bridge link
shows maximum acid hydrolysis followed by –OCH2-, -N(CH2)- and least
with –NH- bridge links. In accelerated acid hydrolysis test (ICI), a test
specimen is immersed in glacial acetic acid solution (1%) at room
temperature for 30 minutes with a liquor ratio of 1:20. The treated specimen
and undyed fabric are placed side by side and the sandwich is placed
between two glass plates and kept at 37±2°C for 6 hours. The fabrics are
dried at a temperature less than 60°C. The change of colour and the
staining on adjacent fabric is assessed.
In case of mono- and dichlorotriazine dyes, the compounds formed with
cellulose are ester-like in character and possess to a greater or lesser
degree the properties normally associated with other esters, which are
capable of hydrolysis under various conditions. In general, these dyes show
good stability in low alkaline conditions, but show unstability under acidic
conditions. Certain DCT dyes give staining on adjacent white material when
deep shades are subjected to humid acidic conditions for some time and
then moistened. The stability of the dye-fibre bond formed derived from
triazines vary with pH on the acid side but the relative hydrolysis levels of
different dyes vary. At one pH value, one dye may show more hydrolysis
than the other, whereas at another pH, the situation may be completely
reversed. The study, with dyes containing the same chromophore linked to
different reactive systems through various bridging groups, showed that
increasing reactivity of di- and trichloropyrimidine dyes is accompanied by a
growing tendency to acid and more particularly to alkaline hydrolysis. The
position at which hydrolysis occurs appears to depend on the nature of the
bridging group. With dyes containing oxygen bridges, alkaline hydrolysis
occurs chiefly between the reactive system and the chromophore, whereas
dyes containing imino or methyimino bridges are cleaved between the
reactive system and cellulose. It was further observed that the differences in
the extent of hydrolysis of dyes bearing different reactive systems on the
same chromophore could be less than the differences between the dyes
bearing the same reactive systems.
The materials dyed with vinylsulphone dyes show unusually high
resistance towards acid hydrolysis. The dye-fibre link appears to be more
stable under these conditions than the glucoside linkages of cellulose.
Because of this stability towards acids, no bleeding occurs when the fabrics,
dyed with vinylsulphone dyes, are stored in acidic atmosphere.
The poor stability of Remazol dyes on dyed cellulosic material under
alkaline conditions has led to considerable discussion as to whether the dye-
fibre bond really is an ether linkage. Whereas a true ether linkage should be
resistant to alkaline hydrolysis, the Remazol linkage is not. The dye stripped
off by alkali is capable of fixation to adjacent material to give a permanent
stain, which implies that the dye removed is reactive. Ratee [30] said that
537
although the reaction scheme implies ether formation, what is actually

formed is an ester of the hydroxyethylsulphone; as an ester, it displays an
analogous behaviour to that of the β-sulphatoethylsulphonyl dye used for
making the dye. The action of strong alkali, therefore, causes a reversal of
the fixation reaction to liberate the VS dye.
Venkataraman [31] on the other hand, cites nuclear magnetic resonance
spectroscopic evidence to suggest that the dye-fibre links are true ether
links. There is no anomaly in the lack of fastness of Remazol dye on dyed
material to alkali, because a base-catalysed β-elimination to give the
vinylsulphone is to be expected. The controversy appears to have arisen
due to confusion about the terms, ether and true ether link. The Remazol
linkage is, therefore, probably best referred to as an activated ether linkage,
the activation favouring β-elimination. Whether it is triazine dye or
vinylsulphone dye, the dye-fibre compound produced in any reactive dyeing
operation is never completely inert but is, in effect, another reactive dye of
lower reactivity than that used in the dyeing process. There is no essential
difference of character between the Remazol-cellulose compound and β-
sulphatoethylsulphones; both have the same tendency towards cleavage
under alkaline conditions.
The most characteristic features of VS dyes arise from their good stability
under neutral and acidic conditions and their greatly depressed stability
under alkaline conditions. These dyes are very popular in Europe where the
fabrics are mostly machine-washed with liquid low-alkali detergents.
However, if the fabrics are washed with high-alkali powder detergents, the
colour is liable to be destroyed by repeated wash.
The dye-fibre bond stability over the pH range 3.5-10 of cotton dyed with
Sumifix Supra Brilliant Red 2BF (C.I. Reactive Red 194) was compared with
those of two monofunctional analogues [32]. Under acidic conditions the
bifunctional dyeing showed higher stability than the vinylsulphone dyeing,
which in turn was more stable, than the monofunctional chlorotriazine
analogue. At alkaline pH, on the other hand, the chlorotriazine analogue and
the bifunctional dyeing were virtually identical in stability, both being
markedly more stable than the monofunctional vinylsulphone. For similar
reasons, bifunctional reactive dyeing of the aminofluorotriazine-
sulphatoethylsulphone type showed better allround stability to acidic and
alkaline conditions than analogous monofunctional dyeing based on
dichlorotriazine, monochlorotriazine, monofluorotriazine or vinylsulphone
systems [33].
The relationship between dye-fibre bonding and light-fastness was
examined for ten sulphatoethylsulphone reactive dyes on cellulose and it
was shown that the stronger the bonding between dye and substrate, the
more stable was the dye when exposed to light [34].
538
8.4.5 Liquid Brands

The dusting problem with some reactive dye powder brands can be avoided
by working with granulated or liquid formulations. Cold-dissolving granular
brands such as the Drimarene CDG (Clariant) dyes, are developed which
are non-dusting, free-flowing grains that dissolve readily in cold water and
offer ease of handing in automatic and metering devices [35].
Liquid brands present less of a health hazard to the dyehouse operative
than do dusty solid brands. They are also more amenable to use in
automated metering equipment. The methods for formulating acid and direct
dyes as liquid are simple, and simple aqueous solutions of these are
marketed by several manufacturers. Because of their propensity to undergo
facile hydrolysis, the liquid formulations of reactive dyes are not easy to
prepare. However, considering the advantages, tremendous efforts were
made and liquid brands of more stable sulphatoethylsulphones and
monochlorotriazines are now well established in the market. Liquid brands
are essentially isotropic solutions of dye in water, often with additional
agents like buffer, a cosolvent caprolactum or a solubility enhancing agent,
such as urea and sometimes a polymer, to prevent or minimise solid
deposition. However, the presence of inorganic electrolytes reduces the
effective aqueous solubility of the dye, hence is to be removed before
preparing liquid brands. The removal may be made by physical means using
membrane technology, viz. reverse osmosis, ultrafiltration, electrodialysis
and multi-stage membrane processes. One of the chemical means for
preparing dye solutions of low salt content, is the preparation of insoluble
calcium salt form of the dye, which can be washed to free salts, converted to
soluble lithium salts with lithium sulphate and filtered to remove insoluble
calcium sulphate. The other methods are:
1. Use of salt-free intermediates.

2. Avoidance of mineral acids in the preparation of dyes by utilising
sulphonic groups in the diazotisation.
3. Preparation of a salt-free acid form of dye which can be converted to a
neutral derivative by reaction with an alkali metal hydroxide.
As well as forming true solutions, some dyes form lyotropic liquid crystals
in aqueous media and this effect can sometimes be utilised to prepare
convinient, though more viscous, liquid brands.

Out of the total reactive dyes consumed in Japan, about 64% are VS dyes
and about 24% are MCT dyes [5]. The reasons for global popularity of the
two reactive groups, chlorotriazines and vinylsulphones, are:
539
1. These dyes have reactivity by which levelness and reproducibility can

easily be attained under practical dyeing conditions.
2. A full range of dyes is available for exhaust dyeing, continuous dyeing
and printing.
3. The stability of dye-fibre bond is good, so that there is little problem in
the stability of dyed goods with the lapse of time.
The specific mode of production to be adopted for a given shade in the
dyehouse is determined primarily by the following factors:
1. Nature and condition of the goods to be processed.

2. Machinery available.
3. Limiting processing cost.
4. End use of the fabric, including the nature of the finish applied.
This is true for all classes of goods in all types of dyehouse, although the
importance of the 3rd factor will vary according to local conditions [16].
Broadly, there are three main types of dyeing processes used for applying
reactive dyes to cellulosic fibres, applicable to both cold and hot dyeing
dyes, as follows:
1. Batchwise exhaust processes: dyeing is effected by a cold or hot

(according to reactivity of the dyes) alkaline dyeing process followed
by a hot soaping treatment to remove unfixed dye. Obviously, textile
materials in any physical form can be dyed by these methods.
2. Semi-continuous processes: the material is padded in a solution of
alkali and dye and then batched either hot or cold before soaping.
3. Continuous processes: the cellulosic materials are impregnated with
dye and alkali, either in a single or two stage, followed by drying
and/or steaming to fix the dye. A final soaping-off completes the
process. The semi and fully continuous processes require the
materials as continuous strand, hence are mostly suitable for fabric
form.
Park [3] estimated applicationwise consumption (in percentage) of the

reactive dyes as follows:
Exhaust dyeing – 48%
Pad-batch dyeing – 14%
Continuous dyeing – 10%
Printing - 28%
For most applications, dyes of high reactivity, as typified by DCT dyes, are
preferred largely on the score of economics and convenience of application.
Though the application cost of such dyes is less mostly due to negligible
540
energy requirement, but higher cost and poor storage stability of the dyes,
higher hydrolysis requiring severe washing, are the barriers for their
popularity. Dyes of low reactivity, such as MCT, are preferred by large-scale
dyers for better storage stability, better fastness and a wide range of
shades. The main area of conflict in choice between dyes of high and low
reactivity lies in batchwise and semi-continuous dyeing; in continuous
dyeing the advantage of highly reactive dyes are much more pronounced.
When applying reactive dyes in full depths, especially on compact fabric,
or inefficient washing equipment, difficulties may arise in removing the
unfixed dyes. In these circumstances, it may be found necessary to
aftertreat the dyeing with a cationic dye-fixing agent of the type often used
on direct dyeing. These agents operate by electrostatic association with
sulphonic groups in the dye molecules, forming an insoluble dye-agent
complex. This is retained by the substrate during washing at temperatures
up to 60°C, so that staining of adjacent white material in wet tests is
minimised [7].
Batchwise Processes
Batchwise dyeing of textile materials in various physical forms need specific
machines. Loose fibre, sliver and yarn in packages or cake form may be
dyed in package dyeing machines. The yarns in hank form are dyed in
cabinet type hank dyeing machines. The batches of light delicate and heavy
structurally stable fabrics can be dyed in winches and jiggers respectively.
The general principle in exhaust dyeing of reactive dyes is to exhaust as
much dye as possible onto the fibre using salt under neutral or very slightly
acidic conditions. Under the conditions where the dye does not react or
react negligibly, levelling takes place. The pH of the bath is then raised by
the addition of alkali and the reaction is allowed to undergo for a particular
time at a particular temperature dictated by the reactive group present in the
reactive dyes. Dyes having different reactive groups are advisable not to be
mixed as the reaction conditions differ.
The amount of salt required for dyeing reactive dyes on cellulose is
usually three or four times as much as that required for dyeing direct dyes.
The amount of salt used is on the basis of liquor and can be reduced
considerably by lowering M:L ratio, which also provides a slightly better dye
utilisation.
Reactive dyes can be applied to all types of cellulosic materials and their
blends by batch dyeing methods. These dyes do not cover dead or
immature cotton. It may be sometimes necessary to causticise or semi-
mercerise cotton and viscose fabrics to enhance both appearance and
colour value. Reactive dyes are highly soluble and are not usually affected
by neutral hard water. However, as alkali is used for dye fixation,
precipitation may occur, hence it is advisable to use soft water.
541
The material should be prepared uniformly to get level and reproducible

dyeing as with other classes of dyes. The goods should be free from alkali
and in neutral or preferably slightly acidic condition. Reactive dyes can react
with sizes, especially starch sizes, if they are not removed completely. The
starch-dye complex is difficult to remove and it causes poor wash-fastness
of the dyed materials. The materials should also be free from bleaching
agents, especially hypochlorites and reducing agents like sodium
hydrosulphite. These agents, even in small quantities, deactivate the dye,
preventing reaction with the fibre. This has a more sensitive effect than the
destruction of chromophore.
The three distinct recognised stages of dyeing are:
1. Exhaustion from an aqueous bath containing either common salt or

Glauber’s salt (for brighter shades, e.g. turquoise blue or green),
normally under neutral conditions (primary exhaustion). The maximum
exhaustion is obtained from cold dyebath [3].
2. Addition of alkali to promote further dye uptake (secondary
exhaustion) and chemical reaction between absorbed dye and the
cellulose. The reacted dye being chemically bound to the fibre cannot
migrate and has no levelling power.
3. Thorough rinsing of the dyed fabric followed by soaping to remove
electrolyte, alkali and unfixed dye.
During primary exhaustion, the adsorbed dye can migrate somewhat, so

that levelness due to migration may be expected. In the subsequent
secondary exhaustion, the fixation rate (i.e. rate of reaction with the fibre)
governs the overall dyeing rate. In order to attain level dyeing, it is
necessary to balance the fixation rate with the circulation/stirring efficiency
of the dyeing apparatus.
A dye having low primary exhaustion (C.I. Reactive Blue 19) will
obviously have less migration and consequently less chance of levelling by
migration. The fixation rate should be carefully controlled to obtain level
dyeing.
A dye having high primary exhaustion, e.g. C.I. Reactive Blue 21 as in
case of direct dye will have poor migration due to high substantivity.
Consequently levelling may be difficult to obtain as in the case of direct
dyes.
A dye, in which about one-third to about two-thirds of the amount used, is
adsorbed by the primary exhaustion, as in case of mixed bifunctional dye,
Sumifix Supra dyes (e.g. C.I. Reactive Blue 194), will have good migration
to attain level dyeing. These dyes, therefore, will provide good level dyeing.
542
The steps of standard exhaust method of dyeing Procion MX brand or

Basilen M (DCT, cold brand, commonly known as M-brand) dyes are as
follows:
1. Load the machine with water and material, ensure pH is below 7 and
temperature 30°C, run liquor and/or fabric.
2. Add pre-dissolved dye for 5 minutes and continue for 10 minutes.
3. Add 2.5 g/l common salt and run for 10 minutes.
4. Add 7.5 g/l common salt and run for 15 minutes.
5. Add remainder of common salt (Table 8.4, maximum quantity for
viscose should be 30 g/l) and run for 15 minutes.
6. Add 0.5 g/l soda ash (dissolved and well diluted) and continue for 15
minutes.
7. Add remainder of soda ash (Table 8.4) and continue for 30-45
minutes, for Procion Turquoise MX-G, ICI (C.I. Reactive Blue 140)
raise temperature to 60°C for last 20 minutes.
8. Check the shade and make the addition of dye, if necessary and
continue for fixation of new addition,
9. Drop the dyebath,
10. Rinse cold for 10 minutes, repeat if necessary
11. Soap at boil with 2 g/l soap or requisite amount of detergent for 15-30
minutes.
12. Rinse in warm water (50°C) for 10 minutes.
13. Rinse in cold water until clear wash water and apply finishing agents,
if necessary.
The alkali used in this method may be soda ash only or a mixture (1:1) of
soda ash and caustic soda (low alkali method). In low alkali method, the
total quantity of alkali is less than 1.5 g/l. The pH should be 8.8-9.3 and
10.5-11.0 after the additions of soda ash and caustic soda respectively. In
machines with a high rate of liquor exchange, the dyeing time may be
shortened by adding the whole amount of salt at the start.
Table 8.4 Salt and Alkali Requirements for Cold Brand Reactive Dyes in
Exhaust Dyeing of Cotton Materials [36]
% Depth of Salt (g/l) Soda ash (g/l) at M:L ratio
shade (o.w.m.) 1:15 1:20 Jigger
≤ 0.5 25 5 (0.2) 3 (0.15) 5
0.51-2.0 35 5 (0.3) 4 (0.25) 10
2.01-4.0 45 10 (0.4) 8 (0.35) 15
> 4.0 55 15 (0.6) 10 (0.5) 20
The bracketed quantities represent the amount of soda ash and caustic
soda flakes each (i.e. equal amount) in low alkali method.
543
The method of exhaust dyeing of cold brand reactive dyes is shown

diagrammatically in Figure 8.2.
Dye Salt Salt Salt Soda ash
30°C
10 10 15 15 5 15 5 30-45 Å Time in minutes
Fig. 8.2 Exhaust Dyeing of Cold Brand Dyes
For jigger dyeing:

1. Add dissolved dye for 2 ends.
2. Add salt over 2 ends.
3. Run for 2 ends.
4. Add alkali over 2 ends.
5. Run for further 30-60 minutes (4 ends or more).
6. Rinse thoroughly and wash off.
The exhaust method of dyeing Procion H-E or H dyes is as follows:
1. Load the machine as before.
2. Add pre-dissolved dye for 5 minutes and continue for 10 minutes.
3. Add 5 g/l common salt and run for 10 minutes.
4. Add 20 g/l common salt and run for 15 minutes.
5. Add remainder of common salt (Table 8.5) and run for 15 minutes.
6. Raise temperature by 1°C/min up to 80-85°C during addition of salt.
7. Add alkali (soda ash alone or a mixture of soda ash and caustic soda
flakes, Table 8.5) slowly for 15 minutes.
8. Dye for further 45-75 minutes at 80-85°C.
9. Check the shade and adjust, if necessary, then rinse and soap as
before.
Table 8.5 Salt and Alkali Requirements for H-E/H Brand Reactive Dyes in
Exhaust Dyeing [36]
*
% Depth of Salt (g/l) Soda ash (g/l) Soda ash + caustic soda
shade (o.w.m.) flakes (g/l)
≤ 0.5 30 (20) 10 5 + 0.2
0.51-1.0 45 (30) 15 5 + 0.2
1.01-2.0 60 (40) 15 5 + 0.5
2.01-4.0 70 (55) 20 5 + 0.5
> 4.0 90 (65) 20 5 + 0.5
*
Unbracketed and bracketed amounts are for unmercerised cotton and for
mercerised cotton or viscose respectively.
544
For shade adjustment, if dye additions required is over 25% of the original
recipe, a fresh bath should be set. If shading quantities are less than 25%,
half-bath method or full-bath method may be adopted.
In half-bath shading, the method is:
1. Drop half of the bath and add cold water to reduce the temperature
and electrolyte concentration.
2. Add well-diluted pre-dissolved dye and dye for 10 minutes.
3. Raise temperature to 80°C and dye for 30 minutes.
4. Check the shade.
The full-bath shading is applicable, when faster cooling is possible. The
method is:
1. Cool dyebath at 60°C.

2. Add well-diluted pre-dissolved dye.
3. Dye for 10 minutes at 60°C.
4. Raise the temperature to 80°C.
5. Dye for 30 minutes at 80°C.
6. Check the shade.
The method of exhaust dyeing of H-E or H brand reactive dyes is shown

diagrammatically in Figure 8.3. Several other variations are possible such
dyes, salt and alkali are added together (all-in method) or all additions are
made after raising the temperature to 80-85°C (isothermal method). These
methods are most suitable for circulating type of machines.
In theory, Remazol dyes can be applied to cotton at 20-30°C. However,
this temperature is not generally recommended. Some members of the
range give good colour yields on cotton at this low temperature and in a
commercially acceptable time only if the pH is adjusted to a certain value
with sodium hydroxide. When trisodium phosphate is used as alkali, the
dyeing time needed is far too long for practical use. This means that the VS
group possesses at 20-30°C a distinct, but on the average lower, reactivity
than the DCT group. The latter dyes at this temperature are able to react
with cellulose under pH conditions that can be easily obtained with sodium
carbonate. Cotton can be dyed with Remazol dyes in long liquor at
temperatures at and above 60°C with a corresponding decrease in alkalinity
[17]. Some of the Remazol dyes, such as turquoise blue and green dyes,
can be best applied at 80°C as H-E or H dyes.
The dyeing method is similar to that of H-E or H brand dyes and is shown
in Figure 8.3. The temperature of dyeing is generally 45-60°C, but it is also
possible to dye at 40°C using strong alkali and allowing more time for
fixation, say 90 minutes. These dyes have good levelling properties. Hence,
545
Temperature (°C)
Dye Salt Soda ash
100
80
60
40
Remazol/ME brand
20 HE/H-brand
10 20 30 40 50 60 70 80 90
Time (minutes)
Fig. 8.3 Exhaust Dyeing Methods of Various Classes of Reactive Dyes
as a rule, it may not be necessary to add salt and alkali in portions. The
shades are very bright. Hence, it is preferable to use Glauber's salt and
trisodium phosphate instead of common salt and soda ash, as both of them
may have metallic contamination, especially iron salts. However, those can
be used, if slight alteration of shade is permissible. Mixed bifunctional
reactive dyes, like Sumifix Supra or commonly known as Reactive ME dyes,
can also be dyed exactly in the same way at a temperature of 50-70°C. The
optimum quantities of Glauber’s salt (or common salt) and soda ash for
exhaust dyeing of Remazol and Sumifix Supra dyes are shown in Table 8.6.
Semi-Continuous Processes
Because of their low substantivity during the neutral adsorption and the ease
with which really fast dyeing is obtained in the subsequent alkali fixation, the
reactive dyes have proved eminently suitable for continuous and semi-
continuous dyeing processes. From the mechanical aspect, the simplest
are the semi-continuous methods.
546
Table 8.6 Optimum Amounts of Salt and Alkali for Exhaust Dyeing of
Vinylsulphone and Mixed Bifunctional (ME) Dyes
% Depth of shade (o.w.m.) Glauber’s salt (g/l) Soda ash (g/l)
0.05 3-5 10-15
0.1 3-8 10-15
0.5 15-25 10-20
1.0 25-35 20
2.0 40-50 20
3.0 ≥ 50 20
5.0 ≥ 50 20
The cold pad-batch method consists in applying the reactive dye and a
wetting or penetrating agent together with an alkali, by means of a padding
mangle, after which the fabric is batched up into a roll. For higher
concentration of dye exceeding its solubility, 50-100 g/l urea may be added
in the padding liquor. The liquor pick-up should be 60-70% for cotton and
90-100% for viscose fabric. The mangles with a shore hardness of 45-60°
are normally used. For padding knitted fabrics, softer mangles are used. For
tubular knitted fabrics, special machinery to eliminate edge mark is
developed. Covering the fabric rolls with polythene sheets during storage is
advantageous. The rolls may also be stored in an enclosed chamber where
those are rotated slowly to prevent draining of liquor. Dye fixation is effected
at room temperature and it takes several hours. The critical point in this
whole procedure is the stability of the alkaline padding liquor. There are two
ways to avoid the possible trouble. The first is to reduce the alkalinity of the
liquor sufficiently to ensure adequate stability. However, in this case, fixation
time required may be as high as 24 hours, hence the process is called as
long batching process. The second way to obviate trouble is to use strong
alkali so that the batching time may be 2-4 hours, hence the process is
called as short batching process. In this case, the dye and alkali are
dissolved separately and the two solutions are brought together by a
metering pump immediately before padding. 50-200 g/l urea may be added
in the dye liquor for better solubility. The pumps suitable for the purpose
include piston pumps and diaphram pumps.
The advantages of long batching are:
1. Better coverage of certain materials, e.g. some viscose fabrics,

compact cotton fabrics.
2. Better fixation of some dyes on viscose.
3. May be essential for some dyes, e.g. turquoise blue.
4. Mixer not required.
547
The advantages of short batching are:
1. Easier temperature control.

2. Better uniformity, colour matching and reproduction.
3. Better dye fixation on cotton.
4. Less storage space and batching equipment.
5. Mixer is required, but the cost may offset by the better colour yield, as
high reactive dyes are prone to alkali-hydrolysis during storage for
long time.
Dyeing of excellent quality is usually produced on cotton with all classes of

reactive dyes, with either the short or the long batching technique, although
for reasons of economy, short batching will usually be preferred. The
process is commonly applied to fabrics, but it is also applicable to yarns and
loose fibre in sliver or any other continuous form. The process tends to be
very efficient from the point of view of fixation, since a low M:L ratio of
1:1.6-1 is used and at the low temperature of batching, the rate of hydrolysis
is low. The batch processes are very versatile, with a production capacity
(60 metres/min or more) comparable to that of a continuous dyeing range.
For shorter runs, they are more advantageous than continuous processes.
The longer runs are equally easy, with a minimum of labour.
Much of the productivity of pad-batch process is, however, lost if the
material is transferred to jigs for washing off. If a continuous washing range
is used, the process can no longer be called cheap, though it is cheaper
than fully continuous dyeing processes. Contrary to general belief, only
small amounts of water and low flow rates are necessary if sufficient time is
allowed and the interchange between liquor and fabric is high. A simple
means of achieving these requirements is to batch the padded materials on
to a perforated beam, on which it is stored for the required time. Unfixed dye
is then washed off by passing water slowly through the beam and running
the effluent water to waste without recirculation. A 5,000 m batch may be
washed for 20-30 minutes with a water consumption of about 10 litres per kg
of material, which is about 20-50% of the minimum wash-water requirement
[16]. The equipment is cheap, labour and running costs are lower.
For cold brand reactive dyes, padding liquor of short batching process
(2 hours) contains:
Dye + 2-5 g/l wetting agent + soda ash equal to the weight of the dye
(minimum 3 g/l and maximum 30 g/l).
For long batching (16-24 hours) process:
Dye + 2-5 g/l wetting agent + a mixture of sodium bicarbonate and soda
ash with the quantity of each equal to half of that of the dye (minimum 1.5 g/l
each). For viscose in long batching process, only sodium bicarbonate is
used.
548
The Remazol or vinylsulphone dyes are well suited for the short-time pad-
batch method [37]. The alkali used in this method is sodium hydroxide.
Besides alkali, a salt is added to improve the colour yield and an alkali-
stable wetting agent for better penetration. Dye and wetting agents are
dissolved together, and sodium hydroxide and salt together. The padding
liquor contains:
Remazol dye − x g/l

Sodium hydroxide solution (32.5%) − 10-30 ml/l
(depending on the depth of shade)
Common salt or Glauber's salt − 30 g/l
Wetting agent − 5 g/l (or as required)
e.g. Leonil SR (DyStar).
Dependable working is assured, provided:
1. The liquor is renewed every 5 minutes, necessitating the use of a low-

capacity trough and running the fabric at a high speed.
2. The liquor temperature is not higher than 25°C using less hot liquor for
dissolving.
3. The goods are cooled down before padding.
After padding, the fabric is batched up without selvedge overlap, then the
roll of fabric is wrapped with polyethylene sheet. Dye fixation is effected at
room temperature and it takes 2 to 6 hours. To be on the safer side,
especially with large yardage, the batches are left for 10 hours or overnight
and washed off in an open-width washing machine.
When the padding liquor is to be more stable without reduction in
reactivity, it is advisable to use a buffer. The best buffer is sodium silicate,
100 g/l (100°Tw, Na2O:SiO2 ratio 1:2.6) of which is used with the required
quantity of sodium hydroxide (Table 8.7) instead of salt.
The stability of padding liquor with and without sodium silicate is 20-30
and 5-15 minutes respectively. It also protects the padded fabric against the
action of atmospheric carbon dioxide. As the treatment is at cold, sodium
silicate can be washed out easily and completely.
Continuous Processes
In continuous dyeing, several variations are possible such as:
1. Pad (with alkali)-dry.

2. Pad (with alkali)-dry-bake.
3. Pad (with alkali)-dry-steam.
4. Pad (dye)-dry-pad (alkali)-steam.
549
Table 8.7 Requirement of Sodium hydroxide in Pad-batch Processes of

Remazol Dyes along with Sodium Silicate
Dye Concentration (g/l) Sodium hydroxide (32.5%), cc/l
Long batching method
< 30 5
> 30 10
Short batching method
≤ 20 15
20.1-30 18
30.1-40 20
40.1-50 24
50.1-60 25
70-100 30
In continuous dyeing, the differences between dyes of high and of low
reactivity are of such a nature that radically different methods of application
are needed. DCT dyes require short time for fixation, hence can be fixed by
the pad (with alkali)-dry sequence. However, MCT dyes require a further
baking for 3-5 minutes at 110-125°C or steaming for 3-10 minutes at
atmospheric pressure after drying. When DCT dyes are fixed by steam,
time required is 15-60 seconds so that the materials can be steamed
continuously. MCT dyes are to be steamed discontinuously or to be run at a
slow speed sacrificing production. Wherever the fabric is to be dried after
padding, it is advisable to add some thickeners in the padding liquor to
prevent migration of dyes during drying. This migration inhibitor may be
sodium alginate (1 g/l) or synthetic polymer based thickeners, which are less
reactive to reactive dyes. The drying is best done in a hot flue dryer, and not
on drying cylinders. To prevent reduction during steaming, an oxidising
agent, say resist salt (sodium salt of m-nitrobenzene sulphonic acid) is used.
Procion MX, Cold Brand Dyes
Pad-dry method: The material is padded at 20-25°C with a liquor containing
x g/l dye, 10 g/l sodium bicarbonate, required quantity of wetting agent and
0-200 g/l urea (only for heavy depth of dyes of low solubility), dried and
washed off.
In the recently developed Econtrol process, the relative humidity in the
dryer is maintained at a level of 25% so that urea and other chemicals are
not required. The fabric is padded with Procion MX dyes along with sodium
bicarbonate only and then placed in a dryer in which humidity is maintained
by steam-injection control devices [22].
Pad (dye)-dry-pad (alkali)-steam method: The material is padded at 20-
25°C with a liquor containing x g/l dye, required quantities of wetting agent,
550
migration and reduction inhibitor and dried. The dried material is further
padded with a liquor containing 2 g/l caustic soda flakes and 200-300 g/l
common salt, steamed for 30 seconds at 100-102°C and washed off.
Procion H-E/H Dyes
Pad-dry-bake method: The material is padded at 20-25°C with a liquor
containing x g/l dye, 20 g/l soda ash, required quantities of wetting agent
and migration inhibitor and 200 g/l urea. The padded material is dried and
baked for 1-3 minutes at 150-135°C and washed off.
Pad (dye)-dry-pad (alkali)-steam method: The material is padded at 20-
25°C with a liquor containing x g/l dye, required quantities of wetting agent,
migration and reduction inhibitor and dried. The dried material is further
padded with a liquor containing 200-300 g/l common salt and caustic soda
flakes amounting one-third of the weight of dye, with a minimum of 10 g/l.
The padded material is steamed for 60-75 seconds at 100-102°C and
washed off.
Remazol, Vinylsulphone Dyes
Pad-dry-bake method: The material is padded at 20-25°C with a liquor
containing x g/l dye, 8-30 g/l soda ash or 12-40 g/l sodium bicarbonate (for
5-50 g/l dye respectively), required quantities of wetting agent, migration
inhibitor and 15-80 g/l urea. The padded fabric is dried and baked for the
time and temperature mentioned in Table 8.8 and washed off.
Table 8.8 Temperature and time for Thermofixation of Remazol dyes
Temperature Time in minutes
Soda method Bicarbonate method
100°C 4-6 5-7
120°C 2-4 3-5
140°C 40-60 seconds 60-90 seconds
Pad (dye)-dry-pad (alkali)-steam method: The material is padded at 20-25°C
with a liquor containing x g/l dye, required quantity of wetting agent, 10 g/l
resist salt (mild oxidant), and 0-50 g/l urea and dried.
The dried material is further padded with a liquor containing 200-300 g/l
common salt and 5-20 g/l sodium bicarbonate for the dye concentration of
10-50 g/l respectively. The padded material is steamed for 4-7 minutes at
100-102°C and washed off.
8.4.7 Stripping of Reactive Dyes

Reactive dyes cannot be stripped satisfactorily from cellulosic materials, due
to the formation of covalent bond between dye and fibre. Some of the dyes
551
have azo groups, which may be reduced by a reducing agent (such as

alkaline hydrosulphite solution) to a colourless or lightly coloured
components, one of which will remain linked to the fibre as follows:
Cell-O-R1–N=N-R2 Æ Cell-O-R1–NH2 + H2N-N-R2 (8.11)
The structure -R1–NH2 attached to the cellulose may be lightly coloured
and further discoloured, by a mild hypochlorite bleaching treatment. It should
be borne in mind that the attached residue -R1–NH2 or its derivative after
bleaching, are still attached to the fibres and may show discoloration on
exposure to light, which may or may not be of importance on the redyed
material.
Metal-complex reactive dyes should be first treated with a metal
sequestering agent (2 g/l EDTA) and then washed thoroughly before further
treatments.
For stripping Procion H-E or H dyes, the following treatments may be
used:
1. Treat for one hour at boil with a liquor containing 6-10 g/l soda ash or
caustic soda and 6 g/l sodium hydrosulphite, rinse hot and cold.
2. The above material is further treated with 10 g/l sodium hypochlorite
(15% available chlorine) at cold for 20 minutes.
3. A cold treatment with 2.5 g/l sodium bisulphite for 15 minutes removes
residual chlorine.
4. A mild soaping and rinse are recommended before re-dyeing.
With cold brand reactive dyes, partial stripping is possible by treating with
5-10 ml/l glacial acetic acid or 2.5-10 ml./l formic acid (85%) at temperature
between 70-100°C till the shade is reduced by the desired amount. A
thorough wash is necessary to remove the products of hydrolysis.
8.4.8 Substrate Modification

Effluent control authorities will eventually demand low-salt dyeing of
cellulosics. High electrolyte concentration in dyebath discharges are
undesirable, as increased salinity in rivers upsets the delicate balance of
aquatic flora and fauna. This is particularly objectionable in situations where
discharge of dyehouse effluent can give rise to build-up of salinity, for
example the discharges to fresh water lakes. Sodium chloride is an
electrolyte commonly used, but the alternative sodium sulphate is even
more suspect, as it attacks concrete pipes and also has been associated
with increased acidity of waterways. Reactive dyes, in particular, use very
high concentrations of salt, so are under the most scrutiny. The sodium and
potassium salts of polycarboxylic acids have shown some promise as
alternatives to sodium chloride, but their use is likely to prove too costly.
552
Efforts have been made to produce reactive dyes demanding less salt
during application. The most notable of these is the Cibacron LS range,
which utilises several different reactive groups in a number of arrangements.
The bulk of the dyes are bifunctional, usually bis-monofluorotriazines. Other
groups or their combinations are also used, including MFT and MCT in
combination with VS as well as trifunctional dyes. The ability of these to
function effectively in the presence of reduced salt reflects their high affinity
for cellulose, which is partly due to the large molecular size of these dyes.
Flat dye molecules with hydrogen bonding sites increase affinity for the
substrate.
Hoechst introduced low-salt reactive dyes, Remazol EF range. These are
probably selected dyes from conventional VS range.
The recently introduced hot dyeing Procion XL+ range utilises the MCT
reactive system in combination with conventional chromophores. These
dyes are said to offer several environmental benefits, including high fixation
efficiency, easy wash-off and reduced consumption of energy, electrolyte
and water. Very high bioelimination is claimed – 60% in case of a bluish-red
dye as against 18% or less for other commercial reactive red dyes.
Improving substantivity of cellulose towards anionic dyes will greatly
reduce the need for electrolyte in the dyebath and improve dyebath
exhaustion, serving less residual dye in dyehouse effluent. Several chemical
modifications of cellulose are reported [38]. Introduction of amino groups
into cellulose structure produces a fibre that may be considered analogous
to wool. Unlike cellulose, wool has a natural substantivity towards anionic
dyes, especially under acidic conditions. Methods for amination of cellulose
have been known for quite some time. Recently several other routes have
been tried. Tertiary amino groups have been incorporated into cellulose by
reaction of cotton with β-chloroethyldiethylamine hydrochloride, according to
Harman process, producing DEAE cellulose. The DEAE cotton can be
dyed, in the absence of salt, with direct, acid and reactive dyes. Interestingly
the fixation of Drimarene K (5-chloro- 2,4 difluoro-pyrimidine) reactive dyes
occurs under neutral or slightly acidic condition. However, ethylenediamine
was found in the wash liquors, thus the modification process was considered
unsatisfactory for use in industry.
Lewis and Lei [38] esterified cotton with chloropropionyl chloride
(Cl-(O=)C-CH2CH2-Cl) and then aminated by nucleophilic substitution with
various amines. The aminated cotton materials were dyed with reactive dyes
under neutral to slightly acidic conditions in the absence of salt. Cotton
containing secondary amino residues (treatment with methylamine) gave the
highest colour yield. The apparent amino residues’ efficiency, in terms of
dye uptake, was ranked as:
Secondary > tertiary > quaternary > primary.

553
However, the alkali stability of the propionate ester was poor. A more
severe amination step (amine treatment at 100°C) did not produce modified
cotton containing an ester linkage. Instead, bonds of the type cell-N+R1R2R3
were obtained, which gave reactive dyeing of excellent alkali stability.
A quaternary, amino-epoxy derivatives, glycidyltrimethylammonium
chloride, was marketed by Protex as Glytac A, emphasizing its use as a
compound which offered enhanced dyeability of cotton with direct and
reactive dyes. Dyeing of cotton pretreated with Glytac A in the absence of
electrolyte with reactive dyes gave a high degree of covalent bonding under
boiling, neutral dyebath conditions along with high dyebath exhaustion.
1,1 dimethyl-3-hydroxyasetidinium chloride (DMA-AC) may be prepared
by reaction of dimethylamine and epichlorohydrin. It has similar
characteristics to the Hercosett polymer used for anti-felting finish for wool,
in that it consists of cationic, reactive asetidinium groups capable of reaction
with the hydroxyl groups of cellulose. DMA-AC may be applied to cotton by
pad (with strong alkali)-bake method. The treated material can be dyed with
reactive dyes at pH 7 in the absence of salt. Dye fixation is extremely high
so that long soaping is not required. The dyeing behavior is very similar to
cotton treated with Glytec A. The introduction of tertiary and quaternary
groups into cotton by low molecular mass species improves the neutral
fixation of reactive dyes by increasing cellulose ionisation due to the
proximity of strongly basic groups.
Lewis and Mcllroy [38] showed that nicotinoyl-thioglycollate (NTG) can
react (Eqn. 8.12) with cotton under alkaline pad-thermofixation (optimum
fixation at 210°C, 90 seconds, pH 8) to form nicotyl-cellulose ester. The
modified fibre showed excellent uptake of MCT dyes at boil in the absence
of salt. Optimum dye fixation and exhaustion under dyebath conditions of pH
3 and 80°C. The light fastness was similar and wash fastness was slightly
less than conventional dyeing. Highly reactive DCT and dichloroquinoxaline
dyes gave excellent dyebath exhaustion. However, dye fixation was poor,
probably due to instability, under acid dyeing conditions, of the quaternised
triazine. It was proposed that the dye quaternised with the tertiary amine
residue and then, under boiling, neutral soaping off conditions, the
quaternised dye reacted with cellulosic hydroxyl groups to give normal dye-
fibre bonds.
Cell-O−Na+
N N + Na+ −SCH2COO− +Na (8.12)
COSCH2COO−Na+ COO-cell
The reaction of a quaternised triazine with cellulosate nucleophiles is the

principle mechanism of fixation of Kayacelon React dyes (Nippon Kayaku)
554
on cotton. These dyes react with cellulose at boil under neutral condition,
hence are termed as neutral-fixing dyes. They can also be applied at lower
temperature with a small addition of alkali. Croft et al. [39] found that
derivatives of diazabicyclo-octane (DBCO), nicotinic acid and isonicotinic
acid offer the most potential neutral-fixing reactive dyes.
To systematically investigate the effect of attaching a variety of amines to
the cellulose by a simple pretreatment, Lewis and Lei [40] modified cotton
with N-methylolacrylamide (NMA) (HO-CH2–NH(O=)C-CH=CH2), a
crosslinking agent commonly used for producing durable-press cellulosic
fabrics, in the presence of Lewis acid. The double bond of NMA-treated
cellulose was further modified with various amines. The dyeing of amine-
modified cellulose (especially with ammonia and methylamine) at pH 5 for
one hour at boil in the absence of salt, showed good colour yields. The
Sandene process, developed by Courtaulds and Clariant (formerly Sandoz),
consists of treatment of cellulosic fibres with a cationic polymer, Sandene
8425, which is applied under alkaline conditions by exhaust method to
enhance the dyeability with anionic and reactive dyes. Sandene 8425 is a
colourless cationic pretreatment agent that can be applied to cellulose
substrates by pad or exhaust techniques. Unlike cellulose itself, which in
aqueous medium shows a negative charge, Sandonised cellulose is
positively charged, thereby reversing the dye-fibre repulsion. Moreover, the
cationised fibre not only attracts dye, but also offers new dyeable groups for
fixation that complement the cellulose hydroxyl groups. This results in faster
and more efficient dyeing of the fibre. The ease of application made the
process attractive as a pre-treatment for cotton. The treated substrate had
high neutral substantivity, but reduction of light fastness and dulling effect in
case of some dyes were main drawbacks. One major drawback of this
approach is that the cationic agent is colourless. Sandene pretreatment may
not be uniform on certain materials such as high twist yarns or knotted yarn
hanks, and has to be stripped off with alkaline hydrogen peroxide. However,
the unlevelness can only be observed after fixation of dyes.
Hoechst recommended the application of N-2-sulphatoethylpiperazine
(8-37) by padding along with sodium hydroxide followed by heating to 150°C
for 2.5 minutes for amination [1].
O-SO3H
H-N N
(8-37)
The chemical modification of cellulose, especially cotton, to obtain
enhanced dyeing properties has attracted much research interest. A number
of auxiliary manufacturers are selling reactive aminating compounds for the
purpose, namely:
555
1. Vircotone ECO system commercially used in the USA, claiming no

impairment of handle and physical properties of the substrate.
2. Hydrocol EP 155 from Rudolf.
3. Texamine ECO system from Vütz-Inotex.
The major problem in these products is their lack of substantivity

restricting their application by padding process only. However, fibre
substantive, cellulose cationisation agents are now available, e.g. Texamin
ECE (Vütz-Inotex) or Hydrocol CR (Rudolf).
Whether or not these attempts have a significant market impact depends
on a number of issue [41]. Such procedures will only find commercial
success if the products are cheap and of low toxicity, and if the fibre-
modifying agent can be applied in a way that fits readily into current
dyehouse practice.
8.5 VAT DYES
An estimate made in 1979 showed vat dyes to have a 15% share in the
dyeing of cellulosic fibres, with indigo contributing a further 2%. The
chemical nature of vat dyes and their method of application (solubilisation by
reduction, rapid penetration into the fibre followed by oxidisation into
insoluble pigment) guarantee an exceptional standard of fastness. For
certain sectors, it would be inconceivable not to use vat-dyed qualities.
However, the number of dyes introduced in the range has not increased
much after 1968. A survey in Europe showed that out of 207 dyes
manufactured in 1984, only 19 dyes were developed during the period 1968-
84 [42].
This most important dye-class for cellulosic materials provides excellent
all-round fastness properties, which cannot be attended, by any other dye-
class. This applies not only to their fastness in use, e.g. fastness to washing
and light, but also to those factors important during fabric processing after
yarn dyeing, e.g. fastness to mercerising, soda boiling, chlorine and
hypochlorite bleaching. Vat dyes are, therefore, ideal for coloured woven
goods such as handkerchiefs, shirtings and towelling.
If the dye is readily reducible, poor fastness ratings may be obtained while
washing under alkaline conditions at boil. This applies to the flavanthrones
(C.I. Vat Yellow 1), the pyranthrones (C.I. Vat Orange 9) and to some
extent, the dibenzanthrones (C.I. Vat Blue 20). The problem can be
prevented by adding a mild oxidising agent, e.g. sodium m-
nitrobenzenesulphonate. The indanthrones, especially C.I. Vat Blue 4, are
sensitive to hypochlorites.
556
The substrates dyed by vat dyes are cotton, linen, viscose rayon, blends
and union (warp and weft of different fibres) fabrics containing above
cellulosic fibres. They are used for all outlets where the highest levels of
fastness are required such as:
• Workwear and uniforms for armed forces, police, fire, nursing
services, etc. which are subjected to severe laundry washing and
occasional bleaching with hypochlorite and long exposure to sunlight.
• Clothing and household articles such as shirtings, sports-wear,
towelling, bed sheets, table cloths.
• Furnishing requiring high fastness to light.
• Outdoor fabrics requiring high weather fastness such as parasols,
tenting, tarpaulins
• Yarns like sewing threads and for coloured threads for weaving which
are subsequently piece-bleached with hypochlorite.
However, their applications are to be carefully controlled. They are quite

costly and may not be affordable for all varieties of materials. Most of the
vat dyes have high affinity for cellulosic materials. The dyeing may even be
carried out in grey state and may subsequently be scoured for removal of
impurities, although such processing has no apparent merits except in some
isolated cases.
The use of vat dyes as colouring matter can be traced to ancient times
when people used natural animal and plant derivatives to colour garments
and other textiles. Some of the earliest references to such colouring
substances go back thousands of years when Tyrian Purple was used. The
dye was of animal origin, being an extract from shellfish. Indigo was the
most important colouring material of the age. It has been known in India
since the earliest periods for which historical records last. These dyes are
applied by chemical reduction. Before chemical reducing agents were
available the naturally occurring vat dyes were reduced by fermentation of
organic matter in a wooden vessel referred to as a vat – and this is the origin
of the name vat dyes.
One of the disadvantages of natural indigo was that the proportions of
indigo, indirubin and analogous products were never constant resulting in
poor reproducibility of the dyeing. The manufacture of the substance from
coal-tar derivatives constituted one of the classical triumphs of industrial
organic chemistry. The successful large-scale production of indigo started
from about 1900. Subsequently the synthesis of vat dyes has been an
extremely active field of research and many new members of various
complex chemical structures were incorporated into this dye-class.
Some of the trade names of vat dyes are:
Indanthren (BASF, Bayer, Hoechst), Caledon (ICI), Cibanone (Ciba),
Sandothrene (Clariant), Navinon (IDI, India), Novatic (Atic, India).
557
Vat dyes are used to dye cellulosic materials in relatively dull shades
requiring good fastness to washing, particularly when fastness to chlorine is
essential. They are particularly suited for cotton and rayon substrates. They
are also used to dye nylon and to stain polyester in blends with cellulosic
fibres under proper conditions.
The use of vat dyes for dyeing of polyester-cotton blends in one-step or
two-step process has some significant advantages over reactive dyes. The
colour value, reproducibility of shade and fastness properties are better. The
dyeing is easier to wash off and no reduction clear of the polyester is
necessary. A disadvantage is that a separate oxidation stage is always
necessary. The oxidation and soaping may be combined.
The vat dyes found non-toxic to fish, LD50 values for the acute toxicity of
vat dyes are above 2,000 mg/kg, determined by oral application on rats.
From tests on animals, only C.I. Vat Yellow 4 has so far found to be
carcinogenic.
Vat dyes are mainly divided into two main classes:
1. Indigoid vat dyes which are usually derivatives of indigotin (8-38,
where R = NH) or thioindigo (8-38, where R = S)
2. Anthraquinoid vat dyes derived from anthraquinone (8-39).
O O O
C C C
C=C
R R C
O
(8-38) (8-39)
The anthraquinoid group exhibits superior fastness properties –
distinguished by excellent fastness to light and is the most widely used
group.
The derivatives of anthraquinone are more versatile and are made of
higher condensed aromatic ring systems with a closed system of conjugated
double bonds. The structural elements of several typical important classes
of vat dyes are indanthrones, flavanthrones, pyranthrones, dibenzanthrones,
isodibenzanthrones, benzanthrone acridones, anthraquinone carbazoles,
anthraquinone oxazoles, etc.
The substitution of one and two –NH− groups of indigo by –S− group
produces black, e.g. C.I. Vat Black 1, and brown, e.g. C.I. Vat Brown 5, dyes
respectively. Substitution with two bromine and chlorine atoms on each of
558
the two benzene rings of indigotin results in blue dyes, C.I. Vat Blues 5 and
41 respectively.
While trying to find an anthraquinone analogue of indigo, indanthrone dyes
were developed. They provide blue dyes. Since they are prone to over-
reduction and over-oxidation, they may create problem during dyeing.
However, because of their attractive colour, excellent fastness and
moderate costs, they still form one of the most important classes of vat
dyes. One important member of the class is Indanthrone Blue RSN, C.I. Vat
Blue 4 (8-40). Halogen substitution of indanthrone increases the range of
shade. Thus C.I. Vat Blue 6 and C.I. Vat Blue 11 have two chlorine and two
bromine atoms respectively at positions shown by * marks in (8-40).
Flavanthrone, C.I. Vat Yellow 1 (8-41) was produced by the fusion of 2-
amino-anthraquinone at high temperature. In spite of slow oxidation, lower
wash fastness and a tendency to photochromism, the dye is important for its
good light fastness. This and its derivatives are, in common with the
indanthrones, among the oldest synthetic vat dyes.
O O
C C
C O
NH NH N
O C N
* C C
O O
(8-40) (8-41)
A further development was the fusion of 2-methyl anthraquinone with
*
caustic soda, when the dyestuff C.I. Vat Orange 9 or pyranthrone (8-42)
containing pyrene structure is obtained. Dibromo and tribromo derivatives of
the dye are C.I. Vat Oranges 2 and 4 respectively. The dyes may cause
fibre damage during dyeing and non-brominated product has inferior light
fastness. However, they are used widely because of their good levelling
properties, high colour strength and moderate cost.
Another important dye intermediate is dibenzanthrone, from which many
dark blues, navy blues, greens and blacks (C.I. Vat Blues 16, 19, 20 and 22,
Greens 1, 2 and 9, and Black 9) vat dyes are derived. The best known being
Indanthren Jade Green XBN, C.I. Vat Green 1 (8-43). They have
disadvantages like lower fastness to rubbing, hot pressing and water
spotting. Nevertheless, they have maintained their importance because of
unique hues, good levelling and excellent fastness to wash and light.
559
The isodibenzanthrone dyes include some interesting deep violet colours

(C.I. Vat Violets 1 and 9) that have high colour strength and good fastness
to bleaching, but they suffer the same disadvantages as in the case of
dibenzanthrone dyes.
O
C OMe OMe
O O
C
O
(8-42) (8-43)
The benzanthrone acridones represent another large class, including C.I.
Vat Greens 3 and 13, Black 25. They offer olive greens, olives, browns and
greys. The levelling is difficult with these dyes, but they have excellent
fastness and they protect fibres against the action of light.
Another extremely important class of dyes, the anthraquinone carbazole,
includes C.I. Vat Oranges 11 and 15, Browns 1, 3 and 44, Green 8 and
Black 27. In spite of relatively flat colours, they have good levelling
properties and excellent fastness to wash, light and chlorine.
The main representative of anthraquinone oxazole class is C.I. Vat Red
10, a strong brilliant red that levels well and has excellent fastness.
The derivatives of perylene tetracarboxylic di-imide include C.I. Vat Reds
23 and 32, while those of imidazole include bright light-fast C.I. Vat Yellow
46.
C.I. Vat Blue 66, having excellent levelling properties and good fastness to
chlorine, is a derivative of triazinylaminoanthraquinone. Unlike indanthrone
blue dyes, it is not susceptible to over-reduction [7].
A few of the indigoid group of dyes are outstanding in brilliance of shade.
This characteristic combined with lower fastness to washing and bleaching
of some of the dyes makes them desirable for many uses. They are also
used in some applications simply for economical reasons. Indigoid dyes have
poor substantivity for cellulose. The substantivity can be further reduced so that
the dye remains mostly at the surface called ring dyeing. Such ring-dyed
materials are subjected to stone or enzymes, which remove dyes randomly
from portions of the fabric exposing white surface. This popular style is utilised
in faded jeans or in Denim fabrics.
560
8.5.2 Physical Forms

Unlike other dye-classes, vat dyes are marketed in different physical forms.
These include Paste, Supra Paste, Double Paste, Powder, Powder conc.,
Powder Highly conc., 400 Powder, 800 Powder, 2100 Powder, 4200
Powder, Ultra conc., Microfine, Ultradisperse, FD grains, etc. depending on
the particle size (or dispersion) and dye content in the particular physical
form. The strength is arbitrarily expressed with respect to that of the single
strength paste. Double Paste contains twice the amount of dye present in
single paste. The number indicates the percentage strength with respect to
single strength paste, e.g. 800 means 8 times stronger. Generally, Ultra
Conc. Powder contains double the amount of dye contained in Highly Conc.
Powder of the same dye. The relationship is applicable between various
physical forms of the same dye, and strength of one dye cannot be
compared with that of the other just from the above expressions.
Microfine, Ultradisperse, FD grains and such other brands of vat dyes
contain much less dye than powder brand. These brands are especially
developed for dyeing by pigmentation methods as they give good
dispersions when stirred in water and do not settle at the bottom.
Paste form has been developed mostly for textile printing. The dye exists
as fine dispersion and can be diluted with water without pasting. Vatting in
this form is quick and easy. However, they have the tendency to dry up
causing variation in strength during storage. Transportation is troublesome
and storage conditions are to be carefully controlled. The liquid type could
become even more important as the result of the progressive automation in
textile dyehouses and colour kitchens.
Powder brands are more stable and can be stored for an indefinite time.
However, they need pasting with good wetting agent (e.g. T.R.Oil) before
diluting with water. Powders require longer vatting time than paste brands.
The dye crystals obtained from the synthesis are mostly reduced in size
by wet grinding in the presence of dispersing agent. To improve the
technical properties, particularly with liquid preparations, a stepwise grinding
process in a bead mill, with beads of varying sizes is proposed. With
modern procedures and instruments available for measuring the particle
size, it has been possible to control the grinding process more exactly. The
available top-quality dyes generally have an average particle size of well
below 1 µm.
For drying, the spraying technique (rotating discs or jets) is well
established. With regard to the commercial products available, a trend from
the powder to the granular form is observed with dry preparations.
The granules are mostly produced by injection through nozzles. Rotary
bed granulation is also reported. Thermal degradation of dyes can be
reduced by controlling temperature or by using special machinery.
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The conformity to colour and strength standard is a prime requirement.

Others include rapid vatting, low dusting of powder brands and optimum
behaviour in continuous processes, such as low migration during drying and
no speck formation. Dyes in liquid forms are very advantageous. They
facilitate metering, particularly when used in large amounts. Essentially
these properties are obtained by grinding the batch of dyes together with
dispersing agents and additives, with or without subsequent drying. The
treatment is a trade secret and is known as finish. As dispersing agents,
sulphonated and hydroxyalkylated lignin derivatives and water-soluble of
monocyclic arylalkyl residues and sulphonated aromatic compounds with
two or more condensed rings are mentioned. Suitable Migration inhibitor
may be introduced in liquid preparations. Vatting accelerator, e.g. based on
phenol derivatives may be added to the formulation. The dispersability in
cold water can be improved by addition of amphoteric surfactants, such as
betaine. To reduce foam formation with powder brands, the finish should
include ethylene-propyleneoxide-polyol reaction products.
For producing liquid dyes, 1,1,4,4-tetra-alkylbutine-1,4-diole compounds
are said to be very suitable in the presence of anionic dispersing agents
because they prevent settling during storing of the dispersion. A caproic acid
derivative increases stability of dispersion against heat. The solvents are
mainly used for the preparation of dispersant-free pigments.
The dusting of powder brands can be reduced by incorporating a small
amount of alkyl (e.g. ethyl or butyl) phosphates. Methylcellulose inhibits
migration during drying and polyorganosiloxanolates improves the colour
intensity of prints.
8.5.3 Principles of Application

The vat dyes are insoluble in water and have no affinity for textile fibre so
long as they remain in insoluble state. They all contain two or more keto
groups (>CO) which, when treated with reducing agent, combine with
hydrogen to form leuco compounds (≡C·OH). These secondary alcohols do
not dissolve in water but form soluble derivatives (enolate) in the presence
of alkalis.
(>C=O) 2 + Na2S2O4 + 4NaOH Æ (≡C-ONa) 2 + 2Na2SO3 + 2H2O (8.13)
On exposure to air, the sodium compound is converted to the original
insoluble pigment.
O Reduction OH Solubilisation ONa

(Na2S2O4) (NaOH)
(8-14)
O Oxidation OH Hydrolysis ONa

[O] (H2O)
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It is expected that the relationship between structure and substantivity of

vat dyes should be similar to that in the case of direct dyes. However, many
of vat dye molecules are non-linear (e.g. C.I. Vat Green 1) and deficient in
groups that are capable of forming hydrogen bonds. Earlier it was assumed
that molecular complexity of vat dyes is responsible for its substantivity, but
the explanation is not entirely convincing. The possibility of hydrogen bond
formation cannot be ignored as many vat dyes have substantive amido
groups (-NHCO-). However, hydrogen bond formation cannot be the only
explanation. As the structures of most dyes are very complex, Van der
Waals' forces are also an important factor. Although the molecules may not
be linear, it must be sufficiently planer to permit it to approach each other
within a narrow range so that the binding forces can start acting. The
introduction of substituents in the o-position in the side chain of 1-
benzoamido anthraquinonone pushes the benzene ring out of position and
results in a significant decrease of substantivity. The relationship between
affinity and planer configuration was studied [43] with a number of pairs of
vat dyes of similar structure, but one is coplaner while the other is non-
coplaner. In every case, the affinity of non-coplaner molecules was
extremely low.
Dyeing with vat dyes involves three separate operations:
1. Vatting, i.e. dissolving the dye under alkaline reducing condition,

mostly with sodium hydrosulphite or sodium dithionite (Na2S2O4) and
caustic soda (NaOH).
2. Dyeing, i.e. impregnation of the materials with the dissolved dye.
3. Oxidation, i.e. the insolubilisation of dye to the original pigment.
Generally vatting is done with a small volume of water and the

concentrated dye liquor is slowly added in a large volume of water filled in
the dyeing machine.
During vatting, the indigoids form pale-yellow leuco compounds soluble in
weak alkaline solutions and the anthraquinoid vat dyes give deep coloured
leuco compounds, which are soluble only in strong alkali.
Experiments have shown the following:
1. Vatting proceeds almost twice as rapidly with an increase in

temperature of 10°C.
2. Above pH 12, the rate of vatting is not dependent on the hydroxide ion
concentration.
3. The higher the concentration of reducing agent and dye, the more
rapidly reduction takes place.
4. The rate of vatting is dependent on the crystalline form and particle
size of the dye.
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The amounts of caustic soda and sodium hydrosulphite depend on the

number of reducible keto groups in the dye. However, an excess of
hydrosulphite is required to compensate for oxidation in the presence of
atmospheric and dissolved oxygen. The amount of caustic soda should also
be in excess to neutralise the acid oxidation products formed. The amount of
caustic soda in the dyebath depends on the M:L ratio and the solubility of
the sodium leuco compound in caustic soda solution. Dyes containing one
anthraquinone nucleus, i.e. two keto groups and dyes containing up to six
keto groups in a loosely bound structure such as carbazoles, generally
require low to medium caustic soda content. Dyes with many keto groups,
e.g. ten in Indanthrene Khaki 2G, or with firmly bound polynuclear ring
structures, e.g. dibenzanthrone (nine rings, two keto groups) require a high
caustic soda content. Some sodium leuco compounds may be salted out by
too high a concentration of sodium ions in the liquor and such dyes are
unsuitable for vatting in concentrated solution – they are reduced in full
volume of liquor.
It is essential to ensure that an excess of caustic soda is present during
vatting to prevent undesirable side reactions from taking place. The stability
of the vatted dye solution is effected by:
1. Precipitation
2. Hydrolysis
3. Over-reduction
4. Dehalogenation.
In the presence of multivalent cations (e.g. Ca, Mg or Fe), some leuco

compounds, e.g. C.I. Vat Yellow 1, Orange 2 and Blues 4, 6 and 14, form
almost insoluble salts that have no substantivity for the fibre; the
precipitation can be prevented using a sequestering agent.
Leuco vat dyes containing benzolamino (-NH-CO-C6H5) groups such as
C.I. Vat Yellow 3 and C.I. Vat Orange 15 are hydrolysed at high
temperature and on prolonged vatting.
The defect of over-reduction occurs with vat dyes containing heterocyclic
rings with nitrogen atoms and where all of the keto groups present in the
molecule need not to be reduced such as Indanthrone blue and Flavathone
yellow dyes.
Dehalogenation occurs with halogenated dyes such as C.I. Vat Violets 1,
9, 14, Green 2, Blue 6, Orange 2, etc. High temperature vatting and dyeing
conditions cause dehalogenation when the dye loses chlorine or bromine
atoms and reverts in part to the nonhalogenated compounds, which are of
different colour. Chlorine fastness also suffers as in case of C.I. Vat Blue 6.
During dyeing, additional caustic soda is also required to keep the
reduced vat dye in its leuco form, as the dye is absorbed only in its ionised
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form by cellulosic fibres. The dyebath must have a pH of 12−13 to prevent

formation of almost insoluble acid leuco compound.
In normal dyeing method, the use of triethanolamine in place of part of
sodium hydroxide is said to give several advantages – less tendering of
fibre, better penetration of dye, less over-reduction, and in some cases
increased colour yield.
A number of vat dyes require retarding agents in the dyebath to produce
level dyeing because of their high rate of uptake by the fibre. However, there
are other vat dyes, which are characterised by low rate of uptake by the fibre
and accordingly they do not exhaust well. Therefore, the use of exhausting
agent such as common salt, Glauber’s salt etc., are necessary in those
cases.
Sodium hydrosulphite is very unstable and much of it is wasted by
atmospheric oxygen during dyeing. The stability of the reduced bath is
highly dependent on the degree of aeration, which occurs during dyeing and
upon the temperature; the decomposition is very quick at 70-90°C. It is,
therefore, essential to make regular checks of the presence of sufficient
excess of hydrosulphite in the dyebath by spotting the solution on Vat
Yellow paper during dyeing. The paper is prepared by dyeing it with C.I. Vat
Yellow 1. Satisfactory vatting conditions are indicated by the appearance of
a deep royal blue shade within 1-2 seconds. If the colour changes slowly to
a greenish shade, it is essential to add more reducing agent in the ratio:
caustic soda, 68° Tw – 1.2 litre, sodium hydrosulphite – 1 kg. The caustic
soda should be added simultaneously in order to neutralise the acid-
decomposition products of hydrosulphite and to maintain a strong alkaline
bath (pH 13).
The alkalinity of the dyebath should be checked with phenolphthalein
paper, which changes from white to intense red (pink) in the presence of
alkali.
Vat dyes exhaust very rapidly, even at relatively low temperatures. The
dye is absorbed in two stages. Most of the dye (80-90%) exhausts within
about 10 minutes (stage 1), followed only slowly by the remainder (stage 2).
Consequently, there is the danger of the substrate being dyed unevenly
during the first stage in which the dye is absorbed in the sheath of fibre,
causing ring dyeing. The second stage is governed by the diffusion of the
dye into the core of the fibre. The rate of diffusion rises exponentially with
increase in temperature.
The purpose of the oxidation step is to convert water-soluble sodium salt
of the leuco vat dye taken up by the fibre into insoluble original vat pigment.
Improper oxidation may lead to faulty shades, unevenness and insufficient
fastness properties of the dyed material. After the appropriate period of
dyeing in the reduced state, excess dye liquor from the goods is removed by
squeezing, suction hydroextraction or draining. If it is impossible to carry out
565
any one of these operations, it is essential to rinse the goods in cold water in
order to remove the chemicals and the unexhausted dye. It is a good
practice to rinse the dyed material with cold water as the first step in the
process of oxidation. The dyed material is then subjected to oxidation by
exposure to atmospheric oxygen. This is known as air-oxidation, airing or
skying. Accelerated chemical oxidation may be carried out by acidified
sodium or potassium dichromate (now obsolete), sodium hypochlorite or
peroxygen compounds such as hydrogen peroxide or sodium perborate or
sodium m-nitrobenzene sulphonate (Ludigol, BASF). In alkaline medium, the
peroxy agents react relatively slowly, whereas Ludogol reacts extremely
rapidly. Higher the temperature and lower the pH, quicker the reactions
proceed with the oxidising agents. Care should be taken that the oxidation
conditions are as mild as possible so that the cellulosic material is not
oxidised. This is especially the case when sodium hypochlorite is chosen as
the oxidising agent.
Certain vat dyes containing nitro groups, as in case of some black dyes,
require a strong oxidising treatment for converting their leuco forms to the
original vat dyes. The nitro groups are reduced during vatting. These
reduced amino groups are to be converted into nitro group during oxidation.
Otherwise, an undesirable shade with inferior fastness properties is
produced.
Over-oxidation of some vat dyes by prolonged oxidation may cause
change in the shade. In case of Indanthrone and its substitution products
(blue vat dyes), the yellow azine form of the dye is formed so that the final
shades produced acquire greenish tones with varying degrees of
yellowness. Hydrogen peroxide produces no such adverse effect.
To remove loosely adhered dyes on the fibre surface, the dyed material,
after oxidation, is to be soaped at boiling with 3 g/l soap and 1 g/l soda ash
for 15-30 minutes. The process is very important in vat dyeing. The
fastness to washing and light improves significantly.
The soaping also causes change of shade (mostly to the brighter side)
with most of vat dyes, particularly on mercerised cotton and regenerated
cellulose. Various causes have been put forward such as completion of
oxidation, aggregation or crystallisation of dye particles inside the fibre. It is
believed that the forces between the dye molecule and the cellulosic chain
are weaker after oxidation than before. Examination with an electron
microscope showed that the aggregates took the form of crystallites and
measurement of dichroism with a spectrophotometer indicated increased
orientation of the dye in a direction traverse to the longitudinal axis of the
fibre. Although crystallisation can take place in water, it is greatly
accelerated by a detergent compound. Individual vat dyes vary very much in
the rate at which they crystallise, but the change is more rapid at higher
temperature, and greater consistency in the shade will result if soaping is
566
always carried out at the boil. Valkó [44] has proved, by X-ray examination
of extremely deep dyeing on cellophane film, that in certain cases
crystallisation takes place on soaping (e.g. C.I. Vat Blue 6 and Orange 9). In
other cases (e.g. C.I. Vat Blue 4), X-ray analysis has shown that the dye is
amorphous, both before and after soaping. Indigo dyeing was found to
contain crystals even before soaping. After soaping, the dyed material is
rinsed well with cold water and dried.
8.5.4 Reducing Agents

The production of anhydrous sodium hydrosulphite is a prerequisite for the
industrial use of vat dyes and even today, it is by far the best reducing agent
for vat dyes. The reduction reaction is shown in Eqn. (5.4). Its constitution as
sodium dithionite (Na2S2O4) is known since the end of the last century, but
the erroneous designation hydrosulphite remains popular. The dominant
position of hydrosulphite is due to the particularly favourable relationship
between its properties and its cost. The instability of the dithionite ion (O2S-
–
SO2)2 arises from the presence of the S-S linkage. In the anhydrous state,
the product is quite stable, but in contact with water, it forms sodium
thiosulphate and sodium bisulphite.
2Na2S2O4 + H2O Æ Na2S2O3 + 2NaHSO3 (8.15)
The formation of acid products accelerates the decomposition, which
proceeds exothermically and may result in spontaneous ignition. The same
reaction occurs in aqueous solution (without alkali) and both sulphur dioxide
and sulphur have been identified as reaction product [7].
In the absence of air, hydrosulphite is extremely stable in alkaline
solutions. In the presence of atmospheric oxygen, sodium sulphite and
sodium sulphate are formed.
2Na2S2O4 + 2NaOH + O2 Æ Na2SO3 + Na2SO4 + H2O (8.16)
Depending on the conditions, more sulphite is formed than sulphate.
–
Apparently, the free radical ion (⋅SO ) is the initial transient formed from the
– –
dithionate anion ( O2S-SO2 ). Sodium hydroxide is consumed in the above
oxidation process, hence it should be present in sufficient excess. In the
neutral or acidic conditions, the former hydrolytic reaction takes place. In the
oxidation with oxidising agents other than atmospheric oxygen, only
sulphate (with hydrogen peroxide) or sulphite (with sodium-m-
nitrobenzenesulphonate) are produced from the dithionite [7].
2Na2S2O4 + 2NaOH + 3H2O2 Æ 2Na2SO4 + 4H2O (8.17)
Since sodium dithionite is sensitive to atmospheric oxygen, an excess of
dithionite must always be present. Under the conditions normally employed
567
in dyeing (pH 12-14), oxidation of the sodium dithionate does not appear to
depend to any significant extent on the alkali content of the liquor.
For use in printing, continuous dyeing and automated dyeing processes, it
is necessary to have a reducing agent having better stability towards
oxidation at cold without hampering its reducing properties such as
hydroxymethanesulphinate (Rongolite C) and hydroxyethanesulphinate
(Rongolite 2PH). Various additives are added to increase the storage
stability of sodium dithionite, namely dicarboxylic acids and their salts, or
aldehydes, oxalic acid in the presence of carbonate or borax, sodium
hydrogen sulphite, water-soluble synthetic polymers, urea, cationic, nonionic
or amphoteric surfactants and oxypropylated starch or cellulose. The
stability of sodium dithionite solution can be increased by adding 10% (on
the weight of sodium dithionite) zinc sulphate. A mixture of sodium dithionite
and the bisulphite compound of an aliphatic aldehyde shows better stability
towards atmospheric oxygen in alkaline solution.
A reduction of 40% in the amount of dithionite has been claimed by a
BTRA process [45] using a mixture of dithionite and sodium sulphide (7:3)
for dyeing cellulosic fibres. It is less suitable for polyester-cellulosic blends.
However, works at BASF showed no such synergistic effect; so there is a
risk if the excess dithionite is reduced. The use of a mixture of dextrin and
dithionite enables to reduce the amount of the dithionite to be used by about
50%. Dextrin is said to stabilise the leuco compounds and the sulphite to
retard the oxidation of dithionite. Other anti-oxidants recommended are
sodium borohydride, glucose and dextrose, but they are less suitable.
The addition of hemiacetals of formaldehyde and glycol to liquor
containing dithionite has been recommended to prevent over-reduction,
particularly at high temperature.
The main reason for seeking an alternative to sodium dithionite is the fact
that the effluent from dyeing contains a certain amount of sulphite and
sulphate. An excessively high sulphate concentration can cause damage to
unprotected concrete pipes.
Thiourea dioxide is undoubtedly a strong dye-reducing agent, but in
alkaline solutions it is just as sensitive to atmospheric oxygen as
hydrosulphite. Its low sulphur content and lower equivalent than that of
hydrosulphite lead to better values for sulphite and sulphate in the effluent.
Opinions differ with regard to the stability of the product to atmospheric
oxygen in alkaline liquors – there is rapid formation of
formamidinesulphinates, which is more readily oxidisable than hydrosulphite
[42]. The main prohibitive factor is its price. The addition of formaldehyde is
recommended in one-bath dyeing to prevent premature vatting in padder. In
high temperature process, the product is far more liable than dithionite to
cause over-reduction, especially with indanthrone type of vat dyes. With the
568
said dyes, the results are unacceptable even in exhaust dyeing at 50°C. In
this case, the usual inhibitors, e.g. glucose or sodium nitrate, have no effect.
Sodium borohydride, a good reducing agent, is required in small quantity
due to its very low equivalent weight. It has a strong negative electro-
chemical potential even in alkaline solution. However, at pH above 11, its
reducing effect on vat dyes is completely inadequate without auxiliaries. The
use of borohydride and sodium nickel cyanide, together with
hydroxymethane sulphinate has been widely recommended, especially for
pad-steam process. However, the cost and effluent problems are the
barriers for their commercial exploitation.
Therefore, no reducing agent is available today that can replace
hydrosulphite in all areas. It can be supplied in solution form, which is stable
in the absence of heat, oxygen and thiosulphite.
An important factor in dyeing is the rate of vatting. The rate depends on
several factors such as the type of reducing agent, temperature and pH of
the solution, the dispersion and crystal form of dye particles and its
concentration.
The rate of vatting is influenced by reduction accelerator, which for
dithionite includes aminoanthraquinone sulphonic acids and water-soluble
organic compounds containing at least two primary aliphatic amino groups.
When hydrosulphite is used as the reducing agent, such substances are not
necessary today, as the dye preparations are finished in such a way that
vatting takes place sufficiently rapidly in all processes.
8.5.5. Other Auxiliaries

The addition of wetting agent is valuable in ensuring uniform impregnation of
the goods, in assisting penetration and achieving level dyeing. Turkey Red
Oil or sulphated castor oil is widely used for pasting of vat dyes before
vatting. It acts as a wetting cum dispersing agent. Lenetol WLF and Matexil
WA-HS (ICI) are effective wetting agents for vat dyeing. Nonionic wetting
agents should be avoided as they have restraining action on the yields of vat
dyes. The formation of foam should be low to avoid surface oxidation and
the formation of scum.
Some of the vat dyes have high affinity for cellulosic materials. Their high
initial strike rate causes unlevelness. Two types of levelling agents can be
used. One type of levelling agent competes with the dye for the fibre-sites,
thereby reducing the effective rate of dyeing. The other type of levelling
agent forms loose complex with the dye, the complex has no or little affinity
for the fibre. The complex subsequently breaks, generally with increase in
temperature, making the dye available for dyeing. Auxiliaries developed to
promote level dyeing include polyethylene glycol carboxylic esters, which
have affinity for the dye and saponify during dyeing; products derived from
569
polyamides, oxazine derivatives and water-soluble condensates of ethylene-

urea and an aldehyde. Remol OK (Hoechst), Dispersol VL (ICI), Peragal O
(BASF), Albatex PO (Ciba), Dekol, monopol soap, glue, etc. are some of the
levelling agents recommended in dyeing vat dyes on cellulosic fibres. The
quantity of levelling agent or retarding agent should not exceed 0.5 g/l,
otherwise the colour value will be poor. The addition of a levelling agent in
the dyebath may cause precipitation of certain dyes and the stability of the
dyes towards a particular agent should be checked before addition.
Remol OK is oleyl alcohol-ethylene oxide condensate and has affinity for the
leuco vat dye. It holds back the dye in the dyebath.
Dispersing agents are derived from polymers of vinylimidazole or
ethyleneimine.

The vat dyes may be applied to cellulosic fibres in each of the three forms:
1. As the leuco compound
2. As the pigment (in unreduced form)
3. As the vat acid or acid leuco compound
The leuco vat process is the oldest and most widely used. The other two
methods are becoming popular in continuous processes.
Since in the leuco vat process, the dye is vatted prior to dyeing, the
particle size of the dye is of no consequence as far as subsequent dyeing is
concerned, except that it will affect the rate of vatting.
Vatting may be carried out in:
1. Stock vat of maximum concentration
2. Stock vat of medium concentration
3. Vatting in long liquor, i.e. in the dyebath itself
In actual practice, the vat dye powder (1 kg) is pasted with Turkey Red Oil
(1 kg) and hot water (25-100 litres) is added at 50-60°C. This is followed by
the addition of necessary quantities of sodium hydroxide and sodium
hydrosulphite and allowed to stand for 10-20 minutes with occasional
stirring, when complete vatting takes place. The vatted solution may then be
added to the dyebath containing the required amounts of alkali and
hydrosulphite. In long liquor vatting process, the dye pasted with T.R. Oil is
added to the dyebath previously heated at the vatting temperature and
containing required quantities of alkali and hydrosulphite.
With the introduction of vat dyes in the form of finely dispersed particles, it
is possible to have a uniform deposition of the dye particles in a non-
substantive form either in yarn package (without the danger of filtration, as in
the case of normal powder vat dyes) or on the fabric using a padding
570
mangle. This pigmentation process is followed by vatting process. In a

modification of the process, the circulating liquor containing the unreduced
micro disperse vat dyes, the total quantities of alkali and hydrosulphite,
along with a levelling agent (if necessary) is maintained at room temperature
(30°C) and is circulated for 10-15 minutes. Because of lower temperature,
the dye is not reduced completely during the period and is uniformly
deposited on the fibre in non-substantive form. The temperature is then
raised gradually when the dye is reduced slowly and absorbed by the
material. The process is known as Semi-pigmentation process.
The vat acid process is based on the principle that when a stock vat
solution is treated with acetic acid to neutralise the alkali, in the presence of
an acid-stable dispersing agent, the vat acid, i.e. the leuco compound is
formed as an extremely fine dispersion. The vat acid has no affinity for
cellulose and it can be applied evenly throughout the material without the
complications introduced by affinity. The vat acid dispersion is much finer
than the finely dispersed pigments, hence the penetration is much higher.
Once evenly applied, it can be easily converted to substantive form by the
treatment with sodium hydroxide.
During dyeing in leuco vat process, the pH is around 13, while the pH of
the padding liquor of pigmentation process and vat acid process are 7 and
4.5-5.5 respectively.
In all the methods, the final stage consists of oxidation of the leuco
compound on the fibre to the original dye, followed by ancillary stages, such
as neutralisation of residual alkali, soaping to remove loose dyes and drying.
Batchwise Exhaust Methods
Batchwise dyeing with vat dyes may be carried out by leuco vat process,
prepigmentation process or semi-pigmentation process.
In the leuco vat process, the material to be dyed is entered into a prepared
dye liquor that contains the fully vatted dye, alkali (sodium hydroxide) and
reducing agent (hydrosulphite), together with various amounts of salt,
dispersing agent, sequestering agent and levelling agent, as required.
Theoretically, every vat dye will have its own optimum temperature and
require specific quantity of alkali and reducing agent. For simplicity,
anthraquinoid dyes are classified from application standpoint into three or
four classes, named as Method 1, 2, 3 (Ciba) or for Indanthren dyes (BASF)
as:
1. IK (K for cold or Kält in German)
2. IW (W for warm)
3. IN (N for normal)
4. INS (S for special) dyes
571
The Colour Index classified vat dyes covering three dyeing procedures,
Methods I, II and III, referring to strong alkali and weak alkali at high
temperature and weak alkali at low temperature respectively.
IK dyes – These dyes have low substantivity for cellulose. To overcome
this, they are applied at low temperature (20-25°C) with a small amount of
alkali but a large addition of salt. The manufacture of these dyes has been
discontinued by most of the dye manufacturers. Some examples of dyes
belonging to this class are Orange RK (C.I. Vat Orange 3), Pink RK,
Turquoise Blue 3GK (C.I. Vat Blue 33), etc.
IW dyes – They have moderate substantivity and require common salt for
better exhaustion. They are vatted at moderate temperature of 45-50°C.
Examples of these dyes and the colour of the respective leuco compound (in
bracket) are C.I. Vat Yellow 2 (red violet), Orange 15 (orange brown), Red
10 (olive), Violet 1 (blue), Violet 9 (blue violet), Browns 1 and 3 (orange
brown), Green 12 (dark red brown).
IN dyes – These dyes are highly substantive and may require a levelling
agent to counteract high initial strike. They are applied with an even with
larger amount of caustic soda and without common salt, at a temperature of
50-60°C. The addition of nonionic dispersing agent to the dyebath assists
levelling and penetration, but decreases the degree of exhaustion at
equilibrium. When dyeing heavy shades, therefore, the addition of
dispersing agent may be undesirable. The dispersing agent should be
added to the made-up liquor and not during vatting. Examples of these dyes
and the colour of the respective leuco compound (in bracket) are C.I. Vat
Blue 4 (greenish blue), Blue 14 (greenish blue), Green 1 (blue), Green 2
(blue), Black 8 (blue green).
INS dyes – These are highly substantive dyes. They are applied with even
larger amounts of caustic soda at a temperature of 60°C. All black dyes are
applied by this method, e.g. Novatic Black NB (C.I. Vat Green 9), Novatic
Direct Black AC (C.I. Vat Black 34). In the first case, green shade obtained
after air oxidation is converted to black by chemical oxidation, e.g. sodium
hypochlorite. With the latter shade, black shade is obtained by air oxidation
only.
The vatting and dyeing temperatures may vary from one dye to another,
irrespective of method (e.g. C.I. Vat Blue 6 belongs to IN class, but the
dyeing temperature is 50°C). The methods, however, do not differ
fundamentally and many dyes can be applied by more than one method.
When it is necessary to use two or more dyes to create a matching shade, it
is desirable, wherever possible, to choose those dyes which are applied by
same method.
The indigoid dyes require high temperature for vatting and their application
method differs somewhat from those of anthraquinoid dyes. These dyes
have poor substantivity. The material is dipped in the dyebath for
572
10-15 minutes, the excess liquor is squeezed back and the leuco compound
on the material is oxidised by exposure to air. The first dip will give a pale
shade and the sequence of operations is repeated for 2, 3, 4, 5 times until
necessary depth is obtained.
In all but a few cases, dyes should be vatted in concentrated volume at
the recommended temperature using recommended quantities of chemicals
(Table 8.9) for stock vat preparation. The required quantities and conditions
during dyeing are also reported in Table 8.9.
Total dyebath quantities, including stock vat, required in jig dyeing (M:L
ratio 1:5) and winch dyeing (M:L ratio 1:20) reported elsewhere [46] are
shown in Table 8.10. The required quantities for vatting of 1 g of any powder
vat dye is reported to be 3.15 ml caustic soda (66°Tw), 1.25 g sodium
dithionite and 50 ml water. The vatting is recommended to be done at 50°C
for 10-15 minutes.
Table 8.9 Dyeing Conditions of Various Vat Dye-classes
Methods Æ IK IW IN INS Indigoid
Vatting (quantities on the weight of dye)
Caustic soda Equal Equal Double Double Double
Sod. Dithionite Equal Equal Equal Equal Equal
Temperature, °C 45 50 60 60 70
Time, minutes 15 15 15 15 15
Dyeing (quantities in g/l)
Caustic soda 2 4 6 8 2
Sodium dithionite 4 4 4 5 4
Common salt 25 15 x x 25
Levelling agent (Lyogen V) x x 1 1 1
Temperature, °C 30 50 50-60 60 60
Time, minutes 30 30 30 30 30
Table 8.10 Dyebath Quantities, Including Stock Vat, Recommended for
Jigger and Winch Dyeing [46]
Jigger Winch
% Depth of shade Æ 1 5 1 5
Caustic soda, 66°Tw, ml /l
Method 1 (IN) 25 42 14 20
Method 2 (IW) 15 32 7.5 13
Sodium Dithionite, g/l 10 20 6 9
Common salt (Method 2 only), g/l 10 16 10 16
The recommended dosages for chemical oxidation of vat dyed goods in

various machines with varying M:L ratios are shown in Table 8.11.
573
Table 8.11 Recommended Dosages (g/l or ml/l) of Oxidising Agents for

Vat Dyed Materials
Oxidising agent Temperature, Winch Jig Circulating
°C (1:20-50) (1:3-5) (1:8-12)
H2O2 (35%) and 50-60 0.5-1 3-5 2-3
Acetic acid (80%) 0.5-1 2 1-2
K2Cr2O2 and 50-60 1 1.5-2 1-1.5
Acetic acid (80%) 2 2-6 3-4
Sodium perborate 50-60 1.5-1 3-5 2-3
Sodium hypochlorite 20 x 20 10
Yarn Dyeing
Hanks of yarn, most often made of mercerised cotton, are dyed with
levelling type of vat dyes by leuco vat method or by semi-pigmentation
method. The dyeing may be carried out in hand becks preferably provided
with a hood, by hanging wetted and squeezed hanks on bent sticks and
manually rotating the hanks. The hanks are given several quick rotations
followed by slowed periodical rotations. The hanks are then squeezed,
rinsed with 0.2-0.3 g/l sodium hydrosulphite solution, subsequently rinsed
twice with cold water and soaped. In mechanical becks, the movement of
the hanks is automatic.
In circulating machines, the yarns are on beams or in package form and
dyeing may be carried out by leuco vat process or semi-pigmentation
process. In leuco vat process, the vatted dye is added, using a filter, in two
or four portions during outside to inside flow. The direction of liquor flow is
changed every 2-3 minutes during the first 15 minutes of dyeing. Thereafter,
the flow cycle may be 6 minutes out to in and 4 minutes in to out. After 30
minutes of dyeing, the salt is added in portions and dyeing continued for a
further 15-30 minutes. The material is subsequently rinsed, oxidised and
soaped.
A much improved level dyeing is obtained by carrying out dyeing at 80°C,
especially for mercerised cotton and viscose. All additions to be made below
60°C. 2-5 g/l sodium nitrite or glucose may be added in the dyebath for
dyes, which are sensitive to over-reduction.
Semi-pigmentation method is suitable for automated package dyeing
machines. The steps are [46]:
• Caustic soda is added to the dyebath and circulated for one complete
cycle at 15-20°C. Required amount of caustic soda (66°Tw) is 15-30
ml/l for IN dyes and 10-15 ml/l for IW dyes, depending on depth.
574
• The pigment dispersion is added using a filter and circulated for one
complete cycle.
• Required amount of sodium hydrosulphite (4-8 g/l) and common salt
(8-20 g/l, IW dyes only) is added over 2-3 cycles.
• Dyeing is continued for 20 minutes at 20°C.
• The temperature is raised by 1°C/min to the dyeing temperature.
• Dyeing is carried out for 20-30 minutes for complete exhaustion and
levelling.
• Rinsed, oxidised, soaped and rinsed.
Notes:
1. All additions to be made during outside-to-inside flow.

2. Improved levelling and better penetration, particularly for deep
shades, may be obtained by raising the temperature to 75-80°C at the
final stage of dyeing.
3. For the dyes sensitive to over-reduction, 2-5 g/l glucose or sodium
nitrite is to be added.
4. For hard packages, the pigment dispersion may be added at 60°C,
heated to 80°C, cooled to 60-70°C and then dyeing is continued after
successive additions of caustic soda and sodium hydrosulphite.
Jigger Dyeing [46]
The steps to be followed are :
• The fabric is loaded evenly onto the jig in a crease-free condition, with
selvedge laid upon selvedge to avoid introducing dyeing fault caused
by premature oxidation.
• A blank dyebath is prepared with the required quantity of caustic soda
and sodium hydrosulphite at the required dyeing temperature and is
run one end to remove oxygen from the fabric.
• The reduced stock vat is added over two ends.
• Dyeing is carried out for 6-8 ends (45-60 minutes) at constant
temperature with regular checks with Vat Yellow paper, and necessary
additions are made.
• The dyebath is completely drained and the fabric is rinsed with
overflowing cold water for 2-4 ends.
• Oxidised, soaped and rinsed.
Notes:
Like circulating machines, pre-pigmentation method may be carried out in
jigger for better penetration of heavy fabrics. The bath is filled with 70% of
575
the final volume of water and heated to 80°C. The pigment dispersion is
added over 2 ends. Cold water is added and the temperature is lowered to
60°C. Caustic soda and hydrosulphite are added over two ends and the
dyeing is continued as before.
Dyeing in Winch and Jets
Vat dyes are being used increasingly to meet higher fastness requirements
on cotton knitwear. Cotton knitgoods were formerly dyed mainly in rope form
on winches, or on beams after slitting. The development has been facilitated
by the use of jet and overflow machines, in which the dyeing conditions can
be defined more precisely than in winches due to the rapid liquor circulation
and uniform temperature.
In winch and overflow machines, the best results are obtained by semi-
pigmentation method. The rate of dyeing is best controlled by the slow rate
reduction of the dyes in the cold bath. The steps are [46]:
• The bath is set with wetting agent and carboxymethylcellulose

(0.25-0.3 g/l) at 20°C and run for 10 minutes.
• The required quantity of caustic soda, previously diluted, is added.
• The pigment dispersion, previously dispersed in water is added slowly
and run for 10 minutes.
• The required quantity of sodium hydrosulphite is added over 10
minutes.
• After 10 minutes, the temperature is raised at the rate of 1°C/min to
70°C.
• Dyeing is continued at 70°C for 30-40 minutes.
• Cold rinsed, oxidised and rinsed.
The hot-pigmentation method is preferred in jet dyeing machine, where a

temperature of at least 40°C is required to obtain a sufficiently pliable fabric
for good movement. The fabric is run at 80-85°C in a bath, set with caustic
soda and the dispersion of dyes, before the addition of sodium
hydrosulphite. The method takes the advantage of superior levelling
properties of vat dyes at elevated temperature.
Semi-continuous and Continuous Processes
The most important semi-continuous process is pad-jig dyeing process. In
this process, the fabric is padded with dye and wetting agent, and batched
carefully with selvedge on selvedge, without creases. The development is
carried out over four ends with required caustic soda and hydrosulphite,
together with an addition of dye padding liquor, 10-20 ml/l. Good wetting
agent and migration inhibitor are necessary.
576
In pad-dry-jig development process, antimigrating agent is added in the

padding liquor and the fabric after padding is passed through infra-red
preheater to reduce the moisture content of the fabric to 25-30% before
drying on cylinder or hot-flue dryer. The development is carried out in a
jigger as above.
Continuous methods of dyeing are economical, particularly for dyeing of
long yardage in the same shade. Still the most important continuous dyeing
process for vat dyes is pad-dry-pad- steam method, which was developed in
s
1950 . The unreduced vat pigment is applied on fabric by padding, drying,
impregnating with reducing agent and alkali, and finally reducing and fixing
in saturated steam.
In continuous dyeing, wetting out the prepared fabric with the dye liquor is
always a particularly important operation. Depending on the construction of
the padder and on the processing speed, with an immersion length of 1-2
metres and a running speed of about 40 m/min, only 1.5-3 seconds are
available for the liquor to become uniformly distributed on the fabric. A highly
efficient, non-foaming wetting agent is necessary. The products based on a
diester of phosphoric acid perform better than the products based on
aliphatic sulphonates.
During padding and drying, the dyes may migrate giving a specked effect.
The smaller the particles, the greater the tendency to migrate. The
antimigration agents cause the particles to agglomerate, thus reducing
mobility of pigment particles and largely preventing the migration. Products
that have a cloud point cannot be recommended. Suitable products include
polymers like derivatives of polyacrylic acids, sodium alginate, branched
polysaccharides, etc. However, the agglomeration may start in the padding
liquor causing precipitation, which should be prevented. The sedimentation
will be less if the pH is reduced from 5 to 4. However, this may reduce the
efficiency of the antimigrating agent. Sedimentation is unlikely to occur when
good commercial dye-preparations are used.
The migration can also be minimised by:
1. Using a fine dispersion of the dye and a dispersing agent which

causes solvation of dye particles.
2. Using a neutral or weakly alkaline pad liquor.
3. Drying at a temperature below 75°C.
The problem of tailing is significant in case of direct and reactive dyes due
to high substantivity of those dissolved dyes. The tailing may also be found
in case of padding with insoluble vat pigments. This may happen when the
water of the pad liquor is more rapidly taken up than the dye. Due to the
above reason, initially during padding, a certain length of fabric may appear
lighter and contain much less dye than the remainder of the lot [47].
577
The use of vacuum before or during the impregnation process has also
proved advantageous in the continuous dyeing of loomstate fabric.
Intermediate drying is expensive. In order to stop migration, intermediate
drying process is to be eliminated and the dye is to be applied along with
chemicals. Sodium dithionite is unsuitable for the purpose, because the
reduction starts in the padding trough causing precipitation. Padding of
completely reduced dye is liable to cause tailing. Sulphinic acid derivatives
may be used along with nitrophenol in one bath process, when the nitro
compound inhibits reduction in the padding bath. During steaming, the
inhibitor nitro compound is first reduced to amino compound and then the
vatting of the dye starts. However, the process has not been
commercialised.
After padding with chemical liquor, the leuco dyes are fixed in the
steaming process. If the rate of vatting is adequate, a steaming time of 1
minute or even 30 seconds is sufficient. Higher steaming time may result in
lower depth of shade, due to higher penetration into the fibre. The steaming
may also be carried out in small units. There should be sufficient moisture
on the material in the steamer. After steaming, the fabric is rinsed, oxidised
(with hydrogen peroxide at pH around 7-8) and soaped in a series of wash
becks.
The wet-in-wet method is of great practical importance nowadays. The
dye is applied to the fabric with minimum liquor pick-up and the material is
dipped into the chemical liquor without intermediate drying. This is followed
by squeezing to retain 120-150% of liquor and steaming. The method is now
being successfully applied for pad-cold batch method as in the case of
reactive dyes. The fabric may be padded with vat dye along with sodium
dithionite and batched at room temperature for 2-4 hours. For good results,
adequate pick-up of chemical and efficient covering of the roll of fabric with
plastic sheet to exclude atmospheric oxygen are necessary. There is a
growing interest in this process, particularly with polyester-cotton blends
previously dyed by pad-bake process.
Another continuous method of applying vat dyes is to pad the fabric with
vat dye, dry and then pass the fabric through a continuous washer
containing hot solution of sodium dithionite, caustic soda and an accelerator
for about 10 seconds, when the dye is exhausted into the fabric. This rapid
fixation method dispenses with steaming. The method is suitable for dyeing
in pale and medium shades with all vat dyes except the important
indanthrone derivatives.
Pad-Dry-Chemical Pad-Steam Process [46]
The fabric must be prepared in a way that it will have uniform high
absorbency and ordinarily it is not necessary to add wetting agent and
antimigrant in the padding liquor. However, if the running speed is high
578
(60 m/min) and the wettability of the fabric is not assured, it is advantageous
to add the above two chemicals. The dyes suitable for the pad-steam
process should have:
• Fine particle size and dispersion.

• High speed of reduction.
• Good leuco solubility in low liquor during steaming.
• High reduction potential so that they are readily oxidised after
steaming.
• Minimum sensitivity to variations in soaping.
The padding trough should be small enough so that it can be quickly

replenished. The mangle rollers should be of 65-70° Shore hardness,
capable of giving a controlled liquor pick-up of 60-100% on the weight of
material. The material should be fully dry and no water drop should fall on it
before or after padding.
The drying may be carried out in hot flue dryer or cylinder dryer. In the
latter case, a pre-drying with infrared heater is preferable.
The dried material is to be cooled before chemical padding. The bleed-off
may be prevented by adding 25-30 g/l common salt or 10-30 g/l dye padding
liquor into the chemical padding liquor. For 100% liquor pick-up, the required
quantities of caustic soda and hydrosulphite are 14-48 g/l and 22-80 g/l
respectively, the lowest quantities are for 1% depth and the highest
quantities are for 5% depth. The preferred ratio of caustic soda and
hydrosulphite is 0.6: 1.0. Glucose or sodium nitrite may be added to prevent
over-reduction.
The fabric, after chemical padding, should be immediately steamed for 30-
40 seconds at 102-104°C in air-free condition.
For medium to lightweight fabric, wet on wet, pad-steam process without
intermediate drying may be carried out.
8.5.7 Stripping of Vat Dyes

Faulty dyeing can be corrected by levelling, stripping or over-dyeing.
Levelling can be carried out on winch or jig at 80-90°C, or even above boil in
package-dyeing machines.
It is not easy to remove the colour from vat-dyed materials. By using
reducing agents only, stripping is not possible as the leuco compound
formed is quickly reabsorbed. The stripping from the dyed goods either
partially or to a pale ground shade suitable for redyeing, may be carried out
by using a levelling agent such as Dispersol VL or Matexil DN-VL, 2-5 g/l, or
polyvinylpyrrolidone (Albigen A, BASF) in blank reducing bath containing
caustic soda and hydrosulphite. The latter chemical has a particularly strong
579
action; several successive baths containing this agent at a concentration of

1-2 g/l are preferred over single bath treatment with stronger solution,
because in the latter case redeposition of precipitated dye on the goods may
occur. Complete stripping is possible using Lissolamine V (ICI) in the
caustic soda-hydrosulphite bath. The stripping may be done by treating the
dyed material with 3-5% Lissolamine V, 4-5% caustic soda flakes and 6%
sodium hydrosulphite (all o.w.m.) at a M:L ratio of 1:5 at 85-90ºC for 30-45
minutes. This is followed by cold rinsing, mild bleaching, rinsing and soaping
at boil. Lissolamine V may be added to the bleaching bath to hasten
bleaching.
8.5.8 Denim Processing

Jeans made from blue denim have been popular over a longer period than
any other item of apparel. They are inexpensive, durable, and versatile. The
blue-dyed warps wash down to an attractive blue without staining the white
weft.
Leuco indigo has poor substantivity for cellulose. Hence, only pale depths
are obtainable by exhaust dyeing procedures. Indigo is applied by a series
of dips, with intermediate squeezing and atmospheric oxidation. By
repeating the process, dye is applied to the substrate layer by layer to give
deep dyeing with a relatively low rubbing fastness. Denim cloths (dyed warp,
natural white weft) are dyed in the form of warp sheets or ball warps, usually
continuously. The batchwise dyeing of indigo is of little importance. The
batchwise dyeing of hanks of yarn may be carried out in becks with repeated
short dips, followed by squeezing and atmospheric oxidation. Wound
packages cannot be dyed in full depth with indigo.
In the continuous indigo dyeing of warp yarn, the yarn is in the form of a
full-width warp beam or in ball form, containing 300-400 individual threads. It
passes through several (5-6) vats, each followed by an air passage for
oxidation. The processing speed is 20-30 m/min with an immersion time of
20-30 seconds in each vat. On leaving the vat, the material is squeezed to a
liquor pick-up of approximately 100%, after which the dyeing requires
around 2 minutes for oxidation before it passes into the next vat. Rinsing at
ambient temperature in two or three rinsing baths after oxidation is normally
adequate. The dip tanks are coupled to keep the dyebath composition
exactly same. A good volume of flow with minimum turbulence is essential
to ensure uniformity.
In sheet form, warp sheet from warp beam is scoured, washed, cylinder
dried, sized and dried by passing continuously through a large number of
boxes with intermediate airing. In rope dyeing, 16-40 ropes, each consisting
of 300-450 ends are made by ball warping, dyed in rope form followed by
opening of rope (re-beaming) and sizing.
580
The stock vat is prepared by mixing indigo dye with 0.7-0.8 times caustic
soda (solid) and 0.8-0.9 times sodium hydrosulphite. The vatting is done at
60-65°C for 15-30 minutes.
A typical recipe for dye-liquor would be as follows [7]:
1. Caustic soda (27% by weight), 5 ml/l.
2. Sodium hydrosulphite, 1.5 g/l.
3. Stock vat, 62.5 ml/l.
The stock vat is composed of the following:

1. Indigo Pure (BASF, C.I. Vat Blue 1), 80 g/l.
2. Dispersing agent (Setamol WS), 4 g/l.
3. Wetting agent, 1 g/l.
4. Caustic soda (27% by weight), 130 ml/l.
5. Sodium hydrosulphite, 60 g/l.
Sequestering agent (2 g/l sodium hexametaphosphate) and antifoaming

agent may be added.
The content of caustic soda and hydrosulphite must be checked at regular
intervals to determine what quantities are necessary. The hydrose dosing
may be done by controlling mV of the solution. The pH is kept near about
11.
Careful buffering of the dyebath pH can be an effective means of
conserving indigo and achieving more reproducible dyeing. Depending on
dyebath pH, reduced indigo can exist in three forms: as nonionic enolic acid
leuco compound, the mono-enolate anion or bis-enolate anion. Mono-
enolate moiety is much more soluble than the acid leuco form and more
substantive than doubly charged bis-enolate. Its amount reaches a
maximum at pH 10.5-11.5 and the colour yield correlates closely with its
fractional amount.
The indigo dye remains mostly at the surface, hence the dyeing process
may be called ring dyeing. Such ring-dyed materials are subjected to
treatment with stone or enzymes, which remove dyes randomly from
portions of the fabric exposing white surface. This popular style is utilised in
faded jeans. Microscopy reveals that for indigo dyeing, the cross-section of
the resulting dyed cotton yarn depends on the pH of the bath. When the pH
of the dyebath is decreased from 13 to 11, the denim yarn progressively
becomes more ring-dyed. Associated with the increasing ring dyeing, more
colour yield is obtained making the wash-down process easier. The highest
colour yield was observed within the pH range of 10.8 to 11.2 [48].
Stone washing of denim jeans generally consists of 5 steps: desizing,
bioabrasion, backwash, additional bleaching, finishing.
When indigo is released to the wash liquor during washing, the solution
turns dark blue. Some of the indigo redeposits on the white part of the fabric
581
− the phenomenon is called back-staining. During the short desizing step,

over 30% of total extractable indigo dye is released in the bath. When a
short M:L ratio is used (below 1:6), more backstaining will occur. The
desizing is, therefore, carried out in the presence of an effective dispersing
agent.
In the early years, the surface dyes of denim fabrics were removed by
abrasion with stones. Investigation showed that on treatment with cellulase
enzymes, cellulose is hydrolysed and is removed along with dye from the
surface while the inner portions remain intact. With cellulases, less stones
are required and less damage occurs to the machinery and the garments.
They yield a soft and worn look. Sandoz (presently Clariant) offer different
cellulase preparations, namely:
1. Bactosol CA liq., an acid liq. cellulase with optimum pH 5 and
temperature 60°C, gives high bio-abrasion and high back-staining.
2. Bactosol JN liq. and pwd., a neutral cellulase with optimum pH 6-7
and temperature 60°C, gives high bio-abrasion and very low back-
staining.
3. Bactosol JA Gran., a modified acid granulated buffered cellulase with
an optimum pH 5.5 and temperature 45-50°C, gives very high bio-
abrasion and extremely low back-staining.
In the bio-abrasion step, both mechanical and working conditions have to

be optimised. Depending on the type of cellulase, the water has to be
preheated to the working temperature and pH adjusted to its optimum before
the addition of the enzyme. The dosage of the enzyme depends on the used
product, the level of abrasion, the stones ratio and the process time.
The type of machine also affects the abrasion effect. Generally, a bigger
drum diameter is giving more abrasion since the garment falling is higher.
The rotation of the drum also influences the mechanical action. A high
speed will lead to a centrifugation effect causing reduced abrasion. On the
other hand, a very slow speed will cause further streaks problems with poor
abrasion effect. A speed of 20 to 30 rpm is generally effective.
The mechanical action is optimised by adding the right amount of garment
and minimum volume of water allowing best abrasion and avoiding streaks.
The right machine load depends mainly on the structure and weight of
denim garment and also the type of washer used.
For getting an attractive abrasion look, stones or pumice stones are still
required and combined with cellulases. The ratio of stone is expressed in
percentage of the garment weight. Stone ratios between 50% and 150% are
commonly used. When stones are used, the dosage of enzyme may be
reduced to half.
The standard conditions for the bioabrasion may be as follows:
Bactosol JN powder: 0.6-2% on the weight of material
582
Dispersing agent (Sandoclear IDS liq.): 0.2-2%

PH: 6.5-7
M:L ratio: 1:10-1:3
Temperature: 55-60° C
Time: 40-90 minutes.
8.5.9 Photo-degradation
Several vat dyes, mostly in the yellow and orange colour range, can cause
accelerated oxidation of cellulosic materials under the influence of light. A
few such vat dyes are:
C.I. Vat Yellows 2, 4 and 26
C.I. Vat Oranges 2 and 9
The same dyes can cause accelerated tendering during hypochlorite
bleaching, when the dyed goods have been exposed to light.
It is also known for a long time that when certain light-fast blue and yellow
dyes were dyed in combination, the blue component in the resultant shade
faded rapidly than it would be anticipated. This is apparent only when the
proportion of yellow dye in the recipe exceeds a certain minimum value.
There are, at present, two concepts of the mechanism of photosensitised
degradation of fibres. According to the first mechanism, the dyes are
converted into an excited state by light, and in this form they withdraw
hydrogen or electrons from the fibre and are reduced at the same time. The
fibres thus undergo irreversible oxidative tendering, while the leuco dye is
reoxidised by atmospheric oxygen. An anthraquinone molecule in the
excited state (A*) involving an ηπ* transition is formed. The excited molecule
abstracts hydrogen from the cellulose to give anthydroquinone (AH•) (8.18).
The AH• reacts with oxygen derived directly or indirectly from the air to
hν
Cell + A → Cell + A*
(8.19) ↑ H2O + O2 ↓ (8.18)
Cell radical + AH2 ← AH• + Cell radical
regenerate the anthraquinone (8.19). The number of dyes showing this

property is limited because only those activated by visible light exhibit this
particular property.
According to the second theory, the dye forms a highly active singlet oxygen
from normal oxygen; that is responsible for tendering of fibres.
583
8.6 SOLUBILISED VAT DYES

The vat leuco ester dyes have retained their importance for certain qualities.
They are used for pale shades on cotton and polyester/cotton blends,
particularly when a high standard of fastness is required. Although their use
is not expected to grow in the future, it is neither expected to fall [42]
Vatting is a troublesome operation requiring strict care and there has
always been a strong incentive to find some way of simplifying the
application. In 1921, Bader and Sunder prepared the disulphuric ester of
leuco indigo by reacting its solution in pyridine with chlorosulphonic acid.
The sodium salt of the compound is made by reacting it with the appropriate
quantity of sodium hydroxide. The salt, commercially known as indigosol or
solubilised vat dyes, is stable, water-soluble, substantive to cellulose (and
more to wool) and can be oxidised to insoluble Indigotin (indigo blue). Many
of the indigoid vat dyes are possible to be converted into their solubilised
form. some anthraquinoid vat dyes can also solubilised, such as solubilised
Indanthrone. Later a simpler route of manufacture was discovered. The
sulphuric ester can be formed as a metal complex by the action of fuming
sulphuric acid on the oxidised vat pigment in the presence of pyridine. The
complex is finally converted into the sodium salt by the action of sodium
hydroxide.
Solubilised vat dyes are available as white or faintly coloured powder. The
actual colour, which is quite different from the colour of powder, appears
only after the development under acidic oxidising conditions. These dyes
dissolve in water to give colourless or pale coloured solution.
Their application is comparatively simple. Cellulosic fibres are dyed in
neutral dye liquor and slightly acid baths are used for protein fibres. They
exhaust well at 20 to 40°C, although there are some dyes requiring
temperature ranging from 60 to 80°C. Their substantivity to cellulose is
much less than that of the corresponding sodium salt of leuco vat dye and
high percentages of electrolyte are often necessary. The good levelling and
penetrating quality of these dyes even in light shades on tightly twisted yarn
and tightly knitted cotton fabric is attributed to their moderate affinity and
slow exhaustion. When the dyed material is passed through a solution
containing sulphuric acid and sodium nitrite or potassium dichromate at
50−70°C, the dye is hydrolysed and oxidised to original vat dye, which being
insoluble in water, is immediately precipitated inside the fibre (8.20).
584
OSO3Na OH O
Acid hydrolysis [O]
(8.20)
OSO3Na OH O
For the oxidative development, the use of hydrogen peroxide along with
ammonium vanadate, persulphates, nitric acid is reported [42], the last
process is claimed to produce much better light fastness. For polyamide
fibres, chemical oxidation may be replaced with a heat-treatment at 200°C
using acid-liberating salts.
Trade names of some solubilised vat dyes are Solatic (ICI, now Zeneca),
Indigosol, Soledon, Sandozol (Clariant), Anthrasol (Hoechst), etc.
The main use for solubilised vat dyes is in producing pale shades with
excellent light fastness on cotton, mercerised cotton, linen and viscose
goods. However, high cost and limited depth of colour that can be achieved
(pale shades only) set limits to their usefulness. The present trend towards
continuous dyeing has given further impetus to the use of this class of dyes.
Pale shades on cellulosic fibres and pale to medium shades on polyester-
cellulosic blends can be produced by continuous dyeing methods. After
invention of reactive dyes, they have now lost their former importance in
textile printing.
The storage stability of these dyes is good and varies with dyes. If
oxidation occurs by the action of light or acidic fumes from the atmosphere,
local decomposition, with the formation of the insoluble vat dyes, starts.
Simultaneously a small quantity of sulphuric acid is liberated, which again
decomposes the adjoining dye particles. The process continues until the
entire amount is oxidised. This auto-degradation of the solubilised vat dyes
can be prevented by standardising these dyes with alkaline salts.
These dyes are very sensitive to light and are to be protected from the
exposure of light. The pronounced sensitivity to light of some solubilised vat
dyes, such as C.I. Solubilised Vat Red 1. Brown 5 and Black 6, can be used
for photo-printing. The fabric is padded with the dye and dried in dark. It is
then exposed to an intense light source putting a photographic negative in
the path. In the exposed portion, the insoluble vat dye is regenerated, while
in the unexposed areas the dye is still water soluble and can be washed
away.
The solubilised vat dyes differ in their solubility in water. Many of them are
readily soluble in hot water at 50°-60°C. Some of them such as Indigosol
Brill. Violet I4R, Green IGG and Olive Green IB are to be dissolved in water
containing 1 g/l soda ash. Generally, 5% solution (50 g/l) can be safely
prepared.
585

Since obnoxious nitrous fumes are evolved when sodium nitrite is added to
sulphuric acid, especially at high temperature, an alternate widely used
procedure is to add sodium nitrite in the dyebath itself and then develop the
shade in hot dilute sulphuric acid. The general method of application is to
dissolve the dye in warm, but not boiling water, and add it to the dye liquor
through a strainer, together with the required amount of electrolyte. The
composition of the dyebath is as follows:
Dissolved solubilsed vat dye − x g/l
Soda ash − 0.5 g/l
Common salt − 10-40 g/l
Sodium nitrite − 2.5-5 g/l
With C.I. Solubilised Vat Violet 1, the quantity of common salt should not
exceed 10 parts per 1,000 parts liquor since there is a chance of
precipitation of the dye.
Perfectly neutralised goods are entered in the bath and the temperature is
raised to 40-50°C, or at the temperature of maximum substantivity for the
particular dye (20-80°C), and the dyeing is continued for 30-40 minutes. The
goods are then hydroextracted and transferred immediately to fresh liquor
containing 10 parts sulphuric acid (168ºTw) per 1,000 parts water at 40ºC.
When the solubilised vat dye has low affinity for the fibre, the impregnated
material should be dried before development. As with conventional vat dyes,
the final treatment consists of soaping at boil for 10-15 minutes with a
solution containing 0.1% of soap or detergent and 0.1% soda ash.
Solubilised vat dyes behave towards wool as acid dyes. The rate of
exhaustion is increased by the addition of acid to the dyebath and they are
fixed to the protein fibres by chemical bonds. They are difficult to oxidise on
protein fibres and the oxidation is usually carried out in an acidified solution
of sodium dichromate.
The most important sequence for continuous dyeing of cellulosic fabrics is
pad, sky, and pad with nitrite-sulphuric acid, sky, wash. Some variations
reported in patents such as one bath dyeing in the presence of nitrite and
ammonium sulphate at 100-130°C, pad-bake development in the absence of
acid-forming compound, development by dry-heat in the presence of sodium
metavanadate, etc.
A number of continuous dyeing methods for polyester-cellulosic blends
have been reported. In one method, the dyes are applied by padding
together with an acid or a catalyst and this is followed by drying and baking
at 210°C, without the need for the addition of sodium nitrite. In another
method, the ester is split by treatment with relatively strong alkaline solution
for a few seconds at about 100°C or for some hours at room temperature
586
after intermediate drying. The dye is fixed, as with leuco dyes, by oxidation,
e.g. peroxide and then soaped.
8.7 SULPHUR DYES
The first sulphur dye appeared before direct dyes, but it was not until the
development of the sulphur blacks that this class of dyes made a major
impact on cotton dyeing. Sulphur dyes now constitute the largest class of
dyes in terms of quantity with an estimated worldwide production of more
than 80,000 tons per annum, even though a different picture emerges if the
calculations are made on the basis of price [7]. They are the most economic
dye class, yet for most of them the chemical structures are unknown. They
are normally distinguished in terms of the organic intermediates from which
they are derived and the process of sulphurisation used in their
manufacture. The characteristic feature of the dyes of this class is that they
all contain sulphur linkages within the molecules. There is no black dye for
cellulose, which can compare with the attractive shade and depth possible
with C.I. Sulphur Black 1. It is one of the most widely used dyes in the
world.
Sulphur dyes are important for black, navy, brown, olive and green colours
in medium to heavy depths. The liquid brands are ideally suited for
continuous dyeing in long runs.
Sulphur dyes are used widely on cellulosic fibres and their blends,
especially with polyester, and also with nylon and acrylic. Cotton and
polyester-cotton drill and corduroy are dyed continuously or on the jig, whilst
cotton-nylon and cotton-acrylic knitted and pile fabrics are winch- and jet-
dyed. Since 1985, sulphur black finds increasing use on denim [7].
8.7.1 Manufacture and Structure

s
In the 1860 , chemists observed that colorants are formed when certain
organic nitro compounds are reacted with alkaline sulphides. Nevertheless,
the first commercial brown sulphur was made by Croissant and Bretonniere
in 1873 by heating saw dust and bran with alkaline sulphides, the active
component being lignin. C.I. Sulphur Brown 1 is still manufactured from
lignin sulphonates obtained as a by-product from sulphite bleaching of wood
pulp for papermaking. Many of the sulphur dyes used today are made from
well-defined chemical intermediates and a full range is available covering all
hues except a true red.
The two ways of manufacturing are:
1. Baking the organic material or intermediates with sulphur with or

without sodium sulphide (Na2S). Many yellow, orange and brown
587
sulphur dyes are made by dry baking of intermediates such as 2,4-

diaminotoluene with sulphur above 160°C.
2. Boiling the intermediates with sodium polysulphides, in aqueous or
alcoholic solvents, under reflux conditions. The aqueous reflux method
is used for the production of sulphur blacks, blue-green and violet
dyes from indophenols or more stable leuco indophenol (8-44).
Indamines (8-45) on thionation produce reddish brown to bordeaux
dyes.
N N
O NH2 O
(8-44) (8-45)
The products resulting from thionation processes are varied and complex
mixtures, the common features being essentially benzenoid nuclei linked by
heterocyclic rings such as thiazole, thiazine or phenazine, as well as the
disulphide linkages that enable the dyes to be reduced to the soluble leuco
form [7].
Some knowledge of the structure of the very complex molecules of
sulphur dyes is being accumulated gradually. For example, when sulphur is
heated with p-toluidine, one of the reactions taking place is the formation of
dehydrothiotoluidine (8-46). This repeatedly reacts with more and more
toluidine to form a complex molecule. C.I. Sulphur Yellow 4 and C.I. Sulphur
Orange 1 have similar polythiazole structures with –S-S− bond with benzene
rings.
Some of the sulphur dyes are assumed to be composed of several units of
thiazone (8-47) links together by sulphur atoms. In the past it was assumed
that these linked are invariably disulphide bonds, which are reduced to
mercaptans (R.SH). However, now it is assumed that single sulphur bonds
(−S−) between benzene rings also exist which provide substantivity to
cellulose and survive reduction with sodium sulphide.
N
H3C N
C NH
S S O
(8-46) (8-47)
The classification of sulphur dyes in the Colour Index has become
somewhat confusing owing to frequent deletions and additions, although the
subdivisions are still clear. The four subdivisions are:
588
1. C.I. Sulphur dyes

2. C.I. Leuco Sulphur dyes
3. C.I. Solubilised Sulphur dyes
4. C.I. Condensed Sulphur dyes
Sulphur dye may be defined as a water-insoluble dye, containing sulphur

both as integral part of chromophore and in attached polysulphide chains,
normally applied in alkaline reduced liquor and subsequently oxidised to the
insoluble form on the fibre.
A leuco sulphur dye has the same C.I. constitution number as the parent
sulphur dye, but is a powder or liquid brand containing the soluble leuco
form of the parent dye and the reducing agent.
A solubilised sulphur dye has a different constitution number because it is
the thiosulphuric acid derivative of the parent dye. This non-substantive form
is converted to substantive alkali-soluble thiol during dyeing.
The condensed sulphur dyes are sodium S-alkyl- or S-arylthiosulphates.
Although they contain sulphur, their constitution, methods of manufacture
and application are different.
8.7.2 General Property

Sulphur dyes can be detected by the evolution of hydrogen sulphide gas
when treated with reducing agents. A little of the dye or dyed material is
heated in a test tube, together with little stannous chlorine and hydrochloric
acid, the evolved gas turns a lead acetate-soaked filter paper black,
indicating the presence of sulphur.
Like vat dyes, these dyes are intrinsically insoluble, but they dissolve in a
solution of alkaline reducing agents such as sodium sulphide and become
substantive to cellulose. Once inside the textile materials, they are
converted back to original pigment form by oxidation. Sulphur dyes differ
from vat dyes in being easier to reduce, but more difficult to reoxidise,
different oxidising agents produce variations in hue and fastness properties.
In its simplest possible form, the functional structure of a sulphur dye can
be represented by the formula, D-S-S-D, where D stands for chromophore
or colour-bearing group. The bond formed by two sulphur atoms is known as
disulphide linkage. The two chromophores linked together hint that the
molecule is very large and solubilising groups are absent. When alkaline
reducing agents are added to the insoluble sulphur dyes, the disulphide link
splits into two, forming two leuco anions each accompanied by a sodium
cation, known as mercaptides (or thiolates) (D-S−Na ) and are soluble in
+
water. By addition of acid, the water-soluble sodium salt of the leuco-sulphur

dye can be converted into insoluble acid-leuco form (D-SH) or by acid
oxidation into original pigment form.
589
– +
D-S-S-D ↔ D-S Na ↔ D-SH (8.21)
Unlike vat dyes, reduction causes breaking apart of the sulphur dye
molecule, whereas all the peripheral changes in vat dye molecules leave the
main molecule intact. Again the broken molecule may be further reducible
and depending on the choice of the reducing agent, over-reduction may
result in irreversible changes.
If there are two or more mercaptide groups on the leuco-sulphur dye
anion, oxidation will result in a polymeric or a cross-linked pigment molecule
rather than the simple molecule D-S-S-D. Such products will not crystallise
on soaping. The pendant mercaptan group may not find an adjacent group
to form disulphide link and may remain reactive.
Finally, sulphur dye may form chains of up to about six sulphur atoms in a
row. The linkages may be simply considered as disulphides and a general
– +
formula for the reduced sulphur dye may be written as D-(SnS )m⋅mNa ,
where D is the chromophore, n is zero to five and m is greater than or equal
to one.
The sulphur dyes are cheap and easy to apply. Their wet fastness is good
based on soap, but are less resistant to laundering with detergents and
perborate, particularly above 50°C. The light fastness is satisfactory (in
general between 3 and 4, some even 6-7, e.g. black). Some yellows (e.g.
C.I. Sulphur Yellow 2) have only poor light fastness (rated as 2). The sulphur
dyes all have poor fastness to chlorine. The fastness to rubbing is very
much dependent on the fabric itself, its preparation and the dyeing process,
especially the efficiency of rinsing before oxidation.
In their reduced state, their dyeing properties resemble in many respects
those of direct dyes. They exhaust better in the presence of electrolytes and
vary considerably with the dyeing temperature. They are decomposed by
acids. The use of metal vessels, other than stainless steel, can be
dangerous, as insoluble blackish sulphides formed will stain the goods. The
presence of copper may be harmful.
8.7.3 Reducing Agents

World-wide sulphur dyes are sold in a variety of forms, which include
powders, dispersed powders, dispersed pastes, prereduced liquids and the
liquid or powder forms of solubilised sulphur dyes which have been
chemically converted to the sodium salts of thiosulphonic acids. These
products contain varying amounts and types of alkali and reducing agents.
Sodium sulphide (Na2S), sodium hydrosulphide (NaHS) and sodium
polysulphide (Na2Sx, where x may be one to six) are used as reducing
agents. The first two compounds are available in a variety of strengths, both
in solid and liquid form. In water, sodium sulphide is almost completely
hydrolysed to sodium hydrosulphide and sodium hydroxide:
590
Na2S + H2O ↔ NaHS + NaOH (8.22)

Sodium sulphide solutions have pH values only about 0.1-0.2 units lower
than solutions of the equivalent amount of sodium hydroxide, which means
that the reaction goes about 70% to the right side of the eqn. (8.22).
Sodium sulphide has the remarkable ability to react with up to twice its
weight of sulphur, to give mixtures of sodium polysulphides with the general
formula, Na2Sx, where x may be one to six and is an average value for a
2– 2– 2– 2– 2–
particular product. In solution all possible Sx ions (S , S2 , S3 … S6 )
are in equilibrium not only with one another, but with sodium hydrosulphide
as well. As the average value of x increases, the amount of hydrosulphide
and its accompanying caustic soda are both diminished, resulting in a lower
pH.
Caustic soda and sodium dithionite or hydrosulphite are used for reduction
of vat dyes. However, this combination gives mixed and unreliable results
with sulphur dyes as a whole. This is probably because the chromophores
present in sulphur dyes are sensitive to over-reduction at the high reduction
potentials delivered by this more powerful reducing system. Sulphurised vat
dyes (e.g. C.I. Vat Blue 43, Hydron Blue R) and C.I. Vat Black 11) are
usually sold as pastes and in their reduction behaviour they resemble vat
dyes closely. For them caustic-hydrosulphite combination works well, but not
the sulphides. For most of the sulphur liquid blues, navies, browns and
blacks, the colour yield is considerably diminished by caustic-hydrosulphite.
Glucose in the presence of alkali, usually caustic soda or a mixture of
caustic soda and soda ash, may be used as reducing agent. It is activated at
high temperature of 90-95°C and it has met some success in the application
of sulphur dyes.
Sodium polysulphide is widely used as an antioxidant in dyebaths reduced
with sodium sulphide, hydrosulphide or glucose. It inhibits premature
oxidation of the sulphide reducing agent, thereby promoting better dyebath
stability, especially under adverse dyeing conditions. This lessens the risk of
bronzing, poor rubbing fastness and dark selvedges.
The substantivity of reduced sulphur dyes is high partly because of the
high concentration of salts in the reducing bath. The substantivity varies
from dye to dye. Like other anionic dyes, addition of common salt or
Glauber’s salt increases the substantivity of sulphur dye for cellulosic fibres.
Major sulphur dye manufacturers have introduced products with
considerably reduced sulphides to be applied using a proprietary reducing
agent. These reducing agents not only minimises the use of sulphides, but
are also not very effective to cold, thus ensuring that highly substantive
anionic leuco-vat will be generated gradually in batch dyeing, as the dyebath
temperature is raised, thereby assuring level dyeing.
591
Whenever the exhaust baths of sulphur dyed materials are run to drain,
they will contain sulphides, which in presence of acids alone, produce
hydrogen sulphide gas smelling like rotten eggs at extremely low
concentrations in the air. The gas at high concentration is harmful to health.
+ +
Na2S + 2H ↔ H2S ↑ + 2Na (8.23)
In large dyeing plants, the reducing effluents from the earlier stages of
dyeing are at least partially neutralised by combination with the oxidising
effluents from the later stages of the same dyeing cycle. Both are held in the
treatment ponds, hopefully under controlled pH conditions, while aeration
2– 2–
can take care of oxidising the sulphides (S ) to thiosulphates (S2O3 ) and
2–
sulphates (SO4 ), as below:
2Na2S + 2O2 + H2O → Na2S2O3 + 2NaOH (8.24)
Na2S2O3 + 2NaOH + 2O2 → 2Na2SO4 + H2O (8.25)
8.7.4 Oxidising Agents

Thorough rinsing before oxidation is essential with sulphur dyes if good
fastness to rubbing is to be obtained. It is important that all loose colour
should be removed before the acidic oxidation stage, which precipitates any
unfixed dye on the surface of the fabric or yarn, giving a bronzy dyeing with
low fastness to wet rubbing.
Though both vat and sulphur dyes are dissolved by reducing and oxidised
after dyeing for insolubilisation, the reducing agents used for vat dyes are
very powerful and are unsuitable for sulphur dyes. A similar situation is
duplicated in the choice of oxidants for sulphur dyes.
Worldwide standard oxidant for sulphur dyes has long been sodium
dichromate, known simply as chrome and acetic acid. It oxidises all reduced
sulphur dyes rapidly and completely. For batchwise methods, treatment in
0.25-1.0 g/l sodium dichromate and 0.8-1.2g/l for 15-20 minutes at 60°C is
usually recommended. For continuous dyeing, the recommended quantities
are 5 g/l and 6 g/l acetic acid respectively and dwell time is 20-40 seconds
at 60-70°C. For optimal oxidation, it is essential to maintain pH 4.5-5.5.
However, the presence of heavy metal salts like chrome in effluent has long
been recognised as environmentally undesirable.
The economical per-compounds (e.g. H2O2) are widely used for oxidation
of vat dyes. The use of 1 ml/l hydrogen peroxide (35%) or 1 g/l sodium
perborate at pH 9 and 40°C for 10-20 minutes to give a brighter colour,
especially with sulphur blues, is well-known. However, these compounds
barely oxidise the sulphur red-browns and may over-oxidise sulphur blues.
The over-oxidation may be due to attack on the disulphide linkage to form
592
water solubilising sulphinate and sulphonate groups (8.26) and increases

staining of adjacent fabrics by one point in the Grey Scale.
– –
D-S-S-D → D-SO2 → D-SO3 (8-26)
[O] [O]
Where [O] stands for the per-oxidising species.
When used for sulphur blacks, the result is a bluer, lighter shade with
poorer wet fastness.
In the USA, formulations containing sodium bromate (Na2BrO3) have
ousted most of the other alternative oxidants. The formulations require a
small amount of sodium metavanadate as an oxidation catalyst, as sulphur
red-browns are not properly oxidised by bromate alone. Sodium nitrite is
also included in formulated product to minimise the corrosion of the stainless
steel. The required quantity of bromate oxidant, e.g. Dyetone (Olin) is 1-2 g/l
for batch processing and 5-10 g/l for continuous processing at 60°C. Acetic
acid is added to maintain pH at 4-4.5.
Potassium iodate was the very first acceptable replacement for chrome
and acid. However, iodine compounds are expensive and create problems
of corrosion and pollution.
Hypochlorites and the related chloramines can do the job, but are hard to
control. Sodium chlorite is the active constituent in several proprietary
oxidants, e.g. Oxidurit SK (CAS), Protegal OD (Protex) or Rewin SW (CHT),
the oxidation being carried out at alkaline pH (with soda ash) at
temperatures close to boil. These formulations also include a stabiliser, a
sequestering agent and a detergent. It is claimed that EDTA is essential to
give the fully oxidised hue with optimum yield and levelness. The wet
fastness and handle is good, but it cannot oxidise red-browns. A typical
oxidation treatment at 90-95°C requires 2-3 and 5-10 g/l Protegal OD and 5
and 5-10 g/l soda ash for 15-20 and 1-2 minutes for batchwise and
continuous process respectively.
For practical purposes, there is no suitable alternative for bromate oxidant.
A study [49] showed that the best results with regard to stabilisation of hue
were achieved using hydrogen peroxide or N-chloro-p-toluenesulphonamide
(Chloramine T), the latter may be applied at a concentration of 2 g/l for 10
minutes at 40°C.
Sodium m-nitrobenzene sulphonate (Ludigol, BASF), the alternate vat dye
oxidant, may be effective, but has not attracted much interest. It is claimed
to give complete oxidation on jet machines and winches, typical amount
being 2-4 g/l in the presence of 2 g/l soda ash at pH 9.5-10.5 and 40°C for
20 minutes.
593
8.7.5 Other Auxiliaries

Alkylating agents based on epichlorohydrin give dyeing of markedly
improved fastness to severe washing treatments that use
detergent/perborate formulations. Leuco sulphur dyes, when treated with an
alkylating agent, the thiolate ion loses its electron and may be called
oxidised. Thus, conventional oxidation may be avoided.
– –
D-S + X-R → D-S-R + X (8.27)
−
Where D-S is the reduced dye anion, X-R is the alkylated agent. If the
organic group, R has a sufficiently high molecular weight or if it can cross-
link with two or more groups by having multiple leaving groups, then the
alkylated product can have extremely good fastness to washing. However,
the chromophoric part requires conventional oxidation to develop its true
colour, as in the case of C.I. Sulphur Blue 7. Alkylation may also impair light
fastness. Considering costs and benefits, alkylating agents are not being
widely accepted.
Like other dye-classes, sulphur dyes are affected by hardness of water.
++ ++ +++
The insoluble salts formed by reaction of Ca , Mg , Fe ions with dye are
filtered out at the fibre surface and can result in poor crock fastness or
resistance to rubbing. Careful use of EDTA is recommended to tackle this
problem.
For dyes of high substantivity, it is important that the dye liquor wets out
the materials rapidly and completely. Anionic surface active agents, such as
salts of phosphated ethylhexanol, can be used. However, they are to be
carefully selected as some of them interact with sulphur dye thiolates to form
stable, soluble complexes with virtually no substantivity.
Bronziness, a surface appearance resembling a metallic lustre, is a
characteristic of poorly sulphur-dyed heavy navy, blue or black shades.
Polysulphides added in the dyebath improves the stability of reduced
dyebath towards premature oxidation. Good rinsing prior to oxidation
ensures the absence of a high surface concentration of sulphur dye.
Soaping after oxidation removes surface loose colours. No crystallisation of
sulphur pigment particles within the fibre occurs during soaping as in case of
vat dyes.
Sulphur dyes, as a class, have adequate solubility in the reduced form.
Absorption isotherm is of the Freundlich type, since the sulphur dye can be
built to extremely heavy shades with no saturation value apparent.
Bronziness begins to occur when the depth of shade exceeds the practical
upper limit for individual dyes, but this does not mean that a saturation value
is reached.
Highly substantive leuco-sulphur dyes are not readily stripped with
reducing agents, but a significant percentage of the dye (10-20%) can be
594
removed in a bath containing 5-10 g/l of sodium sulphide and more will be
removed in a fresh reducing bath. This indicates that the sulphur dyeing
process has normal reversible equilibrium with the balance shifted heavily in
favour of the dye in the fibre.

The dyestuff is pasted with equal quantities of T.R. Oil and soda ash.
Sodium sulphide is also added, the quantity varies between half (for browns,
blues) and double (for yellows) of the weight of the dye, in most cases 1½
times. Boiling water (about 10 times) is then added to the paste until the dye
is completely dissolved. The dye solution is strained to remove the insoluble
matters. For blacks and heavy shades with large quantities of dyes, straining
may not be possible, and in such cases the colour must be dissolved in one
or two feet of water at the bottom of the machine.
The dyebath is made up with 5% (o.w.m.) soda ash, 2% (o.w.m.) sodium
sulphide, the dye solution and 5 to 25% (o.w.m.) common salt depending on
the depth of shade. The salt may be added in several portions in the bath at
the commencement or after raising the temperature to 100°C. Surface-
active penetrating agent may be added. The dyeing is continued at boil for
30 minutes. The steam is then turned off and the dyeing continued for a
further ½ hour in the cooling bath. Some sulphur dyes are best exhausted at
70-75°C.
The sulphur dyes do not exhaust well in deep shades and dyeing is to be
carried out with a low liquor ratio. A standing bath is usually used for sulphur
black. After each dyeing, between ½ and ¾ of the original quantities of dye,
sodium sulphide and soda ash are added. When the specific gravity of the
bath exceeds 1.05 (10°Tw), the bath should be discarded or diluted. When
free sulphur appears in the bath, sodium sulphite should be added till the
whole free sulphur is converted to thiosulphate.
Na2SO3 + S Æ Na2S2O3 (8.28)
It is important that the retained liquor should be rinsed out immediately
after dyeing, to prevent deposition of the insoluble product of oxidation on
the surface of the fibres.
Some of the sulphur dyes oxidise very slowly and it may be convenient to
go for chemical oxidation. Some of the sulphur dyes (e.g. C.I. Sulphur Blues
1, 4, 7, 13) give brighter shades when oxidised with hydrogen peroxide. The
treatment is carried out with 1-2% (o.w.m.) of hydrogen peroxide (27.5%)
and a little ammonia for 15 minutes at 40°C.
Sulphur dyed materials are aftertreated with copper sulphate, alone or
along with potassium or sodium dichromate and acetic acid. The treatment
improves light fastness and in some cases, wash fastness. The dyed and
595
rinsed material is treated at 70°C for 20-30 minutes in a liquor containing

(o.w.m.):
Copper sulphate − 1-2%
Acetic acid (60%) − 1-2%
or
Potassium dichromate − 1-1.5%
Copper sulphite − 0.5-1%
Acetic acid (60%) − 1-2%
Sulphur blacks have a tendency to show metallic shine or bronziness. The
reasons are excessively heavy dyeing, air exposure of the material during
dyeing, retention of excessive liquor after dyeing or insufficient sodium
sulphide in the dyebath. The bronziness can be removed by aftertreatment
in a bath containing 0.1% sodium sulphide at 30°C, which removes excess
of dye from the surface of the goods. The alternate treatment is with 2-5 g/l
soap, 1-2 g/l olive oil and 1-2 g/l soda ash for 15-30 minutes at 60°C,
hydroextracted and dried without rinsing.
Certain sulphur blacks, when stored under high temperature and moisture,
cause degradation of cellulosic materials. Earlier it was thought to be due to
free sulphur. However, it has been established now that the dye itself is
oxidised with the formation of sulphuric acid, which is responsible for
tendering. The problem can be minimised by thorough washing before
oxidation and alkaline rinsing as the final stage of processing. Resin
finishing is claimed to inhibit the tendering by sulphur blacks. To prevent
tendering of material during storage, a final treatment of the dyed material
may be done with sodium acetate, which neutralises sulphuric acid, if
eventually formed. The treatment may also incorporate T.R. Oil to avoid
stiffness, if any, caused by sulphur dyeing.
8.7.7 Stripping of Sulphur Dyes

Partial stripping of sulphur dyes can be done by treating in a blank bath of
reducing agent (6 g/l sodium sulphide) at a temperature as high as possible.
A blank bath containing 4.5-9 g/l sodium hydrosulphite, 2-3 g/l
sequestering agent at 90º-95ºC will strip off 10-20% of dye, while addition of
a stripping agent such as polyvinyl pyrrolidine will remove a further 10-20%.
It is advisable to redye from fresh bath.
8.7.8 Solubilised Sulphur Dyes

The water-soluble sulphur dyes dissolve in water and they can be dyed with
sodium sulphide and soda ash. They are easy to handle, contain less
insoluble matters making them suitable for package dyeing and possess
superior levelling properties.
596
The solubilised vat dyes are prepared from the conventional vat dyes by
stabilising the reduced form of the dye. There are various ways of making
stabilised dye. The sulphur dyes solubilised by thiosulphonic acid are
prepared by the action of sodium sulphite or bisulphite on the sulphur dye:
/ /
RSSR Æ RSNa + NaSR Æ 2RSSO3Na (8.29)
(reduction) (Na2SO3)
They may be regarded as Bunte Salt dyes. The thiosulphonic acid

derivative must be treated with a reducing agent to convert it into leuco form,
which subsequently is adsorbed by the fibre. The final stage consists of
oxidation into original sulphur dye.
/
RSSO3Na Æ RSNa Æ RSSR (8.30)
(reduction) (oxidation)
The lack of substantivity of many water-soluble sulphur dyes can be of
assistance in dyeing of tightly woven piece goods or packages. The fabric
may be padded and then transferred to a jig for treatment with reducing
agent.
A few direct dyes which are stable in the presence of sodium sulphide,
can be used for shading of sulphur dyes such as C.I. Direct Yellows 28, 29,
Red 1, Brown 1, etc. However, such additions may hamper wash fastness.
Sulphur dyes may be topped with basic dyes. Because the former act as a
mordant, the resultant wash fastness is good. The sulphur-dyed goods are
entered in a cold bath containing 2-5% o.w.m. acetic acid. The temperature
is slowly raised to 50°C while 0.1-0.5% o.w.m. basic dye (e.g. Rhodamine B-
500 for giving reddish tone on sulphur black) is added in portions. However,
the light fastness will be lowered by this aftertreatment.
8.7.9 Hydron Blues

The Hydron blues resemble sulphur dyes in their chemical structure and
preparation method. However, they cannot be solubilised by sodium
sulphide alone. It is necessary to use sodium hydrosulphite, often in addition
to an alkali sulphide. Hydron Blue R (C.I. Vat Blue 43), a substitute for
indigo, is obtained by treating carbazole with p-nitroso-phenol in
concentrated sulphuric acid, when a compound (8-48) is obtained. This is
treated with sodium polysulphide and sodium nitrite dissolved in butanol,
which yields a product from which the blue dye is isolated.
597
-NH- - OH
(8-48)
Because of their excellent properties, such as good solubility, levelling and
fastness, these dyes are used for dyeing cotton in any form, for instance
loose cotton, sliver, yarns in hank or package and piece goods. Good
covering of dead cotton by these dyes is of special importance for dyeing
piece goods, especially for workmen’s overalls.
These dyes are available as very fine dispersions and are very suitable for
pad dyeing process. They can be also directly added to a bath containing
caustic soda and hydrosulphite, the required quantities are shown in Table
8.12 [50].
Table 8.12 Required Quantities of Caustic Soda and Sodium
Hydrosulphite for Dyeing of Hydron Blue
Caustic Soda (32.5%), ml/l Hydrosulphite, g/l
Shade-depth (%)Æ 1-3 3-5 1-3 3-5
Open vat (1:20) 3-4 4-5 2-2.5 2.5-3
Winch (1:10) 4-5 5-6 2.5-3.5 3.5-5
Jigger (1:5) 8-10 10-12 4-5.5 5.5-7
The dyestuff is pasted with wetting agent and diluted with soft warm water.
The required quantities of caustic soda and hydrosulphite are added in the
jigger and the temperature is raised to boil. The diluted dye solution is added
to the jigger through a sieve. Well-prepared material is entered in the
dyebath and run for two ends through weakly boiling liquor. Subsequently,
the steam is shut off and further four ends are given while the bath cools
down to 70°C. During dyeing, a clean golden yellow vat colour is
maintained and hydrosulphite and caustic soda may be added, if necessary.
After dyeing, the fabric is rinsed and oxidised with:
Potassium dichromate − 1-2 g/l

Acetic acid (60%) − 3-6 ml/l
Four ends at 30-65°C.
598
8.8 OXIDATION COL/OURS

The name is given to a group of aromatic amines and aminophenols, which
can be converted by oxidation into insoluble pigments within fibrous
materials. As far as textile coloration is concerned, only aniline black and
related compounds are of interest. The latter includes such a dye as
Solanile Black (Fran), which is a water-soluble sulphamic acid derivative of a
compound like p-aminodiphenylamine. Although oxidation blacks may be
used for pad dyeing, their most important use is was printing. Due to
tendering and other problems, their use has declined considerably.
The production of jet black colour on textile materials, especially of
cellulosic origin, using direct, sulphur, vat or reactive dyes, involves the use
of large quantities of dyes. So the dyeing costs will be very high and
washing fastness may be poor in many cases. Oxidation colours provide a
cheap means of producing such shades using inexpensive and simple
organic aromatic amines, and these shades are extremely fast to washing
and other wet treatments. The dyeing on cellulosic fibres are fast to light,
washing and fast to bleaching (with the exception of one bath aniline black)
and are relatively cheap to apply.
The production of these ingrain colours involves impregnation of the
material with a solution containing a soluble salt of amine, an oxidising
agent, an acid liberating agent and a catalyst or oxygen carrier. The aniline
salts used most frequently are hydrochloride and less frequently sulphite,
nitrite, ferrocyanide, tartrate, lactate or glycollate. Oxidising agents used are
sodium chlorate and dichromates or their combinations. Ammonium chloride
or nitrate is used as acid liberating salt. The salts of copper, iron and
vanadium are used as catalysts. The impregnation is followed by drying and
ageing or steaming. The oxidation results in polycondensation of aromatic
amines via amino group yielding complex molecules. The various stages of
oxidation of aniline into aniline black are as follows:
Aniline Æ leuco-emeraldine (colourless) Æ proto-emeraldine (violet) Æ
emeraldine (blue) Æ negraniline (dark blue) Æ pernegraniline (greenable
black) Æ aniline black (ungreenable).
A partially oxidised aniline black possesses the property of turning green
in acidic atmosphere. The recipe adopted should ensure to produce
ungreenable black by achieving maximum degree of oxidation along with
minimum degree of tendering.
The application of acid salt with consequent formation of free acid during
development and the presence of oxidising agent together with metallic salts
as catalysts, leads to tendering of cellulosic fibres. Care should be taken to
choose a recipe, which will cause minimum tendering of the material.
The mode of retention of aniline black to cellulose is not clear, but recent
work indicates that negative ionic sites are formed in cellulose by oxidation
599
during the dyeing of aniline black and the colorant behaves as a basic dye,
forming salt linkages with the fibres.
There are great variations in the recipes and considerable skill and
experience is required to apply the colorant satisfactorily. The dyeing
process can be of three types:
1. One-bath process
2. Ageing process
3. Steam process
One bath process is the easiest, but the dyeing is less satisfactory, the
shade is greenable and the fastness to rubbing and bleaching are poor. A
typical recipe for 100 kg cotton yarn in open beck or similar machine is as
follows:
20 kg sodium or potassium dichromate is dissolved in hot water and
added to cold bath. Aniline, hydrochloric acid, ferrous acetate and
concentrated sulphuric acid, 10 kg each, are mixed together with little water
until the aniline is completely dissolved. The solution is added to the bath
just before entering the yarn since the formation of the colorant commences
on mixing. The yarn is worked for one hour at cold and the temperature is
raised slowly to boil. The yarn is removed from the bath after full colour
formation, washed, soaped and treated with an oil emulsion for softness.
The ageing process consists of three stages, namely:
1. Impregnation with aniline salt, oxidising agent, catalyst and a

hygroscopic agent (optional).
2. Development by hanging in warm chamber for yarns or a suitable
apparatus for piece-goods under conditions of controlled temperature
and humidity.
3. Oxidation of partially formed colorant with dichromate.
The catalysts employed are metallic salts of iron, magnesium, copper and
vanadium, the most popular being copper sulphide, copper sulphate and
vanadium chloride. The vanadium chloride has a very high catalytic action
and should not be used where standing baths or stable padding liquor is
required. Ammonium chloride, a hygroscopic agent, is used to provide
moisture during ageing.
A solution is made containing:
Aniline - 60 parts
Copper sulphate - 2½ parts
Sodium chlorate - 19 parts
Ammonium chloride - 2 parts
600
Aluminium acetate (15ºTw) - 24 parts

Water - 400 parts
The yarn is dipped in the liquor and squeezed to contain its own weight of
liquor. It is dried at 35ºC in a chamber having controlled temperature and
humidity. The chamber is heated with dry steam keeping dry and wet bulb
temperatures at 35º and 30ºC respectively. The yarn is treated for 6 hours
with occasional turning of hanks. It is then chromed for 15 minutes at 80ºC
in a solution containing 4% dichromate and 1% sulphuric acid. The hanks
are then washed and soaped.
For fabrics, padding process may be adopted. The padding solution is
made by treating 35 parts aniline with 35 parts conc. hydrochloric acid and
100 parts water.
Just before padding, the following additions are made:
16 parts sodium chlorate
5 parts copper sulphate, both dissolved in 80 parts water.
The material is padded with the solution, aged for 3 minutes at 60ºC,
chromed and soaped. Ageing may be carried out at room temperature for
several hours with lesser chances of tendering.
Steam process uses potassium ferrocyanide as catalyst and the process
is sometimes called prussiate black. The liquor is stable for a longer period
and chances of tendering is less. The padding solution is prepared by
mixing three individual solutions just before padding, namely:
1. 84 parts aniline salt dissolved in 300 parts of water.

2. 49 parts potassium ferrocyanide dissolved in 300 parts water.
3. 27 parts sodium chlorate dissolved in 300 parts water.
The fabric is padded with 100% expression and dried in a hot flue dryer,
aged in a rapid ager for 2-3 minutes at 95-100ºC. It is then treated in ½%
dichromate solution at 50ºC for 15-30 minutes, washed and soaped.
Diphenylamine or diphenyl black base may be applied in the same way,
but acetic acid and lactic acid may be used in this case instead of
hydrochloric acid. Hence, the tendering of cellulose will be less.
8.9 AZOIC COLOURS

While azo dyes are readymade dyes, azoic colours are formed inside the
textile materials by reaction of two colourless or faintly coloured compounds
called naphthols, or C.I. Azoic Coupling Component and fast bases or C.I.
Azoic Diazo Components. At first, the naphthols are applied on textile
materials by a process called naphtholation as they have some affinity for
601
the cellulosic materials. The treated material is subsequently treated with a

soluble diazotised form of the base, when intense colour is formed. The
latter step is known as coupling or development. The solubilisation of the
base is carried out with sodium nitrite and hydrochloric acid at low
temperature and the process is diazotisation.
The advantages of azoic dyeing are the following [7]:
1. They are particularly strong in the orange, red and bordeaux sectors,
the range also include dark blue and black.
2. Certain bright full depths are produced, not achievable by any other
dye-class.
3. Dyeing may be carried out in various physical forms of textile
materials in various machines or even in short batches using domestic
utensils in the absence of machines.
4. Excellent shade reproducibility is achievable.
5. The fastness properties, in general, are good.
6. The dyeing cost is low.

1. The application procedure is complicated and time-consuming.
2. A number of chemicals are to be used and stored.
3. The fastness to rubbing of azoic dyed material has always been a
problem. High substantivity of the coupling component and thorough
soaping is essential for good rubbing fastness. During soaping,
unfixed colorant migrates from inside towards the surface and the
colorant from the surface are moved into the washing liquor. The
substantivity of coupling component to viscose is comparatively higher
and consequently rubbing fastness is higher on viscose rayon than on
cotton.
4. There is limitation of hues available and shade matching is difficult, if
not impossible. With all dye classes, a given shade is matched by
mixing of two, three or four dyes. The same process cannot be
adopted in the case of azoic colours. Each azoic colour is developed
by reaction of a diazo and a coupling component. When multiple
components are mixed, there will be cross coupling, such as two
coupling components will form two pigments with a single diazo
component and vice-versa. The relative quantities of such pigments
formed will depend on several factors and the mixed shades are
unpredictable and non-reproducible. Hence, the compound shades
(by mixing of dyes) are not advised in case of azoic colours, but some
tonal adjustment may be made using a small quantity of a second
naphthol or base.
5. The final shade can be noticeable only after coupling. Hence, any
unevenness, which may have occurred during naphtholation, may be
602
left unnoticed and is visible after coupling when shade correction is

difficult.
Azoic dyeing exhibit exceptionally good wet fastness on cellulosic fibres.
All naphthol combinations withstand washing at boil. The light fastness is
good to excellent in full depth. However, they are not applied in pale depths
because of poor light fastness. Most azoic combinations are fast to chlorine
bleaching, but frequently inadequately fast to hydrogen peroxide. With few
exceptions, the fastness properties of azoic dyeing on mercerising and
perspiration are excellent. The fastness to hot pressing varies from poor to
excellent. The main weakness of azoic dyeing is their limited fastness to
organic solvents used in dry cleaning and spotting. Fastness to rubbing
varies and it is largely dependent on the dyeing process. The presence of
granular particles, particularly of bigger sizes, lowers fastness rating, while
needle-shaped dye particles have little effect.
Azoic compositions of the Rapidogen colour (mixture of naphthol and
stabilised base) represent an alternative to indigo for the coloration of denim
jeans. They can be applied to warp yarns on a simple two-dip sizing
machine rather than a much more extensive indigo dyeing range. By
avoiding the use of a wetting agent, thus ensuring poor penetration of the
azoic components into the yarn, the hue and rubbing characteristics of
indigo jeans can be imitated closely.
The oldest application of this method was in the dyeing of Para Red,
which was produced by coupling diazotised paranitroaniline with β-naphthol.
The great disadvantage of Para Red and the other contemporary azoic dyes
was the absence of affinity of the β-naphthol for cellulose. The great
success came after the invention of β-hydroxynaphthoic acid. The
compound, itself lacked fastness to acid, due to the presence of carboxyl
group. Better fastness to acid was achieved by using anilide of β-
hydroxynaphthoic acid or Naphthol AS (C.I. ACC 2) (8-49) instead of
unsubstituted acid. The position, where the coupling occurs, is shown by *
mark in structure (8-49). Due to poor affinity of β-naphthol, the earlier azoic
colours required intermediate drying. This is time-consuming and the
migration of naphthol during drying results in uneven shade and poor
rubbing fastness. These problems were largely eliminated by using the
substantive β-hydroxynaphthoic acid derivatives. Intermediate drying was no
longer necessary. The rubbing fastness was also improved due to better
substantivity.
* OH
1 2
CONH 3
(8-49)
603
In theory, any Azoic Coupling Component can be coupled with any

diazotised Azoic Diazo Component so that with thirty different naphthols and
fifty fast bases, there can be 1,500 possible combinations. However, not all
such combinations are commercially useful. Many of the shades are similar
and many are discarded because of high cost. Many combinations result in
dirty shades. Several combinations possess excellent all-round fastness
properties on cellulosic textiles, while others may be deficient in one or more
fastness properties. One may be suitable for some textile use, while being
unsuitable for other textile applications. The manufactures’ literature should
be consulted for the shade and fastness properties of various combinations.
The mode of attachment of the final colorant or pigment to cellulose has
not been a subject of much study, but comparison with other soluble azo
dyes, e.g. direct dyes is obvious. The azoic combinations may be regarded
as azo direct dyes without solubilising groups, and the forces similar to
those operating in the direct dye-fibre system may be assumed to act in the
case of azoic combinations. As discussed in Section 8.3.2 and Figure 8.1,
the azoic pigment molecules align at 90º with fibre axis, whereas the direct
dye molecules align parallel to the fibre axis, as the latter have a large
number of substantive groups. Mechanical retention of the large molecules
built up inside the fibre may also play some part in the wet fastness
properties of the azoic combinations.
8.9.1 Azoic Coupling Components

The first Azoic Coupling Component (ACC), which was employed in practice
on a larger scale, was the 2-hydroxy-naphthalene (β-naphthol). This non-
substantive coupling component was later replaced by the arylamides of 2-
hydroxy-3-naphthoic acid discovered in 1911 in Germany. With the new
coupling component, which is known today as Naphthol AS, it became
possible to produce dyeing of hitherto unknown brilliance and fastness. With
different substitutions on the basic structure, several other substantive
naphthols were subsequently developed in the following years which were
named as members of Naphthol AS series. A few products derived from
arylamides of β-hydroxynaphthoic acid are as follows (substituent positions
referred below are shown in the structure 8−49 by numbers):
1. C.I. ACC 20 (Naphthol AS-OL) with a methoxy (OCH3) group in

position 1.
2. C.I. ACC 17 (Naphthol AS-BS) with a nitro (NO2) group in position 2.
3. C.I. ACC 27 (Naphthol AS-AN) with a nitro (NO2) group in position 3.
Later additions to the Naphthol AS range were not all derived from the
anilide of β- hydroxynaphthoic acid. For example, Naphthol AS-G (C.I. ACC
604
5 (8−50) is derived from arylamides of acetylacetic acid and the coupling

takes place at the –CH2 groups. Naphthol AS-G produces yellow shades of
various tones with the bases and, therefore, it is known as yellow naphthol.
CH2 CH2
H3COCH2COCHN NHCOCH2COCH3
(8-50)
The first member of the series, Naphthol AS, was just about sufficiently
substantive to make it serviceable, and exhaustion at equilibrium was only
12%. Higher substantivity demands a linear molecular structure, the
presence of aromatic nuclei in coplaner positions and of hydrogen bond-
forming groups. For example, linear molecular C.I. ACC 7 (Naphthol AS-
SW) exhausts upto about 45%, whereas angular molecular C.I. ACC 4
(Naphthol AS-BO) exhausts to the extent of 25%. Fifty-two Azoic Coupling
Components are listed in the Colour Index.
Besides the arylamides of the 2-hydroxy-3-naphthoic acid (Naphthol AS,
AS-D, AS-OL, AS-E and many others), coupling components having other
structures are:
1. Arylamides of the o-hydroxy-carboxylic acids of anthracene, e.g.

Naphthol AS-GR (C.I. ACC 36, 8-51).
2. Carbazol, e.g. Naphthol AS-LB (C.I. ACC 15, 8-52).
3. Benzocarbazol, e.g. Naphthol AS-SR (C.I. ACC 25) and Naphthol AS–
SG (C.I. ACC 13), and
4. Diphenyl oxide, e.g. Naphthol AS-BT, (C.I. ACC 16, 8-53).
OH CH3
CO-NH
(8-51)
H
OH
N OH OCH3
CO-NH
CO-NH Cl O
OCH3
(8-52) (8-53)
These coupling components enable the production of green, brown and

black tones, some of them with very remarkable fastness properties.
605
Naphthol AS-FGGR (C.I. ACC 108) gives brilliant yellowish green shades
of outstanding fastness properties if used together with a very wide range of
fast bases.
Naphthols are generally produced on an industrial scale by condensing
corresponding o-hydroxy-carboxylic acids or their salts with the required
arylamine in inert solvents such as toluene, xylene or nitrobenzene, using
phosphorous trichloride as a condensation agent. A few yellow naphthols
can also be produced by an additional reaction of diketene (acyl ketene)
with the corresponding arylamine [51].
Naphthols are insoluble in water and are to be converted into their alkali
(sodium) salts to dissolve them. Generally, sodium hydroxide is used for the
purpose. Normally they contain two acidic hydrogen atoms which are to be
replaced by sodium atoms. Some have four such atoms and they require
more sodium hydroxide. The naphthols are first pasted with T. R. Oil, which
acts as a wetting agent and as a protective colloid to prevent crystallisation
of naphthols in solution.
In solution, the sodium salt tends to hydrolyse with the formation of free
naphthol due to reaction with atmospheric carbon dioxide or acidic fumes.
To prevent hydrolysis, formaldehyde may be added to naphtholate solution.
Methylol compounds are formed which have more resistance to hydrolysis
than naphtholates. The coupling power is not hampered if the formaldehyde
treated naphtholate is kept at room temperature. However, if the solution is
heated, methylene compounds (by cross-linking two naphtholate molecules
with –CH2- group) having reduced coupling power are formed. The
naphtholate solution, therefore, should not be heated after the addition of
formaldehyde. A number of naphthols such as Naphthol AS-OL, AS-BS, AS-
LB, AS-ITR, AS-pH, etc. have good stability even in the absence of
formaldehyde. Some other naphthols such as Naphthol AS-SW, AS-G, AS-
LG lose their coupling power when formaldehyde is added. Hence, the
formaldehyde should not be added in these cases.
Naphthols differ widely from one another in their substantivity for the
cotton. It actually denotes the extent to which naphthol is absorbed by the
material under a particular set of dyeing conditions. The substantivity can be
increased by adding electrolytes (common salt or Glauber’s salt) to the
naphtholating bath. The actual amount being absorbed depends on the
following factors:
1. Material to liquor ratio.

2. Concentration of naphthol solution.
3. Amount of salt added.
4. Temperature of impregnation, absorption decreases with increase in
temperature, the usual range is 30-40ºC.
5. Time of impregnation.
606
6. The quality and previous history of material.
The most common naphthols or Azoic Coupling Components (ACC), in

the order of increasing substantivity, are given below:
Naphthol AS (C.I. ACC 2)

Naphthol AS-D (C.I. ACC 18)
Naphthol AS-OL (C.I. ACC 20)
Naphthol AS-PH (C.I. ACC 14)
Naphthol AS-BS (C.I. ACC 17)
Naphthol AS-EL (C.I. ACC 34)
Naphthol AS-E (C.I. ACC 10)
Naphthol AS-TR (C.I. ACC 8)
Naphthol AS-G (C.I. ACC 5) (+common salt)
Naphthol AS-BO (C.I. ACC 4)
Naphthol AS-SW (C.I. ACC 7)
Naphthol AS-BT (C.I. ACC 16)
Naphthol AS-LB (C.I. ACC 15)
Naphthol AS-SG (C.I. ACC 13)
Naphthol AS-SR (C.I. ACC 25)
These naphthols can be classified into four groups depending on their

affinity on cotton.
1. Low substantive naphthols, e.g. Naphthols AS, AS-D, AS-OL, AS-PH

and AS-G.
2. Medium substantive naphthols, e.g. Naphthols AS-RL (C.I. ACC 11),
AS-BG (C.I. ACC 19), AS-LT (C.I. ACC 24) and AS-VL (C.I. ACC 8).
3. High substantive naphthols, e.g. Naphthols AS-ITR (C.I. ACC 12), AS-
BS, AS-BO, AS-SW and AS-E.
4. Very high substantive naphthols, e.g. Naphthols AS-S (C.I. ACC 32),
AS-LB, AS-BT, AS-SG, AS-BR (C.I. ACC 3), AS-LG (C.I. ACC 35),
AS-LR and AS-GR (C.I. ACC 36).
Low and medium substantive naphthols are very suitable for application
by padding process. In exhaust application process, usually common salt is
added to increase the substantivity. In order to minimise the loss of product,
standing baths may be used by replenishing the amount of naphthol
removed by the impregnated material.
607
8.9.2 Azoic Diazo Components

The C.I. Azoic Diazo Components (ADC), known as fast bases, are mostly
derivatives of aniline, toluidine and anisidine. The substituents other than
amino group at the benzene nucleus are chlorine, nitro, cyano,
trifluoromethyl, carboxylic, sulphonic, sulphonamide, arylamino and
acylamino groups. The presence of different substituent groups in simple
bases with respect to the amino group (or -NH2·HCl group in case of
hydrochloride salt of bases having suffix C, e.g. Yellow GC) as per the
positions on the benzene ring indicated in (8-54) are as follows:
Fast Base Position Substituents
Yellow GC (44) 2 Cl (ortho)
Orange GC (2) 3 Cl (meta)
Orange GR (6), 2 NO2 (ortho)
Orange R (7) 3 NO2 (meta)
Red GG (37) 4 NO2 (para)
Scarlet GG (3) 2, 5 Cl
Red RL (34) 2, 4 CH3, NO2
Red GL (8) 2, 4 NO2, CH3
Red RC (10) 2, 5 OCH3, Cl
Red B (5) 2, 4 OCH3, NO2
Bordeaux GP (1) 2, 4 NO2, OCH3,
(The numbers under bracket are C.I. ADC nos. and two substituents
mentioned above are in respective positions)
The first six bases are derivatives of aniline, Red RL of ortho-toluidine,
Red GL of para-toluidine, Red RC and Red B of ortho-anisidine and
Bordeaux GP of para-anisidine. A more complex base is Fast Garnet GBC
(8-55). The light fastness can be improved by introducing electronegative
groups such as NO2, CN, SO3H, or CO·OR in the molecule of the base as in
case of Bordeaux GP.
NH2
6 2 CH3 CH3
N=N NH2·HCl
5 3
4
(8-54) (8-55)
The introduction of a trifluoromethyl group into the molecule of an aromatic
amine gives improved light fastness and high brilliancy of the final pigment
as in case of C.I. ADC 17. Derivatives of mono acetylated
608
paraphenylenediamine such as C.I. ADC 20 (Blue BB Base) are particularly

useful for blue shades. Unfortunately, both the bases are banned now due
to their toxic effects.
In the past, green self-shade was difficult to obtain and the shades
obtained by mixing yellow and blue components were not satisfactory.
Recently, green base has been prepared by condensing sulphuryl chloride
derivative of phthalocyanine with paranitroaniline and subsequently reducing
the nitro to amino group. This base can be diazotised and coupled with
various naphthols.
The free bases are insoluble in water. The hydrochlorides of the bases
are soluble in water, but their solubility varies, some of them are highly
soluble while others are sparingly soluble. The solubility is of great
importance in deciding the method of their conversion into their diazonium
compounds.
The process of conversion of aromatic amines into its reactive form,
diazonium compound, is called diazotisation. This reaction is a valuable tool
not only in the application of azoic colours, but also in the synthesis of a
large number of dyestuffs having azo groups. The reaction involves two
steps:
1. Conversion of the free base into its water-soluble salt, usually
hydrochloride. This is done by treatment with concentrated
hydrochloric acid and by heating or boiling, if necessary.
+ -
R-NH2 + HCl = R-NH3 Cl (8.31)
2. The reaction of the hydrochloride of the base with nitrous acid, is
usually done at low temperature (ideally 0-5ºC). Generally a
temperature range of 8-12ºC is economical and is achieved by adding
ice into the diazotising bath. This is carried out by adding sodium
nitrite into a solution of the hydrochloride of the base in presence of
excess hydrochloric acid.
NaNO2 + HCl = HNO2 + NaCl (8.32)
R-NH3+Cl– + HNO2 = R-N+≡NCl– + 2H2O (8.33)

Clarity of the final solution and the absence of froth indicate successful
diazotisation. During diazotisation, both hydrochloric acid and sodium
nitrite/nitrous acid should be in sufficient quantity. The presence of the
former is confirmed by Congo Red paper, which turns blue when dipped in
solution. A starch-iodide paper turns blue, if nitrous acid is in excess. If
hydrochloric acid is insufficient, diazotised base reacts with undiazotised,
forming an azo dye resulting in loss of base.
609
At the end of diazotisation, the solution contains a large amount of

hydrochloric acid. For proper coupling subsequently, the pH is to be raised
to 5-6 by adding sodium acetate (8.34).
CH3COONa + HCl = CH3COOH + NaCl (8.34)
The release of caustic soda from the naphtholated fabric may increase the
pH of the coupling bath. Hence, an alkali binding agent, namely alum or
acetic acid, is added in the diazotised solution.
Alum releases sulphuric acid in the bath as follows:
Al2(SO4)3 + 6H2O ↔ 2 Al(OH)3 + 3H2SO4 (8.35)
However, the addition of alum may alter the shade of certain azoic
combinations. Hence, acetic acid is preferred. Acetic acid also helps to
maintain pH of the bath stable by buffering action along with sodium acetate.
This diazonium salt is unstable even at room temperature. It reacts with
water and decomposes with the liberation of nitrogen. The decomposition is
enhanced by heat and light. Metals also accelerate decomposition. Hence,
the diazotisation should be carried out in wooden, glass or rubber-lined
vessels.
Diazotisation is troublesome and stock solutions cannot be stored
because of their lack of stability. There has been a great demand for
stabilised diazonium salts, called fast colour salts, which can be readily
dissolved in water (preferably containing a nonionic dispersant and acetic
acid or formic acid for selected salts) and would immediately be ready for
use. The various methods of preparation of such salts are:
Antidiazotates
A diazonium salt, when reacted with excess alkali (mainly sodium
hydroxide), an alkali syndiazotate forms. It rapidly undergoes transformation
into antidiazotate (8.36). The latter is more stable and can be isolated in a
form suitable for storage.
+ - +
R-N≡NCl Æ R·N≡N·OH Æ R-N Æ R-N
(8.36)
Diazonium NaO-N N-ONa
hydroxide Syndiazotate Antidiazotate
On acidification, the antidiazotate forms the diazonium salt. The fabric
may be padded with a mixture of a naphthol and an antidiazotate, and on
acidification coupling takes place. This is not useful in dyeing, but is popular
in printing and the mixture is marketed as Rapid Fast dyes.
Diazoamino Compounds
610
Diazonium salt unites with selected amino compound such as sarcosine

(CH2·NH·CH2·COOH) or N-methyltaurine (CH3·NH·CH2·CH2·SO3H) to form
an inactive compounds and the diazo compound is regenerated on
acidification. Rapidogen Dye is a mixture of a naphthol and fast base
stabilised with such screening agent called stabiliser and is most widely
used in printing.
Double Salts
Many diazonium compounds are stabilised by formation of their double
salts, zinc chloride being the most commonly used. The double salt is
prepared by adding excess quantity of zinc chloride into diazonium
compound solution when the double salt precipitates out.
2 Ar·N=N·Cl + ZnCl2 = (Ar·N2·Cl)2ZnCl2 (8.37)
The double salts or colour salts are used for dyeing and no diazotisation is
necessary as in the case of Azoic Diazo Components.
8.9.3 Development or Coupling

The reaction between a naphthol and a diazonium compound is called
development or coupling, by which an azoic pigment is formed. During
manufacture of dyes and pigments, the reaction is carried out in solutions.
During application of azoic colours, naphthol, which is substantive to
cellulose is first applied on the textile material by a process called
naphtholation. The material is then treated with diazotised base. Thus, a
bright red pigment is formed when a cotton fabric impregnated with Naphthol
AS is coupled with diazotised Fast Red RC base (8.38).
Cl
OH + -
Cl N≡NCl
N OCH3 (8.38)
CONH +
N OH
OCH3
CONH
The coupling reaction, which yields the insoluble azoic colorant in situ, is
irreversible and thus no levelling of the final colorant can take place at this
stage. It is, therefore, essential to achieve uniform distribution of the
coupling component in the material before proceeding to the coupling
611
reaction with the diazo component. If the distribution is uneven, the material
may be treated further with the coupling agent.
The speed with which coupling takes place depends on the naphthol and
diazo component being used and on the pH and temperature. Alkaline
conditions favour decomposition of diazo component into non-coupling form.
High acidity tends to decrease the speed of the coupling reaction. As the
naphtholated material is alkaline, some acid or acidic substance is
necessary to neutralise this alkali when the material is introduced in the
coupling bath. Weak acid, acid salt and buffering salts such as sodium
acetate and phosphates are used to neutralise the alkali and maintain the
pH of the coupling bath weakly acidic. It is essential to maintain conditions
so that coupling takes place as rapidly as possible. The concentration of the
diazonium compound should not fall below 0.5 g/l. The speed of coupling
may be increased by raising the temperature, but most of the diazo
components decompose rapidly in solution above 20ºC.
There is considerable variation in the rate at which coupling takes place
with different bases and fast colour salts, and the rate of reaction can be
controlled by the pH. The diazo components are divided into four groups
according to their coupling energies, related to which are specific pH ranges
at which the reaction will be more rapid [12].
Group 1
High coupling energy, optimum pH-range 4-5.5. No buffer is necessary, but
an alkali-binding agent is essential.
Group 2
Medium coupling energy, optimum pH-range 5-6.5. Acetic acid-sodium
acetate buffer is necessary to maintain pH.
Group 3
Low coupling energy, optimum pH-range 6-7. The bath should be
neutralised with sodium bicarbonate, then buffered with mono- and di-
sodium phosphate buffer mixture (4 and 2 g/l respectively for a liquor ratio of
1:20, double and four times the quantities for liquor ratios 1:10 and 1:5
respectively).
Group 4
Very low coupling energy, optimum pH-range 7-8.2.
The members belonging to a particular group may have different rates of
coupling and accordingly those are sub-classified as rapid, medium and
slow coupling rates. Table 8.13 shows classification of fast bases or Azoic
Diazo Components according to coupling energy and rate.
612
Table 8.13 Classification of Diazo Components (represented by C.I. Azoic

Diazo Component Nos.) According to Coupling Energy and Rate
Coupling Rate Æ Rapid Medium Slow
Group 1 3, 6, 7, 9, 37 2, 8, 12, 13, 16, 1, 4, 5, 17, 19, 21,
18, 34, 36, 44 27, 38, 49, 50
Group 2 30, 46 10, 11, 26, 29, 25, 31, 42
32, 33, 39
Group 3 43 20, 24, 41, 45 15
Group 4 X 22, 35 47, 48
During development, a portion of naphtholate may bleed from the material

into the development bath. This will reduce colour yield as well as hamper
the rubbing fastness by deposition of the pigment formed in the bath on the
surface of the material. This may be minimised by adding common salt in
the bath. A nonionic dispersing agent, such as Remol AS, may also be
added which keeps the pigments as fine dispersions, preventing deposition
on the surface of the material.

The four steps of application of azoic colours are:
1. Dissolution of naphthols
2. Naphtholation
3. Conversion of bases into diazo compounds
4. Development or coupling
The dyeing follows aftertreatment like repeated cold wash, hot wash, acid
treatment for neutralisation and thorough soaping.
Dissolving of Naphthols
Naphthols are insoluble in water. They are treated with caustic soda to make
them soluble in water when they are converted into sodium salt or
naphtholate.
There are two methods of dissolving naphthols, namely:
1. Hot dissolving method

2. Cold dissolving method
In hot dissolving method, the naphthol is pasted with a wetting agent (T.
R. Oil) and a small quantity of hot water is added to make a smooth paste.
The required quantity of sodium hydroxide is added and boiled until the
613
milky dispersion is converted into a clear solution. The remaining quantity of

cold water is added to make the solution of desired concentration. In the
case of Naphthol AS-SW, AS-SG and AS-SR, the powder is pasted with the
wetting agent and required quantity of caustic soda solution (62ºTw or 366
g/l) is added. The paste is heated in a water bath or kept overnight, then
remaining water is added. Formaldehyde, if required, may be added after
cooling down to room temperature.
In cold dissolving method, the naphthol is pasted with industrial alcohol or
methylated spirit. Required caustic soda solution (62ºTw) is added with
stirring. The quantities required are much less than those required in hot
method. The required quantities in hot and cold method are shown in Table
8.14 (29).
Naphtholation
The second stage of application of azoic colours is the treatment of textile
substrates with naphthol solutions. As the naphthols have low affinity for
cellulosic textile substrates, the best method of their application is by
padding method. Hence, the depth of azoic dyeing is normally expressed in
terms of grams per litre naphthol as in case of padding recipes. The
quantity of fast base required is not necessary to be mentioned as it is
dictated by the coupling ratio, i.e. the quantity of fast base required for unit
weight of naphthol, which is constant for a naphthol-base combination.
Table 8.14 Required Quantities (in parts) of Chemicals for Dissolving 1 part
of Naphthol
Naphthol Caustic soda solid Alcohol or spirit 40% Formaldehyde
AS-LB 0.2 (0.2) (1.25) 0.5 (0.5)
AS-SG 0.33 (0.1) (1.0) x
AS-SR 0.33 (0.1) (1.0) x
AS 0.5 (0.2) (1.0) 1.0 (0.5)
AS-E 0.5 (0.17) (1.0) 0.75 (0.5)
AS-BS 0.5 (0.17) (1.5) 1.0 (0.5)
AS-OL 0.5 (0.17) (1.0) 0.5 (0.5)
AS-EL 0.5 (0.17) (1.0) 0.5 (0.5)
AS-BT 0.5 (0.2) (1.0) x
AS-D 0.5 (0.17) (1.0) 1.0 (0.5)
AS-PH 0.5 (0.17) (1.0) 1.0 (0.5)
AS-TR 0.7 (0.17) (1.5) 1.0 (1.5)
AS-BO 0.9 (0.2) (1.75) 1.0 (0.5)
AS-G 1.0 (0.23) (1.0) x
AS-SW 1.3 (0.17) (1.25) 1.0 (0.5)
614
Notes:
The quantity of wetting agent is just that required for pasting, usually equal quantity of
naphthol.
The bracketed quantities are for cold dissolving method.
Alcohol or spirit is required only for cold dissolving method.
For alcohol/spirit and formaldehyde, the quantities are by volume against weight of naphthol.
However, depending on the availability of equipment, different dyeing

methods are used, such as open beck, tub-dip, circulating liquor, jigger,
padding methods, etc. These involve different material to liquor ratio and
concentration of azoic components.
The total quantity of caustic soda present in naphtholation bath
determines the stability of the solution, resistance to air exposure and the
quantity of alkali binding agent required in the developing bath. Minimum
quantities of caustic soda required in naphtholation bath are 1.6 and 3.3 g/l
(2.5 and 5 g/l for both Naphthol AS-SG and AS-SR) for light and deep
shades respectively. For Naphthol AS-G, maximum concentration for deep
shade is 2.5 g/l and minimum for light shade is 1 g/l.
As the naphthol solution is colourless or of slightly yellowish tone, it is not
possible to make a visual assessment of the amount of the coupling
component being absorbed at the end of impregnation. Hence, careful
preparation and control of impregnating liquor is necessary to ensure
consistent final shade. The tables and charts, relating g/l naphthol in the
liquor to the grams absorbed per kg of fibre, are available. Naphthols have
greater affinity for mercerised cotton and regenerated rayons have greater
affinity than that for natural cotton.
Yarn may be dyed by open beck method, tub-dip method or in package
dyeing machine. In open beck method, the bath is prepared with naphthol
solution and common salt, maintaining suitable liquor ratio ensuring
complete impregnation. Generally, 20 g/l common salt is added to the
naphthol solution, except in the case of Naphthol AS-SW and Naphthol AS-
G, where 10 g/l and 15 g/l respectively are used. No addition of common salt
is necessary in case of Naphthol AS-SG and Naphthol AS-SR as they are
highly substantive. Salt should be added just before impregnation. The yarn
is entered and kept for about 30 minutes at room temperature with frequent
turning. The impregnated yarn is then squeezed properly by hand or by
hydroextractor, opened well and carried forward for developing. The bath is
then replenished from feeding bath solution of higher concentration to make
up the original volume entering the second lot of yarn.
In tub-dip method, yarns in small lots (e.g. 0.5 kg) are immersed for a
short period (30-60 seconds) in a small volume of concentrated naphthol
solution taken in a stainless steel or earthen pot at room temperature. It is
then properly squeezed by hand, opened well and carried forward for
developing in a similar manner. The dye bath is then replenished by adding
615
0.25 litres from the feeding bath solution of still higher concentration before
entering a second lot of yarn (0.5kg).
In package dyeing machine, cellulosic materials may be dyed in cops,
cheese, cone, warp-beam, and loose fibre form using suitable carriers. The
material may be treated with naphthol solution for 30-40 minutes, with flow
reversals at intervals of 5-10 minutes. The material is hydroextracted in the
same machine or in an external hydroextractor. The material is returned
back to the same or another dye vessel for development.
Naphthols are extensively used for piece dyeing in jigger or padding
mangle. Naphthol is dissolved and added to the jigger containing necessary
amount of alkali and common salt. The impregnation is generally carried out
at room temperature. However, while dyeing with mixture of naphthols with
varied substantivity, dyeing in pale shades or dyeing heavy fabrics, a little
higher temperature is employed to decrease the affinity. The goods are then
mangled and developed on a jigger by working four ends.
In padding process, the material is given a single run through a fairly
concentrated solution of naphthol. The speed of the machine allows the
fabric only to absorb the liquor mechanically and allows little time for the
affinity of the naphthol to play. A small padding trough is preferred. The
development may be carried out on a jigger or on a second padding mangle.
The materials impregnated with naphthol should be protected from water
spots, acid fumes, steam, chlorine fumes and direct sunlight and the
development should be carried out as soon as possible. Lack of proper
protection or prolonged interval may result in weak and uneven dyeing.
In continuous dyeing, it is advantageous to pass the fabric into a hot-flue
dryer after padding. The drying rate should be slow. Sudden drying may
lead to over-saturation of the residual liquor, so that surface deposition of
naphthol may occur. The drying should be carried out at 90-110°C with
residual moisture of 9-12%.
Diazotisation
Two general methods are used for diazotisation of fast bases namely:
1. Direct method
2. Indirect method
Most of the bases are diazotised by the direct method. The method is
suitable for bases, whose hydrochlorides are easily soluble in water. The
base is pasted with concentrated hydrochloric acid and little cold water. Hot
or cold water is then added with stirring. The solution is then cooled to 10ºC
with ice and the sodium nitrate solution (1:1) is added with vigorous stirring,
maintaining the temperature in the range of 10-12ºC (5ºC for Garnet GBC).
Coupling will not occur if the pH is too low. Hence, after keeping the solution
616
for 20 minutes, the excess hydrochloric acid is neutralised with sodium

acetate crystals. The alkali binding agent, such as aluminium sulphate or
acetic acid, is then added. Alum produces sulphuric acid when dissolved in
water (8.35) and it is this acid that binds sodium hydroxide:
H2SO4 + 2NaOH Æ Na2SO4 + 2H2O (8.39)
The solution is then filtered and made up to the required volume
depending on the concentration of the fast base required. With Red RC and
Red KB, aluminium sulphate is preferred to acetic acid.
The indirect method of diazotisation is used for the bases, hydrochlorides
of which are not easily soluble in water. The fast base is pasted with a little
water and sodium nitrite solution (1:1) is then added. More hot or cold water
is added with stirring. The mixture is added to a solution of hydrochloric acid
32ºTw with continuous stirring, maintaining the temperature in the range of
10-15ºC using ice. After keeping the solution for about 20 minutes, the
excess hydrochloric acid is neutralised with sodium acetate and the alkaline
binding agent, such as acetic acid or alum/aluminium sulphate, is added.
The solution is filtered and made up to the required volume. The quantities
of various chemicals required for diazotisation of fast bases by direct and
indirect methods are shown in Table 8.15 [52]. The solutions of diazotised
bases are sufficiently stable for all normal practical purposes, if the
temperature is kept below 20ºC. A few can be stored, in the absence of
light, for as long as one to two weeks. The stability can be improved by
adjusting pH to between 5 and 6.5. The solution should be discarded if it is
turbid and scum forms.
Table 8.15 Chemicals required in parts for 1 unit of Fast Bases for
Diazotisation
Chemicals (details below)
Fast Bases 1 2 3 4 5 pH
Yellow GC 5+ 1.2 0.5 1.0 0.75 4-5
Orange GC 5+ 1.2 0.5 1.0 0.75 4-5
Scarlet GGS 4 2.0 0.36 2.5 x 4-5
Scarlet RC 20 1.0 0.4 0.75 0.5 4-5
+
Red KB 10 1.0 0.4 0.75 0.6 5.5-6.5
+
Red RC 10 1.0 0.5 0.75* 0.3 5.5-6.5
Garnet GBC 15 1.2 0.32 1.25 x 4-5
*
Orange GR 2.0 2.25 0.55 1.2 0.7 4-5
*
Red B 1.5+ 1.75 0.5 0.85 0.75 4-5
*
Bordeaux GP 2.0+ 1.75 0.5 0.85 0.75 4-5
617
*
marked bases are diazotised by indirect method
Details of chemicals
+
1. Cold water, hot
2. Hydrochloric acid, 32°Tw
3. Sodium nitrite
*
4. Sodium acetate ( Extra 5 g/l required in developing bath),
5. Acetic acid (50%) as alkali binding agent, alternately aluminium sulphate, equal
to the weight of base except for Scarlet RC and Red KB,
pH = Optimum pH for developing bath.
Fast colour salts are freely soluble in water. Before development these are
to be dissolved in water, first by pasting with little water and then by adding
five times water maintaining temperature at 30ºC. The solution is kept for 5-
10 minutes and filtered through a fine cloth.
Development or Coupling
The naphtholated material is treated with the diazonium solution in the
development bath for 20-30 minutes when the final shade appears on the
material. The development may be carried out in long liquor open beck or
jigger or in short liquor as in tub or padding mangle.
An addition of 25 g/l common salt is made in all development baths except

for Fast Black K. 10 g/l common salt is added in case of Garnet GBC base
or colour salt. Common salt is omitted when development is done by
padding or in highly concentrated solutions.
In many cases, the coupling is quite slow, which is unfortunate, because it
allows more time for the naphthol to migrate. To make the reaction as rapid
as possible, the concentration of the diazotised base should at no time fall
below 0.5 g/l. The addition of an assistant, such as a sulphated fatty alcohol
or an ethylene oxide condensate (e.g. Remol AS), tends to improve the
speed of the reaction and also to keep the pigments formed in the solution
as suspension. These are particularly important in the case of package
dyeing machine as the deposition of such pigment may disturb the flow of
liquor.
The actual quantity of diazotised base required in the development
depends on the quantity of naphthol in the naphtholating bath and the
coupling ratio. The coupling ratio is the quantity of fast base required for 1
part of naphthol. The coupling ratios of various naphthols and fast bases are
shown in Table 8.16.
Table 8.16 Coupling Ratios of Various Naphthols and Fast Bases
Naphthol
Fast Bases AS ASG AS-BS AS-SW AS-TR AS- LB AS- SG
Yellow GC 0.95 1.05 0.8 0.8 0.8 0.37 0.31
618
Orange GC 0.95 1.05 0.8 0.8 0.8 0.37 0.31

Scarlet RC 1.2 1.25 1.05 1.05 1.05 0.03 0.47
Red KB 1.05 1.15 0.90 0.90 0.90 0.42 0.42
Red RC 1.10 1.20 0.95 0.95 0.95 0.44 0.42
Garnet GBC 1.47 1.57 1.25 1.25 1.25 0.58 0.53
Orange GR 0.75 0.75 0.60 0.60 0.60 0.27 0.25
Red B 0.90 0.95 0.75 0.73 0.75 0.35 0.30
Bordeaux GP 0.90 0.95 0.75 0.75 0.75 0.35 0.30
For example, when naphtholation is done with 5 g/l Naphthol AS, the
concentration of Yellow GC base in the development bath should be 5 x
0.95 = 4.75 g/l where 0.95 is the coupling ratio.
After-treatments
After developing, the material is washed repeatedly in cold water, then in hot
water and rinsed in acidified water (3 ml/l hydrochloric acid, 32ºTw). It is
then washed again with cold water and carried forward for soaping. Soaping
removes loosely fixed azoic pigments from the surface of the material,
thereby increasing fastness to rubbing, light and chlorine. It also develops
the true shade of azoic combinations. Soaping is carried out at boil with 3 g/l
soap or detergent and 2 g/l soda ash for a period of not less than 15
minutes, giving adequate agitation or squeezing to dislodge the adhering
particles. It is then washed well and dried.
The combinations of Yellow GC with Naphthol AS and AS-SW and
Orange GC with Naphthol AS are to be soaped at 65ºC. The reddish streaks
of Naphthol AS-G combinations with fast bases, namely Yellow GC, Orange
GC, Scarlet GGS, Red KB, and Red RC, caused by faulty dyeing, can be
removed by boiling with soap along with 0.5 g/l sodium hydrosulphite and
0.5 ml/l caustic soda, 62ºTw. With some other combinations, it may lower
chlorine fastness.
8.9.5 Blinding
Azoic dyes sometimes cause a matt or delustred effect, particularly on
regenerated cellulose rayon, referred to as blinding. Microscopic
examination shows blinding is apparent when the pigment ceases to be
distributed with uniform density throughout the cellulose but becomes
aggregated into particles. Blinding is never seen immediately after coupling,
but develops on standing in cold water, or more frequently during wet
treatment at high temperatures, such as in the washing-off process,
particularly under alkaline conditions.
619
8.9.6 Stripping of Azoic Colorants

Azoic dyeing can be stripped with powerful reducing agents, although dyes
based on highly substantive naphthols are difficult to deal with. Certain
yellow azoic dyeing are resistant to reducing agents and can, therefore, be
only partially stripped.
The stripping is carried out with sodium dithionite in the presence of a
cation-active substance such as Matexil SC-A50 (cetyl trimethyl ammonium
bromide). The material is treated at boil for 30-45 minutes in a liquor made
up with 2% Matexil SC-A50 and 4% caustic soda. The temperature is then
dropped to just below the boil and 5-6% sodium dithionite is added. After a
further 30-45 minutes, the liquor is run off and stripping is completed by
bleaching with sodium hypochlorite. Benzimidazoles are also claimed to
increase the stripping action of alkaline hydrosulphite baths.
Polyvinylpyrrolidone, under various proprietary names, e.g. Albigen A
(BASF), is also useful addition to the stripping bath. Combinations from
substantive naphthols may be difficult to strip completely. In general, the last
traces of naphthol are very difficult to remove.
8.10 MINERAL COLOURS
This class of colorant is applied by impregnation of the material with soluble

metallic salts, followed by reaction to produce insoluble metallic salts or
hydroxides in situ. These are mostly applied on cellulosic materials,
especially cotton. The mode of attachment to cellulose is not clear, but may
be due to mechanical retention of the insoluble inorganic pigments by the
fibres. The soluble salts used for the purpose are non-substantive, hence
the application is mostly made by padding process.
Some of the mineral colours are:
1. Chrome Yellow by precipitation of lead chromate.

2. Iron buff and Nankin Yellow by precipitation of hydrated ferric oxide,
the two colours vary in depth only.
3. Prussian Blue by precipitation of ferric ferrocyanide.
4. Manganese Bronze or Bistre by precipitating manganese dioxide.
5. Mineral Khaki by double deposition of chromic and ferric hydroxides
on the fibre.
Except Mineral Khaki, all other colours mentioned above are of historical
interest. Mineral Khaki is still used in India in small quantities for the
manufacture of police and military uniforms, mainly because of low cost,
better microbiological resistance and increase in weight of the material,
making the uniforms heavy.
620
8.10.1 Mineral Khaki

The word Khaki is derived from the Urdu word khak meaning dust. This term
is applied to a peculiar shade of drab and the shade is popular for making
uniforms as it camouflages with the foliage backdrop, making detection by
the enemy difficult. The bulk of Mineral Khaki production in India is based on
ferrous sulphate and chrome alum, whereas in western countries the
tendency is towards the use of chromium acetate and acetate of iron. In the
latter type, chromium content of the dyed material is less and does not stand
severe perspiration fastness tests.
The dyeing liquor essentially consists of ferrous sulphate and basic
chrome tan (chrome alum). Ferrous sulphate is available in green crystals.
Dehydrated white powder may be treated with a little dilute sulphuric acid.
Only clear and decanted solution, usually of 40ºTw is used, and it should not
give more than 3.5% iron when titrated against potassium permanganate
solution in presence of oxalic acid. The ferrous sulphate, which settles
down, may be reused after treating with dilute sulphuric acid.
Chrome alum is also available in ready form in standard quality. However,
it may, be prepared by treating sodium or potassium dichromate with
concentrated sulphuric acid using jaggery or glucose as a reducing agent.
For 100 litres chrome liquor, 35 kgs of dichromate is dissolved in 50 litres of
water. 27 kgs of commercial sulphuric acid (164ºTw) is added. To this
mixture, a solution of 5.4 kgs sugar (in 5 litres water) or equivalent quantity
of glucose or molasses is added. When the reduction is complete, the
mixture is cooled and the volume is made to 100 litres by adding water.
Commercial basic chrome tan crystals are sensitive to moisture and
should be stored in a dry place. It is dissolved in hot water and diluted with
cold water. The bluish green solution should be of about 40ºTw.
The oxides of iron are brown and those of chromium are yellow-green.
The khaki shade may be yellowish as in the case of police uniforms, or olive
as in the case of army uniforms. The skill of the dyer is called for matching a
given shade. A typical khaki drill of the army shade may be prepared by
mixing 100 parts chrome tan (40ºTw) and 13 parts ferrous sulphate (40ºTw).
The fabric prior to padding should be neutral to litmus and the dyeing
liquor should be neutral to faintly acidic, preferably pH 6.5. The padding
should be done with cold liquor, as the solubility of the two inorganic salts
varies differently with temperature. Usually 3-bowl padding mangle is
employed using two dips and two nips. For better wetting-out of heavy drills,
the fabric may be padded more than once. Two or more padding mangles
may be installed in tandem with common drive and counter-current liquor
flow. The padding speed is about 20-25 m/min and the nip expression
should be as low as possible to prevent dripping of liquor from the fabric.
The fabric should be batched after padding and should not to be folded
down.
621
Intermediate drying prevents excessive bleed-off at the development

stage. When development is done in wet state, a light dull shade of more
reddish tone is obtained as basic chrome tan is washed out during
development. Intermediate drying may be carried out by passing over
heated cylinders or preferably in hot flue dryer. Hot copper cylinders should
be avoided. The fabric should be just dry and not baked. After drying, the
fabric should be protected from water drops.
After drying, the fabric is run continuously through a roller vat for ½ to 1
minute containing 50-55 g/l caustic soda solution at about 85ºC. The
concentration of caustic soda and temperature are to be maintained
throughout to avoid tonal variations. The fabric is then squeezed and
batched or folded. Wherever continuous pad-steam range is available, it is
always advisable to steam the developed Khaki prior to soaping in order to
improve the fastness properties.
In the absence of a roller vat, jiggers may be used for development. Two
ends may be given with 10% caustic soda solution at 70ºC and batched at
the third end. It is then kept rotating for 2-3 hours on an another jigger. Four
ends are then given for air oxidation, two ends for hot wash, two ends for
cold wash and four ends at boil with soap, soda and sodium silicate. The
quantity of the last two should be adjusted to get the proper hue and tone
[53].
In conventional dyeing with chromium and iron salts, grey-green mineral
dyeing is produced. By a slight modification in the process, olive-drab
mineral dyeing can be produced from the same two-bath system. In the
conventional system, the fabric is wetted with a solution of chromium and
iron salts, partially dried and wetted in an alkali bath to precipitate metal
hydroxides and soaped. In a unique modification, the fabric after
development (with excess alkali) is heated at 150ºC for 2-3 minutes before
washing [54]. The conventional chemical reactions are:
CrCl3 + 3NaOH Æ Cr(OH)3 ↓ + 3NaCl (8.40)
FeSO4 + 2NaOH Æ Fe(OH)2 ↓ + Na2SO4 (8.41)
In the modified process with excess alkali, heat and air, the reaction
occurs as:
3Fe(OH)2 + 2NaOH + [O] Æ Fe3(OH)8 ↓ + Na2O (8.42)
Fe3(OH)8 Æ Fe3O4 + 4H2O (8.43)
The brownish black ferroso-ferric oxide combines with green chromium
oxide to produce an olive-drab-coloured pigment of the probable
composition as Fe3O4·Cr2O3.
Improved fastness to perspiration may be obtained by treating Mineral
Khaki dyed material with a dilute boiling solution (2ºTw) of sodium acetate or
622
boric acid. Another suggestion for improvement of perspiration is an after-

treatment with alkaline T.R. Oil followed by steaming for one hour.
The studies were made for single bath application by pad-dry-cure
process. It was found that certain non-electrolytes containing hydroxyl
groups, such as cane sugar, glycerol, glucose, etc., ammonium carbonate
and ammonium hydroxide, inhibited the reduction of hexa-valent chromium
compounds in the presence of a soluble sulphite in the padding liquor.
Chromium oxide is produced when the padded material is heated to drive off
ammonia. The padding liquor is prepared by mixing 200 litres of the chrome
liquor with 22.5 litres water and 30 kgs ferrous sulphate crystals, 45 litres
glycerol are then added, together with 67.5 litres of 68% caustic soda
solution. The mixture is allowed to stand overnight and 9 kgs ammonium
acetate is added.
Zirconyl ammonium carbonate substituted for ammonium carbonate along
with copper metaborate or carbonate, ammonium dichromate and
ammonium sulphite, produced a fungicidal single bath grey-green dye
system and the process is known as Zirchrome Process.
The colour of Mineral Khaki dyed material is extremely fast to light and
moderately fast to washing. The colorant may be completely stripped by
treatment in dilute acid solutions, e.g. 0.5% hydrochloric acid and 0.5%
oxalic acid solution at 50-70ºC.
8.11 SOLUBILISED PIGMENT COLOURS
Phthalogen dyestuffs or onium dyes belong to this group. Extremely light-

fast phthalocyanine pigment can be modified to render them water-soluble,
with or without affinity for the textile fibre. After application, the temporary
solubilising groups are removed to form the pigment again in situ.
Alternately, the textile material is treated with solutions from which
phthalocyanine can be synthesised in the fibre.
A number of sulphonated phthalocyanine direct dyes, e.g. C.I. Direct Blue
86, were introduced. However, they have poor affinity as well as poor wet-
In Onium or Alcian X dyes, temporary, alkali-sensitive onium groups
(Section 6.2.3) are introduced in pigments like phthalocyanines, vat dyes
and azoic pigments. The solubilised compounds have some affinity for
cellulosic fibres and become insoluble on treatment with alkali. These dyes
are dissolved in cold soft water. The solutions are cationic in nature and
unstable to anionic wetting and dispersing agents. The pH is set at 3.5-4
with acetic acid. Even distribution is achieved at by commencing dyeing at a
low temperature, gradually raising to boil, and continuing dyeing at boil for a
short period, to achieve good penetration. Cationic retarding agent,
623
Lissolamine A, may be used to control exhaustion. Without intermediate

rinsing, the dyed material is treated in a boiling solution of 3-5 g/l soda ash
for 10-20 minutes. The unfixed dye is removed by boiling in a solution of
3 g/l Lissapol NC for 10-15 minutes. The dyeing may be carried out in batch
machines like package dyeing machine, winch or jigger. The application
may also be carried out continuously in pad-steam-develop or pad-dry-
develop sequence.
In case of Phthalogen dyestuffs, the phthalcyanine pigment is synthesised
inside the fibre by impregnating the textile material with a reactive
intermediate such as 1-amino 3-imino-isoindole, Phthalogen Brilliant Blue
IF3G, Bayer (C.I. Ingrain Blue 2:2). It is applied as a solution or a fine
dispersion together with a metal salt such as Phthalogen K (copper
compound) or Phthalogen NI (nickel compound). Unfortunately, these dyes
have been banned recently.
8.12 RESIN-BONDED PIGMENT COLOURS
Pigment dyeing is a process of overall application of pigment with the help of

a binder, which forms a transparent cross-linked film on the fibre surface,
thereby physically retaining the non-substantive pigments.
Attractive features of this method of coloration are:
1. Wide choice of pigments so that those with the maximum fastness to

light may be selected.
2. The wash fastness can reach a high standard if a suitable binder is
used.
3. Affinity differences between different portions of the fabric (or between
different fibres present in the same fabric) are of little or no
significance.
4. The application may be combined with various finishing agents such
as crease-resisting, glazing or stiffening finishes.
5. The normal method of application to piece goods by pad-dry-cure
sequence is attractive because of the simplicity of application, energy
savings by elimination of washing step and a high production rate with
a small labour force.
The disadvantages are low fastness to rubbing, difficulty of achieving deep

shades in dyeing, degradation of binder film on exposure to light and stiffer
handle of the dyed fabric. Considerable progress has already been made to
minimise the above problems. Pigment printing is commercially very popular
for cellulosic and blended materials. Deep and bright shades are achievable
in printing without difficulty as the emulsion thickening used in the process,
624
keeps the pigment particles on the surface. On the other hand, in pigment
dyeing, the aqueous dispersion used cannot prevent pigment particles from
penetrating into the interior of the yarn and fabric, resulting in poor colour
yield.
The two main components in this process are the pigments and the
binder. The pigments are mostly organic azoic, vat, and phthalocynine
compounds and carbon black. The physical state of the pigment is important
as it is to be dispersed in the binder. The covering power of the pigment is
the most important characteristic for its application. Ebler’s rule states that
the covering power of the pigment increases with diminishing particle sizes,
until this value becomes of the same order as the wavelength of the light
reflected or absorbed. With further reduction of particle size, translucency
begins. The pigment must be fast to light, unaffected by the binder and by
the normal treatments a dyed textile material will receive.
The binder film should attach the pigment to the fibres completely and
permanently, and it should be soft and flexible enough to have the minimum
effect on the handle of the fabric. It should be fast to light, washing and
normal treatments, which the textile material may be given. The binder must
be in liquid form and its viscosity should be readily adjustable to a value
suitable for padding. It is disclosed that the Acramin binders (Bayer) are
made by emulsion co-polymerisation of olefinic unsaturated monomers in an
aqueous medium. These monomers include acrylic acid esters (e.g. butyl or
ethyl acrylate), styrene, acrylonitrile, vinyl chloride, vinyl acetate, asymmetric
dichloroethane, and diolefins such as butadiene. The binders, as made, are
milky liquids and are called synthetic lattices. The solid substances in the
binder are completely polymerised and do not undergo further
polymerisation during curing. The particle size of these solid substances
varies from 0.05 to 2 µ. High quality binders contain up to 6% (on the weight
of binder) reactive groups in the co-polymer, which crosslink the co-polymer
molecules with each other or with the hydroxyl, amino and other groups of
textile fibre during curing at a pH of about 3.
Binder-CH2OR + HO-Textile ↔ Binder-CH2O-Textile + HOR (8.44)
Where R is H or CH3.
Since water or methyl alcohol is formed as a by-product, leading to the
fixation of the binder onto the fibre substrate, the reaction is favoured by
removal of water or methyl alcohol. Curing with fresh air at high temperature
effectively removes these products.
The crosslink ensures optimum fastness properties (especially washing) of
the binder film and the pigment colour.
Some additional crosslinking agents, such as etherified methylol
melamines, e.g. Fixer CL (DyStar), may be incorporated in case of
hydrophobic fibres like polyester or polyamide for improvement of rubbing
625
fastness. However, they should be added in small quantity as they stiffen

the binder film.
For application, an efficient padding mangle, a dryer and a baking or
curing machine are required. No soaping or washing treatments are
required. The bowls of the padding mangle should be of equal hardness to
avoid two-sided effects. The drying may be carried out in hot flue dryers, on
stenters or on drying cylinders. In the latter case, the first few cylinders
should be at a lower temperature than the remainder. One of the problems
encountered during application of binder-pigment dispersion, is the
migration of the pigments during drying causing unevenness of shade.
Migration usually takes place largely on cylinders than on other types of
dryers. The baking is carried out in the usual type of baker used for resin
finishing.
Binder Acramin FKLN (Bayer, Dystar) forms a neutral dispersion in water.
A catalyst, such as ammonium nitrate, sulphate or chloride or diammonium
phosphate is added to the binder dispersion. The recipe for each kg of fabric
may be as follows:
Acramin pigment emulsion – 2-30 g

Acramin FKLN binder – 45-95 g
Acetic acid (30%) − 15 g
Ammonium chloride or nitrate − 3-4 g
The binder is stirred into approximately five times its weight of water and
acetic acid is added. The pigment emulsion is pasted up in about ten times
its weight of water, strained and stirred with the acidified binder dispersion.
The solution is then made up to a little short of the requisite volume,
sufficient water being retained for dissolving the catalyst, which is added just
before padding. A softening agent, Persoftal FKL may also be added after
dilution. Various finishing agents, requiring similar fixation conditions, may
also be incorporated. The padding liquor is strained before padding and
should have a pH of about 4. The material is padded, dried and baked at
135ºC for 4-6 minutes.
The stripping of the resin film is not easy. It is possible, however, to
destroy and to remove some the pigments in the resin film, if these are of
the azoic or vat types. A typical treatment consists of 20 g/l caustic soda
solution (71ºTw), 6 g/l sodium dithionite, 5 g/l polyvinylpyrrolidone (Albigen
A, BASF) and 1 g/l anthraquinone paste. The stripped material is best
redyed with a resin-pigment system, as the residual binder film may interfere
with other dyeing methods.
626
REFERENCES
1. J.A. Taylor. 2000, Rev. Prog. Coloration, 30, 93-107.
2. G.W. Madaras, G.J. Parish and J. Shore. 1993, Batchwise Dyeing Of
Woven Cellulosic Fabrics, A Practical Guide (Bradford, UK: SDC).
3. S.R. Cockitt and K.A. Hilton. 1961, Dyeing of Cellulosic Fibres and
Related Processes, (London. UK: Leonard Hill Books).
4. J. Park. 1986, International Dyer and Printer, December Issue.
5. Sumitomo Chemical Co. (Japan). 1985, Problems of Dyed Goods With
Reactive Dyes and Advantage of Sumifix Supra Dyes,
6. U.S. International Trade Commission (Washington DC)., 1977,
Synthetic Organic Chemicals: United States Production and Sales, P87.
7. J. Shore. (Ed.) 1995, Cellulosics Dyeing (Bradford: SDC).
8. J. Shore. 1991, Rev. Prog. Coloration, 21, 23-42.
9. Bayer AG. 1976, Bayer Farben Revue, No. 4/1, P28.
nd
10. T. Vickerstaff. 1954, The Physical Chemistry of Dyeing, 2 Edn
(London, UK: Oliver and Boyd).
11. Allingham, Giles and Neustetter. 1954, Disc. Farad. Soc., 16, 92.
12. E.R. Trotman. 1984, Dyeing and Chemical Technology of Textile Fibres,
th
6 Edn (London: Charles Griffin).
13. D.M. Lewis. 1998, Rev. Prog. Coloration, 28, 12-17.
14. Z. Yoshida, F. Osawa, and R. Oda. 1964, J. Physical Chem., 2895.
15. N. Bhattacharya et al. 1990, ADR, 79, March Issue, 24.
16. C.L. Bird and W.S. Boston (Ed.). 1975, The Theory of Coloration of
Textiles (Bradford: SDC).
17. W.F. Beech. 1970, Fibre-Reactive Dyes (London: Logos Press).
18. K. Parton. 2004, In: SDC Symposium on Reactive Dyes: A Celebration
of 50 Years of Innovation at Manchester (UK) on 14-16 April.
19. A.H.M. Renfrew and J.A. Taylor. 1990, Rev. Prog. Coloration, 20, 1-9.
20. L. Dongzhi, G. Kunyu and C. Lubai. 1991, JSDC, 107, 319.
21. N. Morimura and M. Ojima. 1985, ADR, 74, February Issue, 28.
22. P.S. Collishaw, M.J. Bradbury, J.A. Bone and R.F. Hyde. 1998,
Colourage Annual, 117-125.
23. S.M. Betrabet, V.B. Bagwe and E.H. Daruwalla. 1987, JSDC, 103, 338.
24. U. Meyer and S. Muller. 1990, Text. Chem. Colorist, 22, 26.
25. M. Haelters. 1980, Melliand Textilber., 61,1016.
26. N. Harada et al. 1991, JSDC, 107, 363.
27. T. Sugimoto. 1992, JSDC, 108, 497.
28. W. Ebenezer. 2004, In: SDC Symposium on Reactive Dyes: A
Celebration of 50 Years of Innovation at Manchester (UK) on 14-16
April.
29. J.A. Fowler and W.J. Marshal. 1964, JSDC, 80, 358.
30. I.D. Rattee. 1964, Chimia, 18, 293.
627
31. K. Venkataraman. 1968, Colourage, XV (1), 59.

32. M. Matsui, U. Meyer, and H. Zollinger. 1988, JSDC, 104, 425.
33. J.M. Sire and P. Browne. 1991, Melliand Textilber., 72, 465.
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35. D. Link and E.J. Moreau. 1988, Int. Text. Bull., 34 (1), 13.
36. ICI Ltd. (UK). Procion Dyes: Cotton Dyeing, Shade Card (Pl229)
37. R. Klein. 1980, International Textile Bulletin, 3/80.
38. D.M. Lewis and K.A. Mcllroy. 1997, Rev. Prog. Coloration, 27, 5-17.
39. S.N. Croft, D.M. Lewis, R. Orita. 1992 , T. Sugimoto, JSDC 108, 195.
40. D.M. Lewis, and X.P. Lee. 1990, IFATCC Congress Book Of Paper,
Lucerne, Switzerland.
41. T. Robinson. 1987, Melliand Textilber., 68 (2),137.
42. U. Baumgarte. 1987, Rev. Prog. Coloration, 17, 29-38.
43. Daruwalla, Rao and Tilak. 1960, JSDC, 76, 418.
44. E.I. Valkó. 1941, J. Am. Chem. Soc., 63, 1433.
45. Balasubramanian, Daruwalla and Kuwaida. 1970, Colourage, 17 (13),
31-38.
46. ICI Ltd. (UK). Dyes Pattern Card – Solanthrene Vat Dyes for Dyeing (Pl
216).
47. U. Baumgarte. and H. Schluter. 1985, ADR 17, 27-32.
48. B. Schmitt. 1998, Colourage, XlV, October, 20-24.
49. L.I. Mukhortova et al. 1987, Tekstil. Prom., 47, Dec., 24.
50. Cassella AG (Germany), The Dyeing Of Hydron Blue.
51. Bayer AG (Germany). 1965, Bayer Farben Revue, Sp. Ed. No. 5E.
52. Atul Limited (India), Dyeing of Cotton Yarn With Tulathols, Shade Card.
53. Dyeing of Mineral Khaki on Cotton. 1975, Colourage, 22, January issue.
54. C.J. Conner. 1974, ADR, 63, 37.
Chapter
Dyeing of Animal Fibres 9
9.1 INTRODUCTION
Wool and silk are the two natural textile fibres having importance next to
cotton. Both are protein fibres obtained from animal sources. Depending on
the species, they are available in wide varieties having varied qualities and
costs. It is difficult to recommend specific processing conditions for them;
the conditions are to be changed depending on the quality of the specific lot
of fibre. Wool is obtained from sheep, while silk is obtained from silkworms.
Both need careful rearing. High qualities of wool and silk are very costly and
need very careful handing. They have complex chemical structure. They are
delicate and very sensitive to alkali and heat.
These fibres can be dyed with various classes of dyes, the most important
being:
1. Acid dyes
2. Chrome dyes
3. Premetallised or metal-complex dyes
4. Reactive dyes
Less important classes, which were once popular, but now are of
theoretical interest, are direct dyes, basic dyes, solubilised vat dyes, etc.
The breakdown of traditional wool coloration processes is estimated [1] to
be as follows:
Loose stock dyeing − 16%

Top dyeing − 16%
Yarn dyeing (hank and package) − 40%
Piece and garment dyeing − 28%
Quick response has become an important factor in the wool-processing

pipeline, and the industry has identified late-stage coloration as a means of
delaying production commitments until the final possible stage. Current
629
emphasis is on improving application techniques in package dyeing, piece

dyeing and garment dyeing to reduce stock holding and shorten delivery
times.
Fibre damage in wool dyeing has been minimised in new machine
designs, incorporating controlled liquor flow, pressure and optimised drying
procedures. Radio-frequency technology has become a standard in wool-
drying systems based on conveyor belt R.F. dryer.
In yarn coloration, dyeing in hank form is still popular, because of the
bulky handle it produces, but the winding and unwinding operations are
inefficient and the restricted liquor circulation and channelling can lead to
unlevelness. Package dyeing provides a much more uniformly dyed
substrate. Horizontal package dyeing machines have the flexibility to keep
liquor ratios constant with varying batch sizes.
Woollen yarns, which are to be dyed in package form, are preferably dry
spun with a minimum quantity of lubricant. Water-soluble lubricants can be
removed by simple rinse – extensive scouring in package form is expensive
and difficult. Yarns for weaving, knitting and carpets are dyed with acid
milling and metal-complex dyes at pH 5.5-6.0 in the presence of a levelling
agent and optionally a moth-proofing agent such as Eulan WA (DyStar,
formerly Bayer). Wool fibres, which have been given a shrink-resist
treatment in sliver form, are generally dyed with reactive dyes.
In fabric dyeing, the limited liquor circulation found in winch machines has
restricted their use to applying levelling and Sandolan MF half-milling dyes.
However, with modern jet dyeing machines, milling acid dyes can be applied
in a level manner [2].
The four major stages in woollen fabric processing are carbonising,
scouring, milling and dyeing. The processing stages can be carried out in
various sequences [3]. Grey carbonising allows maximum removal of
cellulosic contaminants, but unless selected lubricants (mostly saponifiable
types) are used, the acid solution is contaminated. Least damage of wool is
claimed, but long storage in highly acidic condition may cause damage and
yellowing. Acid treatment, followed by an alkaline treatment without care,
can cause serious damage. Scouring before carbonising means that a larger
number of lubricating oils can be used by the spinners, but burr removal
may be difficult, especially for highly contaminated materials, due to
consolidation of fabric during scouring. Acid and alkaline milling techniques
give fabrics of different quality; the former gives denser felting. When
carbonisation is done before dyeing, neutralisation is not necessary for
levelling acid dyes and 1:1 metal-complex dyes. The following sequence
gives significant economics in acid consumption.
Scour Æ carbonise Æ semi-neutralise Æ acid mill Æ dye with levelling
acid dyes.
630
Discharge printing is popular on silk material. To prepare discharge

ground shades, selected direct dyes are used. Substantive direct dyes are
also suitable for covering component fibre. These are also used for covering
cellulosic components coming from dust in the weaving mill in heavy silk
fabric (e.g. shantung) and also in schappe blends. Direct dyes are applied in
dyeing under the same conditions as those for acid dyes.
The affinity of basic dyes for wool and silk is probably due partly to
electrostatic attraction between the basic group in the dye and the carboxylic
groups in these fibres and partly to non-polar Van der Waals’ forces. In
general, the affinity is not very high, so they show only moderate exhaustion.
Basic dyes are now rarely used for wool and silk dyeing, more so since acid-
modified Rhodamine and triphenylmethane dyes for very brilliant shades in
green and turquoise blue hues are available. Certain basic dyes are used as
discharge-resistant illuminating colour in discharge printing. Basic dyes may
be applied on silk material at 85ºC using 0.5 g/l acetic acid. Fastness can be
improved by treating the dyed material with 1% (o.w.m.) tannic acid for 20
minutes at 60ºC or alternatively for overnight at cold. After squeezing, the
material is further treated with a cold or lukewarm solution having 0.5 g/l
tartar emetic, followed by washing.
Solubilised vat dyes can also be used as discharge-resistant illuminating
colour in discharge printing of silk. Most of the solubilised vat dyes are
suitable for application on wool. Indigosol O, derived from indigo, behaves
like milling acid dyes, but dyeing is followed by strong acid treatment to
regenerate the parent vat dye by hydrolysis and oxidation, and then by
soaping to develop the true shade and maximum fastness properties of the
dye. The method, mainly of interest for loose wool and slubbing, is to start
dyeing at 40ºC with 5% ammonium sulphate, the temperature is raised to
boil and kept for 30 minutes. 1-6% formic acid (85%) is added and dyeing is
continued for a further 30 minutes. If exhaustion is incomplete, 2% sulphuric
acid is added further. After dyeing and rinsing, the colour is developed by
oxidation for 30 minutes at 80ºC in a bath containing 5-7½% ammonium
persulphate and 10-20% sulphuric acid, all percentages are on the weight of
material (o.w.m.). With Indigosol O, oxidation may also be carried out with
sodium nitrite and sulphuric acid. Rinsing, neutralising and soaping for 15
minutes at 70ºC, in a bath containing 0.5 g/l Lissapol N (ICI) completes the
process.
Acid dyes are comparatively cheaper and produce bright dyeing, while
dyeing with the chrome mordant works out to be expensive. These dyes
they produce dull shades of good all round fastness. The major objection to
their application is the release of objectionable chromium compounds in the
effluent water. Metal-complex or premetallised dyes are easy to apply and
produce dyeing of reasonably good fastness. Reactive dyes find application
631
on these fibres nowadays and produce bright dyeing with good fastness
properties.
One of the major problems of wool dyeing is the uneven dyeing or skittery
dyeing. If the wool cuticle is damaged by localised chemical attack or by
abrasion, more rapid strike of dyes occurs on the exposed cortical cells. At
low dyeing temperature, all dyes are taken up preferentially by damaged
fibres and fibre tips. At higher temperature, the more polar the dye is, more
strongly it is absorbed by the damaged fibres. Dyes of low molecular weight
cover damaged fibres well and they produce less skittery dyeing by
subsequent migration. With dyes of higher molecular weight, particularly
sulphonated 1:2 metal-complex dyes, good coverage can be achieved by
the use of cationic auxiliary products. They form hydrophobic complexes
with anionic dyes, and these complexes are less sensitive to differences in
dyeability of wool fibres [4]. Moreover, wool fibres are very porous and
entrapped air in these pores causes the fibres to float on the dyeing liquor
during dyeing. Sufficient precautions are to be taken so that the material is
dipped under the liquor during dyeing.
Since 1960s, after the advent of the domestic washing machines, our
requirements for clothing have changed. In the past, formal attire was
probably of great concern. Now, we live to a far extent in a wash-n-wear
culture. The synthetic fibres and cellulosic natural fibres were able to
conform to new culture, whereas wool had a marked disadvantage – it has a
tendency to shrink even in mild hand or machine washing. Shrink-resist
processes modify the wool fibre to restrict its natural ability to undergo felting
shrinkage. An additional application of a polymer resin renders wool
knitwear fully machine washable. This modified fibre is not only more
receptive to dye, but also exhibits a markedly lower colourfastness.
In blends of wool with synthetic fibres, the good handle, comfort and drape
properties of wool have been complemented by the additional easy-care
properties of synthetic fibres, which impart strength, washability and stability
to a blend. This has been further enhanced by the introduction of synthetic
microfibres. Blends of wool with nylon are common in knitwear and footwear
and blends with polyester are common in woven articles. Elastomeric fibres,
such as spandex, are also becoming important.
These developments led to a need for faster dyes that could withstand
domestic washing, even in deep shades. As a result, new dye ranges of
higher colour fastness are demanded and 1:2 metal-complex and reactive
dyes find more application on wool at present. However, the higher colour
fastness of 1:2 metal-complex and reactive dyes is to some extent negated
by their poor level-dyeing properties, and as such, their use is restricted to
dyeing loose fibre and slubbing. Further developments are required so that
they can be applied in yarn or garment forms.
632
Levelling agents are always used in wool dyeing. Glauber’s salt is the
main levelling agent. It promotes migration with levelling acid dyes, but may
precipitate milling and 1:2 metal-complex dyes of large molecular weight due
to aggregation. Fibre-substantive cationic type levelling agents are very
popular. They reduce dye-uptake by complex formation and promote
migration of adsorbed dye. Fibre-substantive amphoteric type levelling
agents, such as Lyogen TP (Clariant), are also popular. They improve
coverage of the inherent variations of wool (such as tippiness) and
increased yield with some dyes [2].
9.2 ACID DYES
Acid dyes are so called, because the original members of this class were
applied in a bath containing mineral or organic acids. Another reason is that
nearly all of them are sodium salts of organic acids and the anion is the
active coloured component. They are mostly sulphonic acid salts, but a few
of them contain carboxyl groups. The acid dyes have direct affinity towards
protein fibres and are the main class of dyes used for dyeing of wool and silk
and also for synthetic polyamide fibres or nylons. Most of them do not
exhaust well on cellulosic fibres, but since they resemble direct dyes in
chemical constitution, a reasonable number of them can dye cellulose quite
well. A few such dyes are C.I. Acid Red 134, Blues 83 and 118, Blacks 7
and 48. However, they are not commercially used for cellulose mainly
because of poor wash fastness.
Acid dyes are sold under various brand-names, such as Sandolan
E/N/P/Fast P/MF, (Clariant, formerly Sandoz), Acidol K/M, Palatine Fast
(BASF), Supranol, Telon (DyStar, formerly Bayer), Polar (Ciba), Tulacid
(Atul), etc.
These dyes are mainly confined to three chemical classes, viz. azo,
anthraquinoid and triphenylmethane, although other classes, e.g. azine and
xanthene, provide individually important dyes.
According to chemical constitution, the acid dyes may be classified into
several groups [5], such as:
1. Azo groups – a very large number of acid dyes contain one or more
azo groups. C.I. Acid Reds 1 and 142 are examples of mono and
disazo dye respectively. As the number of azo groups within the
molecule increases, the shades tends to become dull, darker and
flatter. Hence, the number of trisazo acid dyes is limited. This class
includes most of yellows, virtually all the oranges and scarlets, and
633
most of the reds. The blue acid azo dyes are rather dull and not very
important, except for the navy blues. Green and violet azo dyes are
dull in shade. Brown azo dyes can be made by mixing. The azo class
has a virtual monopoly for the black dyes.
2. Pyrazolone azo dyes constitute an important group having
comparatively good light fastness combined with ease of application
and very level dyeing. The first member of this group, Tartrazine, was
discovered in 1884. Other examples are C.I. Acid Yellows 13, 17, 27
and 41.
3. Triphenylmethane derivatives − this is the oldest class, the first
member of this group, Nicholson Blue was first made in 1862. A few
others are C.I. Acid Blues 1, 3 and 7, and Greens 5 and 50. This class
provides brilliant blues, greens and violets. Among the other blues well
known is C.I. Acid Blue 69. The greens include C.I. Acid Green 16
and the violets include C.I. Acid Violet 15. Dyes of this class have poor
wash fastness, a few have moderate fastness.
4. Xanthene derivatives – these are closely related to the
triphenylmathane dyes. Examples are C.I. Acid Reds 50 and 52, and
Violet 9. They are widely used for brilliant pinks, in spite of their
moderate fastness to light.
5. Azine derivatives – this class includes important dyes like C.I. Acid
Blues 59 and 102. These dyes have high tinctorial power and the
class provides bright navy blues of good all round fastness.
6. A number of nitrated aromatic compounds are classified as acid dyes,
e.g. C.I. Acid Yellow 1 and picric acid.
7. Anthraquinoid derivatives – They cover mostly blue hue range and are
characterised by a high degree of wash fastness. Examples are C.I.
Acid Blues 43, 45 and 127, and Red 80.
8. Phthalocyanine derivatives – they provide very bright greenish-blue
and green dyes of very high light and washing fastness, e.g. C.I. Acid
Blues 224, 249, and 275 and Green 97.
9. Carbolan dyes – they do not form a separate class, but are
characterised by their high fastness to milling and wet treatments.
These dyes were developed by ICI by introducing long alkyl chains
(C12H25 or two C4H9 groups) in the dye molecule. The hue is not
greatly influenced by this incorporation. The yellows and red are
probably azo dyes and the others anthraquinoid. The presence of a
fatty acid chain in these dyes causes frothing in the dyebath [6].
In general, the chemical class of the dye does not determine its dyeing
and fastness properties. Thus, the azo class includes equalising and milling
acid dyes as well as dyes that are very fast to light and others that have
poor fastness. One property of the dye, which is important to the dyer, is
634
governed by chemical constitution, viz. behaviour towards reduction

stripping. All azo dyes are reduced by sodium hydrosulphite and sodium
sulphoxylate-formaldehyde. The colour may be discharged to white, in other
cases a yellow or fawn colour remains after stripping. Triphenylmethane
dyes are also decolourised, but the reduction products revert to the original
dye to a greater or lesser extent in the presence of an oxidising agent.
Anthraquinoid and azine dyes are reduced to coloured leuco compounds,
which revert to original dye by air or oxidising agent. However, the suitability
of an acid dye for discharge printing cannot be deduced from its chemical
class. Azo group incorporates dyes with varying degree of dischargability.
The reduction components of some triphenylmethane dyes revert back to
original dyes partially and are suitable in pale shades for discharge printing.
Anthraquinoid and xanthene dyes can be used as non-dischargable
illuminating colour in discharge printing paste.
In general, acid dyes, with increasing molecular weight, show increasing
anion-affinity and therefore, require a less strongly acid dyebath for
adequate exhaustion. In practical use, acid dyes are classified by their
dyeing behaviour and wet fastness properties, rather than by chemical
composition. Dyeing behaviour is, however, determined to a great extent by
the molecular weight and the degree of sulphonation.
Acid dyes used for wool dyeing are arbitrarily classified into four groups
[1], namely:
1. Level-dyeing or equalising acid dyes

2. Fast acid, half-milling or perspiration-fast dyes
3. Acid milling dyes
4. Supermilling dyes
The above list is in order of increasing fastness and decreasing levelness,

although there may be overlap between adjacent categories.
Level-dyeing or Equalising Dyes
The dyes belonging to this group show rapid adsorption at pH 2-3 even at a
temperature as low as 40ºC. This group covers more than 50% of the total
acid dye listed in Colour Index. Though these dyes are commonly referred to
as level dyeing acid dyes, some members of this group provide only
moderately level dyeing. Moreover, many dyes belonging to other groups
also give level dyeing. The old term, equalising acid dyes is thus preferable,
such as Sandolan E dyes (Clariant). They are also known as molecularly
dispersed dyes, because their state when in solution is such. Nevertheless,
most of the dyes belonging to this group give level dyeing, e.g. C.I. Acid
Yellow 17. These dyes have low anion affinity and therefore, migrate readily.
Dye and process costs are low, but only moderate to poor fastness can be
635
achieved. There is a risk of damage of high quality wool at the low pH

required for dyeing.
Due to excellent levelling properties, these dyes are suitable for dyeing
woollen and worsted fabrics in traditional wool winches and yarn (particularly
carpet yarn) in hank form on Hussong-type machines. Because of low
relative molecular mass (r.m.m.), these dyes can penetrate satisfactorily on
tightly woven fabrics such as gaberdines. This property is also utilised on
hard twist carpet yarns as well as traditional soft yarns where optimum
levelness is required and wet fastness requirements are less critical.
The levelling acid dyes are most often used for pale to medium-depth
shades, where a high degree of fastness is not required.
There are two broad subdivisions of equalising acid dyes –
monosulphonated and disulphonated. There are also a few tri- and tetra-
sulphonated equalising acid dyes.
The monosulphonated dyes have r.m.m. in the range of 300-500. These
dyes migrate well and give good coverage of dyeability differences within
the fibre.
Disulphonated dyes have slightly higher r.m.m. (400-600) values. They
are less capable of covering differences in dyeability than monosulphonates.
The monosulphonated dyes are slightly superior to the disulphonated in
terms of coverage and fastness, but are also somewhat more costly to
manufacture. The choice between monosulphonated and disulphonated
dyes will depend upon the performance requirements of the final product,
the homogeneity of the wool in the material to be dyed and economic
limitations.
The chemical structures of a monosulphonated (C.I. Acid Blue 40) and a
disulphonated equalising acid dye (C.I. Acid Blue 45) are shown in (9-1) and
(9-2) respectively. Both have very poor fastness to alkaline milling (rating 1).
O NH2
SO3Na OH O NH2
NaO3S
O NH NHCOCH3 SO3Na
NH2 O OH
(9-1) (9-2)
Both mono and disulphonated equalising dyes are applied in the same
manner. About two-thirds of all equalising acid dyes are recommended only
for dyeing from a sulphuric acid dyebath. The remainders can be applied by
more than one method, the best being from sulphuric acid dyebath.
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Some important members of equalising acid dyes (* - suitable for tertiary

combination), best suited for specific purposes, are as follows [3]:
1. For good coverage of carbonising faults – C.I. Acid Orange 3, Red 80,
Blue 40.
2. Good levelling but poor fastness – C.I. Acid Yellows 17 and 23, Reds
1, 37 and 52, Violet 7, Blues 2, 7 and 52, Green 16.
*
3. Higher fastness and reasonable levelling – C.I. Acid Yellow 29 ,
* *
Orange 53, Reds 57 , 240 and 289, Violet 41, Blues 67 and 72 .
*
4. Very high fastness – C.I. Acid Yellow 25 , Reds 130 and 145, Violet 4,
*
Blue 271 , Black 26:1.
Fast Acid Dyes
This group, also known as half-milling or perspiration-fast dyes, are
generally monosulphonated and of r.m.m. about 500-600. The class is
exemplified by Sandolan P/Fast P (Clariant) and Supramin GW (DyStar)
dyes e.g. C.I. Acid Blue 62 (9-3). They exhibit superior wet fastness
properties over equalising acid dyes but retain similar migration property [1].
The shade range of this group is not as extensive as that of the levelling or
milling dyes but still covers a usefully wide gamut. The dyes are used on
piece goods or yarns where equalising dyes cannot provide required
fastness – for example, in heavy shades. These dyes can also be used for
garments and knitwear or hand-knitting yarn requiring certain degree of
fastness to washing and good levelness. The levelness provided by the
wash-fast dyes like milling or metal-complex dyes are unacceptable in these
cases.
Acid Milling and Super Milling Dyes
Acid milling dyes are so named because they have some degree of fastness
to milling processes, which indicates a higher level of wet fastness than
other acid dyes. Even within the class, there is a further subdivision, the so-
called supermilling acid dyes. These dyes have still higher wet fastness
properties attributed to longer alkyl side chains. This group comprises dyes
of high anion affinity requiring minimum amount of acid. They are commonly
known as neutral dyeing acid dyes.
The milling acid dyes are sold under various trade names, such as
Supranol (DyStar), Polar and Irganol (Ciba), Sandolan N/Milling N and
Lanasyn Brilliant (Clariant) dyes.
Some important milling acid dyes are [3]:
C.I. Acid Yellow 79, Reds 111 and 134, Violet 48, Blues 80 and 138,
Green 25
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These dyes are of high molecular weight (r.m.m.) of about 600-900. C.I.
Acid Red 86 (9-4) is a disulphonated milling acid dye having alkaline milling
fastness of 3-4.
O NH2 OH OH
SO3Na CH3O OCH3
N=N N=N
CH2 CH2
O NHCH CH2
NaO3S SO3Na
CH2 CH2
(9-3) (9-4)
These dyes diffuse much more slowly than typical levelling acid dyes and
exhibit higher wet fastness. However, the migration and coverage properties
are poor. Poor migration may be attributed to nonpolar Van der Waals’
forces and hydrophobic interactions between such big molecular dye and
fibre. These dyes result in tippy dyeing, i.e. the affinity for the tip of the fibre
is different from that for the bulk of the fibre. To obtain a slower and more
uniform rate of absorption, the addition of a levelling agent may be
necessary. Milling acid dyes are not easily combinable as other acid dyes,
and they are most suitable for self-shades and for brightening shades of 1:2
metal-complex or chrome dyed material. Milling acid dyes are used for those
applications where good wet fastness properties are necessary – loose fibre
or slubbing for multicolour yarn, e.g. yarns for colour-woven worsted fabrics.
Milling acid dyes are also used for garment and knitwear yarns where
machine-wash fastness is not required, although in pale shades the super-
milling may be adequately fast even for machine-washable performance.
Milling acid dyes are mostly used for brighter shades of good fastness
properties, whereas the more economical chrome or metal-complex dyes
are generally used for the darker or duller shades.
Super-milling acid dyes are similar to conventional milling acid dyes, but
contain higher alkyl substituents (e.g. butyl, octyl, dodecyl) to impart more
hydrophobic character to the molecule, as in the case of Carbolan acid dyes
introduced by ICI. At a price, this confers higher neutral affinity, better
coverage of dye uptake differences in the fibre and exceptionally high wet
fastness. They do not form a separate chemical class. The increased
fastness to milling and other wet treatments is obtained by introducing one
C12H25 or two C4H9 groups into the dye molecule. Such alteration in structure
does not greatly influence the hue. For example, C.I. Acid Red 138 (9-6),
has the same chemical structure as C.I. Acid Red 1 (9-5) except that it
carries a dodecyl group on the benzene ring. The presence of this group
enhances the affinity of C.I. Acid Red 138 for wool and its fastness
638
properties are better than C.I. Acid Red 1. Alkaline milling fastness of the
dye is very high (rating 5). For woollen fabrics, higher levels of wet fastness
are required, because of the greater degree of wet finishing and milling that
are often needed. For this reason, loose wool and yarn for woollen fabrics
are normally dyed with supermilling dyes. In pale shades, the supermilling
dyes may be adequately fast even for machine-washable performance.
NHCOCH3 NHCOCH3
OH OH
SO3Na SO3Na
—N=N— C12H25 – —N=N—
SO3Na SO3Na
(9-5) (9-6)
The complete exhaustion of these dyes may be obtained with either acetic
acid or ammonium sulphate, but the latter is preferred because the
adsorption of dye is slower and consequently more even. Some dyes have a
critical temperature range (generally between 70º and 80ºC), where the rate
of adsorption is very high. This is likely to cause initial unlevelness that can
be subsequently corrected by migration at boil. During dyeing the
temperature should be raised very gradually through the critical range. In
certain cases, the temperature should be kept constant for some time when
the lowest temperature of the critical temperature range is reached.
The purpose of adding ammonium salt in the dyebath is twofold, namely:
1. Liberation of a small amount of acid at boil by partial decomposition
NH4OOCCH3 Æ NH3↑ + CH3COOH (9.1)
2. Neutralisation of residual alkali of wool at boil, thereby preventing the
increase of pH in dye bath.
Na2CO3 + 2NH4OOCCH3 Æ 2CH3COONa + (NH4)2CO3 (9.2)
Even if no acid has been added, the dyebath may not be neutral. Before
dyeing, wool usually contains 0.1-1.0% residual sodium carbonate absorbed
while scouring in loose, yarn or piece form. This retained alkali dissolves in
the boiling dye liquor and the pH may rise as high as 9-10, resulting in some
damage of wool and permanent creases in piece goods. In order to
neutralise residual alkali, a weak acid or an ammonium salt is added in the
dye bath. The material is run in the machine for 15-20 minutes at the starting
temperature, with only the dyeing auxiliaries present in order to establish a
substantially uniform pH throughout the material.
There is no sharp division between the different classes of acid dyes and
some dyes do not behave typically in all respects. For example, some
equalising acid dyes aggregate in solution up to 80-90ºC, whilst others
639
exhaust considerably from neutral dyebath. The general properties of most

of the members of the three sub-classes of acid dyes are shown in Table
9.1.
Table 9.1 Typical Properties of Different Classes of Acid Dyes
Property Equalising Half-Milling Milling/Super Milling
Solution Molecular Colloidal Colloidal
Aggregation Low Medium High
Anion affinity Low Medium High
Rate of dyeing Rapid Medium Low
Neutral dyeability Very low Low High
Levelling by Na2SO4 High Low None
Migration Rapid Slow Very low
Wet fastness Low High Very high
On the basis of early dye diffusion work, it was believed that whilst some
dyes may be aggregated at low temperatures, acid dyes would not be
aggregated to any appreciable extent at the high temperature and in the
presence of usual amounts of salt and acid employed in dyeing. Recent
works, however, showed that many acid dyes remain aggregated even at
boil. The problems of dyeing of wool with a few sparingly soluble acid dyes
are due to:
1. The formation of dye aggregates that cannot easily enter the wool
fibre because of their large molecular size.
2. A high affinity of the dye, making it difficult for these dyes to be readily
migrated and readsorbed to achieve a uniform distribution of dye in
the wool.
Tetrasulphonated C.I. Acid Red 41 (8-8) (Section 8.3.1) has been shown
to be monodisperse in aqueous solution by both diffusion-based and light
scattering techniques, as the four sulphonic groups confer upon the
molecule a high degree of hydrophilicity. When the number of sulphonic
group is reduced to one (by eliminating three sulphonic groups from
naphthalene ring) as in C.I. Acid Red 88, then the aggregation is expected
to increase. The aggregation is high below 25ºC and the dye dissociates at
high temperature and even monomeric at 50ºC.
C.I. Acid Orange 7 (9-7) and C.I. Acid Red 88 have the same chemical
structure, except that in former the sulphonate group is on a benzene rather
than on a naphthalene ring as in the latter. Thus the orange dye is less
hydrophobic than C.I. Acid Red 88 and can be expected to be more soluble
in water and less aggregated. However, various studies indicate that the dye
is aggregated below 60ºC.
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OH
NaO3S N=N
(9-7)
The aggregation also increases with the introduction of hydrophobic alkyl
groups. When n-butyl group (-C4H9) is introduced in a disulphonated dye,
the dye shows considerable aggregation. The aggregation increases
dramatically when the n-butyl group is replaced with an n-octyl (-C8H17)
group. Monosulphonated dyes with identical hydrophobic groups will be
more hydrophobic and more highly aggregated than the corresponding
disulphonated dye.
Many wool dyes are highly aggregated and more hydrophobic the dye, the
more likely it is to aggregate. Levelling agents conceivably reduce the
aggregation of the dyes. Urea accelerates the rate of dyeing particularly at
low temperature, possibly by desegregation of dye and weakening of the
binding forces at the interface, thereby allowing easier penetration of the
dye.
9.2.2 Dyeing Methods

Adequate wetting out of the fabric before dyeing is essential. With
carbonised fabrics a pre-rinse may be given to remove excess acid. Uniform
neutralisation may be difficult to achieve, so that appropriate choice of dyes
and process is important. The level dyeing properties of 1:1 metal complex
and equalising acid dyes at low pH can be utilised to dye uniformly
carbonised fabrics, which have not been neutralised. With most classes of
dyes, however, it is necessary to even out pH before dyeing.
Equalising acid dyes
They are usually applied from a dyebath containing 2-4% (o.w.m.) sulphuric
acid (168°Tw) or 1-3% formic acid and 5-10% (o.w.m.) Glauber’s salt. The
goods are entered at 50°C, pH is checked (2.5-3.0) and the dissolved dye is
added in portions. The temperature is then raised to boil in 30 minutes and
boiled for a further 45-60 minutes, rinsed and dried. Triphenylmethane dyes
are less sensitive to pH than other members of the group and may be
applied from neutral as well as from a sulphuric acid bath. Those of low
molecular weight have low affinity for wool and exhaust only 50-60% from
sulphuric acid bath. Dyes of higher molecular weight have higher affinity.
641
Occasionally when unlevel dyeing is encountered, the concentration of

sodium sulphate can be increased to 15-20% and boiling is continued for a
further 30 minutes under such conditions. Mild stripping action occurs with
increased migration. However, preparation faults in piece dyeing cannot be
corrected by this method.
Shade adjustment can be easily made by steps as follows:
• Turning off the steam supply

• Adding predissolved shading dye
• Running for five minutes
• Raising temperature to boil and running for 30 minutes
Fast Acid Dyes
The goods are entered at 50ºC into a dyebath containing 1-3% acetic acid
(80%) and 5-10% Glauber’s salt. The pH is adjusted to 4.5-5.5. The
temperature is raised to boil in 30-45 minutes, kept at boil for a further 45-60
minutes, rinsed and dried. If the exhaustion is insufficient, a little more acetic
acid, or some formic or phosphoric acid may be added. The levelling agent
(1%) may be added, if necessary.
Milling and supermilling dyes
Dyeing is started at 50ºC with 2-5% ammonium sulphate or acetate or 2 g/l
sodium acetate. The pH is set at 5-7.5 with acetic acid. The dyeing pH
depends on the depth of shade and nature of substrate. Pale shades require
a higher pH (6.0-7.5) in order to reduce the rate of dyeing, thereby achieving
level dyeing. On loose stock or tops, however, the level dyeing may be less
critical than, for example, on yarn or piece goods, and lower pH values (5.0-
6.5) may be used. The temperature is raised at boil in 45 minutes, dyeing is
continued at boil for a further 45 minutes, rinsed and dried. If the exhaustion
is incomplete, it may be necessary to add 1-2% of acetic acid (30%) after
boiling for 30 minutes. Ammonium sulphate is available as crystalline
anhydrous salt. Deliquescent ammonium acetate can be prepared by the
dyer by adding ammonia to diluted acetic acid until it is neutral to litmus
paper.
The effect of Glauber’s salt on the level-dyeing performance of milling
dyes is negligible and at neutral pH values used to apply these dyes,
sulphate ions can accelerate dye adsorption. Additions of large amounts of
sodium sulphate are, therefore, normally avoided.
These dyes tend to give more tippy dyeing than levelling acid dyes, i.e. the
affinity for the weathered tip of the wool fibre is different from that for the
bulk of the fibre. For this reason and to obtain a slower, more uniform rate of
adsorption, it may be necessary to add a suitable levelling agent such as
1.0-2.0% Lyogen SMK (Clariant) in the starting dyebath.
642
Shading additions, if necessary, may be done in two ways:
1. Small adjustments may be made by adding levelling acid dyes after

cooling to 90ºC, with little risk of the additions being unlevelled. The
fastness properties are not affected by such small additions.
2. When larger adjustments are to be made or when critical fastness is
required, milling acid dyes may be added after cooling down the
dyebath to 60-70ºC to avoid unlevelness.
Most of the dyes in this group, as well as some dyes from other groups,
may be applied from a dyebath containing 10-40% Glauber’s salt only. The
method is suitable for union dyeing, where acid is undesirable. Good
exhaustion is seldom obtained under these conditions. The damage to the
wool caused by residual alkali is increased if Glauber’s salt is present,
probably due to either hydrolysis of salt, or due to an increase in the internal
pH arising from the Donnan membrane effect [7].
9.2.3 Dyeing Theory

Wool is heterogeneous in character. However, for dyeing theories most
researchers choose to assume models based upon homogeneous fibres.
Apart from the wool’s intrinsic heterogeneity and the different origins of the
wool, other factors such as the moisture content of both the dye and wool
fibre (contributing to concentration errors) and the initial pH of wool, can
greatly affect the reproducibility of colour matching.
The theory of wool dyeing has been studied extensively and the two
famous theories by Gilbert-Rideal [8] and Donnan, have been described by
Peters [7] and others. However, recent works show that neither of the two
theories adequately explains the dyeing behaviour of wool, especially for
dyes with a high hydrophobic character.
Wool is regarded as containing equal numbers of amino and carboxylic
groups loosely held together as the salt linkages which bridge the main
peptide chains. When wool is immersed in water, the amino and carboxylic
groups will exist in the ionised or zwitterion form. At the isoelectric point, the
wool carries no net charge because there are equal numbers of positively
charged ammonium groups and negatively charged carboxylic anions. The
isoelectric region of wool is between pH 4.8 and 7. When acid is added to
the system, hydrogen ions from the acid react with the carboxylate anions to
form carboxylic acid groups, leaving the positively charged ammonium
groups available to act as dye sites for acid dyes as shown in Eqn. (9.3).
Under alkaline conditions, on the other hand, hydrogen ions are abstracted
from the positively charged amino groups. The carboxyl anions then confer
a negative charge on the substrate as in Eqn. (9.4).
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+ + –
H3N -wool-COOH ↔ H3N -wool-COO ↔ H2N-wool-COO–
(acid condition) (9.3) (isoelectric condition) (9.4) (base condition)
The maximum acid-binding capacity of the fibre is governed by the

number of carboxyl groups present. The maximum bound acid or bound
– 1
base is about 0.82 mequiv. g , which is in close agreement with the
number of amino and carboxyl groups in wool. The titration curve for wool
shows that very little acid or base is bound to the wool between pH 4 and
10.
The fibre, therefore, contains equal numbers of positively and negatively
charged sites upon which anions and cations, respectively, can be
absorbed. Gilbert and Rideal [8] assumed that all the sites of one type have
exactly the same properties and the adsorbed ions are free to occupy any
site, irrespective of whether the adjacent sites are occupied or not. Anions
and cations must be adsorbed by the fibre in equivalent amounts to maintain
electrical neutrality. When wool is immersed in a solution of strong acid,
such as hydrochloric acid or sulphuric acid, hydrogen ions are absorbed on
–
the negative sites (-COO ) and a positive potential is established on the fibre
as discussed earlier and shown in Eqn. (9.5).
+ - +
-NH3 OOC- + H+ = -NH3 HOOC- (9.5)
This potential cannot exceed a very small amount, however, so chloride

+
ions are adsorbed on the positive (-NH3 ) sites to restore electrical neutrality
as shown in Eqn. (9.6), although the chloride ions possess very little intrinsic
affinity.
+ - +
-NH3 +Cl = -NH3Cl– (9.6)
Hence, hydrochloric acid or sulphuric acid is adsorbed by wool because of

affinity of the hydrogen ions for the negative sites in wool. In case of a free
acid of a dye, the anion as well as the cation possess affinity for the fibre.
The reaction with strong acid is a reversible one. Hence, equilibrium can
also be reached from the right-hand side by immersing acid-containing wool
in water.
Until fairly recently, most of the dyes used on wool were acid dyes, and
the original theories of wool dyeing were based on the adsorption of acids
by the wool. When wool is dyed with acid dyes, the dyebath normally
contains dye anions, hydrogen ions from the acid, electrolyte, sodium ions
– 2–
from the dye and the counter-ions (Cl , SO4 etc.) from the acid. When wool
is immersed in the dyebath, it would be expected that the smallest and most
rapidly diffusing ions would be quickly adsorbed while the larger and more
slowly diffusing dye anions would follow more slowly. As shown in Figure 9.1
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Cl–
Concentration of
Ions in Bath Æ D–
H+
Time Æ
Fig. 9.1 The Rate of Adsorption of Ions by Wool from an Acid Dyebath
+
[1] initially there will be very rapid adsorption of hydrogen ions (H ) and
–
chloride ions (Cl ). As time proceeds, the more slowly diffusing dye anions
–
(D ) displace the chloride ions from the wool, as demonstrated by the
increase in the concentration of chloride ions in the bath. The dye anion is
preferentially adsorbed owing to its much higher affinity as in Eqn. (9.7).
If the number of hydrogen ions present exceeds the number of dye
+ - - + - -
-NH3 Cl + D ↔ -NH3D + Cl (9.7)
anions, the difference is made up by adsorption of sulphate or chloride ions

in order to restore electrical neutrality, in spite of their low intrinsic affinity.
Conversely, if the number of dye anions exceeds the number of hydrogen
ions, the difference is made up by adsorption of sodium ions, which also
have very low affinity.
The dyeing of wool with acid dyes, therefore, follows Langmuir isotherm
and the dye uptake obeys Eqn. (6.32).
Besides the dye and the acid, a third component, viz. a neutral salt is
normally present. In fact, Glauber’s salt, 10-20% on the weight of wool, is
almost always present in dyebath containing sulphuric or acetic acid.
Consequently, there may be some 50 or more sulphate anions for each dye
anion. The two types of anions compete for the positively charged amino
groups. Dye anions are preferentially adsorbed owing to their much higher
affinity, but sulphate ions are present in such large numbers that they
succeed in replacing some of the dye anions, thus exerting a levelling
action.
The effect of Glauber’s salt can be expressed by the Eqn. (9.7),
considering chlorides as sulphate ions. It follows from the law of mass action
that addition of sulphate ion will disturb the equilibrium and the reaction will
proceed from right to left.
With increase in the affinity of the dyes, Glauber’s salt becomes less
effective as a levelling agent, i.e. it is more effective with equalising dyes
applied from a sulphuric acid dyebath – especially if they are
645
polysulphonated – than it is with milling acid dyes, which are applied under
neutral condition or in the presence of acetic acid.
Sodium sulphate is used in preference to sodium chloride because the
affinity of the chloride ion is very low. For the same levelling action, the
amount of NaCl required may be about four times as much as Na2SO4 being
required. Common salt also causes corrosion of stainless steel machinery.
In a neutral dyebath, exhaustion is mainly through non-polar forces, so
Glauber’s salt exerts no levelling action. However, the supermilling dyes, viz.
Carbolan dyes, are readily aggregated and the aggregation is promoted by
Glauber’s salt followed by transfer to the hydrophobic fibre phase. Glauber’s
salt, therefore, in this case acts as an exhausting agent as in the case of
direct dyes on cellulosic fibres.
The equalising acid dyes have comparatively low affinity for wool, and
they combine with it largely because of ionic attraction. The positive charge
–
on the wool arising from the suppression of the charge on the COO side-
chains increases with the amount of acid adsorbed, i.e. with decreasing pH.
Sufficient strong acid must, therefore, be added to the dyebath to bring pH
at about 3 and to make a sufficient number of positively charged groups
available so that sufficient exhaustion of dye takes place. At higher pH
values fewer sites are available, so the exhaustion is less. In a neutral
solution, where the fibre is uncharged, a little dye is still adsorbed due to the
affinity of the anion. In alkaline solution, some of the basic groups lose their
charge as shown in Eqn. (9.8). The wool fibre becomes negatively charged
and the dye is repelled.
+ - - -
-NH3 OOC- + OH = -NH2 OOC- + H2O (9.8)
Since the equalising acid dyes also diffuse rapidly, some of the dye is
readily removed from the fibre by hot water and considerably more by hot
alkaline solutions. So, in general, these dyes do not possess good fastness
to wet treatments, especially with alkaline detergents.
Acid dyes contain one to five sulphonic groups. The number of sulphonic
groups in the dye molecule influences:
1. Exhaustion of the dye at different pH values.
2. The response to the presence of Glauber’s salt.
3. The rate of dyeing and migration.
While the introduction of non-polar groups (e.g. methyl) increases the

affinity of dye anion, that of a sulphonic group decreases the affinity of the
anion by about the amount contributed by a benzene ring. However, the
affinity of free dye-acid will be more with disulphonated dye due to
absorption of another hydrogen ion as compared to monosulphonated. The
exhaustion of polysulphonated dyes at pH 3 in the absence of Glauber’s salt
646
will be higher than that of the monosulphonates. In neutral solution, on the

other hand, where the affinity is due to the anion, exhaustion will be very low
with polysulphonated dyes.
Since the restraining action of Glauber’s salt is due to anion competition,
this salt is most effective with dyes of low anion affinity. Hence,
polysulphonated dyes with 20% Glauber’s salt at pH 3 will show the lowest
exhaustion.
Rapidly adsorbed dyes also desorb rapidly. The rate of dyeing decreases
with increasing sulphonation and so does migration. Hence polysulphonated
dyes show poor migration properties.
Acid dyes of higher molecular weight and proportionally fewer sulphonic
groups have higher anion affinity. They diffuse slowly and also migrate
slowly, thereby having higher wet fastness and good fastness to milling and
are termed as milling acid dyes. These dyes, though have moderate anion
affinity, depend on ionic attraction for adequate exhaustion of the dyebath,
but to a smaller extent than equalising acid dyes. Since fewer sites are
necessary, a dyebath of higher pH is required, which is most conveniently
obtained by adding a weak acid. With Carbolan and other supermilling acid
dyes, anion affinity is sufficiently high to provide adequate exhaustion at a
pH of about 6-7, when wool is substantially uncharged. At dyebath pH value
as high as 8, acid dyes are adsorbed largely as the free acid instead of
sodium salt. At lower pH, the attraction is too high, leading to a very rapid
strike as well as unlevel dyeing which is not overcome by subsequent
migration.
The so-called Donnan membrane effect relates to the distribution or
partition of ionic species between two different phases. Donnan was able to
show that whilst the sodium and chloride ions were able to diffuse through a
paper membrane into an outer solution, the large dye anions of a direct dye,
Congo Red, were not able to penetrate the membrane and colour the outer
solution. As the penetration into the membrane was dependent upon the
size of the penetrating molecules, the membrane was described semi-
permeable. In dyeing of wool, anions are assumed to have no specific
affinity for the protein, and the various groups in the protein are simply
considered to come to equilibrium with the ions in the external phase. The
Langmuir isotherm, based on Gilbert-Rideal theory (i.e. dye sites) gives
better prediction of affinity than the Donnan theory. However, several
models showed that affinity due to electrostatic attraction is not the sole
force binding dye ions to wool. The Donnan approach predicts that over-
dyeing can occur without the need for extra sites in the fibre.
More recently, Meybeck and Galafassi [9] showed that the release of
chloride ions during dyeing is very slow compared with the amount of dye
adsorbed. For slightly hydrophobic dyes, only about 10% of the bound
chloride ions are released, while for more hydrophobic dyes, the amount
647
was not measurable. This and similar other works indicate that coulombic
forces between the cationic sites in the wool and the dye anions play a very
small part in bonding the dye to the fibre.
Based on their studies, Meybeck and Galafassi [9] made three
conclusions in relation to wool dyeing, namely:
1. Hydrogen bonds do not form between the dye and the fibre.
2. The coulombic forces play a part in attracting the anionic dye to
hydrophobic sites within the fibre only where the dyes become
strongly fixed.
3. Dyes having a high affinity for the wool must have a hydrophobic
character. This hydrophobic character must be created in the dye by
placing the hydrophobic substituents as far as possible from the polar
group in the molecule.
Hydrophobic interactions are important in the dye-wool adsorption process

and dye binding, especially at low temperatures. As the temperature rises,
the hydrophobic interactions decrease and at about 60ºC are no longer
important.
Like surface-active agents, acid dyes may be regarded as consisting of a
polar or hydrophilic portion (e.g. sulphonic group) which imparts water-
solubility, and a hydrophobic portion (e.g. benzene rings or long alkyl chain)
which resists dissolution in water and promotes dissolution in organic
solvents. Keratin is largely hydrocarbon in nature and on this view it is the
non-polar portion of the dye, which imparts affinity for wool to acid dyes.
Dyeing is thus analogous to the extraction of a non-polar substance from
+ –
aqueous solution by an organic solvent. In addition to the ionic (-NH3 D )
linkage, the dye anion is attached to the wool through Van der Waals’
forces, the strength of which increases on passing from the equalising to
milling acid dyes.
Therefore, the acid dyes are adsorbed by wool as a result of two quite
different chemical forces of attraction, namely:
– +
1. Ionic attraction between –SO3 of dye and –NH3 of wool fibre, and
2. Non-polar Van der Waals' forces exerted between the hydrophobic
portions of dye and fibre.
The two types of linkages are as shown in Figure 9.2 by a simple model
[6].
9.2.4 Role of Fibre Structure

While studying the thermodynamics of dyeing process in Gilbert and Rideal
or Donnan model, the major concern was the dye uptake at equilibrium and
the wool fibre was considered as a cylinder of uniform composition. They,
648
Wool
↔
↔
↔
↔
↔
↔
↔
↔
– +
Dye SO3 NH3
Å Van der Waals' Æ Åionic bond Æ
forces
Fig. 9.2 Linkages between Wool Fibre and Acid Dye
however, provided little information on the mechanism of the dyeing process

itself.
In recent years, there has been a growing concern on the importance of
diverse morphological structure of wool in determining its dyeing behaviour.
In order to obtain satisfactory shade and fastness, complete penetration of
dye into the interior of the fibre is essential. The rate at which this occurs is
controlled by the rate of dye diffusion across the fibre surface and
throughout the whole interior. Fick’s law of diffusion (Eqn. 6.35) states that a
plot of dye uptake versus the square root of time should be a straight line
over most of the dyeing curves. In case of wool, however, the dyeing curve
is initially concave and becomes linear only after some time. It is, therefore,
assumed that a barrier, with a small capacity for dye, exists at the fibre
surface. This barrier is responsible for the non-Fickian isotherms obtained
with wool.
Earlier it was thought that the epicuticle is a continuous membrane and it
acts as a barrier to dye penetration. It has now been proved that the
epicuticle is not a continuous membrane, however, but it surrounds each
individual cuticle cell. Thus, gaps exist between the scales where the
intercellular material extends to the exterior of the fibre. The gaps between
the scales allow the dyes to penetrate wool without diffusing through the
cuticle.
The present findings support the view that the cuticle, probably the highly
crosslinked A-layer of the exocuticle, is a barrier to dye penetration, in that
the dyes are directed to the gaps between the scales in order to reach the
cortex. It appears, however, that the lipids present in the intercellular
junctions are also a barrier to the diffusion of dyes into the non-keratinous
regions of the cell membrane complex.
The intercellular mode of dye penetration applies to unmodified wool. The
dyeing behaviour drastically changes when substantial physical or chemical
damage of the fibre occurs, namely reduction of the A-layer of the
exocuticle, complete removal of cuticle or severe surface abrasion.
After initial penetration into wool fibres, the dyes must diffuse throughout
the entire cross-section. Cuticle cells are separated from the underlying
649
cortex, and the cell membrane complex separates the individual cortical
cells from each other. A fine wool fibre can, therefore, be considered as an
assembly of cuticle and cortical cells held together by the cell membrane
complex, which is the only continuous phase in wool. There is no universally
accepted definition for what constitutes the cell membrane complex. Rippon
[1] considers it to consist of three components, namely:
• An easily swollen intercellular cement containing lightly crosslinked

non-keratinous protein (the δ layer).
• A hydrophobic lipid component, which may be associated with the β
layers.
• A chemically resistant proteinous membrane that surrounds each
cortical and cuticle cell.
Several workers have suggested that the continuous network of the cell
membrane complex provides a pathway for the diffusion of reagents into
wool. As the dyeing cycle proceeds, dye progressively transfers from the
non-keratinous regions of the cell membrane into the sulphur-rich proteins of
the matrix that surrounds the microfibrils within each cortical cell. Dye also
transfers from the endocuticle into the exocuticle, particularly the A-layer.
The hydrophobic proteins located in these regions have a higher affinity for
wool dyes than the non-keratinous regions, which are important in the early
stage, but are virtually devoid of dye at the end of dyeing.
For non-reactive dyes, therefore, thermodynamic equilibrium with wool is
not established until the process of dye transfer into the keratinous region is
complete. If dye remains largely in the non-keratinous region, rapid diffusion
out of fibre may occur resulting in poor wet-fastness properties. This is the
reason why a prolonged time at an elevated temperature is required for
producing satisfactorily dyed wool.
Reactive dyes, however, may show a somewhat different equilibrium
distribution between the keratinous and non-keratinous regions of wool. As
reactive dyes can form covalent bonds with the proteins of the non-
keratinous region, they may be present in the cell membrane complex and
endocuticle to a greater extent than in non-reactive dye [1].
9.2.5 Damage of Fibre

Conventional wool dyeing methods involve prolonged treatment at or near
boil in order to achieve good levelling and penetration into the fibre. The pH
is maintained between 2 and 7 depending on the type of dye and equipment
used. Under these conditions, wool proteins may be damaged resulting in
unacceptable levels of yellowing, impairment of fabric properties such as
abrasion resistance, reduced productivity and yield.
650
Damage to wool in hot aqueous, acidic dye liquors occurs mainly by

hydrolysis of peptide chains. Alkaline hydrolysis is less selective and more
rapid than under acidic conditions. It is now believed that that preferential
attack on the readily swollen non-keratinous regions, particularly cell
membrane complex, is a major factor in the impaired physical performance
of wool often found after dyeing. When wool is dyed at boil, soluble proteins
of low cystine content, termed as wool gelatins by Zahn and Meienhofer [10]
are extracted from the fibre, the yield of which is regarded as a measure of
fibre damage. The amount of extract is relatively small compared with the
total fibre mass, but its effect on the physical properties of the fibre may be
large. The extraction of 2% (o.w.m.) wool-gelatins may result in a decrease
of 25% of its wet tensile strength. At a given pH, the yield is proportional to
the treatment time. This is an indication that unnecessarily lengthy dyeing
cycles will cause more fibre damage.
It has been demonstrated that the level of damage is kept to a minimum
when wool is dyed at a pH value within the isoelectric region of the fibre (4.9
at 20°C and 4.6 at 90°C). Under these conditions, the concentration of salt
linkages is at a maximum level, hence their stabilising effect on the wool
proteins is greatest. Peryman [11] concluded that minimum fibre damage
occurs when wool is dyed at pH 3-3.5, whereas Elöd and Reutter [12]
suggested that pH 4.5-5 gives optimum results. Some others suggested the
pH range of 3.5-4. Except with 1:1 metal-complex or acid levelling dyes,
dyeing is carried out between 4 and 7 with the latent risk of changes in wool.
Although the effect of dyebath pH on fibre damage has been known for a
long time, it is only recently that the ranges of dyes have been marketed
which are especially suitable for application at or around the isoelectric
region of wool.
Amide bonds can be readily hydrolysed under acidic or alkaline
conditions, whereas the cystine disulphide crosslink is increasing cleaved by
hydrolysis reactions at pH values greater than 3. Thus, in dyeing processes,
the damaging effect of dyeing at pH 1.8-3.0 is mainly due to amide bond
splitting, whereas above pH 3, the damage is increasingly associated with
disulphide bond hydrolysis. If dyeing is performed in alkaline side, as in the
case of wool-cotton blend dyeing with reactive dyes, then the damaging
process involves both disulphide and amide bond cleavage.
The original fibre protecting agents were the protein hydrolysates added to
loose wool dyebaths to give softer handle and to reduce fibre losses in
carding, such as Protegal BR (Protex), Levana WO (Clariant), Meropan EW
(CHT), etc. However, the protein derivatives have a deleterious effect on
fastness properties, especially wet rubbing. The formaldehyde-based
protective agents can cause harsh handle, reduction of some dyes and are
not eco-friendly. Irgasol HTW (Ciba) liberates free formaldehyde slowly at
high temperature, 3% (o.w.m.) of which should be employed. The probable
651
active constituent of the product, dihydroxymethylethylene urea (DHMEU),

offers better fibre protection than formaldehyde.
Lanaset (Ciba) are especially selected fast dyes, which with acetate buffer
and an auxiliary, called Albegal SET, allows level dyeing at pH 4.5 with
minimum fibre damage. BASF proposed the use of 6% sulphamic acid and a
special auxiliary, Uniperol 5700 (1%) instead of 8% sulphuric acid with 1:1
metal-complex dye.
The results from the dyeing at 120°C indicate that the full depth dyeing
with bifunctional reactive dyes is at least as effective as formaldehyde or
formaldehyde precursors (e.g. Irgasol HTW of Ciba) in controlling damage
during dyeing, thus offering dyers of wool-polyester blend fabrics a real
alternative. For wool-cellulosic blends, acceptable limits of wool damage
can be achieved if the cellulosic component is dyed by limiting the carbonate
concentration to 7 g/l and the treatment time to 75 minutes at 40°C [13].
Disulphide bond hydrolysis is associated with permanent setting of wool in
boiling water. When this set is acquired in dyeing process then the effect
can either enhance or detract the quality of wool. Examples of setting effects
in dyeing include:
(a) Irreversible loss of bulk in package dyeing leading to yarn leanness.

(b) Improved yarn set and maintenance of bulk in hank dyeing.
(c) Formation of running marks and crows feet during piece dyeing in
winches.
(d) Flat setting of wool pieces during beam dyeing or in pad-batch dyeing,
In their natural state, wool fibres are essentially straight apart from their
natural growth crimp. During processing, bends and sometimes, sharp
bends are introduced into the fibre. These bends become permanently set
during dyeing, placing the fibres under great strain during subsequent
processing. The likelihood of fibre damage is increased and processing
performance reduced. The Basolan AS (jointly developed by IWS, CSIRO
and BASF) process involves a dyebath additive that inhibits permanent
change to the shape of wool fibre. This also prevents the wrinkle of seams
when wool garments are made in dry condition and exposed to high
humidity. Bulk is lost in conventional package dyeing because the yarns are
set under tension on the package. Basolan AS enables yarns to return
closer to their original state after dyeing [14].
The fibre damage caused by dyeing is reduced markedly when wool is
dyed at temperature below boil. The low temperature dyeing methods have
been discussed in Section 9.8.
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9.2.6 Unlevelness and Levelling Agent

A certain amount of unlevelness is permissible in wool dyed in the form of
loose fibre or slubbing, because subsequent mixing evens out small
irregularities. With yarn and fabric, level dyeing is of utmost importance.
Level dyeing is more difficult to obtain in pale shades as compared to dark
shades.
Initially the dye is not taken up uniformly. Some part of the material comes
in contact with fresh liquor more frequently than others and so are dyed
darker. The degree of unevenness largely depends on the initial strike, i.e.
the dye adsorption in the first few minutes. The permissible degree of initial
unlevelness depends on the extent to which it can be eliminated by
subsequent migration from heavily dyed to less heavily dyed portions of the
material. Equalising acid dyes migrate better than milling acid dyes, whilst
supermilling acid dyes migrate very little.
Unlevelness may also be due to inherent defect, or faulty preparation of
material, or due to poorly designed or improper working of the dyeing
machine. Even if the above factors are properly controlled, unlevelness may
occur due to unsatisfactory control of the dyebath. Two such causes are the
existence of a critical temperature range where the temperature should be
raised slowly and the use of additional acid to exhaust the dyebath resulting
in lowering of pH and subsequent rapid exhaustion. Shading dyes used at
the end of dyeing may also cause unlevelness. For equalising dyes, the
levelness may be achieved by continued boiling for a sufficient length of
time. With milling acid dyes, the shading may be a problem as addition of
such dye at boil may cause unlevelness. Lowering of temperature by
replacing some of the boiling dye-liquor with cold water will shift the
equilibrium and some dye may come out of the material to the bath, thus
making shade matching more difficult. The two properties governing the
levelness are the migration and the rate of dyeing. Poor migrating dyes may
be dyed at a slower rate by increasing the pH.
For migration test, a dyed material is boiled with an equal quantity of
undyed material in a blank dyebath containing acid and Glauber’s salt as
required in dyeing for 90 minutes. If the desorption is sufficiently rapid, the
equilibrium will be attained during the time – both materials will be dyed to
the same depth with a small amount of dye remaining in the dyebath. In
most cases, the equilibrium is not reached in 90 minutes and the degree of
transfer indicates migration property of the dye.
A comprehensive test will be very useful for the dyer. In strike-migration
test [6], a 5-gram wool pattern is placed in a boiling dyebath. Further
patterns, each weighing 1 gram, are then added at intervals of 5, 10, 15, 20
and 25 minutes from the commencement of dyeing. The dyeing is continued
for a further 45 minutes at boil. The levelling power of the dye is then
assessed by comparing the 1-gram patterns with the 5-gram pattern. A poor
653
levelling dye will show a sharp depth difference between the 5-gram pattern
and the 1-gram pattern entered 5 minutes later, whilst the 1-gram pattern
entered last will be almost undyed. For an excellent levelling dye, there will
be no colour difference in the first case and 50% depth in the second case.
The contrast may also be assessed by SDC Grey Scale for assessing
change of colour.
In Egli test (Clariant) [6], a solution of dye at 100ºC is circulated repeatedly
through a vertical column of felt discs. A band of colour passes gradually
down the column and the distance moved by the point of deepest colour
(usually near the middle of the band) is a measure of migrating power and
rate of dyeing. The test can be carried out at different pH values.
On the basis of standardised tests, manufacturers rate the level dyeing
behaviour of their dyes on a 1-5 scale, where 1 indicates poor levelling and
5, the excellent. The rating refers only to the specified optimum conditions of
dyeing and is particularly significant with supermilling acid dyes. With
equalising acid dyes, migration is very rapid and such gradation may not be
possible.
The dyes, which provide good wet fastness on wool, may not give level
shades and a powerful levelling agent is required. The levelling agents are
required for supermilling acid dyes, selected monosulphonated equalising
acid dyes and 1:2 metal-complex dyes.
Levelling agents, which possess both nonionic and cationic properties,
combine with the dye and perform the following functions:
1. Owing to restraining action, they slow down the rate of dyeing and
levelling is greatly improved in either neutral or slightly acidic
conditions. Dyeing may be started at high temperature and thus
dyeing time may be reduced. However, there may be a decrease in
exhaustion, especially in neutral dyebath and for pale shades, when
excessive quantity of such auxiliary is added.
2. When a mixture of acid dyes is being used, these products reduce the
differences in dyeing behaviour between individual dyes, thus
facilitating the production of solid shades.
3. The pH sensitivity of the dye is reduced, thus enabling neutral dyeing
acid dyes to be applied from an acetic acid bath preserving the quality
of wool.
4. Tippy or skittery dyeing is prevented on unevenly chlorinated,
carbonised or abraded wool.
5. Aggregation of dye is reduced. Many wool dyes are highly aggregated
even at boil. The more hydrophobic the dye is, the more likely it is to
aggregate. The products like NP30 (an adduct of a branched
nonylphenol and ethylene oxide, containing an average of 30 ethylene
oxide moles for each mole of nonylphenol) was found to have a
654
significant effect on the 1:2 metal-complexes. For many such levelling

agents, such as Albegal A and Albegal B (Ciba), the disaggregating
effects are highly specific to the dye. Urea is the only one that
significantly disaggregates all the dyes at both 55 and 95°C.
Most of the milling acid dyes dissolve appreciably in the micelles of

nonionic compounds owing to the hydrophilic sulphonic groups. When a
cationic compound is present, the sulphonic group is inhibited with the
formation of a sparingly water-soluble complex which is also soluble in the
micelles of nonionic compounds. Therefore, levelling agents, such as Atexal
LC-CWL (ICI), Univadine W (Ciba), Avolan UL (DyStar), and Lyogen WD
(Clariant), are developed in which nonionic and cationic segments are
(CH2CH2O)4CH2CH2OH
C17H35N
(CH2CH2O)4CH2CH2OH
(9-8)
combined in a single molecule such as (9-8).

The balance of the nonionic-cationic properties is important. The
compounds should be weakly cationic, otherwise the dye will be held too
strongly – due to high restraining action, dye exhaustion will be poor. It is
important that the dye should combine with the auxiliary product and then be
liberated gradually for combination with the fibre as the temperature of the
weakly acid dyebath is raised. With products like Avolan UL, sodium
sulphate is added in order to promote micelle formation.
The coverage of tippy wool is due to inhibition of sulphonic group, as a
result of which acid dye behaves in a manner nonionic like disperse dye,
which covers tippy wool extremely well. The dye-auxiliary complexes,
however, appear to have no affinity for the fibre and uniform coloration
depends on the presence of a very dilute solution of free dye, together with
those migrated by desorption.
1:2 metal-complex dyes are less hydrophilic than non-metallised dyes and
more weakly cationic products with lower affinity, e.g. Lyogen SMK
(Clariant) and Irgasol SW (Ciba), which are possibly a mixture, are required.
These are suitable for both metallised and non-metallised acid dyes and
also for their mixtures. A similar product, Lyogen DK (Clariant), is
recommended for neutral dyebath of wool-cotton union materials and
minimises the differences in the rate of dyeing between the individual direct
dyes.
655
When a levelling and restraining agent is used, several drawbacks, apart

from the extra cost, may be encountered. Some products may create
excessive foam causing floating of the material, hampering liquor circulation
and unlevel dyeing. Silicon-based defoamers can minimise foam generation.
If the temperature is raised above cloud point of the nonionic product, the
complex separates as globules and adheres to the material. There may be
the problem of static charge generation in spinning due to complete removal
of oils.
9.2.7 Decomposition of Dyes

Most of the acid dyes used for wool are stable in dyebath. However, azo
linkage of a few acid dyes is sensitive to the mild reducing action of cystine
in wool, which is exerted in hot, alkaline solutions, especially while dyeing
around boil. One of the most important milling acid dyes, C.I. Acid Blue 113,
suffers from the drawback that the shade frequently turns brown, possibly
due to steam contaminated with alkali, the presence of iron in the dyebath
and the alkaline condition of the fabric after scouring. The rate of
decomposition is largely governed by the pH of the dye-liquor and the rate
increases above pH 7. The decomposition can be largely prevented by
adding 5% ammonium sulphate and retarded by 1% acetic acid. The other
dyes, which tend to hydrolyse on prolonged boiling above 100ºC, are C.I.
Acid Blue 120 and Black 24. To counteract this problem, it is customary to
add ½% potassium or sodium dichromate while using these dyes.
C.I. Acid Red 1 loses acetyl group on prolonged boiling in an acidic
dyebath, the shade becomes bluer and duller and less fast to light. Some
anthraquinoid acid dyes show alteration of shade in the dyebath in the
presence of traces of iron or nitrite in the acid dyebath. C.I. Acid Blue 45
changes to the corresponding tetrahydroxy compound, which is dull reddish
blue and the dyeing is unlevelled.
9.3 CHROME DYES
Chrome dyes or acid mordant dyes are acid dyes having additional groups
which enable the dye to form a stable co-ordination compound with
chromium or with the fibre, thereby improving light and wet fastness. The
complex formation is accompanied by bathochromic shift of the colour and
the hue may change from red to blue. An example of such a dye is C.I.
Mordant Blue 79, when applied as a levelling acid dye it produces a bright
red shade, but as an afterchrome dye it produces a deep blue shade. The
red acid dye has poor wet fastness, whilst the blue chromed dye has
exceptionally high wet fastness. Both dyes give equally level dyeing as they
are applied in the same way prior to chroming.
656
In the unchromed state, the dyes are not fast to alkali. Chrome dyes are
not as bright as acid dyes and the shades are similar to 1:2 metal-complex
dyes. The latter dyes are suitable for pale to medium shades, while chrome
dyes are best for full depths. The light fastness of some chrome dyes is not
good in pale depths. The dyes of both dye-classes are often brightened by
adding to the recipe a small amount of milling acid dyes.
Chrome dyes have a special position in wool dyeing, since when applied
by the afterchrome method, they have very good level-dyeing and migration
properties and excellent wet fastness after chroming. Because of their high
fastness performance and economy, chrome dyes are most widely used for
heavy shades, such as navy and black, and their good level-dyeing
properties make them suitable for all substrates.
Some important chrome dyes used for specific shade areas are as follows
[3] :
C.I. Mordant Red 7 (maroon), Blue 47 (navy), Brown 27 (brown) and Black
9 (black) and Yellow 5 (shading dye).
The disadvantages of chrome dyes include long dyeing times, potentially
high level of fibre damage, severe changes in colour during chroming,
difficulties in correction of faulty dyeing and chromium residues in the
effluent. The disadvantages may eventually lead to ceasing the use of
chrome dyes in near future.
Some chrome dyes have poor aqueous solubility and may be deposited
on the surface of the dyed material in the presence of hard water and acid.
Francolane (Francolour) dyes were marketed in finely dispersed free acid
form. As the temperature of the dyebath is raised between 70 and 80ºC, the
dye gradually dissolves and is adsorbed by the wool to give a level, well-
diffused dyeing.
Except for bright shades, chrome dyes are used for all branches of wool
dyeing, namely loose wool, rags, slubbing, yarns and pieces, where
fastness required is higher than that obtainable with acid dyes. One problem
with chrome dyed loose wool is that chromium soaps are formed with free
fatty acids in spinning oil, which are difficult to remove by scouring and
causes poor fastness to rubbing.
9.3.1 Chemical Classification

Chrome dyes may belong to various chemical classes, namely
1. Azo
2. Anthraquinoid
3. Triphenylmethane
4. Xanthene [6].
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Azo
About 80% of chrome dyes belong to azo group, mostly monoazo with a few
important disazo dyes. These cover the whole hue range except bright
blues, violets and greens. Azo chrome dyes show highest fastness to light
and wet treatments. They can be applied by all three mordanting methods
described later, with a few exceptions. The azo dyes may be subdivided
into:
/
1. o,o -dihydroxyazo dyes, the most important member of the sub-group
is C.I. Mordant Black 11 (9−9). Other important members belonging to
this sub-group are C.I. Mordant Green 15, C.I. Mordant Black 15, and
pyrazolone derivative, C.I. Mordant Red 7.
/
2. o-amino-o -hydroxyazo dyes incorporate important brown dyes such
as C.I. Mordant Brown 48 (9−10). Other important members are C.I.
Mordant Browns 1 and 33. These dyes have less aqueous solubility,
especially in the presence of acid, due to the absence of sulphonic
and carboxylic groups.
OH HO
O2N OH H2N
NaO3S -N=N-
-N=N- NH2
O2N CH3
O2N (9−9) (9−10)
3. Salicylic acid derivatives incorporate nearly all yellows and oranges

and a few of the browns, and are characterised by bright hues, e.g.
C.I. Mordant Yellows 3 (9−11) and 5.
The above three sub-groups include most of the azo chrome dyes. Other
smaller sub-groups containing important individual azo chrome dyes are:
/
1. o-hydroxy-o -carboxyazo dyes incorporate one important dye, C.I.
Mordant Red 9 (9−12),
2. Azo chrome dyes in which the metal-complex formation is
accompanied by oxidation to the quinone form, e.g. C.I. Mordant Black
9.
Anthraquinoid
The parent dye in the anthraquinoid group is alizarin or 1,2-
dihydroxyanthraquinone. The dye was originally obtained from madder, a
natural product, and then manufactured synthetically. It has no affinity for
658
NaO3S OH COONa
COON -N=N-
-N=N- OH
NaO3S NaO3S
(9−11) (9−12)
wool and can be applied after mordanting. The sulphonated product (3-
sulphonic acid), C.I. Mordant Red 3 is water-soluble and may be applied by
the after-chrome method. The other members, e.g. Anthracene Brown (1,2,3
trihydroxyanthraquinone) and Alizarin Orange (3-nitro derivative) have very
low aqueous solubility. They behave like disperse dyes. The most important
chrome dye of this group is C.I. Mordant Black 13 (9−13) and 38.
Triphenylmethane
Triphenylmethane group incorporates important bright blue chrome dye, C.I.
Mordant Blue 1 and Violet 3. These dyes are derivatives of salicylic acid.
Like all the triphenylmethane dyes, their fastness to light is only moderate.
Xanthene
The members belonging to this group are very few, but brightest chrome
red, C.I. Mordant Red 27 (9−14), belongs to this class.
+
(C2H5)2N O N(C2H5)2
O OH SO3Na
C
–NH–
-
COO
NH– –SO3Na HOOC

O
OH
(9−13) (9−14)

During application of chrome dyes, it is not only necessary to fix the dye on
wool, but also to apply the chrome mordant ensuring the combination of dye
and mordant inside the fibre.
Historically, dyers used to apply natural mordant dyes with different
mordants in order to produce a range of colours from each dye. With the
659
development of synthetic mordant dyes, however, chromium has become

the almost universally used metal in mordant dyeing.
The chromium compound used is sodium or potassium dichromate. The
sodium salt (Na2Cr2O7, 2H2O) is hygroscopic, slightly more soluble and
slightly cheaper. Chromate salt may also be used instead of dichromate,
one changing to another on addition of acid or alkali respectively.
2Na2CrO4 + H2SO4 = Na2Cr2O7 + Na2SO4 + 2H2O (9.9)
Na2Cr2O7 + 2NaOH = 2Na2CrO4 + H2O (9.10)
The chromium is occasionally used in the form of oxalate or fluoride.
The chromium mordant may be applied in three stages before, during or
after dyeing, namely:
1. Chrome mordant, prechrome or on-chrome method before dyeing.
2. Metachrome or chromate method during dyeing.
3. Afterchrome method after dyeing.
The method employed depends on the dyes used and the type of material
being dyed.
Chrome Mordant Method
This is oldest but less important method than the other two. In this method
wool is first mordanted with a chromium compound and then dyed. The
method gives good coverage of wool fibres of different dye-affinity and
permits simple shade matching. The uptake of chromium is also greater on
undyed wool as against dyed wool – in dyed wool protonated amino groups,
which attract anionic chromate or dichromate ions, are partially neutralised
by the anionic groups of the dye.
Chrome mordant process requires two separate baths, and is
consequently expensive on time, energy and water. Fibre damage is also
more as compared to modified after-chroming method. The wet fastness is
also slightly lower than that obtained in the latter method. Some of the less
important chrome dyes, e.g. Alizarin and its derivatives, and natural mordant
dyes, e.g. Logwood, must be applied by this method as they do not have
any affinity for wool fibre. The method is particularly suitable for light and
medium shades on worsted fabrics [4].
For mordanting, the bath is prepared with 1-3% dichromate and
auxiliaries, dissolved separately and the material is entered at 60ºC. The
temperature is raised to boil within 45 minutes and the treatment is
continued for 60-75 minutes. 0.5% acetic acid (30%) is added to the
mordanting bath to neutralise residual alkali retained from scouring and that
liberated during chroming. The dichromate itself, however, exerts buffering
action, being converted into chromate by alkali.
660
The chrome mordanting may be of three types:

1. Reduced chrome with a reducing acid or acid salt.
2. Sweet chrome without reducing agent.
3. Sour chrome using 1-3% sulphuric acid.
Some chrome dyes, e.g. C.I. Mordant Red 7, are readily oxidised by
chromic acid. In these cases, a reducing acid or acid salt, such as 1-3%
potassium hydrogen tartrate, 1-2% formic acid, 1-3% oxalic acid or 3-5%
lactic acid along with 1% sulphuric acid is added. These compounds
complete the conversion of Cr(VI) to Cr(III) and by exerting a chelating
action, transfer Cr(III) from the wool into solution. This facilitates migration
and even uptake throughout the material. Both sweet chrome and sour
chrome methods give oxidised mordants. These yellow-coloured mordanted
materials should not be exposed to light as yellow Cr(VI) is partially reduced
to greenish grey Cr(III) causing uneven dyeing. The sour chrome
mordanting is rapid and may be uneven.
After chroming, the material is rinsed and is entered into a fresh dyebath
containing dyestuff and 1-5% acetic acid (30%) at 50ºC. The temperature is
raised to boil in 45 minutes and the dyeing is continued for 60-75 minutes.
Further acid may be added, if the exhaustion in incomplete. The fastness to
milling can be improved further by afterchroming with 0.5% dichromate for
30 minutes.
Metachrome Method
The method relied on the simultaneous application of dye and chromium salt
in a dyebath at neutral pH (6.0−7.0). Obviously, the application is restricted
to those dyes, which have reasonable neutral affinity for wool. A high degree
of levelness is achieved due to dyeing at neutral pH and thus the method is
widely used for piece dyeing of fabrics. There is little interference from iron
or copper contaminants as these are insoluble at neutral pH. The suitable
dyes should not be precipitated by the chromate or dichromate and the latter
should not be precipitated by the dye.
The disadvantages of the process are:
1. The availability of a limited number of suitable dyes having neutral
affinity.
2. Difficulty in getting heavy shades due to limited exhaustion at neutral
pH.
3. Poor rubbing fastness in heavy shades.
4. High residual chromium in the dyebath.
Despite the disadvantages, the technique is still popular for piece dyeing
and for specific shades such as browns, e.g. C.I. Mordant Brown 48.
661
The metachrome mordant consists of one part sodium chromate and two
parts ammonium sulphate. The latter reacts with the alkali resulting from
adsorption of chromic acid by wool, thereby maintaining pH between 6 and
8.5 and minimises damage to wool.
(NH4)2SO4 + 2NaOH = Na2SO4 + 2NH3↑ + 2H2O (9.11)
However, in a closed machine, the dyebath will be increasingly alkaline.
The dye is added in the dyebath at 50ºC and 3-8% (or less depending on
the dye) predissolved and well-diluted metachrome mordant is added. The
material is now entered and the temperature is raised to boil in 45 minutes.
The dyeing is continued at boil for 60 minutes. There are many variations of
the method. 10% Glauber’s salt or acetic acid may be added. Ammonium
sulphate may be substituted by ammonium acetate.
Afterchrome Method
The afterchrome method is now the most widely used technique for the
application of chrome dyes. The dyeing and chroming processes, although
separate steps, are often carried out in the same bath, thereby reducing
dyeing time, water and energy requirements. However, the dichromate
should be added after exhaustion of the dye, otherwise the chromium-dye
complex may precipitate in the dyebath. Presumably, some trivalent
chromium is removed from wool in an acid dyebath. There is also a risk of
partial destruction of dye through oxidation. Like metachrome method, there
is no restriction on shade. Milling and potting fastness properties are better
than those obtained by the other two methods.
However, shade matching is difficult with afterchrome process – the shade
of the dyed material changes after chroming. Hence, shading additions are
often made with milling or 1:2 metal-complex dyes, which will be sufficiently
fast at the low levels used for shading. Shading dyes must, of course, be
stable in the presence of chromate or dichromate ions.
The dyeing is started at 50ºC in a bath containing the dye, 2-5% acetic
acid (30%) and 10% Glauber’s salt. Some chrome dyes are of equalising
acid type (e.g. C.I. Acid Red 14), dyeing of which are to be carried out with
2-4% formic, sulphuric acid or phosphoric acid. For dyes, which are difficult
to level (e.g. C.I. Mordant Green 15), 5% ammonium acetate or sulphate is
used instead of acetic acid. The temperature is raised to boil in 45 minutes
and the dyeing is continued for 30 minutes. The complete exhaustion of the
dyebath is to be made by adding, if necessary, more acetic acid or ½ -1%
sulphuric acid and by further boiling. The dyebath is then cooled to 70ºC and
¼ -3% dichromate is added. The temperature is then again raised to boil
and the boiling is continued for a further 30-60 minutes.
The addition of dichromate at low temperature ensures even adsorption of
chromate ions. The dyeing may be otherwise uneven. The quantity of
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dichromate should be one-fourth to one-third of the weight of dye. Excess of

dichromate may oxidise some chrome dyes. Certain excess, however, is
necessary in order to obtain better fastness to milling.
The shade and fastness properties of some afterchrome dyes depend on
the pH of the chroming bath. Low pH values favour 1:1 complex formation
instead of usual 1:2 complex. A mixture of the two types may form, which on
subsequent alkaline treatment, e.g. milling, may cause a change of shade
due to conversion of 1:1 to 1:2 complex.
9.3.3 Theory of Chroming

Chromium is added to the chroming bath mainly as sodium or potassium
dichromate. In solution, the chromium species present vary according to pH,
although in the region of most importance in chrome dyeing (pH 3.0-7.0) the
2–
dichromate anion Cr2O7 is predominant. The dichromate reacts with basic
side-chains in the wool, as with organic acids and dye-acids (9.12).
+ - +
2 -NH3 OOC- + Cr2O72– + 2H+ Æ -NH3 2 Cr2O72– + 2 -COOH (9.12)
As dichromate ions are adsorbed, hydrogen ions are taken up

simultaneously to restore electrical neutrality, thus leading to liberation of a
little alkali and a slight increase in pH.
2– 2–
Other species like chromate (CrO4 ), bichromate (HCrO4 ) and
polychromate also present. They may also participate in the reaction with
wool.
The uptake of chromium on wool is influenced not only by pH but also by
the nature of any acidifying agent. Lower pH results in increased uptake of
chromium from the chroming bath. Dibasic acids, such as sulphuric acid, are
not effective as monobasic acids such as hydrochloric or nitric acid. The
decreased uptake of chromium is also observed in the presence of
Glauber’s salt. The reason may be the increased competition for protonated
amine groups in wool by divalent sulphate ion. Other polyvalent anions
would, presumably have a similar effect.
The kinetics of adsorption of chromium on undyed wool shows that the
uptake decreases with increase of temperature. This may be due to the
formation of Cr(III), which cross-links amino and carboxyl groups. The
alternate explanation is the absorption of hydrogen ions during the reduction
of Cr(VI), thereby changing the internal pH of the fibre.
2–
Cr2O7 + 14H+ + 6e– Æ 2Cr3+ + 7H2O (9.13)
The reverse is the case with dyed wool, probably due to steric hindrance
by the presence of dye on the fibre, higher liquor pH and repulsion of the
chromium (VI) anion by the negatively charged dye molecule.
663
Although it is the Cr(VI) anion which is adsorbed by wool, the dye complex
is formed with Cr(III). During the chroming process, therefore, hexavalent
chromium is to be reduced to the trivalent form. Since Cr(III) has little affinity
for wool, the reduction process must take place on the fibre. Earlier cystine
disulphide bond of wool was considered to be responsible for such
reduction. However, recent work [15] shows that at low pH values Cr(VI)
solution oxidises disulphide bond directly. At high pH values, the hydrolysis
products of disulphide bonds act as reducing agents. Additionally tyrosine
and lysine amino acid residues of wool are oxidised, the latter only above
pH 7.0. The reduction is negligible below 60ºC.
Hartley [15] proposed the reduction sequence for hexavalent to trivalent
chromium, Eqn. (9.14), as follows:
VI IV
1. Oxidation by disulphide, Cr Æ Cr
2. Oxidation by disulphide or tyrosine, CrIV Æ CrII
3. Reaction with carboxyl groups of wool, CrII Æ CrII-carboxyl complex
II III
4. Oxidation, Cr -carboxyl complex Æ Cr -carboxyl complex
The overall reaction results in a loss of hydrogen ions from the solution,
leading to increase of pH during chroming of wool. On dyed wool the
reactions will be similar, but the final product will be dye-chromium complex.
Earlier it was thought that the complex contains two dye molecules to each
atom of chromium, but a recent study showed that both 1:1 and 1:2
complexes may exist. The increase in fastness after chroming should be
attributed to both the structures. With 1:1 complex, there may exist a
coordinate linkage between the chromium atom and the oxygen or nitrogen
groups in the wool fibre. For 1:2 complexes, improvement of fastness has
been contributed to:
1. Physical entrapment of the big complex molecules in the spaces
within the fibre. However, the dye molecules or chromium ions easily
come out of the fibre.
2. Van der Waals’ forces, which is greater for the large complex than the
small dye molecule.
3. Hydrogen bonds forming linkage between the complex and fibre.
Hartley [15], however, concluded that for C.I. Mordant Violet 5, the 1:2
complex could not form a chromium-fibre linkage because of steric
considerations.
9.3.4 Recent Developments

Because of their economy, their high fastness and particularly their intensity
of shade in blacks and navies, chrome dyes still represent the greatest mass
664
of any dye class used on wool. Effluent problems and control of the dyeing
system have favoured the afterchrome method and this is now the only
technique which is commercially important. The fibre damage is incurred
during chrome dyeing due to use of excessive amounts of dichromate and
prolonged treatment time. The damage can be minimised without hampering
shade and fastness, by chroming with reduced amounts of dichromate and
by carrying out dyeing and chroming at temperature below boil. The
traditional rule of using dichromate equivalent to 50% of dye concentration is
wasteful and damaging. The lowest residual chromium is achieved by
chroming at pH 3.5 in the absence of sulphate ions. The optimised level of
dichromate additions, as recommended by various chrome dye
manufacturers (up to a maximum of 1.5 % o.w.m.) at specified conditions,
minimises the oxidation and cross-linking of the fibre and thereby reducing
fibre damage.
The equivalent fastness with reduced fibre damage can be obtained at
85ºC using specific dyeing auxiliary such as Lyocol CR (Clariant). It is a two-
component product, containing a mild reducing agent to reduce residual
Cr(VI) to Cr(III), together with a very specific chelating agent which
complexes with Cr(III) and exhaust to wool. However, the method is suitable
for selected chrome dyes. The same effect can also be obtained for all
chrome dyes by dyeing at 90ºC, followed by chroming at 85-90ºC (as
against boil in conventional method) along with the addition of sodium
thiosulphate towards the end of chroming. Both Lyocol CR and thiosulphate
permit low temperature dyeing of wool at 80-90ºC and the method is now
well established for all substrate forms with the benefit of reduced fibre
damage.
Although Cr(VI) is more toxic than Cr(III), uncertainty as to subsequent
oxidation during burning of sewerage sludge has led the authorities to set
limits for total chrome (typically 2 mg/l) rather than separate limits for
different valency states.
With the newer limits imposed by many countries for chromium and/or
heavy metals in the effluent, optimised chrome dyeing methods have been
developed in order to minimise residual dyebath chromium levels.
Obviously, the residual levels of chromium depend on the amount of
dichromate added in the chroming bath. The chromium requirement varies
from dye to dye and for the dyes with low chromium requirements,
dichromate additions may be reduced with benefits to the effluent.
Incomplete exhaustion of dye may cause precipitation of chromium
complex hampering fastness and increasing effluent load. The exhaustion
can be improved by lowering dyebath pH and by cooling the dyebath to 80-
90ºC at the end of dyeing. Optimum results can be obtained by draining the
dye liquor and setting a fresh bath for chroming.
665
The optimum pH for chroming 3.5-3.8 should be maintained with formic

acid throughout the chroming cycle. Interfering chemicals like sequestering
agents, citric acid and sulphate ions (through sodium sulphate and sulphuric
acid) should be absent in the chroming bath.
The recommendation of Ciba for chrome addition suitable for all chrome
dyes is as follows:
Dichromate (%) = 0.2 + (0.15 x dye concentration) (%) (9.15)
The chroming is carried out as usual for better levelling followed by
lowering of pH to 3.5-3.8 after treating for 10 minutes at maximum
temperature.
The Sandoz (Clariant) method uses minimum dichromate levels,
calculated for each dye. A proprietary chemical, Lyocol CR (Clariant)
amounting to ¼ of the chromate addition, is added to reduce residual
hexavalent chromium to trivalent chromium ions facilitating complex
formation.
Trivalent chromium cations (e.g. chromic chloride) form 1:2 Cr(III) complex
anions readily with selected ∝-hydroxycarboxylic acids (e.g. lactic, citric,
salicylic acids etc. in 1:2 molar ratio). This reaction can be completed in less
than 5 minutes at 98°C and pH 3.5-4.0, which are normal chroming
conditions in industry. The anionic Cr(III) complexes are absorbed by the
wool fibre under hot conditions, the maximum uptake occurs between pH 2
and 4. The after-chroming of mordant dyes with this new chroming agent is
much better than that achieved with the trivalent chromium alone. The
replacement of dichromate with the Cr(III) complex anion as the chroming
agent is thus possible for many chrome dyes, so completely avoiding the
highly toxic hexavalent chromium species and incurring less wool fibre
damage [16] .
From 1998, in many European countries, the effluent restrictions have
been more stringent and the maximum allowable limit for total chromium is 1
mg/l. Insufficient amount of chromium gives poor reproducibility and in
practice slight excess is required. C.I. Mordant Blue 79, for example,
requires a minimum of 1.8% chrome for deep shades. In practice, Clariant
recommends a low-chrome addition of 2%. In which case at least 1 g/l
hydrated sodium chromate, equivalent to 300 mg/l chromium, is to be
applied. By using special methods for reduction of Cr(VI) to Cr(III) and
complexing chrome with the carboxylic groups within fibre and even with a
further dilution from rinsing water, it is still a huge challenge to reduce the
chromium level from 300 mg/l to just 1 mg/l. The future of afterchrome
dyestuffs is, therefore, questionable [17].
The use of aluminium sulphate as alternative to sodium dichromate in the
dyeing of wool by the afterchrome process is suggested [18]
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9.4 PREMETALLISED DYES

During the last half of the 19th and early part of the 20th century, the use of
chrome mordant dyes on wool was widespread due to excellent all-round
fastness properties. However, several disadvantages of the dye-class, such
as complicated and lengthy processes leading to damage of wool, change of
shade after chroming and difficulty in shade matching, were well known. As
a consequence, a much simpler dye-class, metal-complex or premetallised
dyes, was introduced in the early 20th century. Acid dyeing 1:1
premetallised dye was introduced in 1919 and neutral dyeing 1:2
premetallised dyes in 1951.
As the name implies, in metal-complex dyes one metal atom, commonly
chromium, is complexed with either one (1:1) or two (1:2) molecules of a
typically monoazo dye that contains groups (such as hydroxyl, carboxyl or
amino) that are capable of coordinating with the metal. In the Colour Index,
metalcomplex dyes are included in the Acid dye class, though they have
distinct differences from nonmetallised acid dyes. The 1:1 and 1:2 metal-
complex dyes resemble levelling and milling nonmetallised acid dyes
respectively in terms of general application conditions. The increased
popularity of these dyes, which has occurred mainly at the expense of
mordant dyes, can be attributed to health and effluent hazards associated
with the use of chromium in mordant dyeing and the comparatively simple
application procedures of metal-complex dyes. The 1:1 metal-complex dyes
have been gradually replaced by 1:2 metal-complex due to superior all-
round fastness properties and less damaging application conditions of the
latter.
Metal-complex dyes depend on formation of co-ordinate links between the
dye and metal. The co-ordinate link occurs with atoms such as oxygen and
nitrogen having a lone pair of electrons, in the outer shell, which can be
shared by another atom. In covalent bond, on the other hand, each atom
contributes one electron. Thus with two atoms A and B, the two types of
bond formations may be shown as follows:
Covalent bond, A⋅ + ⋅B Æ A:B

Coordinate bond, A: + B Æ A:B
The final result is same, but the mode of formation is different.

The atom (e.g. nitrogen or oxygen) providing both the electrons is termed
as the donor (or the legand) and the atom (e.g. metal like chromium) sharing
them is termed as the acceptor, the linkage is indicated by an arrow pointing
from the donor to the acceptor. Thus, the oxygen in the carbonyl group and
a nitrogen atom will co-ordinate with chromium. The chromium atom, after
the loss of its three valency electrons to give the chromic ion Cr(III), readily
667
takes up six pairs of electrons in its outer shells by way of coordination, thus
acquiring a stable structure.
In order that the metal atom may be firmly bound to the dye, at least two
bonds are necessary, so in the case of chromium a maximum of three dye
molecules can coordinate with the metallic atom. The metal atom in a dye-
metal-complex is pictured as being firmly held by the two pincers (chela) of
the crab or lobster – hence the process is termed as chelation.
When chromium reacts with alizarin, the first stage is the formation of
covalent bond with the hydroxyl group. Since chromium is trivalent, it can
replace three hydrogen atoms, but only one alizarin molecule (instead of
three) is shown in (9.16) to combine with Cr(III). The other bond, which
appears in the second stage and is represented by an arrow, is a coordinate
link. It provides an additional six-member ring and results in a structure of
greater stability. A similar mechanism can be used to account for complex
formation of azo dyes with hydroxyl groups in ortho position with respect to
azo groups. While the hydroxyl groups form covalent bonds with hexavalent
chromium atom, azo nitrogen forms coordinate bond as shown in (9.17)
Cr(III)
O OH
O O
OH
OH (9.16)
O
O
Cr
OH HO O O
(9.17)
N=N N=N
With azo dyes derived from salicylic acid, chelation may occur with the
formation of coordinate bond with hydroxyl group and covalent bond with
carboxyl groups. However, the fastness is not improved much and there is
no marked change of hue, as the chromophoric azo group is not involved. In
/
contrast, with oo -dihydroxyazo dyes, the complex formation improves the
stability of azo bond. With certain azo dyes, e.g. C.I. Mordant Black 9, the
oxidation to a quinone formation precedes complex formation.
Thus, for chelation, the dye should have:
1. A salt-forming group, which is usually hydroxyl (but may be carboxyl).
668
2. An unsaturated atom such as oxygen or nitrogen, present in such

groups as keto (>C=O) or azo (-N=N-) and acting as an electron donor
to the central metal atom.
Most commonly, metal-complex dyes for wool incorporate tridentate,

/
bicyclically metallisable monoazo dye ligands, notably oo -dihydroxyazo, o-
/ / /
carboxy-o -hydroxyazo, oo -hydroxyaminoazo, oo -dihydroxyazomethine,
and o-hydroxyarylazopyrazolone dyes.
Coordination of these trifunctional ligands with a metal ion, in which a
nitrogen atom of the azo, azomethine or azopyrazolone group participates,
involves the loss of a proton from each of the o-substituted hydroxyl, amino
or carboxyl groups of these dyes. This results in a structure comprising one
five- or one six-member ring (as in the reaction product of 9.17).
The metal ion used is most commonly trivalent and hexa-coordinate and is
3+ 3+
usually either Cr (predominantly) or Co , because of superior stability (i.e.
resistance to demetallisation during application or processing) of chromium
and cobalt complexes.
9.4.1 (1:1) Metal-complex Dyes

1:1 metal-complex acid dyes were introduced in 1919. The various ranges of
such dyes are Palatin Fast (BASF), Ultralan (ICI) and Neolan (Geigy). Those
/ /
are almost exclusively Cr(III) complexes of (primarily) oo -dihydroxyazo, oo -
/
hydroxy-aminoazo and oo -hydroxypyrazolone dyes as represented by C.I.
Acid Brown 144 (9−15), C.I. Acid Green 12 (9−16) and C.I. Acid Red 183
respectively. The 1:1 metal-complex dyes are always dyed at very low pH
(1.8-2.0) in order to achieve extremely levelled, yet fast, dyeing on piece
goods. The boiling under such severe acidic conditions brings about
significant fibre degradation. The chromium ion is coordinated with a single
monoazo dye ligand and other three ligands, usually water, although the
Neolan P (Ciba) range of dyes, introduced in 1988, utilise colourless
OH2
OH2 H2O OH2
H2O OH2
O Cr NH
O Cr O
O2N N=N
HO N=N OH
SO3Na
NaO3S
(9−15) (9−16)
669
hexafluorosilicate ligands. The advantages of this brand over conventional

1:1 metal-complex dyes claimed [19] are:
1. Minimum fibre damage as dyeing is carried out at pH 3.5−4.0.

2. Good fibre to fibre migration give high exhaustion level.
3. Excellent reproducibility.
4. No neutralisation (of residual sulphuric acid) is required after dyeing
as in the case of conventional 1:1 metal-complex dyes.
The 1:1 complex is prepared by heating the parent dye at a temperature

up to 130ºC with an aqueous solution of a salt of trivalent chromium, such
as chromium (III) formate or fluoride, the pH being below 4. The 1:2 complex
is also prepared in a similar manner, but under alkaline conditions.
Solubility in water of 1:1 metal-complex dyes is conferred by the presence
of one or more sulphonic acid groups, although C.I. Acid Orange 76
contains nonionic amino-sulphone or sulphamoyl groups (−SO2NH2) as
solubilising aids. Such dyes containing no ionic solubilising group have an
overall positive charge because of the presence of chromium cation.
Depending on the nature and number of the solubilising groups and the
nature of the monodentate ligands present, the conventional 1:1 metal-
complex dyes either are effectively uncharged or carry an overall negative
charge as in C.I. Acid Green 12 (9−16) and Red 183 respectively.
Theory of Dyeing
The 1:1 metal-complex dyes are applied to wool from a strongly acid
dyebath and at no stage dichromate is added. With a few exceptions, these
chromium-containing dyes require the addition of at least 8% (o.w.m.)
sulphuric acid (pH 2). Under such strongly acidic conditions the dyes exhibit
excellent migration power at boil due to ion-ion interactions. The dye
substantivity arises predominantly by virtue of ionic interactions operating
between the anionic dye and protonated primary and secondary amino
groups in the fibre.
The dyes show maximum exhaustion in the pH range 3-5. Nevertheless,
such conditions with smaller amounts of acid give very tippy dyeing of
inferior wet fastness. Dye exhaustion decreases with decreasing pH of the
dyebath below pH 3, probably due to lack of dye coordination with amino
groups. At such low pH (below 3), the secondary amino (-NH-) groups in
wool are protonated and cannot, therefore, coordinate with the dye.
Coordination is, however, possible with unionised carboxyl groups which
plays no part in dye adsorption. In contrast, the presence of such
coordination may account for the skitteriness that occurs during application
at pH 3 and above in the absence of a levelling agent.
670
The quantity of acid is about twice as much as that required for equalising
acid dyes. A prolonged boil is necessary for complete development of the
dye. Glauber’s salt practically has no levelling action in this case. Hence, the
dyeing process is quite different from that of the application of acid dyes to
wool.
These dyes behave differently depending on whether they contain one or
two sulphonic groups. The chromium in the complex, being positively
charged, will neutralise one of the sulphonic groups, thus forming a
zwitterion.
The various possible interactions taking place between the dye and wool
fibre are as follows:
1. Like acid dyes, the second sulphonic group, if present, will combine
with the basic side chain of wool (protonated amino groups) (Dye-
– +
SO3 H3N-Wool).
2. In a neutral dyebath, the positively charged chromium ion may
+ –
combine with the carboxyl groups of wool (Dye-Cr OOC-Wool).
3. Additional coordination bonds may be formed between the chromium
of the dye and suitable groups, such as imino groups of wool (Dye-Cr
←NH-Wool).
4. In addition, Van der Waals' forces (ion-dipole, dipole-dipole and
related forces) may act between the big dye molecules and the fibre.
With increasing acidity, adsorption due to first interaction will rise to a
maximum as with acid dyes, but as a result of the second interaction, will
– +
decrease because of back titration of carboxylic groups (−COO + H Æ
−COOH). The third linkage involving imino groups mainly controls dyeing.
These groups are only weakly basic, but at low pH values they become
+ +
charged (Wool-NH + H Æ Wool-NH2 ) and will no longer coordinate with
chromium. The addition of 8% sulphuric acid thus reduces the amount of
dye adsorbed and produces a levelling action. So under these conditions,
these dyes behave like equalising acid dyes. The affinity due to Van der
Waals’ adsorption is not large, as the size of the complex is not very high.
If dye-fibre coordination were a major factor, then the dye would, by virtue
of this strong attachment, be expected to exhibit very high wet fastness on
wool. The fastness of these dyes to wet treatments is only moderate,
however, slightly greater than that of their nonmetallised acid dye
counterparts of similar molecular size. This slightly higher fastness is
proposed to be due to a greater tendency of the 1:1 complexes to aggregate
within the fibre.
Dyeing Methods
The material is wetted out at 60ºC for 15 minutes in a bath containing 8%
(o.w.m.) sulphuric acid. After adding the dye in solution, the temperature of
671
the bath is raised to boil in 30 minutes and kept at boil for 1½ hours. The
goods are rinsed thoroughly and neutralised, if necessary. The prolonged
boiling probably facilitates the production of non-skittery dyeing through
attack on the surface of the fibre.
The amount of acid required varies with the M:L ratio and in every case,
the pH should be about 2.0. As prolonged boiling under such low pH
conditions can cause fibre damage, either reduced amount of sulphuric acid
or other acids such as 8−10% (o.w.m.) formic acid (85%) may be used.
The amount of acid can be reduced to 5% if an auxiliary product like
Lissapol N (ICI) (9-17), Neolan salt P (Ciba) or Uniperol O (BASF) is added
in the dyebath.
C9H19 –O-(CH2·CH2·O)9-10 –H
CH3
(9−17)
These compounds are nonionic ethylene oxide condensates. In aqueous
solution, they form aggregates, which combine with the dye. They, in fact,
do not improve levelling or migration. However, they reduce skitteriness
when added to the extent of 2% (o.w.m.) in the dyebath.
The dyes can also be applied at 80ºC with suitable auxiliary such as
Albegal B (Ciba). The product is reported to be an amphoteric surfactant
sufficiently hydrophobic to have affinity for wool as well as anionic dyes.
BASF suggested the use of sulphamic acid (4% o.w.m. plus 1 g/l) in place
of sulphuric acid. The initial pH of 1.9−2.1 increases to 3−3.5 as the
temperature approaches to boil, due to hydrolysis of sulphamic acid
(NH2SO3H + H2O Æ NH4HSO4), leading to less fibre damage. The
simultaneous use of sodium sulphate (5% o.w.m.) and an auxiliary, Uniperol
5700 (BASF) is recommended.
The Neolan P (Ciba), 1:1 chromium complexes of sulphonated azo dyes
containing colourless hexafluorosilicate ligands, can be applied to wool in
the pH range 3.5-4 with 2.5-4% (o.w.m.) formic acid, thus minimising fibre
damage. They are applied in conjunction with an amphoteric auxiliary,
Albegal plus (Ciba) (3% o.w.m.) that contains an ethoxylated fatty amine
and ammonium hexafluorosilicate. 6-10% (o.w.m.) sodium sulphate is also
added.
Slubbing can be dyed continuously by a pad-steam method. The padding
is done with the x g/l dye, 15−20 g/l acetic acid, 25−40 g/l Primasol KW
(BASF) and 4-10 g/l suitable thickener. The padded material is steamed at
100−102ºC for 45−60 minutes.
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9.4.2 (1:2) Metal-complex Dyes

In spite of lower wet fastness properties as compared to chrome dyes, 1:1
metal-complex dyes were popular for over a quarter of a century for their
excellent migration and penetration properties, ease of application, good
light fastness and comparatively brighter shades. However, their popularity
diminished with the invention of neutral-dyeing 1:2 metal-complex dyes in
1951 because of their applicability under weakly acidic to neutral conditions
as against strong acidic conditions for 1:1 metal-complex dyes.
1:2 metal-complex dyes are suitable for the following materials:
1. Machine-washable woollen materials.
2. Tropical suiting where level dyeing combined with better fastness to
wet treatments is desirable.
3. Men’s suiting, uniform and blazer cloth in light and medium shade,
4. Carbonised pieces and blanket cloths, which require no washing
before dyeing.
5. Pieces that have been exposed to the atmosphere and become
weathered.
6. Suitable for carpet yarns which are in public places and subjected to
prolonged exposure.
7. The dyed material to withstand hypochlorite finish to imitate Persian
rugs.
8. The ease of reduction of some of the 1:2 complexes enables them to
be used in discharge printing.
The neutral-dyeing 1:2 metal-complex dyes are chromium or cobalt

complexes of azo dyes. Like 1:1 complexes, they are prepared from azo
/
dyes, in particular from oo -dihydroxyazo dyes. A few of them are
azamethine derivatives in which the azo group is replaced by –CH=N-, the
nitrogen of which can form a coordinate bond with metals. Most of them are
chromium complexes. A few of them are cobalt complexes, which have
higher fastness to light and a lower rate of dyeing. The two parent dye
molecules forming complex with each metal ion may be same or different,
the symmetrical complexes being more stable.
Depending on the absence and presence of sulphonic groups, the 1:2
complexes are of the following two types respectively:
1. Weakly polar 1:2 complexes
2. Strongly polar 1:2 complexes
These complexes are salts of strong acids and they dissociate completely
– +
in dilute solution and acquire negative charge (D Na ). The free acids have
very low aqueous solubility, whilst the salts show considerable aggregation
673
in solution at room temperature and low solubility in presence of inorganic

salts.
There are typically three types of 1:2 metal-complex dyes: unsulphonated,
monosulphonated and disulphonated. The disulphonated type is most
soluble and has greater pH dependence. This means that they have a low
neutral affinity and require more acid to exhaust. They also exhibit the
lowest cross-staining in domestic washing because any desorbed dye has
only limited affinity for adjacent fibres at the pH condition used by domestic
detergent [2].
In the most popular first type, sulphonic solubilising groups are absent,
since their presence leads to dyes that are unsatisfactory from the point of
view of levelling and skitteriness. Instead, nonionic groups are incorporated
in the molecule to improve the aqueous solubility and decrease the rate of
dyeing. These groups, in fact, distinguish the ranges offered by different
manufacturers. The most popular are methylsulphonyl (−SO2CH3) and
sulphamoyl (−SO2NH2) groups; their hydrophilic character being due to
hydrogen bonding with water. Both have similar solubilising properties, but
the latter exhaust more slowly. Other solubilising groups reported are mono-
or di-alkyl-substituted sulphonamide, ethylsulphone and cyclic sulphone.
The typical examples are C.I. Acid Violet 78 (9−18) and Black 60 (9−19).
H3CO2S SO2NHCH3
N=N O
H3C NH N O O N C
O O C Cr HN CH3
Cr N N
O O O
O O
N=N H3CHNO2S
SO2CH3
(9−19)
(9−18)
Weakly polar 1:2 metal-complex dyes are sold under the names Irgalan
(Ciba), Lanasyn (Clariant), Isolan K (DyStar), Ortolan (BASF), etc. They
display very good to excellent light fastness and very good fastness to wet
treatments on wool in pale to medium depths. The dyes exhibit good
levelling and penetrating properties and typically yield non-skittery dyeing.
They are used on loose stock, slubbing and yarns for outwear, carpet and
knitting yarns and knitted goods. Owing to their tendency to intensify barré
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dyeing (variations due to structural differences), they are less widely used
for piece dyeing.
However, weakly polar 1:2 metal-complex dyes have limited solubility in
water. Hence, the dye manufacturers came out with strongly polar 1:2 metal-
complexes with sulphonic groups having high solubility. While weakly polar
dyes are mostly symmetrical (i.e. two identical dye molecules complexed to
one metal ion), strongly polar dyes are mostly asymmetric. The examples
are Irgaren (Geigy), Isolan S (DyStar), Lanasyn S (Clariant), etc.
Lanacron S (Ciba) and Neutrichrome S (Kuhlman) are asymmetrical 1:2
metal-complex solubilised with one sulphonic group.
The Elbelan (LBH) range consists of symmetrical 1:2 metal-complexes
solubilised with two carboxyl groups.
Acidol M (BASF) and Azarin (Hoechst, now DyStar) are the disulphonated
symmetrical 1:2 metal-complexes.
Strongly polar 1:2 metal-complex dyes provide high colour build up – 1/1
standard depth can be obtained with 0.7−1.2% dye as against 1.6−2.7% in
case of weakly polar dyes. Hence, they are economical especially in dark
shades. They provide very good wet fastness in full depths. The fastness to
hot water is very good for strongly polar dyes. Moreover, they are
inexpensive to prepare.
The dyes, however, possess lower levelling power. The disulphonated
variants possess the lowest levelling characteristics and they are, therefore,
rarely used on woven fabrics. Skitteriness caused by differential affinity of
wool for dyestuff arising out of uneven dye absorption between the root and
the tip of the wool fibre is somewhat more difficult to cover with strongly
polar dyes than do their weakly polar counterparts.
With the introduction of solubilising groups like –SO3H, the exhaustion of
the dyestuff shifts to a higher temperature (e.g. 80−85ºC), which is
approximately 10ºC higher than the weakly polar 1:2 complexes. The
dyebath pH for optimum exhaustion is 5.5−6 as compared to 6.5−7 for the
latter.
Theory of Dyeing
In 1:2 metal-complex dyes, the metal ion is fully chelated with the dye – no
further coordination with the fibre is possible. The dyes are sensitive to pH
due to overall negative charge of the complex, but the sensitivity is less than
that of milling acid dyes because the charge is not localised as in the latter
case. The dye exerts strong Van der Waals' force due to its large molecular
size, resulting in slow rate of dyeing and high fastness to wet treatments.
1:2 metal-complex dyes behave very much like neutral dyeing acid dyes,
the two types of bonds being:
1. Like acid dyes, these anionic dyes form ionic bond with protonated
– +
amino groups (Dye H3N-Wool).
675
2. Powerful Van der Waals’ forces may act between the big dye
molecules and the fibre.
The ionic attraction between the dye anion and the protonated amino
groups in the substrate is expected to contribute to dye-fibre substantivity.
The ionic interaction will be more pronounced in the case of strongly polar
dyes which carry comparatively greater and also localised negative charge
than in the weakly polar dyes with non-localised single negative charge.
Weakly polar 1:2 metal-complex acid dyes carry a single negative charge
due to the loss of four protons from the two component dye ligands. In
strongly polar 1:2 metal-complex dyes, the monosulphonated and
disulphonated varieties will possess two and three negative charge
respectively.
However, the dyes are applied to wool under weakly acidic to near-neutral
pH conditions when the number of protonated amino groups in the substrate
is small. The hydrophillicity of the dye is due to the anionic charge of the
molecule, which is low for both weakly and strongly polar dyes. The dyes
are predominantly hydrophobic in nature. Therefore, hydrophobic
interactions, operating between the dye and hydrophobic regions within the
fibre, make an important contribution to the substantivity.
Due to hydrophobic interactions, dye aggregation within the fibre will
probably arise resulting in higher wet fastness or reduced tendency of dyes
to diffuse out of the fibre during wet treatments.
The fastness to milling and potting of various metal-complex dyes, in
terms of shade change and staining of adjacent materials observed to be in
the decreasing order as follows:
1:2 (disulphonated) = 1:1 > 1:2 (monosulphonated) > 1:2 (unsulphonated) >
1:2 (SO2NH2).
The wet fastness properties of the Elbelan (LBH) range of 1:2 complexes
solubilised by carboxylic groups are superior to those of conventional 1:2
metal-complex dyes. The fastness properties in practice, however, depend
on many other factors.
Dyeing Methods
Levelling of 1:2 metal-complex dyes depends on the pH and temperature of
application and is enhanced by proprietary levelling agents. The use of such
compounds is essential for strongly polar dyes. Amphoteric auxiliaries,
usually polyethoxylates (9−20) having both cationic and anionic sites, are
particularly effective in the coverage of tippy wool. Albegal A, Albegal B,
Albegal SET (Ciba), Uniperol SE (BASF), Lyogen FN and Lyogen UL
(Clariant) are a few commercial levelling agents suitable for the purpose.
676
(CH2CH2O)nCH2CH2OH
+
R–NH
–
(CH2CH2O)nCH2CH2OSO3
(9-20)
Uniformity of substrate pH is important for successful dyeing. Any residual

acid from carbonising or acid shrink-resist treatments should be neutralised
with ammonium hydroxide buffered with sodium acetate (5-8%). Soft water
should be used. Organic chelating agents should be avoided as they
promote demetallisation of some dyes.
Neutral-dyeing premetallised dyes can be applied to wool at all stages of
manufacture. They are particularly suitable for pale to medium shades.
Weakly polar 1:2 metal-complex dyes, due to absence of sulphonic and
carboxylic groups, cover tippy wool very well. They do not show fibre
selectivity when a blend of different types of wool is being used, e.g. for
carpets. They are usually applied to untreated wool in the pH range 5 to 6,
although pH values between 4 and 7 are used in some applications.
The usual method of application of weakly polar 1:2 metal-complex is as
follows:
The yarn or fabric is treated at 40ºC for 10 minutes in a bath set with
2−4% (o.w.m.) ammonium sulphate or acetate. Dissolved dye is then added
and the temperature is raised to boil in 45 minutes. After 30−60 minutes at
the boil, the bath should be exhausted to the extent of about 95%. With
loose wool and slubbing, the ammonium salt may be replaced by 2%
(o.w.m.) acetic acid (40%), but shading is difficult. If acetic acid is used, the
bath should be neutral at the start and pH should be gradually lowered to
5.5−6 during dyeing to increase substantivity. The dyeing may also be
carried out at high temperature (106−110ºC). At lower temperature (80ºC),
there may be a tendency to skittery dyeing.
In order to enable brighter shades, a small range of milling acid dyes,
having dyeing and fastness properties similar to 1:2 metal-complex dyes,
are provided for shading purposes, such as Irgalan S (Ciba) dyes.
Addition of suitable nonionic auxiliaries enable the dyebath pH to be
lowered to 4.8-5.5 which is desirable for carpet yarn, as slight yellowing is
caused by dyeing at higher pH. 1-2% (o.w.m.) Lyogen SMK (Clariant), 10%
(o.w.m.) Glauber’s salt and 1.5 % (o.w.m.) acetic acid may be used for the
purpose.
Several continuous dyeing methods have been developed for wool, such
as:
677
1. Pad-steam
2. IWS cold pad-batch
3. Vicontin CR process (Carp-O-Roll)
4. Lanasan pad-store
5. Fastran EDF
The last two systems involve the use of radio-frequency energy.

A pad-steam method for the continuous dyeing of slubbing, is to pad dye
with 10−20 ml/l formic acid (85%) (pH 2.8−3) along with dispersing and
levelling agents, followed by steaming at 100ºC for 15−40 minutes and
rinsing.
In continuous dyeing of textile material, a surface frostiness (light coloured
fibre at the surface) can develop due to dye migration to the interior of the
material as a result of lower moisture content at the surface. Antifrosting
agents used for resolving the problem, are a combination of powerful film-
forming wetting agent and short-chain ethoxylated products, which form a
second liquid phase of higher dye concentration close to the fibre surface.
Commercially these may be readymade mixtures, such as Irgapadol (Ciba)
or two products to be added separately such as Lyogen V and Lyogen CW
(Clariant).
The strongly polar 1:2 metal-complex dyes give cheaper dark shades.
They can be applied in the similar manner as above, but a proper levelling
agent must be used to achieve level dyeing. The temperature is to be raised
more slowly. The dyeing is carried out at pH between 5 and 7 although a pH
of 4 may be used. The dyeing may be carried out at boil, at low temperature
of 80ºC (mostly monosulphonated dyes, e.g. Isolan S dyes of DyStar) or at
high temperature above boiling.
Shrink-resist wool may be dyed with weakly and strongly polar dyes.
However, substantivity will be considerably higher due to their cationic
nature. Strict control of pH, temperature and time of dyeing is essential for
achieving level, uniformly penetrated dyeing. The exhaustion is usually
carried out at a lower temperature than untreated wool to counteract greater
substantivity.
The dyeing may be carried out with an organic ester type acid donor, such
as Eulysin WP (BASF), which under hot aqueous conditions decomposes to
an acid to bring down the dyebath pH to 5. The dyebath is prepared with
1−2 % (o.w.m.) ammonia (25%), 1% (o.w.m.) Uniperol SE (BASF), 0.5−1 g/l
Eulysin WP (BASF) and the required amount of dye. The temperature is
raised to 60ºC at 1.5ºC/min and thereafter 1ºC/min up to boil and the dyeing
is continued at boil for 30−60 minutes. In order to achieve optimum fastness,
an aftertreatment may be carried out with a cationic agent, 4% (o.w.m.)
Basolan F (BASF) at pH 7.5 and temperature 40ºC for 15 minutes, followed
by rinsing.
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While dyeing with 1:2 metal-complex dyes, the dyebath exhaustion

achievable is very high and by further dilution with rinsing water, the levels
of chromium can be kept below discharge limits. However, dyeing in deeper
shades, using less rinse water or achieving poor exhaustion, will push
effluent over the limit. The rinse water is generally fairly clean. Most of the
contamination is in the exhausted dyebath, which should be considered for
reuse. A standing bath may be employed to dye the same shade repeatedly
for five times [17].
Mostly iron-complex dyes and to a lesser extent aluminium-complex dyes
as substitute for chromium-complex dyes are suggested to avoid pollution
problems. The colour of the dyes ranges from violet, blue, brown to black
[18].
9.5 DYEBATH BLEACHING

Wool may acquire a yellowish tint during dyeing due to high dyebath pH and
temperature and long time of processing. The pigments produced in dyebath
yellowing are very sensitive to photobleaching. To counteract the potentially
disastrous change in shade during a relatively short light exposure (yellow
fade), the dyers add certain dyebath bleaching aids, namely:
1. A mixture of sodium bisulphite and sequestering agent, which is more

common.
2. Hydroxylamine sulphate, the chemical mechanism of this unusual
method developed by Clariant is not known.
9.6 AFTERTREATMENTS
The first cationic agent for aftertreating wool dyed with 1:2 metal-complex
and acid milling dyes was Sandopur SW (Clariant). It dramatically improves
washing and alkaline perspiration fastness of selected sulphonated metal-
complex and milling acid dyes and is really effective for wool subjected to
oxidative-shrink resist treatment. Later, more cationic products, such as
Sandofix L (Clariant), Fixogene MW (ICI), etc. were developed which were
effective to a greater extent in removing dye held in the cationic resin layer
of Hercosett-treated wool.
Subsequently, reactive products such as Lanasan MW (Clariant) were
introduced, which could additionally provide shrink-resist effect as Hercosett
125 resin. However, such aftertreated products are difficult to reprocess and
are prone to soiling with anionic dyes during laundering [1].
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9.7 STRIPPING OF DYES

Faulty wool dyed material may be stripped with zinc formaldehyde
sulphoxalate e.g. Arostit ZET (Clariant), which is reasonably stable under
acid pH [1]. The conventional alkaline stripping with sodium hydrosuphite
and soda ash causes severe damage to woollen material. Other stabilised
hydrosulphite-based stripping agents are less effective.
It is often possible to level up a dyeing or to reduce the depth to allow
shade correction by partial stripping with cationic surfactants,
polyethoxylated quaternary ammonium compounds, often, under mild
alkaline conditions with ammonia. Such products are fully ionised even at
pH 8.
9.8 LOW TEMPERATURE DYEING
The prime motive for low temperature dyeing is energy conservation as well
as protection of wool, by limiting the temperature or the time at highest
dyeing temperature during dyeing.
But several problems are encountered while dyeing at low temperature.
For a given wool fibre, the rate of diffusion or penetration is related to the
amount of energy put into the system in the form of heat and the molecular
structure of the dye molecule. Larger molecules require more energy for
good penetration, but the amount of dye present also affects the energy
requirements for total diffusion. As cuticle is the main barrier to fibre
penetration, we can reduce the energy requirements by damaging the fibre
scales. However, by doing this the fibre quality is hampered in the same way
as by dyeing at boil.
Each dye behaves differently at reduced dyeing temperature. Thus, dyes
compatible at the boil will not be so at lower temperatures. A reduction in the
degree of penetration will affect both shade and fastness, but the degree of
variation will differ from dye to dye and with depth of shade. A high degree
of shade reproducibility is essential for any dyeing system to have real
value. Low-temperature dyeing can cause problems in this area due to two
factors [20]:
1. Reduced dyebath exhaustion
2. Varying degree of penetration
With dyes of low substantivity such as acid levelling dyes and some
chrome dyes, good exhaustion can be obtained at 80-85ºC even in normal
dyeing time. With dyes of larger molecules, however, ring dyeing is
obtained. These molecules do not readily penetrate the fibre at low
temperature, resulting in reduced wash and rubbing fastness and shade
680
change during steaming or finishing. The various techniques for improving

diffusion at low temperature are [1]:
1. Solvent dyeing.
2. Use of alkyl phosphates.
3. Use of ethoxylated alcohols with short polyethoxy chains.
The auxiliaries operate most effectively at or close to their solubility limit.

They have very high dissolving power for ionic dyes and form auxiliary-rich
phase of high dye concentration adjacent to the fibre surface and thereby
increase the rate of dyeing without hampering levelness.
Water-soluble solvents like butanol and benzyl alcohol are uneconomic,
as they are required in high concentration, while chlorinated hydrocarbons
are rejected on eco-toxicological grounds. Ciba proposed Irga-solvent
process. Alkyl phosphates such as Dilatin VE (tributyl phosphate, Clariant)
have also been recommended.
In mid-1960s, CSIRO [21] recommended a process of dyeing at 85ºC at
pH 3−5, using a polyethoxylated nonylphenol having 6-10 ethylene oxide
units per molecule. The practical process was, however, tedious, as there
were different recommendations for different dyes. The dissolving of the
surfactant was also a problem as it had a very low cloud point. The
incorporation of a long-chain dispersing agent would have probably
improved their applicability as in products like Baylan NT (DyStar), Lanasat
LT (Clariant), etc., which were developed later. Such nonionic products are
acceptable from the view of cost and toxicological considerations.
It has been observed that some dyestuffs do not exhaust well at
temperatures below boil. Even when low-temperature dyeing auxiliaries are
used, the dyestuffs with low substantivity for wool are likely to give poor
reproducibility. When dyes of very high substantivity are applied below boil,
the penetration into the fibre may be so poor that surface dyeing may occur,
which can lead to fastness problems and severe shade changes in
subsequent processes. With unsulphonated 1:2 metal-complex dyes, there
can be problems of exhaustion and reproducibility, while with disulphonated
types surface dyeing, fastness and shade changes can cause difficulties.
The best results are obtained with monosulphonated types such as
Neutrichrome S (Crompton and Knowles) dyes. Carbolan dyes give good
results because they have lower molecular masses than metal-complex
dyes. The fibre protection is much better [20].
Early attempts for low-temperature dyeing were based on a simple
method that involved the use of single auxiliary and a fixed dyeing
temperature for all dyeings. As the method is simple, it is very attractive.
However, such a process could never be totally successful, throwing out
problems of shade reproducibility and wet fastness. The correct application
681
of low-temperature dyeing is very complex. For every dyestuff, there is a

point at which the effect of poor penetration becomes critical. This point is
called limiting depth. For a given dyestuff, the limiting depth is the depth of
shade above, which it will fail to give a wet-fastness rating of 4. The depth is
specific to the dyestuff, the specific fastness test and is dependent on
dyeing temperature employed.
An auxiliary is needed which does not cause fibre swelling, but assists in
even exhaustion and diffusion at temperature below boil. Crompton and
Knowles developed Intrasol MFD, which should be added in the dyebath in
varying amounts, depending on the type of goods being dyed and the liquor
ratio. It is still essential to obey limiting depth rule for good results, although
MFD does raise limiting depths at all temperatures below boil. A computer
program based on concept AFD [20] allows selection of minimum dyeing
temperature for dyes, considering limiting depths based on the chosen
fastness test according to washing requirements (e.g. dry clean, hand wash,
machine wash and carpets).
Low temperature dyeing exaggerates incompatibility problems with some
1:2 metal-complex dyes. Sandoz (Clariant) developed Lanasan CF dyes
consisting of selected 1:2 metal-complex and acid milling dyes which can be
dyed with Lanasan LT at 85ºC, claiming comparable fastness and
reproducibility with those dyed at boil.
Pretreatment of wool with a water-soluble, cationic polyamide-
epichlorohydrin polymer Hercosett resin (Hercules) greatly increases the
possibility of effective low temperature dyeing of medium to light depth. The
simplest sequence of such treatments on dry-combed or pre-scoured tops to
prepare shrink-resist machine-washable wool in back washing machine
(Figure 4.14) is as follows:
1. Chlorination by applying sodium hypochlorite having 1.5−2.0% active

chlorine on the weight of wool at pH 1.5−2.0.
2. Antichloring and neutralisation in the second bowl with sodium
sulphite or metabisulphite and sodium carbonate or bicarbonate.
3. The Hercosett 57 resin treatment (5 g/l solid) in the third bowl at pH
7.5 and temperature 30ºC.
4. The final bowl consists of a nonionic polyethylene softener such as
Alcolube CRT at alkaline pH.
5. Finally the tops are subjected to drying and curing (for resin).
Batchwise exhaustion techniques may also be followed.

BASF proposed the use of quaternised resin, Basolan F, for both shrink-
proofing wool and improving wet fastness of anionic dyes, especially milling
and 1:2 metal-complex dyes. The process sequence is different than that of
Hercosett. The wool top is chlorinated with acid hypochlorite, antichlored,
682
rinsed and dried. The top is subsequently dyed and treated with 2−6%
(o.w.m.) Basolan F resin at pH 7−8.5 with ammonium hydroxide at a
temperature of 40−50ºC for 10 minutes or by padding.
The chorination may also be carried out with dichloroisocyanuric acid or
DCCA.
The advantages of shrink-resist wool over untreated wool are much less
tendency for producing skittery dyeing at low temperatures and increased
reactivity towards reactive dyes at low temperature. Obviously, a highly
reactive dye should be used.
The studies on the relationship between fibre structure and the dyeing
properties of wool have led to new approaches for dyeing wool at
temperatures below boiling. These are based on removal of the non-
keratinous regions of the fibre, for example, pretreatment of wool with
proteolytic enzymes or polar organic solvents, n-propanol-water or formic
acid. However, long pretreatment with enzyme is necessary and
environmental factors preclude the use of solvents.
Protein and lipid materials may be removed by scouring under mild
alkaline conditions using a special type of amphoteric surfactant [22]. The
most likely source of the extracted materials is the cell membrane complex.
The scoured wool can be dyed at pH 4.5, without the addition of levelling
agents to the dye liquor. The pretreatment improves the rate of diffusion
inside the fibre at low temperature. The fastness properties, comparable to
those from conventional dyeing at boil, can be obtained at 80−90°C. An
important consequence of the improvement in levelness is the superior
coverage of affinity differences between fibre tips and roots, compared to
conventional methods.
9.9 REACTIVE DYES

The reactive dyes suitable for wool should satisfy the following criteria:
1. A high degree of covalent bond formation after dyeing, minimising
rinsing treatment to give maximum wet fastness. Excessive rinsing
may cause felting and damage of material.
2. The rate of adsorption should be higher than the rate of reaction,
otherwise the dyeing will be uneven. The reactivity should be
moderate. A highly reactive dye will react even at low temperature,
reducing the possibility of levelling and migration. A dye of low
reactivity, on the other hand, requires extended time of dyeing at boil
with consequent damage of material.
The success of dyeing wool with reactive dyes is not possible without the
use of suitable auxiliaries. These amphoteric or weakly cationic auxiliaries
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prevent skittery or tippy dyeing of wool by forming dye-surfactant complexes

which at low temperature exhaust more evenly and extensively on to the
surface of wool than does the dye alone. At high temperature the complex
breaks down, allowing the dye to penetrate and react with the fibre. The
amount of such auxiliary recommended is 1−1.5% (o.w.m.) The reactive
dye-classes suitable for wool, their make, reactive group and respective
dyeing auxiliary are shown in Table 9.2.
Table 9.2 Reactive Dyes for Wool
Commercial Maker Reactive groups Auxiliary
name
Lanasol Ciba α-bromoacryl amido Albegal B
Hostalan Hoechst β-sulphatoethyl sulphone Eganol GES
Hostalan E Hoechst N-methyltaurine-ethyl sulphone Eganol GES
Drimalan F Clariant 5-chloro-2,4-difluoropyrimidyl Lyogen FN
Verofix Bayer (DyStar) 5-chloro-2,4-difluoropyrimidyl Avolan REN
Lanasol dyes (Ciba, 1966) are most successful reactive dyes for wool.
Trichromatic dyeing (i.e. matching of a large number of shades with three
dyes) is possible using Lanasol Yellow 3G, Blue 3G and Red 6G (C.I.
Reactive Yellow 39, Blue 69 and Red 84 respectively) as they have almost
identical dyeing properties including the coverage of tippy wool.
These dyes are essentially bifunctional dyes, provided sufficient
neucleophilic groups are available for reaction and these reactions are not
sterically hindered. The dyes are reported to be α,β-dibromopropionyl-amide
dyes, which are being converted to α-bromoacrylamide by simple
elimination of hydrogen bromide on dissolving in water (9.18).
D-NH-C-CH-CH2Br Æ D-NH-C-C=CH2 + HBr (9.18)
O Br O Br
Some Lanasol dyes have two α-bromo-acrylamide groups, e.g. Lanasol
Red G (C.I. Reactive Red 83) and Red 2G (C.I. Reactive Red 116). The
level of fixation of these dyes on wool is very high, leading to very high wet-
With the amino-peptide chains of wool, both nucleophilic substitution and
addition reactions occur, with the formation of the aziridine ring (9.19), which
is capable of further reaction with nucleophilic amino groups.
D-NH-C-C=CH2 + Wool-NH2 Æ D-NH-C-CH-CH2
(9.19)
O Br O N-Wool
Hostalan (Hoechst now DyStar, 1971) and Procilan E (ICI) dyes are
blocked vinyl sulphone dyes, which gradually activate to the reactive vinyl
684
sulphone at elevated temperatures, even under slightly acidic conditions

(9.20).
– +
D-SO2CH2CH2OSO3 Na Æ D-SO2–CH=CH2 (9.20)
(β-sulphatoethyl sulphone) (vinyl sulphone)
Hostalan E brands are most level-dyeing N-methyltaurine adducts and the
other Hostalans are β-sulphatoethyl sulphone. It appears that the N-
methyltaurine groups are also readily eliminated in dilute acidic solution at
pH 5.5 at temperature above 80ºC, with the formation of vinylsulphone
species. The rate of conversion is important in determining the levelness
and final fixation of the system.
ICI (now Zeneca) introduced Procilan E dyes for wool which were also
vinylsulphone precursors, but the range has now been withdrawn.
Drimalan F (1969, Clariant, formerly Sandoz) and Verofix (DyStar) are
chlorodifluoropyrimidine dyes. The latter range was withdrawn in 1987. They
are regarded as bifunctional in their substitution reactions with the
neucleophilic sites in wool. The fluorine atom at position 4 reacts first, while
that at position 2 reacts at boil. The bifunctional nature and high resistance
to hydrolysis at pH 5−7, leads to a high degree of covalent bond and
consequently high wet fastness.
Most of Levafix EA (DyStar), Drimarene R and Drimarene K (Clariant)
reactive dyes for cellulosic fibres are also chlorodifluoropyrimidine dyes and
selected dyes from these ranges are also suitable for wool.

Untreated wool is dyed with reactive dyes in loose stock, top, yarn form and
less frequently in piece form by exhaust methods. The dyeing is carried out
at pH 5−5.5 for full depths and pH 5.5−6.0 for paler depths. Exhaustion is
poor at high pH and very rapid at low pH causing unlevelness. Optimum
fixation is achieved after boiling for one hour for medium shades and 1.5−2
hours for deep shades. A hold time of 30 minutes is allowed at 70ºC for
better migration and levelness. Suitable auxiliaries and 5% Glauber’s salt
are added during dyeing of Lanasol, Drimalan and Verofix range of dyes.
In order to achieve maximum wet fastness, it may be necessary to
aftertreat the dyed material in a fresh bath containing 1.5 g/l ammonia (pH
8.5−9.0) for 15 minutes at 80ºC and then the material is neutralised in a bath
containing acetic acid at pH 5−6.
Most reactive dyes on untreated wool are used for dyeing red, scarlet and
maroon shades and their usage is progressively growing for other shade
areas.
Machine-washable wool is prepared by a chlorine-resin (Hercosett)
treatment. These resins are cationic in nature and the treated wool absorbs
685
anionic reactive dyes very rapidly. The best fixation and wet fastness are
achieved after dyeing for 30 minutes at 110ºC. The fastness to alkaline
perspiration declines as dyeing is continued longer than 60 minutes at boil
or 30 minutes at 110ºC.
For excellent wet fastness, an after-treatment of the dyed material having
depth more than 1% (o.w.m.) with dilute ammonia or sodium bicarbonate
solution at pH 8.5 for 15 minutes at 80ºC is necessary. The ammonium
hydroxide treatment may have damaging effects on loose wool and tops.
Instead, 2.5% (o.w.m.) hexamethylenetetramine (hexamine) may be used,
which decomposes at boil into ammonia and formaldehyde, the latter
protects wool. The process deserves further investigation.
Selected Procion H dyes may be applied on wool at pH 5.5−6.0 (with
acetic acid) together with 2% nonionic Atexal DN-VL500 (ICI) and 1%
cationic Atexal SC-A50 (ICI). The dyeing is started at 70ºC, raised to 80ºC in
15 minutes and kept for 15 minutes, raised to boil in 30 minutes and kept at
boil for at least 45 minutes.
Cold pad-batch dyeing is possible with Procion MX dyes. The wool fabric
is padded with cold liquor containing dye, urea (300 g/l), wetting agent and
acetic acid to give a pH of 5, a suitable thickener and an antifoaming agent.
The padded fabric is batched for 24 hours. Batching time can be reduced to
8 hours by adding 10−20 g/l sodium bisulphite, if compatible. The batched
material is washed with 3 g/l ammonia at 50ºC, followed by water at 50ºC
and cold acetic acid to bring pH at 5. A wide range of bright colours of very
good wet fastness can be obtained without any yellowing of wool.
9.10 RECENT ADVANCEMENTS
The wool piece dyers have a number of demands, such as:

1. Level dyeing
2. Good coverage i.e. non-skittery dyeing
3. Ability for shade rectification
4. Maintaining wool quality
5. Good wet fastness
6. Good reproducibility
Traditionally, wool piece dyers use di- and mono-sulphonated levelling

acid dyes. The Chrome dyes, except black and navies, are not used
because of poor reproducibility. 1:2 premetallised dyes are avoided, since
like reactive dyes they act as a good indicator for preparation faults. 1:1
metal-complex (and modified Neolan P dyes) dyes are used world-wide for
dyeing woollen and worsted fabrics to meet most piece dyeing requirements
[19].
686
A recent development in wool dyes is the introduction of dye ranges

primarily based on mixture dyes. The purpose of this approach is to derive
shades and dyeing performance characteristics that are not available with
the existing homogeneous dyes. In order to have optimum compatibility, all
the dyes in a range should have similar substantivity, migration, selectivity
and fastness. Sandolan MF (Clariant) is one of the these optimised dye
ranges, based solely on acid dyes. By careful selection of dyes and the use
of a specific dyeing auxiliary, Lyogen MF (Clariant), better wet-fastness
properties can be achieved without sacrificing high degree of levelness. The
system gives good coverage of root-tip differences in the fibre and high
degree of exhaustion, ensuring shade reproducibility. Although the dyes are
normally applied at pH 4.5−5.0, which is close to the optimum for least
damage to wool in dyeing, they still have good substantivity for wool at pH
values as high as 6.0. An acid donor is often used – that is, a product which
hydrolyses slowly during the dyeing cycle, to release the acid. The Sandolan
MF range has a wide gamut and can be supplemented by half-milling dyes.
Another range of dyes selected from various classes having similar dyeing
characteristics is the Lanaset (Ciba) range. This contains acid milling,
reactive and 1:2 metal-complex dyes and, therefore, shows better wet
fastness than Sandolan MF dyes. Dyeing of Lanaset dyes is carried out at
pH 4.5−5. Fibre damage is minimised and high dyebath exhaustion assures
good shade reproducibility.
Sandoz (Clariant) further introduced Lanasan CF dyes as a part of their
Optilan package for wool. This is based on six 1:2 metal-complex dyes and
three bright milling dyes with suffix CFB. The range offers good compatibility
and coverage of fibre differences when applied at pH 4.5−5.0 in presence of
a dyeing auxiliary, Lyogen UL.
The benefits of these optimised dye ranges can be summarised as:
1. A wide, fully combinable range.

2. The same dyeing method for all shades and thereby less risk of
application error.
3. They are applied at a pH that minimises fibre damage.
4. High dyebath exhaustion and good shade reproducibility.
5. Good coverage of fibre differences.
In general, migration decreases with increasing relative molecular mass

(r.m.m.) of the dye, while substantivity and wet fastness increases. The dyes
with high wet fastness migrate to a lower extent than those with low affinity,
except for the case of chrome dyes. Chrome dyes have very good migration
properties before chroming. The other factors, namely dye structure, degree
of sulphonation, the presence of dyeing auxiliaries etc. can also influence
both migration and fastness properties. The relative overall migration and
687
fastness properties of various dye classes [1] are shown in Figure 9.3,
where L, F, M, SM, C and R are levelling, fast, milling, super-milling, chrome
and reactive dyes respectively. MC and MF stand for metal-complex and
Sandolan MF dyes respectively.
L 1:1 C
MC MF
F
M SM/
1:2
Migration
MC
R
Fastness
Fig. 9.3 Migration and Fastness Properties of Different Dye-classes on Wool
Wool can also be dyed with acid dyes at high temperature, especially in
package dyeing of wool yarn, the advantage being the greater rate of
levelling, with the consequent reduction of dyeing time. However, at 120ºC,
there is significant degradation of wool. Therefore, wool is never dyed above
110ºC, at which the duration of operation should not exceed 60 minutes and
the pH should be between 3 and 6.5. Many dyers prefer to dye at 105ºC.
Some acid dyes are degraded at high temperature and sufficient
precautions should be taken (Section 9.2.7).
9.11 SILK DYEING

Silk being a natural polyamide or polypeptide fibre, its dyeing properties are
very similar to those of other natural polypeptide fibre, wool as well as
synthetic polyamide fibre, nylon. They can be dyed by similar methods. Very
fine fibrillar structure and high orientation of fibre molecules are the two
characteristic properties of silk which determine its dyeing behaviour.
The fineness of polyamide yarns is about 2.5−4 denier (weight in grams of
9,000 metres of yarn) and wool carpet yarns as high as 7−20 dtex (weight in
gram of 100 metres long yarn) i.e. 630−1800 denier, whereas that of
Bombyx mori silk is only about 0.8−1.4 denier.
688
These fine fibrils produce a large fibre surface. This means, firstly that the
colour yield on silk is on an average 50% of that of wool or synthetic
polyamide fibres, so that about twice the amount of dye must be used to
attain the same shade depth. Secondly, it means that a given dye or class of
dyes produces lower wet fastness properties on silk than on the other two
fibres in equivalent shade depths.
The large fibre surface also leads to a high strike rate even at very low
temperature of 20−30ºC, comparable to the kinetically most rapid-dyeing
carpet wool fibres. The fast strike rate is due to rapid saturation of the freely
accessible amino groups at the fibre surface. The uptake of about 60−80%
may occur at the very beginning of dyeing. Once the superficial saturation
with dye takes place, the high orientation of the fibres, which is actually a
barrier to diffusion, causes the remaining dye to be absorbed very slowly, in
the same as a highly drawn polyamide fibre for the clothing sector [23].
Silk is comparatively easier to dye and is less sensitive to temperature.
However, there is always a risk of damage of silk filaments during dyeing
and the dyeing on the damaged material may apparently look like faulty
dyeing.
As a natural polyamide or polypeptide, silk fibroin exhibits not only free
amino and carboxyl groups, but also phenolic substituents with accessible
hydroxyl groups.
Since silk fibre has a slightly cationic character with the isoelectric point at
about pH 5.0, it is primarily suitable for coloration by anionic dyes – acid,
metal-complex and selected direct dyes. Due to the presence of carboxyl
groups, basic dyes can also form an ionic bond with the fibre. In recent
years, reactive dyes have also become very important for colouring silk,
owing to steadily increasing fastness requirements and fashion trends.
Based on their dyeing behaviour and the ever increasing fastness
requirements, the large molecular weakly acid milling or neutral dyeing
supermilling acid dyes (e.g. Sandolan N/ Milling N of Clariant) are now the
choice for brilliant shades, while 1:2 metal-complex dyes e.g. Lanasyn and
Lanasyn S dyes (Clariant) are the choice for muted tones.
The classical small-molecule levelling dyes are less used for their low
fastness properties and extremely high strike rate with exceptions such as
Rhodamines, bright blues and greens.
Owing to fast strike rates of acid and metal-complex dyes on silk, the
temperature should be as low as possible at the beginning of dyeing in order
to give enough time for the dye to become evenly distributed. The dyeing
temperature should also be adapted to the form of the goods and the type of
machine. For dyeing less sensitive yarn form, higher dyeing temperature up
to 80−90ºC is advantageous for good penetration, but for more sensitive
piece goods, lower dyeing temperature of 60−70ºC is recommended to
prevent chafe marks.
689
Good build-up is achieved with many milling, super-milling and 1:2 metal-
complex dyes as long as low temperature is used. There is little chance of
unsatisfactory bath exhaustion. These dyes are preferably applied in the
neutral to weakly acid region, i.e. at pH 5−7. With very dark shades such as
navy, black or dark brown, it is advisable to work at pH 4.5−4. It is best to
use a buffer system for adjusting the pH in these regions, e.g. sodium
acetate and acetic acid. When dyeing in the weakly acid region, it is
recommended to use a dye-substantive levelling agent such as Lyogen MF
(Clariant) for acid dyes and Lyogen SU (Clariant) for metal-complex dyes so
as to reduce first strike and promote surface levelness. In many cases,
suitable crease prevention agents are added to prevent chafe marks, e.g.
Imacol S (Clariant).
Articles that are difficult to penetrate because of a structured surface and
high weight (shantung, satin, velvet, etc.) are often dyed in a soaping bath
even in the alkaline pH, especially when the goods are processed in star
machine. The bath is set either with pure fresh Marseilles soap or with
corresponding amount of degumming liquor. 5−20% Glauber’s salt is added
for better exhaustion at pH 8−8.5.
For dyeing with milling, supermilling acid dyes and 1:2 metal-complex dye,
the recipe (% o.w.m.) is:
Dye −x%
Lyogen MF or SU liquid − 0.5-1.5%
Imacol S liquid − 1-2%
Sodium acetate − 1-2 g/l
Acetic acid for pH 4.5−7, depending on depth.
The chemicals are added in the bath at 20−30ºC and then the dissolved
dyes are added slowly or in instalments. The temperature is raised slowly to
the ambient temperature of 60−70ºC or 80−90ºC depending on the material
and the dyeing is continued for 60 and 45 minutes for the respective
temperature ranges.
For dyeing in soaping bath:
Dye − x%
Marseilles soap − 1-2 g/l
Glauber’s salt − 5-20%
pH 8.0-8.5
The wet fastness of silk dyed with acid and metal-complex dyes may be
improved by aftertreating with a cationic product such as Sandofix WE
(Clariant) or stronger fixing agents like Indosol E-50 or Lanasan MW
(Clariant).
Amino acid analysis of hydrolysed reactive dyed silk indicates that the
reaction between fibroin and reactive dyes takes place mainly at ε-amino
690
group of lysine, the imido group of histidine and the terminal α-amino group
in the peptide chain. In an alkaline medium the hydroxyl groups of tyrosine
and serine also react. The reactions hardly occur if the pH in the dyeing bath
is lower than 5, due to protonation of the amino and imino groups in silk,
which results in a great reduction in nucleophilicity. The silk fibre can be
cross-linked by a reagent containing bifunctional reactive groups in a weakly
acidic or neutral medium (pH 5.5 to 7).
In comparison with cellulose-reactive dye bonds, the fibroin-dye bonds are
very stable in an aqueous media of pH 4 to 10. Since there is negligible
bond hydrolysis even at high temperature and in a medium of pH 2, the
cleavage of the bond is not a problem in reactive-dyed silk. The bond
stability is highest with monochlorodifluoropyrimidine dye e.g. Drimarene K,
Drimalan F (Clariant), Verofix and Levafix E-A (Bayer) (8-21b), both in acidic
and basic media.
The dyes containing 5-chloro-2,4-difluoro-pyrimidine groups, e.g. Drimalan
F (Clariant), give satisfactory properties in silk dyeing and can be applied in
either a neutral or weakly acidic medium with good exhaustion and fixation.
However, relatively higher cost of production and environmental pollution by
fluorides, may limit their wider application.
Only a few of the dichlorotriazine dyes are used in silk. For example, C.I.
Reactive Red 2 can give a brilliant red shade on silk with high fixation and
good wet fastness when applied in weakly acidic or neutral media at 95°C.
Monochlorotriazine dyes are rarely used in silk dyeing due to their low
reactivity.
The vinylsulphone dyes, such as C.I. Reactive Blue 19, can give brilliant
shades with very strong fibroin-dye bonds.
Reactive dyes containing N-methyl-taurine-ethylsulphone groups (e.g.
Hostalan E brand of Hoechst) can be applied in a neutral bath giving good
fixation, brilliant shades and good fastness on mulberry and tussah silk.
Lanasol dyes (Ciba) containing α-bromo-acrylamide or α,β-
dibromopropionamide groups can give high fixation on silk in alkaline
medium. When two reactive groups are present in the dye, fixation is about
97%.
The brilliancy of commercial reactive dyes can hardly match the shades of
acid dyes derived from xanthene or triphenylmethane chromophores [24].
Reactive dyes can be applied on silk in three ways [24]:
1. Exhaustion in acidic or neutral bath and fixation in alkaline media –
this is a conventional method and widely used in practice giving
satisfactory exhaustion and fixation, but the silk fibre may suffer some
damage in the alkaline bath and at high temperature. This two-step
process is somewhat lengthy.
2. Exhaustion and fixation by one step in acidic or neutral bath – this
simple method is suitable for highly reactive dyes such dichlorotriazine
691
(DCT), difluoromonochloropyrimidine (DFMCP), 2-methoxy-4-

chlorotriazine and vinyl sulphone dyes. These dyes react with fibroin
in the pH range from 5.5 to 7.5. The problems of unlevel dyeing and
fibroin protonation arise if a further decrease of dyeing pH is
exercised.
3. Cold pad-batch in alkaline medium – the alkalinity and batching time
depend on the reactivity of the dyes. Some sulphatoethylsulphone
(SES) and chlorotriazine dyes are recommended.
Optimum pH values for dyeing of silk at 90°C with reactive dyes having
anthraquinone chromophore and various reactive groups were determined.
For DCT and DFMCP, SES, α-bromoacrylamino and MCT dyes, the
optimum pH values are 6-7, 7-8, 8-9 and 9 respectively. The values were
identical for both mulberry and tussah silks and fixation (%) was above 80.
Exhaust dyeing of silk may be carried out with fluorochloropyrimidine
reactive dyes, namely Drimalan F and selected Drimarene K (Clariant) dyes.
Good yield is obtained at 60−70ºC depending on the substrate structure with
these dyes under weakly alkaline conditions.
The dye is added in the bath at 20−30ºC and is allowed to exhaust for
about 15−20 minutes and then Glauber’s salt (20−60 g/l depending on
depth) is added in portions while the temperature is slowly raised to
60−70ºC. After dyeing for about 20 minutes at this temperature, 2-5 g/l
sodium bicarbonate is added in portions and the dyeing is continued for a
further 40 minutes. Crease-prevention agent, Imacol S, if necessary, is
added.
The material is soaped with a detergent (0.5 g/l Sandopan DTC) and
sodium bicarbonate (1 g/l) for 30 minutes at 70ºC after dyeing and rinsing.
Silk may be dyed by pad-batch method with Drimalan F or Drimarene K
dyes by padding the material at room temperature with a liquor containing:
Dye − x%
Urea (solubilising agent) − 50-100 g/l
Sodium bicarbonate − 10-20 g/l
Wetting agent, e.g. Sandozin AMP − 0-2 g/l
The padded material is batched for 24 hours. Adequate colour yield and
fixation may not be achieved with certain large-molecular dyes such as
turquoise and green types.
In summary, both wool and silk are costly and delicate fibres. Under
adverse conditions, they are damaged severely. High alkalinity and high
temperature are harmful for these fibres. Apart from stiffening of fibres
during dyeing, wool may be felted into an entangled mass, while silk
filaments may be broken or chafed. Both the fibres are rich in active
692
chemical groups. A number of dye-classes are available which can provide

bright and deep shades of moderate to high fastness properties. As these
materials are delicate and are handled very carefully, fastness requirements
are not very high. The dyed material should possess satisfactory fastness
meeting washing ISO washing fastness test no. 3 standard.
REFERENCES
1. D.M. Lewis (Ed.). 1992, Wool Dyeing (Bradford, UK: SDC).
2. K. Parton. 1997, JSDC, 113, 341-343.
3. I. Bearpark, F.W. Marriott and J. Park. 1986, A Practical Introduction to
the Dyeing and Finishing of Wool Fabrics (Bradford, UK: SDC).
4. M.L. Gulrajani. 1990, Wool Dyeing and Printing, book of papers for
short-term course arranged by IIT, New Delhi, India.
5. E.R. Trotman. 1984, Dyeing and Chemical Technology of Textile Fibres,
th
6 Edn. (London, UK: Charles Griffin).
th
6. C.L. Bird. 1972, The Theory and Practice of Wool Dyeing, 4 Edn.
(Bradford, UK: SDC).
7. R.H. Peters. 1975, Textile Chemistry, Vol. 3, (Oxford, UK: Elsivier).
8. Gilbert and Rideal. 1944, Proc. Roy. Soc., A182, 335.
th
9. J. Meybeck and P. Galafassi. 1970, Proc. 4 Int. Wool Text. Res. Conf.,
part 1, 463.
st
10. H. Zahn, and J. Meienhofer. 1965, Proc. 1 int. Wool Text. Res. Conf.,
Vol. C, 62.
11. R.V. Peryman. 1954, JSDC, 70, 83.
12. E. Elöd, and H. Reutter. 1938, Melliand Textilber., 19, 67.
14. New Products. 1995, JSDC, 111, 305.
15. F.R. Hartley. 1969, Wool Sci. Rev., 37, 54.
16. D.M. Lewis and G. Yan. 1995, JSDC, 111, 316-323.
17. K. Parton. 1998, JSDC, 114, 8-10.
18. K. Barras. 1989, JSDC, 105, 103-104.
19. A. Doran. 1993, JSDC, 109,15-20.
20. J. Hine and J.R. Mcphee. 1963, Dyer, 132(7), 523.
st
21. J.A. Rippon and F.J. Harrigan. 1990, Proc. 8 int. Wool Text. Res.
Conf., Vol. 4, 50.
22. Silk and Colour. 1985, (Basle, Switzerland: Sandoz)
23. W. Zuwang. 1998, Rev. Prog. Coloration, 28, 32-38.
Chapter
Dyeing of Synthetic
Fibres and Blends 10
10.1 INTRODUCTION
Dyeing of natural fibres (such as cotton, wool, silk etc.) which are essentially
hydrophilic in nature, involves the use of water-soluble or temporarily
solubilised dyes such as direct, reactive, acid, basic, azoic, vat and sulphur
dyes. When the hydrophobic synthetic fibres made their appearance, they
presented a serious problem, in that they could not be dyed with the then-
available dyestuffs. The search for a new dye-class then began resulting in
the development of the disperse dye-class.
Among synthetic fibres, the major area of interest is the coloration of
polyester fibres, although cellulose acetate, nylon, acrylic and polyolefin
fibres are also dyed in considerable quantities.
The story of development of disperse dyes is one which started with the
use of cellulose acetate varnish or dope in the First World War for imparting
flame resistance coating in aeroplanes. At the end of war, the outlets for
cellulose acetate dried up and attention turned to the possibility of
converting the product into rayon. The difficulties experienced in attempting
to dye the so-called acetyl silk compelled C.M. Whittakar to say it put every
colour chemist on scratch because of its intractability in dyeing. It was
observed that the suitable acetate dyes should be simple in structure and
insoluble or of comparatively low solubility in water. Such dyes were
successfully developed in 1923 by British Celanese Ltd. (SRA dyes) and
British Dyestuff Corporation Ltd. (Dispersol dyes). After 30 years of
existence, in 1953 the name acetate dyes was changed into disperse dyes.
Aliphatic polyamides, now generally referred to as nylons (mostly nylon 6
and nylon 6,6), were the first truly synthetic fibres introduced into the market
in the 1940’s primarily as replacements for silk filaments. Polyamides
contain primary amino end-groups that confer substantivity for acid dyes,
which were sensitive to variations in the number of such groups. The dyeing
with acid dyes was not without difficulty – the greatest problem was the
variation in substantivity in different batches due to irregularities in chemical
and physical properties of the fibres. Disperse dyes were unaffected by
chemical variations and, therefore, yielded more uniform dyeing. In course
694
of time, there was great improvement in the regularity of polyamide fibres,

with the result that acid dyes could be used with great success. Use of
disperse dyes on nylon is restricted to pale shades because of poor colour
build-up and poor wet-fastness properties.
Polyester is the leading man-made fibre in production volume and owes its
popularity due to its versatility alone or as a blended fibre in textile materials.
Polyester is highly crystalline and markedly hydrophobic. It is not, therefore,
easily penetrable for dyes with large molecules. It also has no chemically
active groups and cannot combine with dye anions or cations. Though it can
be dyed with a few azoic combinations, in practical terms the only dyes
which can be used with success are the disperse dyes. Their exhaustion at
equilibrium is good, but the diffusion into the fibre is extremely slow. The
increased demand for polyester fibres has revived the preparation of new
disperse dyes to meet the special requirements associated with the fibre. As
polyester is much more thermal-stable compared to other synthetic fibres, it
is possible to carry out dyeing at high temperature (130ºC) and high
pressure when good colour build-up is obtained with most of disperse dyes.
The dyeing with many disperse dyes may also be carried out at boil under
atmospheric pressure, but the presence of some auxiliaries, namely carriers,
are necessary.
Acrylic fibres have now found a wide spectrum of use where soft, wool-like
characteristics are desired. Polyacrylonitriles can be dyed with disperse
dyes at boil, but the exhaustion and colour build-up are poor. Better
exhaustion can be achieved at high temperature. However, when acrylic
fibres are subjected to aqueous treatment above 110ºC, excessive
shrinkage occurs. To improve the dyeability of acrylic fibres, co-polymers
containing anionic co-monomers were developed. Acrylic and modacrylic
fibres contain less and more than 15% such anionic co-monomers
respectively, which attract basic or cationic dyes. Presently, acrylic fibres
are mostly dyed with these dyes at temperatures little above boil (105-
110ºC). Cottage dyers even dye acrylic fibres with selected basic dyes
under atmospheric pressure at boil.
Disperse dyes can, therefore, be applied to most of the synthetic fibres,
namely acetate, acrylic, aramid, modacrylic, nylon, olefin, polyester, Saran
(vinyl) and triacetate fibres. However, for polyester and acetate fibres,
disperse dyes are really the only practical means of coloration.
All of these fibres are thermo-plastic, i.e. the fibres soften instead of
decomposing or igniting when exposed to sufficient heat. Unless the
material is heat-set, it will shrink and creases will form during hot aqueous
treatments such as dyeing. In order to make the material dimensionally
stable, heat-setting may be carried out in a medium of hot air, steam or hot
water, as discussed in Section 4.6.1. The materials are also to be scoured
and bleached, if necessary.
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10.2 MASS COLORATION

The difficulties of dyeing synthetic fibres forced colourists to search for
alternate methods of coloration. One such method is mass coloration, mass
pigmentation or dope dyeing [1,2], sometimes also known as solution-dyed
or spun-dyed. The method is applicable for all man-made fibres –
regenerated (e.g. viscose) and synthetic. In this process, insoluble pigments
(including vat pigments) and selected dyes are incorporated in the solution
or melt of polymer before it is spun into filament. The reported data [2] on
mass-coloured fibres and colorant used for the purpose for the year 1972
are shown in Table 10.1.
Table 10.1 Global Production of Mass-coloured Fibres in 1972
Fibre type % of total Weight of fibre Weight of Colorant
production (tonnes) used (tonnes)
Cellulosic 6 2,20,000 6,000
Nylon and
polyester 1 50,000 500
Acrylic 3 40,000 400
Polyolefin About 100 1,50,000 1,200
The advantages of mass coloration are:
1. It is economical when a manageable range of shades is produced in
larger quantities.
2. Absolute shade uniformity, even over very long runs.
3. The mass-coloured fibres have excellent all-round fastness of the
dyes.
4. The fibre qualities remain unimpaired. Most of the man-made fibres
are delicate and undesirable changes may occur during dyeing for a
prolonged period, especially at high temperature. Mass coloration is
simultaneous with fibre production, hence fibre properties are not
hampered.
5. No additional treatment involving various dyeing machines is
necessary. Hence, coloration cost is low.
6. In dyeing, a significant quantity of unfixed and unexhausted dye is
wasted. In mass coloration, the wastage of Colorant is negligible.
7. There is considerable economy in production time, water, energy and
chemicals – their supply and disposal.
1. Unlike yarn or fabric dyeing, there can be no speedy adaptation to
quick-changing fashion trends, especially where the varied demands
are spread over small lots.
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2. The flexibility in fibre production is minimised.

3. Man-made fibre production sequences are continuous in nature
assuring large volume of production. However, during mass
coloration, the production is to be interrupted from time to time for
change of colour and for cleaning of the equipment from residual
colour.
The fibril diameter of man-made fibres used in textile applications is within
the range 16-25 µm, depending on fibre fineness (denier) and specific
gravity of polymer. The incorporation of coarse pigment particles would not
only impair tensile strength, but would also jeopardise subsequent
processing as a whole. Hence, it is important that the average pigment
particle size should be less than 1 µm, although individual particles of up to
2 or 3 µm in size may be tolerated. Pigments, which normally occur in
coarse crystalline forms, are subjected to special grinding process in the
presence of a dispersing system. The stabilised formulation may be either
solid or liquid.
10.2.1 Mass Coloration of Viscose

The mass-coloured viscose staple and filament yarns are very popular. In
viscose spinning, the spinning solution is strongly alkaline and because of
the presence of sulphur compounds, the solution has a strong reducing
tendency. The Colorants are required not only to be stable to the violent
change of pH, but also to the long-term action of approximately 10%
sulphuric acid in the precipitation bath. The situation is further complicated
by the presence of carbon disulphide, which is a good solvent for various
materials. The incorporated dyestuffs (or pigments) are also subjected to
considerable attack during after-treatments like reduction clearing (with
caustic soda and sodium hydrosulphite to remove sulphur) and bleaching
(with hydrogen peroxide or hypochlorite). The temperature sensitivity of the
Colorant may not hamper its use in the mass coloration of viscose.
Mass coloration was first practised using a single-bath discontinuous
system in which the pigment dispersion was incorporated into a large
quantity of viscose in a large mixing tank followed by sending the mixture for
spinning. In this method, a large section of the plant is to be washed during
change of colour.
In continuous master-batch system, a quantity of viscose is mixed with the
pigment paste to prepare a concentrate, which is injected into a blender fed
with metered uncoloured viscose from the main supply. The blender was
located near the spinning machine to facilitate cleaning. Subsequently,
highly efficient homogeniser and devises have been developed to reduce
human element in the laborious repeated preparation of master batches.
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The next development was elegant automatic control systems or direct

injection systems giving constant pigment:viscose mixtures irrespective of
the fluctuating demands at the spinning machine. Introduction of high
efficiency mixer together with precision piston and flexible diaphragm pumps
capable of metering diluted pigment dispersion of water-like viscosity
accurately against the high-pressure flow of viscose enabled the master
batches to be dispensed with altogether. This direct injection system is
widely popular now.
Some of the Colorants suitable for mass coloration of viscose are as
follows (all azo except otherwise mentioned):
C.I. Pigment Yellows 1, 13 and 49
C.I. Pigment Orange 13
C.I. Pigment Reds 2, 5, 7 and 168 (anthraquinoid)
C.I. Pigment Blue 15 (copper phthalocyanine)
C.I. Pigment Violet 23 (dioxazine)
C.I. Pigment Green 7 (phthalocyanine)
C.I. Pigment Browns 1 and 22 (nitro)
C.I. Pigment Black 6 (lamp black)
C.I. Vat oranges 7, 9 (both anthraquinoid)
C.I. Vat Blues 1, 4 and 9 (all indigoid)
C.I. Vat Violet 1 (anthraquinoid)
In case of vat type Colorant, some oxidising agent like resist salt (m-
nitrobenzene sulphonate) is to be used in order to prevent reduction of the
Colorant and consequent oxidation at the spinnerets, thereby causing
choking problem.
Very attractive lustrous transparent colours can be obtained by
incorporating reactive dyes into viscose dope and several patents have
been filed. However, no significant commercial production has started
because only a few dyes give adequate fixation and fastness.
10.2.2 Mass Coloration of Acetate

Both single-batch and master-batch methods are used. Direct injection
system may be practised with solvent-soluble dyes, but the problems arise
from limited solubility of dyes and control of volatile solvents.
Two broad classes of Colorants have been established – pigment and
solvent-soluble dyes. The chemical types of pigments suitable for acetate
are more than those of viscose as the pigments do not have to withstand
strong alkali and acid, but all must be insoluble in acetone.
Some of the Colorants suitable for mass coloration of acetate fibres are:
C.I. Pigment Yellows 3 and 17
C.I. Pigment Reds 2, 7 and 144
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C.I. Pigment Blues 15 and 60

C.I. Pigment Brown 22
C.I. Pigment Green 7
C.I. Pigment Black 7
C.I. Vat Yellow 4
C.I. Vat Blue 1
Most of the solvent-soluble dyes mentioned in the colour index can be

used for mass coloration of acetate fibres and they give lustrous transparent
colours. Nevertheless, fastness with all such dyes may not match with that
obtained with pigments. Chemical types include monoazo, metal-complex
azo, anthraquinone and phthalocyanine compounds – anionic, cationic or
nonionic. They are commercially pure dyes, free from standardising and
dispersing agents. The criterion for selection is the solubility of the dye in the
dope at spinning concentration.
10.2.3 Mass Coloration of Acrylics

The lack of suitable dyes and dyeing processes for acrylics created a spur
to mass coloration. The spinning of acrylic polymer may be carried out in
four ways:
1. Dry spinning from dimethylformamide (DMF) solution

2. Wet spinning from dimethylformamide (DMF) solution
3. Dry spinning from dimethylacetamide (DMA) solution
4. Wet spinning from sodium thiocyanate solution
Clearly, dyes soluble in the specified solvent cannot be used in the

respective wet spun process. Even such dyes can cause severe spinneret
incrustation due to the high temperature of the spinning solution (150ºC) and
high extrusion temperature (400ºC). High-grade pigments like the
quiniacridone and perylene types are particularly valuable because of their
high solvent resistance.
The acrylic filament, wet-spun from sodium thiocyanate solution and
destined for staple fibre, may be dyed in tow form. The filaments after
extrusion are washed in tow form and then dyed by a continuous process
with modified basic dyes having the required solubility and stability at low pH
and at low concentration of sodium thiocyanate.
10.2.4 Mass Coloration of Nylon

Compared with other thermoplastic fibres, polyamide fibres offer a much
lower choice of Colorants, because these are exposed in the melt not only to
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high thermal energy but also to reducing chemical nature of nylon. The
mass coloration of nylon is restricted to filament only. Nylon can be mass
coloured in three ways:
1. Autoclave coloration i.e. addition of Colorants before polymerisation.

Unlike acetate or acrylic fibres there was no problem during initial
development in finding dyes, which could colour nylon 6 and nylon 6,6
satisfactorily. Nevertheless, the method has not survived because of
the combined effects of the strongly reducing character and
temperature of nylon melt (250ºC for nylon 6,6 and 215ºC for nylon 6).
In addition, hot monomer may cause flocculation of pigment slurries.
Colorants first used were mostly inorganic such as cadmium
pigments, oxides of iron and chromium, carbon black, etc. Numerous
heat-stable organic pigments have also been suggested, namely
phthalocyanine, anthraquinone and quinacrydone derivatives. Highly
pigmented master-batch chips were produced for mixing with
uncoloured chips before spinning. The processes for simultaneous
mass coloration and polymerisation are also developed.
The incorporation of Colorants in the autoclave has declined
considerably. The process of changing of colour is inconvenient and
cost of cleaning is high. Moreover, there are chances of degradation of
the polymer and subsequent undesirable effects on yarn quality.
2. Chip coating i.e. addition of Colorants after polymerisation and before
spinning. The method is comparatively better as the time of contact,
between Colorants and molten polymer, is less and autoclave
contamination is eliminated.
In chip coating, Colorants in one form or other are applied to the
surface of the chips. If the coating is consistent and stable, the
technique leads to uniform distribution of Colorant in the polymer and
special mixing procedure is not necessary. It is desirable that the
Colorant is an integral constituent of the extender (Colorant vehicle)
particles. The use of water-miscible liquid aliphatic acids, hot water-
soluble alcohols, high temperature grinding and plastic-milling with
formic acid are suggested.
Although the benefits of flexibility and improved fibre quality resulting
from chip coating as compared with autoclave coloration, were
recognised, some disadvantages of chip coating came into light.
These included colour variation due to dusting off and requirement of
large amounts of costly extenders. An approach to these problems
was chip dyeing, i.e. dyeing of nylon chips before spinning into fibres
in aqueous dyebath using processes and equipment somewhat similar
to those used for dyeing of nylon textiles. The method is frequently
used for nylon 6 and to a less extent for nylon 6,6. The dyeing may be
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simultaneous with aqueous monomer extraction process, an essential

step for nylon 6 (not for nylon 6,6). The dyes should have necessary
heat stability. Numerous metal-complex azo and anthraquinone dyes
are suitable for the purpose. The dyes should have sufficient
absorption power, which is also influenced by chip size and liquor
ratio. No dyeing auxiliary is necessary. The pH is set below 7 using
ammonium acetate, acetic acid or formic acid. A dyeing time of 1 to 5
hours may be necessary. Dyeing in autoclave at 120º-130ºC improves
bath exhaustion and shortens dyeing time.
Dyeing immediately after raw material production, i.e. before
granulate is dried and spun, necessitates long-term dispositions.
Consequently, market demand cannot be satisfied at short notice. The
environment-compatibility expected from dope dyeing is not assured,
owing to the large volume of wastewater. Intermediate storage of large
quantities of polymer in several shades may be unavoidable.
3. Mixing of Colorants with polymer just before spinning, either by batch-
wise admixing (directly or master batch system), continuous admixing
in a mixer before spinning or injecting melts of master batch, and
spinning polymer into the discharge zone of the main extruder with a
mixing pump.
10.2.5 Mass Coloration of Polyester

Mass-coloured polyester fibres are available in both staple and continuous
filament forms, the staple fibre form being more important. Though the
temperature of polyester melt is high (260ºC), it does not have reducing
nature.
Autoclave coloration or chip coating may be done with pigment dispersion,
but chip dyeing is not popular. This is because polyester is dyed either with
carriers at boil or at high temperature. In the first case there is chance for
contamination of the polymer-melt, while in the second case, polymer
hydrolysis is liable to occur.
The range of stable pigment Colorants roughly matches that for nylon. The
use of pigments is not excluded, but it seems likely that polymer-soluble
Colorants will be preferred for both nylon and polyester. For nylon,
anthraquinone derivatives and chrome-complex dyes, and for polyester,
azo, anthraquinone and azopyridones are suitable.
10.2.6 Mass Coloration of Polyolefins

Polyolefin fibres are defined as fibres spun from polymers or copolymers
of ethylene and propylene. For textile applications only polypropylene is
successful to some extent. Coloration of polyolefins is difficult, because the
homo-polymers are of very inactive nature and are virtually undyeable.
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The various efforts made for coloration of these fibres are:
1. Surface oxidation of methyl to carboxylic groups. However, the

method is not very successful.
2. Copolymerisation with other monomers having affinity for dyes. But
the comonomers may inactivate Ziegler-Natta catalyst, which is used
for stereo-regular polymers.
3. Grafting of dye on to the fibre.
4. Introduction of metal salts during spinning and subsequent dyeing with
metal-complexable dyes.
But none of the methods described above is commercially successful.

Hence, polypropylene, at present is almost fully mass coloured. Because of
lower melt temperature (165ºC), a wider range of pigments including chrome
pigments, inexpensive azo pigments and toners are used. However, fine
filaments are extruded at temperature as high as 300ºC and high thermal-
stable pigments, similar to those used for nylon and polyester, are to be
selected for that purpose.
10.3 DISPERSE DYES
The Society of Dyers and Colourists (UK) defines disperse dye as a

substantially water-insoluble dye having substantivity for one or more
hydrophobic fibres e.g. cellulose acetate or polyester and usually applied
from fine aqueous dispersion.
Disperse dyes are sold under various brand names such as Dispersol
(BASF, earlier ICI), Foron (Clariant), Palanil (BASF), Terasil (Ciba),
Tulasteron (Atul), Navilene (IDI), Terenix (JDL), etc.
While dyeing from aqueous media the bulk of the dye is in suspension, but
at least during the initial stage of dyeing, transfer of dye into the fibre takes
place from a very dilute aqueous solution of the dye. Such pockets
containing dissolved dyes are continuously replenished by progressive
dissolution of particles in suspension.
Due to nonionic nature, disperse dyes are volatile and the dye-vapour is
strongly adsorbed by hydrophobic fibres. This is the basis for thermosol
(heat-fixation) dyeing and heat-transfer printing processes.
Disperse dyes are mainly used for acetate and polyester fibres. The dyes
for secondary cellulose acetate are well established. For highly hydrophobic
triacetate fibre, the molecular size of the dye is the limiting factor. Polyester
fibres are dyed at high temperature. The dyed and printed polyester
materials are often subjected to heat treatment. Hence, dyes of greater
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molecular size having good sublimation and light fastness and giving good
colour-yield on polyester are desirable.
On nylon, disperse dyes can cover barré effect (structural differences) due
to variation in end amino-groups. However, due to limited fastness
properties, dyeing is restricted to pale and medium shades on nylon hosiery
and carpets.
On acrylic fibres, light fastness of disperse dyes is good, but limited colour
build-up restricts the dyeing to pale shades only.
Some characteristics of disperse dyes are as follows:
1. Disperse dyes are low molecular weight substances, mostly derived
from azo, anthraquinone and diphenylamine.
2. Disperse dyes are crystalline materials of high melting point (>150ºC).
They are milled with dispersing agents to produce stable dispersions
in dyebath and 0.5 to 2µ in particle size. As they are applied in the
form of very fine aqueous dispersions, both particle size and
dispersion stability are extremely important. Ideally, disperse dyes
should disperse extremely rapidly when added to water and give a
stable dispersion of very fine and uniform particle size. The dispersion
should be stable during dyeing in the presence of auxiliaries, including
carriers and levelling agents. Some aggregates of dye may precipitate
on the fibre surface in the presence of surface-active agents and at
temperature higher than 100ºC, which are to be removed after dyeing
by reduction clearing.
3. Disperse dyes are marketed in both powder and liquid forms. The
powder brand contains considerable amount of dispersing agent e.g. a
naphthalene sulphonic acid-formaldehyde condensate and possibly a
wetting agent. The liquid dyes are concentrated and free-flowing
aqueous dispersions. The advantages claimed for the liquid brand are
freedom from dusting, easy preparation of dyebath and padding liquor
and suitability for automatic metering systems called auto-dispensing.
They contain lower amounts of dispersing agents and give higher
colour-yield and brighter dyeing in pad-bake process.
The conventional disperse dyes give insufficient colour yield by
super-heated steam fixation method and also have poor compatibility
with synthetic thickeners in printing due the presence of anionic
dispersing agents or electrolytes. Nonionic disperse dyes have now
been developed which are especially recommended for printing and
continuous dyeing, e.g. Kayalon Polyester N paste (Nippon Kayaku).
These dyes are dispersed with nonionic dispersing agents.
4. These dyes are nonionic in nature devoid of strong solubilising groups
like sulphonic or carboxyl groups, although weak solubilising groups
like aromatic or aliphatic –NH2, −NHR and –OH groups may be
present.
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5. These dyes have relatively low solubility (at least 0.1 mg/l) in aqueous
medium under dyeing conditions. Aqueous solubility at 80ºC ranges
from 0.2 to 100 mg/l. As solubility increases logarithmically with
temperature, a considerable amount of dye may be in solution at
130ºC. On cooling, the dye may crystallise as large particles.
6. The saturation level of pure disperse dyes in the fibre is relatively high
(30-200 mg/g of fibre).
7. Due to the absence of ionisable groups, disperse dyes have the
tendency to sublime without decomposition. Consequently, colour of
disperse-dyed fabric may fade while ironing. It is, therefore, necessary
to test sublimation fastness or fastness to dry heat of the dye. The
fastness rating is useful for deciding by which method the dye can be
applied most successfully and the performance of the dyed material
for various end-uses. The test may be mild (M), intermediate (I) or
severe (S) depending on the temperature of testing (150ºC, 180ºC or
210ºC respectively). The fastness to heat treatment improves with
increase in molecular size.
8. The colour yield, brightness and shade of disperse dyes remain
unaffected in the presence of hard water of 50º English hardness.
Demineralised water containing sodium ions is alkaline and needs
suitable buffering. A number of disperse dyes are susceptible to
copper or iron and form a blue-violet complex with them. This may
cause change of shade or staining. If the use of hard water is
unavoidable, it is advisable to use a sequestering agent such as 0.5
g/l of disodium salt of EDTA and pH should be buffered at 4-5. EDTA
salts are alkaline. Tetra-sodium salt is not recommended due to its
high alkalinity. The addition of sequestering agent (1 g/l) is also to be
made in reduction clearing and subsequent processes, if the water is
hard. After reduction clearing, it is advisable to treat the goods with
1−2 g/l acetic acid (60%). If the undesirable metal-complex dye is
already diffused into the fibre, a treatment with sequestering agent,
anionic dispersing agent and carrier is to be made at pH 4-5 and
temperature 130ºC for 2 hours. The dyes sensitive to copper and iron
are [3]:
C.I. Disperse Orange 25
C.I. Disperse Reds 55, 60, 75, 91, 92 and 93,
C.I. Disperse Violet 35
C.I. Disperse Blues 79, 94, 128 and 148
9. Soon after the introduction, it was noted that the colour of cellulose
acetate materials dyed with certain disperse dyes had a tendency to
fade when stored in an atmosphere having fumes from gas heaters.
The most susceptible dyes were reds and blues based on amino-
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anthraquinone, but certain azo dyes were also affected to a lesser

extent. It was established that the active constituents of the burnt gas
fumes were nitrogen oxides. In the late 1940s and early 1950s
numerous disperse dyes resistant to fading by gas fumes were
introduced. The resistance is increased when basicity of the dye is
decreased. However, this may lead to inferior dyeing properties and
the most successful of the newer gas-fume-fast dyes have more
complicated chemical structure in order to maintain dyeing properties.
The fastness to gas fumes can be improved by substituting one of the
two –NHCH3 substituents of C.I. Disperse Blue 14 with aminobenzene
(−NHC6H5) substituent as in case of C.I. Disperse Blue 24. However,
dyeing properties of the latter is inferior. Better dyeing properties can
be achieved by adding -CH2CH2OH group on aminobenzene
substituent and substituting other –NHCH3 group with hydroxyl group,
as in the case of C.I. Disperse Blue 27 (10-8) (Section 10.3.3).
10. With other dyestuff classes, identity of chemical structure establishes
all dyeing and fastness properties. But It is not true with disperse
dyes. The disperse dyes having identical chromophore (indicated by
C.I. number) produced by different manufacturers, may not give
identical shades on dyeing. The shade produced depends on several
factors like shape, size and volume of the dye crystals, coloured
impurities or isomers, type and amount of dispersing agents and
products added for standardisation.
11. Disperse dyes show thermal migration, i.e. migration of dye from core
to surface while drying of dyed goods at 170ºC or above. Migration is
more in case of disperse dyes of high molecular weight having high
sublimation fastness. Whenever thermal migration poses a problem of
low wash fastness, the remedy is to post-scour the dyed material
followed by drying at 140ºC or below. Some processing aids (e.g.
spinning or knitting oils) and finishing agents may also cause thermal-
migration of disperse dyes. During storing of the dyed or printed
material, some disperse dyestuffs have the tendency to be desorbed
from polyester and be reabsorbed in the layer of oil or finishing agent,
particularly under the influence of heat, humidity and pressure. As the
dye migrates from the core to the surface of the material, the fastness
to light, sublimation and wet treatments may be adversely affected.
Broadly speaking, nonionic emulsifiers and finishing agents are
responsible for thermal-migration. Anionic and cationic agents are less
harmful. Polyvinyl acetate and cross-linking agents like DHDMEU with
magnesium chloride catalysts are safe.
12. In case of dyeing of polyester with disperse dyes, abnormal fading in
light occurs in several combinations of yellows and blues. In case of
other dye-classes, blues are selectively destroyed in the presence of
705
yellows, but with disperse dyes both the dyes undergo destruction or
the light fastness of the final green shade is lower than that expected.
The examples are compound shades of C.I. Disperse Blue 56 with
either of the following yellow disperse dyes:
C.I. Disperse Yellow 50
Similarly, when C.I. Disperse Blue 183 is combined with several red
dyes, abnormal fading was observed [4].
On nylon, catalytic fading occurs with many combinations of acid dyes,

especially in combinations of yellows and blues. A few worst examples are
combinations of C.I. Acid Yellow 112 with the following dyes:
C.I. Acid Violet 4
C.I. Acid Red 267
However, both the dyes are not commercially manufactured at present.
10.3.1 Finishing and Testing

The finishing of disperse dyes after manufacture consists of several steps:
1. Precipitation
2. Filtration
3. Grinding in the presence of dispersing agents
4. Drying
The finishing qualities dictate to a larger extent the behaviour of disperse

dyes towards dyeing. Various special grinders are used for grinding press
cakes in order to bring the dye into a uniform fine dispersion. The various
milling machines used for the purpose are:
1. Impact mill, where the material is ground between a stationary and a

rotating set of steel rods.
2. Carborundum disc mill consists of a stationary and a rotating disc.
3. Sand mill, where the dye is whirled around with sand in an aqueous
sludge, followed by filtering off sand.
4. Ball mill consists of a large steel cylinder partly filled with ceramic
balls.
In order to obtain powder form of disperse dyes, an aqueous paste of the

dye is subjected to finishing and drying, mostly by spray drying technique.
The temperature during drying is crucial to retain fine dispersion.
Liquid preparations also need thorough grinding followed by
standardisation to ensure constant tinctorial power. Stabilisers are added in
706
them to prevent premature settling and drying. Liquid brands often have a
higher degree of dispersion than the corresponding powder brands and for
this reason the liquid dyes are particularly suitable for continuous dyeing
processes.
A material of good particle-size distribution contains very few coarse
particles and a high proportion of small and very small particles. The coarser
components can lead to many difficulties in dyeing and printing and amongst
other things, can cause specks in thermosol dyeing. Two types of tests may
be carried out to check particle size distribution of disperse dyes, namely [5],
1. Sedimentation analysis
2. Filter tests in aqueous dispersion
In simple sedimentation analysis, a 30-cm high glass tube with a base

which is divided into eight sections, has proved very satisfactory. A dye
dispersion is prepared with 5 g/l dye in this cylinder and allowed to stand
overnight. A sample is taken from each section carefully with the help of a
pipette. The concentrations of dye in all eight sections are determined
colorimetrically after adding acetone and ideally, these should not differ.
Normally, however, a difference in concentration is found between the
topmost and lowest sections, and this means that some coarse particles
have settled out.
The sedimentation test may be carried out within a shorter time with the
help of a centrifuge. While coarse particles will settle out even at low
rotational speed, finely dispersed particles will not settle even at speeds of
several thousand revolutions per minute. However, sedimentation tests
provide results in terms of relative fineness – no information is given about
the absolute size of dye particles.
The filter test can, with some reservations, be called an absolute test of
particle fineness. A specified amount of dye is dispersed at room
temperature and stirred for sometime. It is then sucked through a Buchner
funnel containing two standardised quality filter papers, one on top of the
other, by creating a vacuum of 35-110 mm mercury with the help of a
vacuum pump. The appearance of the filter paper is then checked. Once it
was customary to weigh the amount of dye filtered off and from this to
assess the quality. However, with the present quality of disperse dyes, a
good dye will hardly leave any weighable residue on the filter paper.
In less common flow test, 1 ml of 5 g/l dye dispersion is dropped on a
round filter. The filter paper is best placed on the top of an empty glass
beaker so that the drop can spread uninhibited. A dye of good dispersion will
spread so uniformly that the point of dropping can no longer be
distinguished from its surrounding. The more pronounced the formation of a
rim on the filter, the lower is the quality of the fineness of the given dye.
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Sometimes it may be necessary to check the stability of dye dispersion in

the dyeing conditions. This is done by treating a dye dispersion to the dyeing
process using chemicals and auxiliaries but in the absence of textile
material. The dye dispersion is then subjected to a filter test. The reliability
of the test may be questioned. During the test, the whole amount of dye
remains in the dispersion, whereas in actual dyeing much of the dye is
exhausted into the substrate before the maximum dyeing temperature is
reached. Moreover, the test results cannot predict the filtering out of the dye
during package dyeing as filtering depends not only on the quality of dye,
but also on the type and packing-density of the material.
The dusting properties of disperse dyes may be measured by allowing a
known quantity of dye (30 grams) to fall through a tube of precisely
determined length (50 cm). The optical density of the dust is measured by a
photocell, both immediately and after 30 seconds. The dusting value is the
sum of the two values and should be below 15 for a low-dusting dye [5]. The
value for a dye may change on storage.
BASF characterised their Palanil disperse dyes by diffusion number, which
is based on the degree of penetration of the dye into polyester film under
defined dyeing conditions. The number is important for assessing some
important properties of disperse dyes, notably its combinability and
suitability for a particular application. The larger the molecular size of the
dye, slower will be the rate of diffusion and higher energy will be required for
its application. The dry-heat or sublimation fastness for such dye will also be
higher. Therefore, disperse dyes may be classified into three categories –
low, medium and high-energy dyes.
The Committee on disperse dyes of the Society of Dyers and Colourists
(UK) formulated tests [6] for classifying disperse dyes on cellulose acetate
on an A-E scale. Class-A dyes have best migration properties, widest range
of application temperature, best colour build-up and fastest in dyeing rate.
Class-E is the worst in the above properties and the dyeing rate is slowest.
The work was subsequently extended to cover triacetate and nylon.
On the basis of exhaust dyeing of polyester at high temperature (130ºC),
four tests were published in 1977 [7] covering critical dyeing temperature,
migration, build-up and diffusion rate. Control dyes are specified for use in
each test and the behaviour of the dye under test is expressed on either an
A-D or A-E scale, where A represents the most satisfactory in relation to the
above properties and D or E represents least satisfactory for the respective
scale.
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The properties of various classes of disperse dyes are listed below:

1. Dyes with no suffix, e.g. C.I. Disperse Yellow 13 (10−1), are suitable
for acetates and nylon.
2. Class-A dyes, e.g. C.I. Disperse Violet 1 (10−2), are suitable for
acetates and nylon. They are of some use for polyester, but fastness
to heat treatment is low.
3. Class-B dyes, e.g. C.I. Disperse Blue 56 (10−3), show excellent
dyeing behaviour on polyester fibres. They provide good coverage of
physically variations as in textured yarn. Heat fastness of dyed
material is moderate. Selected dyes are suitable for acetates and
nylon.
HO O NH2
OCH3 O NH2
Cl
O
O NH2 H2 N O OH
(10−1) (10−2) (10−3)

4. Class-C dyes, e.g. C.I. Disperse Orange 30 (10-4, No. 3), in general,
are suitable for acetate and triacetate. They are all-round suitable for
dyeing polyester by carrier method, high temperature method and dry-
heat-fixation method, giving better heat-fastness than Class-B dyes.
5. Class-D dyes, e.g. C.I. Disperse Blue 183 (10-4, no. 4), are intended
for polyester dyeing of maximum fastness to heat treatment including
resin finishing. Application is recommended by high temperature
method and dry-heat-fixation method. However, they are unsuitable
for carrier method. Selected dyes are suitable for nylon dyeing of high
wet fastness.
ICI disperse dyes (Dispersol) had been classified into A, B, C and D

classes (dyes without suffix are obsolete), whereas Clariant disperse dyes
have been classified into S (low-energy), SE (medium energy) and E (high-
energy) classes.
Disperse dyes may also be rated according to their penetrating or diffusing
power. Diffusion test may be carried out by rolling polyester film (50 cm x 4
cm) on a glass rod (6 cm length, 0.4 cm diameter) under water or spirit to
prevent entrapping of air. The ends of the roll are sealed by a heated
spatula with the rod. A second rod is bound tightly with the former under
uniform tension, which gives the undyed boundary line between the layers of
709
film. The composite specimen is immersed in a dyebath of M:L ratio of 1:200

at 60ºC with 5 g/l dye under test and control bath with 5 g/l C.I. Disperse
Orange 13, e.g. Palanil Orange G (BASF) separately. The temperature is
raised quickly (generally 3ºC per minute) to 130ºC and kept for 2 hours. The
samples are washed with water and the number of layers penetrated is
counted (up to a contrast less than 4-5 on Grey Scale)
N
Diffusion index = —— x 10 (10.1)
NS
Where N and NS are the number of layers penetrated by the dye and
Palanil Orange G respectively.
The diffusion indices and rates of diffusion of control dyes are shown in
Table 10.2. Unfortunately C.I. Disperse Red 15 is banned at present, Blue
22 having near about structure may be tried. The said dye has a single
substituent NH.CH2, whereas Red 15 has two substituents, NH2 and OH.
Table 10.2 Diffusion Indices and Rates of Diffusion (Rating) of Control
Dyes in Diffusion Test
Name of dye C.I. Disperse Index Rating
Cibacet Red 3B (Ciba) * 17 A (rapid)
Red 15
Dispersol Blue B-R (ICI) Blue 56 12 B
Palanil Orange G (BASF) Orange 13 10 C
Dispersol Blue D-2R (ICI) Blue 83 7 D
Foron Navy S2GL (Sandoz) Blue 79 5 E (slow)
Although these classifications provide useful information about the
behaviour of disperse dyes, they do not enable the dyer to choose rate-
compatible mixtures for dyeing polyester in the way that the compatibility
value tests do for basic dyes on acrylic fibres (Section 10.5.1). In fact, there
is no simple system for formulating rate-compatible recipes for dyeing
polyester materials with disperse dyes. Considerable work has been done to
develop methods of reducing dyeing cycle times in polyester dyeing. One of
the main difficulties in defining such optimised dyeing cycles arises from the
fact that the rate of dyeing of disperse dye on polyester is very much a
function of the depth of dyeing, i.e. the concentration of dye in the bath. It is
practicable and useful to characterise the rate of dyeing at a particular depth
by a single parameter called V number which is based on time of half dyeing
as shown in Eqn.(10.2).
70 - t 1/2
V= (10.2)
10
V is always a positive number, in fact always greater than one. The
higher the V number, the faster is the rate of dyeing [8]. If in a given recipe,
the component dyes have similar V numbers, then the mixture will be rate-
710
compatible and will build up tone on tone throughout the dyeing cycle.
Furthermore, this prediction of compatibility has been shown to be largely
unaffected by considerable changes in the dyeing conditions employed.
These observations support the generally held belief that disperse dyes
applied in mixture behave essentially independently of one another.
It is, therefore, evident that no mixture of (say) three individual dyes of
different colours can build up on-tone (same tone) over a wide range of
depths. It is, however, possible, from knowledge of V numbers, to formulate
rate-compatible recipes, which will give on-tone build-up.
In order to save time, dyeing should be started at the highest possible
temperature and the rate of temperature rise should be highest possible
without hampering levelness. The critical temperature test has been
developed in which visual estimations are made of the temperature at which
50% exhaustion of specified amount of dye is obtained within 20 minutes. In
fact, two tests are carried out at light and medium depths using one-fifth and
twice the amount of dye needed to produce ISO 1/1 standard depth.
Standard depths are series of shades of various hues, e.g. 1/1, 2/1, 1/3,
1/12, etc. (Section 6.9). Each series have equal lightness. 2/1 set is darker
than 1/1 set, while 1/3 set is lighter.
The dyeing is carried out for 20 minutes at five temperatures, namely 85,
90, 95, 100 and 130ºC. The temperature at which colour yield is half of the
final exhaustion (i.e. 130ºC) is defined as the critical temperature for the
particular dye. The average rate of exhaustion at the critical temperature is
about 2.5% per minute. For the older type of jet machine where the rate of
flow is slow (1.5-2.0 cycles/min), the starting temperature should be below
critical temperature to avoid unlevelness. In modern rapid jet dyeing
machines, the rate of flow is rapid and dyeing can be started at the critical
temperature. Disperse dyes may be rated as A, B, C and D according to
critical temperature of the disperse dyes (≤ 85º, 90º, 95º and ≥ 100ºC
respectively).
According to Clariant, critical temperature zone for the high-temperature
dyeing is the temperature zone in which the last 80% of the dye is
exhausted into polyester fibre. Level dyeing can be obtained if the heating
rate is controlled through this temperature zone. Depending on the dye type
and amount applied, the critical temperature zone also depends on the
chemical system in the dyebath and the polyester substrate. With dye
combinations, the lowest and the highest critical temperatures of the dyes in
the combination dictate the limits of the critical temperature zone. The
critical temperature zone for three Foron Dyes (Clariant) belonging to three
energy classes are as shown in Table 10.3.
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Table 10.3 Critical Temperature Zones of Three Foron (Clariant)

Disperse Dyes at Light and Dark Shades
Dye Depth Zone Depth Zone
Yellow S6GLI (231) 0.13 100-121 0.8 111-130
Red SE4BLI (281) 0.17 108-124 1.0 114-134
Navy S-2GRLI (79) 0.54 102-120 4.8 115-136
Note: Depths are in % and represent 1/3 and 2/1 standard depth (light
and deep respectively), Zones represent temperature ranges in ºC. The
bracketed numbers are C.I. nos. (C.I. Disperse Yellow, Red and Blue
respectively).
In conventional jet dyeing machines, the maximum heating rate is 2ºC per
minute, whereas in rapid jet dyeing, the rate normally is 6ºC per minute and
in advanced machines like Hisaka and Calibaut-de-Bliqy Jet Dyeing
machines, 8-10ºC per minute. The various parameters in conventional and
rapid dyeing machines are shown in Table 10.4.
Table 10.4 Comparison of Various Parameters in Conventional and
Rapid Jet Dyeing Machines
Parameter Conventional Rapid
Heating rate,ºC/min Maximum 2 6
Usual 1-1.5 2-5
Liquor interchange (cycles/min) 2 6
Rate of liquor flow (l/min/kg) 25-30 60-80
Cooling rate (ºC/min) 2 5
Dyeing cycle (hour) 2½ - 3 1-1½
M:L ratio 1:10-15 1:6-8
Flow capacity (l/min) 2,500 8,000
Below critical temperature, the temperature can be increased at a higher

rate. In rapid jet, the rate may be 6ºC/min followed by about 2ºC/min in the
critical temperature zone. In conventional machines, the maximum heating
rate may be 2ºC/min, which is to be further reduced to 1-1½ºC/min in the
critical zone.
To reduce the dyeing time further, quick-fixable rapid dyes may be
selected so that satisfactory diffusion and fixation may be achieved within
10-20 minutes in rapid dyeing machine as compared to much higher time
(even 50 minutes) by the conventional dyes in conventional jet machines.
The total dyeing cycle may be reduced to 50-70 minutes as compared to
180 minutes in conventional process.
712
Clariant has produced rapid dyes, Foron RD range consisting of Foron

Yellow RD-4GLS, Red RD-GL, Rubine RD-GFL, Blue RD-GL, Navy RD-2RL
and Black RD-RL.
The main characteristics of these rapid dyes are:

1. Perfect dispersion stability at all dyeing temperatures up to 140ºC.
2. Uniform absorption on the fibre.
3. High colour build-up, equivalent to 6/1 standard depth.
4. Due to high rate of diffusion, fixation time is shorter – 20 minutes at
130-135ºC even for jet-black shade.
5. Good combinability and reproducibility.
6. Moderate fastness to sublimation, i.e. of the Foron SE-standard.
A typical exhaust dyeing application sequence for polyester can be divided

into three phases, namely:
1. The heating or adsorption phase
2. The high temperature or diffusion phase
3. The reduction clearing phase
In optimising dye selection to maximise Right-First-Time production, it is

important to know the behaviour of disperse dyes in each of these three
critical phases. In particular, the Controlled coloration approach demands
that a consistent selection of dyes be made in each shade area, which
display good compatibility through the three phases of dyeing.
The compatibility of disperse dyes is unimportant and any combination of
dyes can be used, provided sufficient time is given and appropriate
auxiliaries are used. The choice of disperse dyes for polyester is not
influenced by dye interactions or competition for dye sites, as in the case of
acid dyes on nylon. In practice, however, to optimise the productivity of the
operation, it is essential to minimise process times. In modern rapid dyeing
for polyester, compatibility of dyes is important, as the process does not
necessarily allow for the late dye to adsorb or poor levelling dye to migrate
or the slowest dye to diffuse.
If shades are dyed with a range of compatible disperse dyes, with the
same combination used in each area of colour space, then each dyeing
becomes predictable and consistent. Choice of the dye for matching is then
driven by Right-First-Time through the use of guidelines of selection with a
colour map, as illustrated for the compact Dispersol C-VS dyes range from
BASF. This approach allows for a build-up of a shade bank of production
recipes and software such as Smart Match (Datacolor) can be utilised to
predict new recipes solely based on actual production shades on a particular
quality of substrate, rather than requiring laboratory matching.
713
The compact Dispersol C-VS (BASF) dyes are a short range of selected
medium energy dyes, which demonstrate similar application characteristics
in rapid dyeing cycles on polyester. The disperse dyes with similar
adsorption characteristics are used for combination shades so that the
adsorption behaviour and critical temperature range for control are
reasonably consistent and predictable. To minimise time at high
temperature, dyes with relatively rapid diffusion rates should be employed.
Achievement of Right-First-Time also depends on meeting the customer's
fastness specification, so that it is important that the selection of dyes and
choice of treatment in the reduction-clearing phase is appropriate. A key
criteria in the selection of dyes for the compact Dispersol C-VS series is
their ease of clearing, so that high standard of fastness can be achieved
without reduction clearing in the majority of shades [9].
10.3.3 Chemical Structure

The various chemical structures found among disperse dyes are:
1. Azo
2. Nitrodiphenylamine
3. Anthraquinone
4. Methine
5. Heterocyclic rings
Azo Dyes
Azo dyes represent the largest and most important group, and chiefly cover
yellow, orange and red hues. The dyes are relatively cheap and generally
they do not require numerous intermediate stages during manufacture.
The most important sub-group, aminoazobenzene derivatives [10], has the
general formula (10−4).
R2 R5
R6
R1 -N=N- N
R7
R3 R4
(10−4)
Where R1 = electrophilic group
R2 and R3 = H or electrophilic groups
R4 and R5 = H or neucleophilic groups
R6 and R7 = H or alkyl or substituted alkyl groups
Examples are:
714
1. C.I. Disperse Orange 5, where R1 = NO2, R2, R3 = Cl, R4, R5, = H, R6

= CH3, R7 = CH2CH2OH (class-A dye, suitable for secondary acetate).
2. C.I. Disperse Red 19, where R1 = NH2, R2, R3, R4, R5, = H, R6, R7 =
C2H4OH (class-B dye, suitable for secondary acetate, dull scarlet on
nylon)
3. C.I. Disperse Orange 30, where R1 = NO2, R2, R3 = Cl, R4, R5 = H, R6
= C2H4CN, R7 = C2H4OCOMe (class-C dye).
4. C.I. Disperse Blue 183, where R1 = NO2, R2 = CN, R3 = Br, R4 =
NHCOEt, R5 = H, R6, R7 = Et (class-D dye, suitable for polyester).
5. C.I. Disperse Red 73, where R1 = NO2, R2 = H, R3 = CN, R4, R5 = H,
R6 = C2H4CN, R7 = Et.
Some other popular monoazo disperse dyes are:
1. C.I. Disperse Yellow 5

2. C.I. Disperse Reds 5 and 118.
Blue azo disperse dyes, based on benzenoid diazo components, have

continued to make inroads into the areas formerly dominated by
anthraquinone dyes and it is now possible to cover the range from bright
royal blue to greenish blue with good, all-round fastness properties. Such
dyes derived from (10-4) are as follows:
1. R1, R2= NO2, R3 = Br, R4 = NHAc, R5 = OEt, R6, R7 = C2H4OAc.

2. R1 = NO2, R2, R3 = CN, R4 = NHAc, R5 = H, R6, R7 = Et.
3. R1, R2= NO2, R3 = CN, R4 = NHAc, R5 = H, R6 = Et, R7 = CH2C6H5.
Disazo dyes have attracted increasing attention with the advent of

polyester fibres where they give satisfactory properties at a reasonable
price. However, the use of relatively cheap intermediates is counterbalanced
to some extent by the need to carry out diazotisation and coupling, twice
each. They are particularly important for yellow and orange colour dyes such
as C.I. Disperse Orange 13 (10−5) and Orange 29 (10−6).
-N=N- -N=N- -OH O2N- -N=N- -N=N- -OH
OMe
(10−5)
(10−6)
715
Nitrodiphenylamine Dyes
This continues to be a relatively small class of dyes covering mainly yellow
and orange-yellow hues. They are still used on account of their low cost,
ease of manufacture, very good fastness to light in pale colours and their
usefulness in producing greens with blue anthraquinone dyes whilst
maintaining good fastness to light. By increasing molecular size or by
introducing polar groups, sublimation fastness can be improved. The basic
type of structure used in dyes for polyester fibres [11] is (10−7), where R1
and R2 = H or Alkyl or aryl, R3 = H or substitutent.
NO2
R1R2 NO2S -NH-

R3
(10−7)
Probably the best known commercial dye of this type is C.I. Disperse
Yellow 42, a Class-C dye, where R1 = phenyl, R2 = R3 =H.
The colour strength of the dye may be increased by the addition of an azo
chromophore.
Anthraquinone Dyes
This is also a large and important group and capable of covering the range
from greenish yellow to bluish green. However, these dyes are particularly
valued for the production of bluish red, violet, blue and bluish green dyeing.
The simple anthraquinone dyes are bright and stable under dyeing
conditions. Dyes of this class will probably not increase their market share in
the near future because:
1. They are somewhat weaker in tinctorial value than many azo dyes.
2. Several intermediate stages are often required in their production
necessitating a relatively high capital investment.
3. Many dye intermediates required for their production are derived from
anthraquinone-α-sulphonic acid, which require a mercury catalyst.
This may create pollution problems and alternate methods are to be
established.
Examples are C.I. Disperse Violet 1 (10-2) and Blue 56 (10-3). A few other
anthraquinone disperse dyes are:
1. C.I. Disperse Yellow 77
2. C.I. Disperse Oranges 5, 6
3. C.I. Disperse Red 86
4. C.I. Disperse Blue 73.
716
Anthraquinone dyes containing primary or secondary amino groups are

susceptible to fading by burnt gas fumes, e.g. 1, 4, 6, 8 tetra-
aminoanthraquinone, in case of dyeing and printing on secondary acetate
and triacetate. Introduction of electronegative groups (e.g. –OH) ortho to the
amino groups, arylation of the amino groups (as in case of C.I. Disperse
Blue 27 (10−8), and/or omission of amino groups altogether, increases
resistance to burnt gas fumes. The dye (10−8) is a Class-D having high
fastness to nitrogen oxides (rating 5 on acetate). The sublimation fastness
of the dye is also improved due to the hydroxyethyl group attached to the
pendant phenyl ring. Similarly, C.I. Disperse Blue 73 (10−9) has very good
fastness to light and adequate sublimation fastness to most of the end-use.
However, if the molecule becomes weakly acidic, instability to alkali results
and consequently deterioration in dyeing properties.
Quinizarin is a traditional and readily available anthraquinone
intermediate, which condenses readily with arylamines particularly in the
presence of a proportion of leuco quinizarin to produce violet to green dyes
for polyester, e.g. C.I. Disperse Violet 27 (10−10).
HO O OH
O2N O NH- -C2H4OH
(10−8)
NH2 O OH O OH
-OR
OH O NH2 O NH-
(10−9) (10-10)
Azo disperse dyes are largely unaffected by burnt gas fumes. However,
azo blues are much duller and less light-fast than anthraquinone blues.
717
Methine (Styryl) Dyes

This small group was originally introduced for producing greenish yellow
dyes for secondary acetate. A typical methine dye suitable for polyester is
(10−11).
RH4C2 CN
N- -CH=C
H5C2 CN
CH3
(10−11)
The early dyes of this type (R = OCONHPh) were somewhat lacking in
sublimation fastness and rather unstable when applied at high temperature,
especially under alkaline conditions. However, improvements were made by
increasing the molecular size by using groups like 4/-benzyl-β-phenoxyethyl.
Dyes having more complex structures than the above type are prepared
by condensing pyrene, triphenylamine and phenoxazine with reactive
methylene compounds like malonitrile. They are all fluorescent greenish
yellow dyes with the exception of the latter which is orange.
Heterocyclic Dyes
A number of heterocyclic dyes are particularly useful for producing bright
colours, especially greenish yellow. For example, C.I. Disperse Yellows 54
and 64 are quinophthalone compounds, but are banned now. Another
member belonging to this group is C.I. Disperse Yellow 206. Although not as
green and bright as many of the styryl dyes, they, however, possess good
colour build-up and good fastness to light with the advantage of a high
degree of stability under most application conditions, like anthraquinone
dyes.
A number of other heterocyclic dyes are also useful for the production of
bright colours, although application and fastness properties are not always
ideal. Coumarin dyes (10−12, R = heterocyclic radical) are useful for the
production of fluorescent greenish yellow dyes for polyester.
R
Et2N O O
(10−12)
Thiophene based azo dyes (Dispersol XF dyes) cause minimum staining
on cellulose, a high transfer of dye from cellulose to polyester during
718
thermofixation and can be cleared easily in hot alkali without lengthy

reduction clearing.
Benzodifuranone dyes represent a new class of dye covering mostly red
hues. These dyes possess very bright shades and excellent fastness
properties. With the increased pressure on domestic washing fastness
requirements, disperse dyes must withstand the most severe washing
detergents even after resin finishing. Incorporation of benzodifuranone
groups has resulted in disperse dyes of virtually zero thermal migration
during finishing and the highest levels of wet fastness.
10.3.4 Dyeing Theory

When a low-molecular weight crystalline solid is heated, there is a change
of state at the melting point. The individual molecules separate
spontaneously and the solid changes to a free-flowing liquid. Polymer
molecules cannot separate so easily because their length inhibits the
spontaneous molecular disengagement, which characterises the melting of
a simpler solid. Instead, only segments of any polymer molecule can
separate as the temperature is raised. The temperature at which the
separation begins is well defined and is called glass transition temperature
or Tg. When the temperature is exceeded, the frequency of the change in
the position of polymer segments, called segmental jumps (Section 6.13.3),
increases exponentially with increasing temperature. In fibre, this leads to a
rapid increase in the rate of dyeing. The abrupt changes in properties permit
the experimental location of Tg. Furthermore, in the presence of certain
compounds, the glass transition temperature (Tg) of the polymer lowers.
They are referred to as plasticising agents. The most familiar plasticising
agent for thermoplastic fibres is water, but generally, plasticising agents are
more complicated organic compounds.
In recent times, the theoretical principles of plasticisation have been
formulated. The semi-empirical WLF equation [12] describes the variation of
the viscosity of polymer solutions or the viscoelastic properties of solid
amorphous polymers with temperature. The free-volume theory (Section
6.13.3) derived from WLF equation proposes that all electrical and
mechanical relaxation properties of polymers or viscoelastic properties like
creep, stress relaxation, etc. – are interrelated and are determined by
segmental mobility and the free volume (space not occupied by polymer
molecules) available for movement of the polymer chains. For amorphous
rubber-like polymers in which only Van der Waals’ forces operate, the
viscoelastic properties of polymer will be similar at equal values of (T – Tg).
Thus, the speed of diffusion of a dye increases with increase in (T – Tg).
Numerous organic compounds of relatively small molecular size increase
the rate of uptake of disperse dyes by thermoplastic fibres. Such
719
compounds are called carriers. The concept that the carriers function by
opening fibre structure was first proposed by Schuler in 1957 and is still the
best mechanistic explanation of carrier activity. Since free-volume is
temperature-dependant, one explanation of carrier effects is that they
reduce the thermal energy needed to achieve adequate free-volume for
dyeing.
The polyester fibres shrink when immersed in aqueous solutions of carrier
and the effect is regarded as swelling phenomenon. The temperature at
which shrinkage begins is also an indication of Tg. It has been found that the
reduction of Tg is proportional to the concentration of carrier applied and the
relationship between the diffusion coefficients of the dyes and (T - Tg) fits
the theoretical curve calculated using WLF equation.
Ingamells [13] concluded that
1. Plasticisation or lowering of Tg of the fibre by the carrier is the

controlling influence on the diffusion of dyes into the fibre.
2. Plasiticisation action can lead to other changes in the fibre, which may
or may not result in fibre swelling.
3. Fibre swelling is not necessarily associated with the enhanced
diffusion of dyes into fibres.
4. Plasticisation leads to increased accessibility of dye-sites in acrylic
and basic-dyeable polyester fibres.
The four stages of dyeing with synthetic fibres with disperse dyes are as
follows:
1. Some of the dye dissolves in the water of the dyebath.

2. Molecules of dye are transferred from solution to the surface of the
fibre.
3. The solution in the dyebath is replenished by the dissolution of more
solid dye from the dispersion.
4. The adsorbed dye diffuses monomolecularly into the fibre.
The process of transfer of dye from aqueous solution to the fibre is

comparable with the extraction of a solute from one solvent by a second
immiscible solvent resembling the partition of a solute between two
immiscible solvents. The dye, in other words, forms a solid solution in the
fibre. Laws of partition are applicable and distribution coefficients are related
to the solubility of the dye in the aqueous and fibre phases. The rates of the
first and second phases of the process mechanism are governed by the
solubility in both phases. The crystal forms are of considerable importance,
some forms of crystal promote equilibrium with stronger aqueous solutions.
720
The aqueous solubility of disperse dyes are quite small, they lie between
0.3 and 200 mg/l at 100ºC and between 0.6 and 900 mg/l (majority between
2 and 70 mg/l) at 130ºC. The slow dissolving of disperse dyes in water is
promoted by the fine dispersion maintained by the dispersing agents.
The main functions of dispersing agents are:
(a) To assist the reduction of particle size during finishing of disperse
dyes.
(b) To facilitate reverse change from powder to dispersion when the
dyebath is prepared.
(c) To maintain dispersion during dyeing.
Soap, T.R. oil, etc. cannot meet the requirements and special dispersing
agents are necessary. Ligninsulphonic acid obtained from Kraft paper
process is recommended. For more hydrophilic disperse dyes, lignin of low
degrees of sulphonation should be used. However, some lignosulphonates
are brown in colour and may discolour fibres by absorption. In enclosed
vessel, they may also act as reducing agents destroying some azo disperse
dyes. Modern dispersing agents are high molecular weight compounds and
some may be polymeric versions of sodium dinaphthylmethane sulphonate
(10−13). Anionic dispersing agents may be based on methylated
naphthalene sulphonic acid-formaldehyde condensate. Nonionic dispersing
agents are not recommended in dyeing with disperse dyeing, as they tend to
desorb dye from the dyed fabric. Some of the commercial dispersing agents
recommended in dyeing are Setamol WS (BASF), Lyocol OI (Clariant), etc.
NaO3S -CH2- SO3Na
(10−13)
Valko [14] suggested that during milling of the dye, the dispersing agents
are adsorbed on to the dye surface, with a non-polar backbone adjacent to
the dye and pendant solubilising groups turned outwards from the complex.
By such means, the dye is supplied in a form from which the dyers can
readily prepare stable aqueous dispersions. Under practical dyebath
conditions, the stability of the dispersion is far from ideal. In the presence of
electrolyte and some types of surface active agents, there is a tendency for
the larger particles of the dispersion to increase in size at the expense of the
smaller particles. Eventually aggregates may form and deposit on the dyed
goods.
Dye molecules that adsorbed on the fibre surface diffuse into the interior
of the fibre by a relatively simple mechanism obeying Fick’s law. The law
states that the rate of diffusion of dye through unit area at any point in the
fibre is directly proportional to the concentration gradient of the dye at that
721
point (Eqn. 6.35). The amount of dye taken up by the fibre from a bath of
constant concentration is found to be proportional to the square root of
dyeing time until saturation value is approached. The rate of dyeing is quite
independent of the concentration of dyebath, practically up to equilibrium.
The dyeing behaviour with disperse dyes of polyester differs from other
synthetic fibres like nylon and secondary acetate in the rate of dyeing.
Polyester fibres dye very slowly below 100ºC. At 85ºC, the temperature at
which secondary acetate is normally dyed, dyeing rate on polyester is
between 700 and 1,000 times slower than those on nylon and acetate.
However, if sufficient time is allowed for the polyester fibre to come nearly to
equilibrium with the dyebath, it can takes up approximately the same
amount of dye as had secondary acetate, and in most cases about twice as
much as nylon.
The coefficient of distribution of the dye between the fibre and the solution
phase in the bath decreases as the temperature of the bath increases. The
apparent higher colour yield at higher dyeing temperature is due to higher
rate of dyeing. At 85ºC, for example, the process of building-up a medium-
depth of dyeing on polyester may require several days. The rate of dyeing of
polyester materials continues to increase as the processing temperature is
raised, so that at temperatures in the neighbourhood of 200ºC, fully
penetrated dyeing can be produced in a very short time (one or two
minutes).
There is reason to believe that hydrogen bonding takes place between
primary amino groups of dye and acetyl groups of acetate fibres. Van der
Waals’ forces and dipole interactions may contribute to the retention of the
dye after it has diffused into the fibre.
Work on dyeing of polyester fibre with disperse dyes revealed that this
fibre can be treated for 2 hours at temperatures up to 160ºC in pH range
2.8-7 without reduction in its toughness factor [15]. If the dyebath is allowed
to become alkaline, degradation may set in rapidly at temperatures above
100ºC. The large majority of disperse dyes acquire moderate to good
exhaustion in 60 minutes at 120ºC and can be used economically even for
the heaviest of dyeing.
The effect of pH on the uptake of various azo disperse dyes were studied
[16] and disperse dyes may be classified into three groups:
1. For aminoazobenzene dyes, the dye uptake increases as pH

increases due to basicity of the amino groups. In acidic medium the
amino group adds a hydrogen proton to form conjugate acid (lyonium
ions) as follows:
+ +
D-NH2 + H Æ D-NH3 (10.3)
Where D is the chromophore.
722
With the formation of conjugated acid, the solubility of the dye

increases, thereby lowering its affinity for the substrate in acidic
medium. In alkaline medium, the solubility of the dye is minimised and
its affinity is enhanced.
2. In dyes having hydroxyl groups, the unshared electron pair of the
oxygen of the hydroxyl groups may be pulled by nitro or other groups.
The hydroxyl group can successfully add hydroxide ions from the
solution and forms the conjugate base (lyate ion). The conjugated
base is highly dispersed in alkaline medium and has low affinity for the
substrate, resulting in lower uptake at higher pH. Again at very low pH,
the uptake is lower due to very low dispersibility. Moderate or slightly
acidic media constitute the best environment for dyeing polyester with
these dyes. The maximum uptake is achieved at pH 5-6, when
conjugate base cannot be formed and the dye acquires high affinity to
the substrate.
3. The third type of disperse dyes are not affected by the pH of the
dyeing medium. No advantage is gained by adding acids deliberately
to the dyebath and dyeing is best carried out at pH 5-6 irrespective of
the dye type. It is better to use ammonium sulphate-formic acid buffer
system.
For the dyeing to be level and even, it is essential that the colour
dispersion remains stable during the dyeing cycle. A few factors leading to
instability of dye dispersion are:
1. Unfavourable pH above 6.
2. Low M:L ratio and high dye concentration.
3. Influence of certain electrolytes and levelling agents. For disperse-
reactive dye combinations on polyester-cellulosic blends, common salt
and soda ash are to be added only after disperse dyes have diffused
into polyester.
4. Fibres of low absorption capacity.
5. Liquor turbulence as in jet dyeing.
6. Disperse dyes form solid solution in polyester. As a result, a single
dyestuff tends to reach saturation level in polyester at a certain depth
(usually 4-5 times of 1/1 standard depth). When dyeing is carried out
at a depth higher than saturation depth of the particular dye, the dye
not only precipitates on the material, but also on the dyeing
equipment. The rubbing fastness also deteriorates in spite of reduction
clearing. Fastness to sublimation is adversely affected and thermal
migration may lead to tinting of adjacent material. To remove the
deposits on the machine, reduction clearing using 3 g/l caustic soda, 3
g/l hydrosulphite and 4 g/l Lyogen DFT (Clariant) is required. Filament
polyester has lower saturation value than staple fibres, as the former
723
absorbs approximately 25-30% less dye. While dyeing heavy depths,

it is advisable not to use a single dye. A combination of two or more
dyes having similar hues but of different chemical structures (i.e.
different C.I. No.) may be used. A number of disperse dyes have low
saturation values, the estimated values for some disperse dyes on
staple polyester at high temperature of 130ºC are reported to be as
follows:
C.I. Disperse Yellows 42, 126, 229, 236 - about 3%

C.I. Disperse Red 73 - about 3%
C.I. Disperse Red 167 - about 4%
C.I. Disperse Violet 63 - about 3%
C.I. Disperse Blue 183 - about 4%
(All percentages are o.w.m.)
It is not feasible to arrive at saturation values in thermosol dyeing.
7. Red, purple and blue disperse dyes of anthraquinone group are
susceptible to metal ions present in process water and sequestering
agents are to be added in the dyebath, if required.
Barré is a dyeing problem due to chemical and/or physical structural

differences in thermoplastic fibres. It is defined by AATCC as an
unintentional repetitive visual pattern of continuous bars or stripes usually
parallel to the weft in the woven fabric or to the course of circular knitted
fabrics.
This may be due to several reasons such as differences in thermal history,
texturising conditions, yarn tension, denier and origin of the synthetic fibre.
AATCC method of detecting the ability of dye to cover barréness is to heat-
set three pieces of knitted polyester fabric at 160, 180 and 200ºC separately
and then stitch them together followed by dyeing (2% o.w.m.) at pH 5 and
temperature 130ºC. The variations in dye pick-up of the three pieces are
compared. The extent of variation may be compared with those of control
dyes. C.I. Disperse Blue 56 (low energy) dye and C.I. Disperse Blue 79
(high energy) dye suppresses and enhances affinity differences respectively
and accordingly the dye may be classified in a scale of 1-5. Low energy
disperse dyes can cover barré at any depth since they have good migration
at 130ºC. High energy disperse dyes have less ability to cover barré, which
can be improved by using speciality chemicals like Sandogen PES
(Clariant). These are synergistic mixtures or chemicals having dispersing
and migrating action on dyes. By swelling, they aid in the opening up of the
fibre structure and improve diffusion of dyes. Sometimes barréness can be
levelled out by dyeing at higher temperature of 135-140ºC.
724
10.3.5 Dyeing of Acetate Fibres

For dyeing, the liquor is set with 1-2 g/l dispersing agent and the pH is
adjusted to 6.5-7 for secondary acetate and 4.5-6.5 for triacetate. Sodium
dihydrogen phosphate is recommended as the pH-controlling agent.
The dye is stirred with 10 to 20 times its weight of water at 50 to 60ºC and
allowed to stand for 10 minutes, with occasional agitation. If the mixture is
not sufficiently fluid, more warm water is added. Boiling water should not be
used. Pasting should not be done in the presence of highly concentrated
surface-active auxiliaries.
The previously dispersed dye is added in the dyebath through a sieve.
The material is entered at cold and temperature is raised slowly to 70-85ºC
and dyeing is continued for 1 hour or until the shade is levelled. Disperse
dyes differ greatly in the rates of exhaustion and level-dyeing properties. In
combination, it is advisable to choose dyes of similar properties. For
cellulose triacetate, dyeing is carried out at boil. Higher wet-fastness can be
achieved by dyeing triacetate fibres at 130ºC and reduction clearing with
2 g/l sodium dithionite, 2 ml/l ammonia and 2 g/l detergent for 30 minutes at
50ºC. A fibre lubricant, often a cationic softening agent, is usually applied in
the final rinse after which the material is hydroextracted and dried.
10.3.6 Dyeing of Polyester Fibres

The sequence of operation is to dye, rinse, reduction clear to remove dye
deposited on the surface and finally to soap. Reduction clear may be
omitted in case of pale shades. Dyeing may be carried out in three ways:
1. Carrier method
2. High-temperature method
3. Dry-heat or thermosol method
Carrier method
Limitation on colour yield and the initial lack of pressure-dyeing equipment
prompted an early search for carriers, the products which increase dye
uptake by the polyester fibre. Numerous water-insoluble organic compounds
of relatively low molecular weight were appreciably absorbed by the
polyester fibre and were effective in this respect. Typical chemicals
accelerating dyeing of hydrophobic fibres are:
1. Aromatic hydrocarbons – diphenyl, naphthalene and toluene.

2. Phenols – phenol, o- and p-chlorophenols, o- and p-phenylphenol and
m-cresol.
3. Chlorinated aromatics – mono, di and trichlorobenzene and
chlorinated naphthalene.
725
4. Aromatic acids – benzoic, chlorobenzoic and o-phthalic.

5. Aromatic esters – methyl benzoate, butyl benzoate, dimethyl and
diethylphthalate, dimethyl terephthalate, phenyl salicylate.
6. Aromatic ethers – p-naphthylmethyl ether.
7. Miscellaneous – acetophenone, phenyl cellosolve, phenylmethyl
carbinol, methyl salicylate and benzanilide.
The ideal carrier for bulk use should produce appreciable colour yield at
boil in practicable dyeing time at low carrier cost, without seriously affecting
physical properties of fibre or fastness properties of the dyes. It should not
cause carrier spotting and should be free from toxic or noxious effects
during dyeing, in the fibre and in the effluent. No carrier meets all these
requirements and the selection at any time is necessarily a compromise.
In early years of polyester dyeing, the preferred carriers were o-
phenylphenol and diphenyl. O-phenylphenol is supplied in the form of water-
soluble sodium salt having no carrier action. The free phenol is produced by
acidification. In inverse method, the bath is initially set acidic in which
sodium-o-phenylphenol is added in portions when the carrier is gradually
released. The bath is acidic throughout dyeing, thereby avoiding
decomposition of alkali-sensitive dyes. It, however, calls for careful handling
of solid carrier. It is, therefore, supplied as either an emulsifiable liquid, e.g.
Optinol B (ICI) or a ready-to-use emulsion, e.g. Matexil CA-OPE or
Tumescal OP (ICI). The merits of o-phenylphenol as carrier are:
1. Negligible toxicity
2. Applicable up to pH 9
3. Suitable for pre-set goods
The demerits of o-phenylphenol as carrier are:
1. Risk of staining.
2. Impairment of light fastness of a number of disperse dyes even after
subsequent heat treatment for removal of carriers [17].
3. Difficult to remove from fabric.
Diphenyl was used in the early years as a substitute for o-phenylphenol. It

is a cream-coloured powder, insoluble in water, but in a readily dispersible
state. The merits of diphenyl as carrier are:
1. Less effect on light fastness.

2. Application over whole pH range.
3. Nonionic in nature, suitable for dyeing cationic-dyeable polyester with
cationic dyes.
726
4. Better levelling of dyes.

5. Suitable above 100ºC.
The demerits of diphenyl as carrier are:

1. Greater volatility of diphenyl causes carrier spotting in open
equipment. It is to be added above 80ºC. All other carriers may be
added at the start, i.e. at 50ºC.
2. Strong odour. It should be removed by thorough washing because, if
left in, it gives a sickly sweet smell to the goods.
3. Colour-yield is moderate on pre-set goods.
4. Tends to crystallise out below 80ºC.
Methylnaphthalene is a carrier supplied in the form of self-emulsifiable
liquid, which may be directly added to the dyebath (2-3 g/l) at 50-60ºC. It
gives slightly greater loss of light fastness, but is easier to remove.
Dichloro- and trichloro-benzene are good carriers, which do not affect light
fastness of the dyeing and are easily emulsifiable. They give good colour
yield even in dyeing below 100ºC and are easy to remove. The carrier action
is unaffected by the change in pH. However, they are volatile and are
recommended to be used in enclosed dyeing machines. Due to toxicity, they
have been banned recently.
In the early 1950s, carrier dyeing at the boil was of great importance for
polyester slubbing and polyester-wool blends. The former use has declined,
as pressurised vessels became available. But the latter use has persisted
because of the limitation imposed by the presence of wool. With the raising
importance of texturised polyester, the use of carriers has increased
significantly.
The introduction of carrier dyeing in the early 1950s had an immediate
effect on dye selection. All of the A-type disperse dyes recommended for
dyeing at boil without carrier had been dropped and the recommended
range consisted of B-type dyes with a few C-type dyes. They have,
however, low to medium fastness as compared to D-type dyes, which can
only be applied by high-temperature method. Some of the disperse dyes
recommended for carrier dyeing are [4]:
C.I. Disperse Yellows 42, 218, 229 and 236
C.I. Disperse Oranges 13, 25 and 37
C.I. Disperse Reds 13, 50, 60, 73, 91, 92 and 343
C.I. Disperse Violets 26 and 28
C.I. Disperse Blue 56
The dyebath should be set at 60ºC with 0.5-1 g/l dispersing agent and
carrier such as 6.5-9.0 g/l Tumescal OP liq. (45%). The pH is set with acetic
acid at 5.5-6.0 and the goods are run for 10 minutes. Required amount of
pre-dispersed dye (Section 10.3.5) is added slowly and the temperature is
727
raised to boil over 30-45 minutes. The pH should lie between 5.5-6.0
throughout dyeing process and acetic acid should be added, if necessary.
For heavy shades, higher quantity of carrier may be used. Shading dyes, if
necessary, should be added after 40 minutes and a dyeing period of 30
minutes should be allowed after each addition.
After dyeing, the bath should be dropped at a temperature not less than
85ºC to prevent deposition of oligomers or low-molecular-weight
compounds. The principal oligomer is a cyclic trimer of ethylene
terephthalate and small quantities of pentamer, dimer, etc. The quantities of
oligomers present in commercial fibres are reported to vary between 1.5 and
3.5%.
The material is thoroughly rinsed and reduction cleared with 2 g/l caustic
soda (flakes), 2 g/l sodium dithionite and a dispersing agent, e.g. 1 g/l
Dispersol VL, Matexil SC-50 (cetyl trimethyl ammonium bromide) or long-
chain polyglycol ethers of stearyl alcohol, for 30 minutes at 70ºC. Due to
hydrophobic nature of polyester fibre, only the dyes on the surface will be
reduced and the chemicals cannot penetrate to react with the absorbed dye.
The treatment improves rubbing fastness of disperse dyed material. Low-
pilling polyester and polyester-wool blends are susceptible to caustic alkali
and caustic soda may be replaced with ammonia. At the end of the process,
the bath should remain alkaline to phenolphthalein and should maintain
reducing property, which may be tested with vat-yellow paper.
This is followed by soaping with 1 g/l Lissapol D paste and 2 g/l soda ash
at 70º-80ºC for 30 minutes.
High-temperature Method
There are many advantages associated with dyeing polyester at
temperatures ranging between 120 and 130ºC. The advantages are:
1. Heavy shades can be obtained with disperse dyes without a carrier,

saving the expense and time because rinsing out of carriers is a
lengthy operation.
2. A shorter dyeing cycle is possible under high temperature conditions
using rapid dyeing machines.
3. The deleterious effect of carriers on light fastness of certain dyes and
the odour of most carriers, are eliminated.
4. A better combination of level-dyeing and fastness properties is
obtained by high-temperature dyeing as compared to carrier dyeing at
boil.
5. Dye selection for high-temperature dyeing is not restricted as in the
case of carrier dyeing at boil, and for obtaining adequate colour yields
virtually any type of disperse dyes may be used.
728
For high-temperature dyeing, dye choice can be such to meet

requirements on fastness properties as a first priority, although dyeing
properties cannot be altogether neglected for several reasons. The most
important is the level-dyeing behaviour in respect of coverage of barré in
fabric dyeing or of package-to-package variations in yarn dyeing. The
coverage property is better with low-molecular dye, i.e. B-class > C-class >
D-class. It is not, therefore, a sound practice to select dyes of the highest
fastness properties (D-class) where these are not needed, since the risk of
unlevelness increases by selection of D-class dyes.
A second factor of importance is the optimum machine utilisation, in view
of the high cost of pressurised machines compared with atmospheric
machines. Rapid dyeing machines are developed with this object. Machine
utilisation is severely reduced if much shading additions are necessary. The
aim is, therefore, to eliminate shading additions altogether by using a sound
recipe established by small-scale trial before proceeding to bulk. It is
important, wherever possible, to use combinations of dyes whose yield is
relatively insensitive to small variations in dyeing conditions. This is best
achieved by using dyes that are close to equilibrium at the end of dyeing
sequence. This again argues for the use of rapid diffusing B- or C-class
rather than slow diffusing D-class [17].
The early importance of polyester slubbing in the wool trade led to the
development of pressurised top-dyeing machines. Similar design factors are
applicable to the dyeing of yarn in package form, hence this type of high-
temperature equipment was also manufactured at an early date.
Pressurised jiggers developed for dyeing polyester woven fabric were not
very successful due to various mechanical difficulties and high cost in
relation to output. A much successful development for fabric dyeing was the
pressurised beam-dyeing machine. This became the preferred equipment
for high-temperature dyeing of flat polyester fabric, the appearance and
handle of which is unaffected by the pressure generated on the fabric.
The rise in importance of the dyeing of circular-knit, texturised polyester
fabric in the 1960s led to the development of HT winch. These machines
gave expected advantages of high-temperature method, but suffered from
disadvantages like elongation of the fabric with consequent reduction of
width and rope marking or creasing. The most important development for
high-temperature rope dyeing has undoubtedly been the HT jet machine.
The first commercial successful example was Gaston Country Jet, but this
had been followed by many other designs. The turbulent conditions created
by the jet itself automatically ensure that the fabric is moved in its folds so
that rope creasing is much reduced (Section 7.4.3).
The general method of dyeing is to prepare the dyebath with 0.25 to 2 g/l
of dispersing agent (Lyocol OI powder, Clariant). The pH of the bath is set at
5.0-6.0 with sodium acetate-acetic acid (approx. 1 and 0.25 g/l respectively)
729
or ammonium sulphate (1-2 g/l)-formic acid buffer. Additionally a levelling

agent such as 0.5-1 ml/l Lyogen DFT (Clariant) may be added in case of
light shades. It is nonionic aliphatic polyglycol ether substantive to disperse
dyes. It acts as a levelling cum dispersing agent. In higher dosage, it acts as
a stripping agent (5-10 ml /l along with 1-4 ml/l carrier, Dilatin EN (Clariant)
at 130ºC for 1 hour). Any alkali used during scouring must be completely
removed from the fabric, otherwise degradation of polyester may occur at
high temperature. The dyeing should be started at 70ºC. The temperature is
raised slowly to 130ºC and maintained for a period of 30-60 minutes.
Shading dyes, if necessary, may be added at 120 to 130ºC, allowing 20
minutes after each such addition.
On completion of dyeing, the bath should be dropped at a temperature not
less than 85ºC to prevent deposition of oligomers on the surface of the
material. The oligomers present in the dye liquor will deposit crystals on any
unpolished surface and in regions of high hydrodynamic shear (as in a
pump), when the bath is cooled or even without cooling, if crystals are
already present. The oligomers deposited on the internal surfaces of dyeing
machines are difficult to remove without severe cleaning. It is advisable to
clean the machines at regular intervals of 100 hours running time. The
cleaning process must be more severe than that used for clearing dyed
fabrics and a stripping agent like Lyogen DFT (Clariant) (4 g/l) may be
added.
When heavy shades are dyed, it is advisable to give a reduction clearing
treatment to avoid poor rubbing fastness. This is followed by rinsing and
soaping with 1 g/l Lissapol D paste at 70-80ºC.
Some of the faults and remedies in exhaust dyeing of polyester are listed
below [18]:
1. Ending or tailing due to unstable colour dispersion or combination of

dyes of different migration properties. The remedy is careful selection
of dyes.
2. Barré dyeing mostly due to variation in stretch during texturising. The
remedies are the use of low energy dyes and/or speciality chemicals.
3. Skittery dyeing due to inadequate preparation, quality variation of
fibre, poor solidity of shade in blends, irregular yarn-tension in
weaving or knitting. The remedies are proper pretreatments, careful
controls in fabric manufacture and dyeing.
4. Localised pale dyeing due to air pockets in the materials. The remedy
is the use of suitable non-foaming wetting agents.
5. Precipitation of dye when the dyeing depth exceeds saturation value
of the dye. The precipitation may be prevented by lowering the depth
of dyeing or by using 2-3 dyes of varying chemical structure, but of
similar hue.
730
6. Blue spot on red dyeing may be due to the use of higher dosages of
anthraquinone disperse dyes or due to the presence of greasy
impurities on goods. The fault may be rectified by thorough cleaning of
goods and/or using sequestering agents during dyeing.
7. Low colour build-up and low brightness due to alkaline process water.
An efficient buffer is to be used during dyeing to maintain pH at 4-5.
8. Moiré effect in beam dyeing caused by inadequate heat-setting of
polyester and inadequate shrinkage of cellulosic component.
Adequate heat-setting is to be done and the fabric may be causticised.
9. Poor light fastness in carrier dyeing due to residual phenolic type
carrier. The remedy is to heat-set after dyeing at 170ºC.
10. Listing due to inconsistent heat-setting, irregular tension in weaving or
faulty batching. The remedies are the use of low energy dyes and
proper control in fabric manufacture.
11. Center-selvedge variation because of poor winding, irregular liquor
flow, incompatible selection of dyes or poor heat setting. The
remedies are proper control on winding, use of airflow meter and
control of width-wise temperature variation in stenter and selection of
dyes of similar migration properties.
Dry-heat Fixation or Thermosol Method
In the early 1950s, Dupont developed Thermosol method, a continuous
method of dyeing polyester or polyester-blended fabric in which the fabric is
padded with aqueous dispersion of dye, dried and baked at 180-220ºC for a
period of 30-60 seconds. Because of the hydrophobic characters of fibre
and dye and high temperature of treatment, rapid diffusion of dye takes
place into the fibre in the absence of carrier or pressurised equipment.
The advantages of thermosol process are [19]:
1. As a continuous process, a large yardage can be dyed more

economically than by batch processes.
2. Dye utilisation is excellent.
3. No carrier is required; consequently the chances of spotting and
impairment of light fastness are eliminated.
4. The fabric is processed in open width, thereby eliminating the problem
of rope marks.
5. Dyeability is not affected by previous heat-setting.
6. The energy consumption is lower than batch procedures primarily
because of shorter dyeing cycles, lower M:L ratio and use of energy
recovery devices.
The method, however, was not commercialised for nearly 10 years after
its discovery, because of the lack of suitable machinery and the requirement
731
of larger yardage of fabric to be dyed in a lot or in a single shade. The initial

use of polyester was for blending with wool. For that purpose, polyester
used to be dyed in slubbing or yarn form, for which padding method was not
developed at that time on a commercial scale.
Dry-heat method became popular for woven polyester-cotton blends from
about 1960s onwards in the USA, the UK and other parts of the world where
continuous cotton-piece dyeing was already established. Numerous process
sequences are possible, but for polyester component, the most popular
sequence is:
Pad with an aqueous dye dispersion Æ dry Æ bake Æ wash off.
The selection of disperse dyes for such blended fabric is complicated. The
larger part of disperse dyes after padding and drying, is situated on the
cellulosic component due to its hydrophilic nature. During baking, disperse
dyes are transferred from the cellulosic component to the polyester,
essentially by vapour transfer rather than contact migration. The final colour
yield on the polyester is dependent on the efficiency of transfer, and the
fastness properties depend on the residual dye on cellulosic component,
which acts as staining, causing poor fastness. Optimum transfer occurs with
B-class and C-class dyes, whereas D-class dyes showed low transfer due to
poor volatilisation. The disperse dye-stain is largely removed by subsequent
reduction clearing. However, where reduction-clear is not possible (when
reducible cellulosic dyes are present), selection of disperse dyes to minimise
staining is important to produce the best fastness.
When impregnated material is dried, the disperse dye particles are in a
very fine state of uniform distribution in the capillary network. If this
homogeneous distribution is maintained during drying, the efficiency of
fixation during subsequent heat treatment would be quite high indeed. This
distribution, unfortunately, is not maintained during drying as the dye
particles migrate to the surfaces of evaporation where particulate
aggregation occurs. Particulate migration in fabric padded with disperse
dyes during intermediate drying prior to thermofixation can be a serious
problem which can lead to variations of shade and levelness in continuous
dyeing operations. Clearly, migration in the warp direction is hardly of much
concern. However, migration in the filling direction can occur under
conditions of great imbalance in the drying rates. Migration in fabric
thickness, i.e. from back to face or from the fabric interior to exterior – will
always occur to some extent, even under most properly balanced drying
conditions possible in commercial operations. Migration is best minimised
by:
• Keeping the pick up in padding as low as possible.
• Batching the impregnated fabric before drying.
732
• Drying uniformly without shock.

• Using dyes of low dispersing agent content.
• Employing wetting agent judiciously.
• Including commercial antimigrants in the padding liquor.
The commercial antimigrants, e.g. Amamigrant AM (American Colour &

Chemical), Primasol AM (BASF), Superclear 100-N (Diamond Shamrock),
etc. are essentially polymeric electrolytes. They bring about a very slight
coagulation of the dye particles which reduces the tendency of the dye to
move within the fabric capillary network, although the aqueous medium in
which the particles originally were dispersed continues to flow to the
evaporating surfaces during drying.
With increased use of texturised polyester fabrics, the thermosol method
seems to be promising. However, the immediate problems of thermosol
dyeing with 100% polyester fabric are migration of dyes on the surface
during drying, with consequent poor penetration, inadequate fixation of dye
by dry-heat and impairment of bulkiness of the yarn. The combination of
efficient migration inhibitor and urea, gives good migration prevention and
good fixation. Urea is a beneficial as fixation accelerator. By use of 100 g/l
urea in the pad-liquor, good colour yields are obtained with B-class and C-
class dyes after baking for 2 minutes at 170ºC. However, the use of urea
may cause several problems, such as:
1. Inconsistent colour yield and dulling of shades.

2. Severe browning and hardening of thickeners.
3. Crystallisation of urea on the machines.
4. Decomposition of urea forming ammonia which may degrade the dye.
Migration inhibitors are high viscosity acid-stable alginates or polyacrylic

acid dispersions sold under the brand names of Sansapol AM (Clariant),
Primasol AMK (BASF), Manutex F (Alginate Industries, UK),
carboxymethylcellulose, modified guar gum, etc.
At present, a number of fixation accelerators are available for improving
colour yield in high temperature steaming and dry-heat fixation, which are
mostly ethylene oxide condensation products of fatty acids or their amides
with ethylene diamine. A few commercial accelerators are Awolan IW,
Levalin DHT, Levagal MSF (Bayer, presently DyStar), Noigen EI-40 (Dai-
ichi), Matexil PN-HT (ICI), Ekaline FI (Clariant), etc.
The careful dye selection is necessary. High molecular, high-energy dyes
should be of first choice. Medium energy dyes serve as shading elements.
The material is padded cold using 50-60% pick-up with padding liquor
consisting of:
Disperse dyes – x parts
733
Migration inhibitor – 5-20 parts or

Sodium alginate – 2 parts
Sequestering agent (if necessary) – 1 part
Water to make – 1,000 parts
Tartaric acid is added to set pH at 5 (about 5 g/l).
A small capacity trough should be used and the dye liquor should be
continuously replenished. The padding bowls should have 60-70º shore
hardness and ideally the fabric should be padded with vertical nip.
In case of 100% polyester and blended fabrics with pronounced structures
where it is difficult to get a level shade, it is advisable to add a levelling
agent such as 5-12 ml/l Lyogen DFT (Clariant).
After padding, the material is passed through a pre-drying unit, which may
be a hot flue chamber, heated can, or an infrared pre-dryer. It is then
thermofixed at the desirable temperature between 180 and 220ºC for 30-60
seconds. In some countries, pre-heaters are hardly available and instead of
thermosoling unit (Section 7.4.6), pin stenters are used for fixation.
Optimisation of fixation times may be done by:
1. Accelerating diffusion using highest possible thermosol temperature.

2. Achieving maximum operational reliability with the use of dyes of
similar diffusion rate and similar activation energy of diffusion.
3. Using pre-heated fabric - the heating-up time for polyester fabric may
be 5-15 seconds.
It is then reduction-cleared and soaped as usual.

Fixation is also possible on the continuous loop steamer where dry hot
superheated steam replaces hot dry air; the conditions are 8 minutes at
180ºC for high-energy dyes and 6-7 minutes at 175-180ºC for medium
energy dyes.
Some of the faults and remedies in thermosol dyeing of polyester are
listed below [20]:
1. Listing due to differing nip pressure and migration of colour in

intermediate drying. The nip pressure should be checked at various
points, the wet pick-up should be low and migration inhibitors should
be used.
2. Two-sidedness may occur due to uneven drying from two sides or due
to uneven padding bowl. The temperature and air-current in predryer
and the shore hardness of both the bowls should be checked.
3. Pale spots or specks may be due to condensation of water or foam.
The remedies are the checking of overhead heating in dryers and
734
steamers, less vigorous agitation during padding and the use of

defoamers in the padding liquor.
4. Pale spots due to residual alkali on the goods. The goods should be
treated with acetic acid before dyeing to bring pH at 6.
5. Coloured specks due to incorrect padding liquor. The dispersion of
dyes should be checked and the padding liquor should be properly
filtered.
6. Ending or tailing due to high affinity of the dyes. The remedies are the
use of smaller trough, higher padding speed, combination of dyes of
similar affinity.
7. Pale shade in intersections due to poor penetration of dye. The fault
may be overcome by increasing nip pressure and impregnation time
and by using wetting agents.
8. Dark or pale selvedges may be due to feeding liquor from one side of
the trough. The liquor feed should be checked and controlled.
9. Fuzzy or frosted dyeing may be caused by colour migration in
intermediate drying or thermosoling. The remedies are the use of
migration inhibitor and low wet pick-up.
10. Widthways variation in drying may be minimised by checking of air jets
and velocity of air circulation in stenter.
11. Generation of foam may be caused by the use of excessive dispersing
agents and other chemicals in pad liquor. The remedy is the use of
suitable defoamers.
10.3.7 Colour Correction on Polyester

Excellent reproducibility of colour can be obtained on polyester material if
certain standardisation procedures are followed. The three major colour
faults are mismatching, uneven dyeing and inadequate fastness.
Mismatches may be due to wrong formulation or loss of dye. The dye may
agglomerate or decompose because of unbuffered process water, alkaline
dyebath or reduction of dye.
A small reduction of depth is possible by dropping all or part of the
dyebath and setting a new dyebath. The temperature of the new bath is
raised to the dyeing temperature when a new equilibrium is established at
lower depth. Small correction additions may also be made in the normal
manner. In carrier dyeing at boil, the degree of stripping is small, unless
excess carrier is added and the process is prolonged. Under high-
temperature conditions, stripping is quicker, but depends on aqueous-
solubility of the dyes. The degree of stripping can be raised by 30% by
adding an ethoxylated product of low cloud point, which provides an external
phase capable of dissolving and retaining disperse dyes. The product must
be thoroughly removed before redyeing.
735
For complete stripping, the dye should be destroyed in the aqueous phase
as desorption proceeds. The destruction may be done by treating with
1-2 g/l caustic soda for 20 minutes at 125-135ºC. Some polyester material
may be damaged and some disperse dyes may be unaffected. A milder
treatment may be applied with sodium sulphoxalate-formaldehyde and soda
ash or zinc sulphoxalate-formaldehyde and acid. The former may be treated
with a carrier at boil at a pH of 4-5. Many disperse dyes may be stripped at
pH 4 (formic acid) with sodium chlorite at boil, but a yellowish ground colour
may result. The two treatments may be carried out successively. It should
be kept in mind that a long time treatment of polyester at high temperature,
especially at high pH, is harmful.
For most light and medium depths, the bulk transfer or strike phase of
dyeing is completed before the temperature of the bath reaches 105ºC.
Levelling at this stage is negligible. Barré effects and minor bulk unlevelness
may, however, be levelled by prolonging the normal dyeing process and by
small additions of carrier to the high temperature bath. When unlevelness is
detected after processing, the goods should be reprocessed under high-
temperature conditions by adding about 3 g/l suitable carrier. The vessel
should not be overloaded as it will prevent good liquor circulation. The
dyeing temperature should be as high as permissible for the type of goods,
preferably 5ºC higher than that in the original process. For carrier dyeing at
boil, extra carrier up to twice the amount used in dyeing may be used, but
only a moderate degree of levelling is expected. The temperature should be
as close to the boil as possible. The lowering in the rate of migration by a fall
of 4ºC in temperature may be equivalent to half of the normal addition of
carrier. The depth of dyeing may be reduced by about 20% in the
reprocessing and an addition of dye will be required to bring back the depth.
Many faults that can arise in initial stages of processing become clearly
visible only after dyeing and the dyer should be aware of such indications.
10.3.8 Dyeing of Texturised Polyester

Dyeing of texturised polyester needs some additional precautions and
criteria as against normal varieties of polyester. Scouring, besides removing
the impurities, also brings the relaxation of the fabric involving its shrinkage,
which is of great importance. Scouring may be carried out in winch or open-
width washers. The bath is set at 60ºC with 1 g/l anionic detergent, e.g.
Lissapol N and 2 g/l soda ash. The temperature is raised to 80ºC and the
goods are treated for 20 minutes and washed thoroughly.
The main problem in dyeing of texturised polyester material is barréness
or strippy dyeing. This produces lighter or deeper horizontal lines produced
at regular intervals across the fabric width. Besides barréness problem, the
texturised materials also produce shade variations at regular intervals
736
across the length and width of the fabric. The dye selection is best on its
ability to cover structural differences or barréness. There are several tests
like Rhodiaceta test, Dupont transfer test, BASF methods, etc. The simplest
method is to dye at a very light shade and to check uniformity of dyeing
visually. The dyeing may be carried out by carrier or high-temperature
methods. The carriers, which were developed to accelerate the rate of
dyeing of polyester fibre at boil, are found useful in getting barré-free dyeing
on texturised polyester due to higher migration of the dyes. The non-
acceptance of thermosol process on large scale for texturised polyester is
that it affects aesthetic properties such as bulk and texture of the fabric.
However, under carefully controlled thermosoling conditions, the fabric with
satisfactory handle can be obtained.
Some of the dyes suitable for texturised polyester are listed below [21]:
Carrier method
C.I. Disperse Yellows 8, 42, 87, 99
C.I. Disperse Oranges 25, 59
C.I. Disperse Reds 60, 78, 86, 91, 138
C.I. Disperse Violets 8, 27
C.I. Disperse Blues 95, 118, 120
High-temperature method
All the above dyes and C.I. Disperse Yellow 88, Red 65, Blues 55, 56, 64,
87.
Dyeing in hank form
The hanks are to be cross-wound and tension during winding must be
uniform and minimum. The hanks are subjected to relaxation treatment by
hanging freely under steam at atmospheric pressure for sufficient time,
when they shrink due to release of tension. Due to high bulk of the yarn, it is
advisable to put the hanks in cages. The dyeing is preferably done at high
temperature using 1 g/l non-foaming anionic levelling agent (Albegal C, ICI),
1 g/l mono-sodium phosphate and 2 g/l formic or acetic acid. The material is
treated in this solution for 10 minutes and then the dye is added at pH 5.5-6.
The temperature is raised to 95ºC and for atmospheric dyeing, the treatment
is continued for one hour with carrier. For high-temperature dyeing,
levelness of the dyeing may be checked after dyeing for 15 minutes at 95ºC.
If unevenness is due to foam, defoamer is added. The material is run for
another 20 minutes at 95ºC, then the temperature is raised to 130ºC over 40
minutes and dyeing is continued for 45 minutes. The material is
subsequently reduction cleared.
737
For stabilised bulk yarn used in circular knitted goods, stabilisation is not
required. All texturised goods shrink, both in width and length, during dyeing,
but pre-heat-set (at 175ºC) material shrinks six times less in width and twice
less in area.
10.3.9 Dyeing of Modified Polyester

There are several modified varieties of polyester in the market, a few are:
1. Lustrous trilobal variety

2. Micro polyester fibres
3. Easy dyeable polyester
4. Anionic modified or cationic dyeable polyester
Lustrous trilobal fibres are made by passing the polyester melt through a
spinneret having a trilobal (or dog bone) cross-section instead of a circular
cross-section. As a result, lustre is enhanced and the surface area for a
given weight increases. The dyeing properties are similar to normal
polyester, but more dye is required – about 10% more for pale shades and
20-25% more for deep shades.
Micro multi-filament comprises filaments that are less than one denier.
The actual denier per filament is between 0.3 and 0.9 for micro fibres and
less than 0.3 for ultra-micro fibres. Lightweight polyester can also be
produced by the causticisation process. Although it gives a silk-like lustre,
the properties required for apparel application, i.e. skin sympathetic and
eye-catching are lacking. The advantages of micro fibres are:
• Soft and flexible
• Good breathing qualities
• Easy care
• Skin sympathetic
• Eye-catching, velvet touch
• Water repellent
• Higher bulk in the fabric
• Better drape of the fabric
• Weather-friendly
The disadvantages of micro fibres are:
• High cost
• Very delicate nature
• High covering area
• Lower dye pick-up, more dye required than conventional fibres
• Lower light and wash fastness
738
• Lower productivity, longer washing and drying cycle
The micro filaments are used for all kinds of sport-wear, ladies apparel,
bathing suits, men’s wear, skiing outfits, wind-cheaters, raincoats, shirts,
blouses, scarves, neckties, draperies, etc.
With such a fine denier fibre, certain precautions are to be taken during
processing. The processing is preferably to be done under tensionless
condition. Scouring should be done with a mild detergent at 90-95ºC and
washed carefully. Micro fibres take up dyes faster and may cause levelling
problem. The dyeing should be started at lower temperature (10ºC lower
than that for normal polyester) and the temperature is to be raised slowly
(maximum 2.5ºC/min). The dyeing time at the maximum temperature
(usually 130ºC) should be at least 30 minutes for better levelling. Dyestuff
with good levelling properties should be used. Due to very high surface
covering and compactness of the packages, beam dyeing should be
avoided. It is advisable to dye the fabric in winch, overflow or jet dyeing
machine [22].
Easy dyeable polyester (EDP), e.g. Nirster super (Nirlon, India) has
similar density and melting point as normal polyester. However, the glass
transition temperature (Tg) is approximately 10ºC lower. Hence, disperse
dyes show a higher rate of diffusion and can give deep shades at 100ºC
even without using any carrier. EDP has less pilling tendency than normal
polyester. It is more hydrophilic. Weight reduction is possible using caustic
soda solution of lower strength than that for normal polyester. The lowering
of Tg may be achieved by copolymerisation of polyethylene terephthalate
with comonomers like polyethylene oxide, aliphatic dicarboxylic acid,
polybutylene terephthalate, etc.
EDP behaves differently on heat-setting. Normal polyester, on heat-
setting, absorbs less dye than unheat-set up to 200ºC. With EDP, dye
saturation steadily increases with increasing heat-setting temperature. The
effect is more pronounced with slower diffusing dyes – opposite to that for
normal polyester. Dyeing of EDP is started at 40ºC (pH 5) with anionic
dispersing agent and the temperature is raised to boil over 40 minutes. The
dye is almost completely exhausted within 30 minutes at boil and hardly
any residual dye is left in the dyebath. The material is given hot and cold
wash followed by reduction clearing at 40-50ºC and soaping at 70-75ºC
[23].
Many disperse dyes show lower light fastness (by 1-1½ grade) and
slightly lower wash fastness (ISO Washing Test No. 3) on EDP.
Dacron 64 (staple fibre) manufactured in 1958 by Dupont was the first
modified polyester fibre having affinity for basic or cationic dyes (CDP).
Later Dupont manufactured trilobal filament, Dacron 62 from the same
polymer. Both CDP are manufactured by introducing about 1-3% sodium-5-
739
sulphoiso-phthalic acid into polyester during trans-esterification or

polycondensation reaction whereby it becomes a part of the polymer [24]. In
India, CDP is produced only in dimethylterephthalic acid base and not in
terephthalic base. The fibre is made by charging sodium 5-sulphodimethyl-
isophthalate (10−14) into dimethylterephthalate (10−15).
The property of CDP to absorb basic dyes is of practical significance in
finishing. As the dyes are held by ionic bonding, the shades remain
unaltered in resin finishing and no thermal migration occurs as in normal
polyester finishing.
H3C-O-C C-O-CH3
H3C-O-C C-O-CH3
O O
O O
SO3H
(10−14) (10−15)
In addition to basic dyes, CDP is also dyeable with conventional disperse
dyes. Unlike EDP, disperse-dyed CDP does not show lowering of washing
and light fastness. CDP finishing follows the normal sequence as per
conventional polyester.
Disperse dyes, in general, have higher affinity for CDP than normal
polyester. For some dyes, light fastness is slightly lower on CPD. 4-6 g/l
Glauber’s salt is employed in the dyebath to protect the fibre. The pH should
not be below 4, otherwise the hydrolysis of the fibre may occur. For colour
fixation, the highest temperature recommended is 120ºC. If cationic dyes
are simultaneously used for brightening in carrier method of dyeing, the
carrier should be nonionic in nature. The material is rinsed, reduction-
cleared with soda ash (2-3 g/l), sodium hydrosulphite (2 g/l) and nonionic
detergent for 20 minutes at 70-80ºC. The goods are rinsed warm and
acidified with acetic acid.
10.3.10 Dyeing of Nylon with Disperse Dyes

As disperse dyes are held by physical bonding forces, the dyeing is
unaffected by the structural variations, i.e. variations in end amino groups of
nylon. Disperse dyes are, therefore, preferred for nylon having distinct
barréness. The application method is simple and the dyeing is level.
However, most of the disperse dyes have moderate affinity for nylon,
moderate light fastness and low washing fastness, particularly in heavy
depths. The washing fastness to ISO Washing Test No. 3 at 60ºC is
inadequate in most cases. The dyers, therefore, prefer acid and metal-
complex dyes for nylon in spite of their poor coverage to barréness.
The dyebath is set at 30ºC with 1 g/l nonionic dispersing agent and 0.5 g/l
sodium hexametaphosphate and the pH is set to 6.0-7.0. The selected
740
disperse dyes are dispersed in warm water and appropriate dispersing

agent, sieved and added to the pre-set dyebath. The temperature is raised
at 2ºC/min for simple disperse dyes and 1ºC/min for high-molecular dyes to
near boil and maintained at that temperature for a minimum of 45 minutes
before sampling. Once the desired shade is attained, the material is rinsed
cold and soaped with 1 g/l nonionic detergent at 40ºC for 10 minutes and
finally rinsed cold.
The low-molecular weight, good levelling disperse dyes are widely used
for dyeing of nylon hose and tights, carpets and woven and warp-knitted
fabrics, whenever end-use requirements do not require high wash fastness.
Low-molecular weight disperse dyes cover chemical variations present in
the fibre, but they are sensitive to fine structural differences like those occur
in texturised materials. The washing and sublimation fastness properties are
better, but migration and levelling properties are poor. A typical trichromatic
combination of high-molecular weight disperse dyes which has proved
satisfactory under commercial processing conditions consists of the
following three dyes:

C.I. Disperse Red 91
Other disperse dyes suitable for nylon exhibiting good light fastness are:
C.I. Disperse Orange 30

C.I. Disperse Reds 50 and 60
10.4 DYEING OF NYLON FIBRES

The dyeing characteristics of nylon are influenced by two important fibre
characteristics, namely:
(a) Amino end group content and

(b) Physical structure − internal and surface.
The variation of lustre may be due to differences in internal structure,

surface characteristics or both. If only surface characteristics vary, then,
although identical amounts of dye are present in the fibre, the apparent
depths may be different.
Four simple dyeing tests are recommended [10] to find the cause of
strippiness or non-uniformity in dyed nylon, namely:
741
1. Dyeing with 0.33% C.I. Disperse Blue 56 at 85ºC for 45 minutes in the
presence of 1 g/l nonionic dispersing agent. Any unevenness in
dyeing will be due to lustre difference as the dye is insensitive to the
other two causes.
2. Dyeing with 5.0% C.I. Acid Blue 45 at 100ºC for 1 hour in the
presence of 4.0% formic acid (90%). The dye is very sensitive to
differences in end amino groups. It is also relatively sensitive to lustre
variation and slightly sensitive to physical differences.
3. Dyeing with 2% C.I. Direct Blue 74 at 100ºC for 1 hour in the presence
of 3.0% acetic acid (90%). The dye is very sensitive to both
differences in end amino groups and physical structure. It is also
relatively sensitive to lustre variation.
4. Dyeing with 10% Multamine Black B (mixture dye developed by ICI) at
85ºC for 45 minutes in the presence of 1 g/l nonionic dispersing agent.
It is very sensitive to lustre differences and mostly insensitive to the
other two factors.
Equivalent weight for chemical compounds (or polymer) is defined as that

weight which contains one gram-equivalent weight of the component taking
part in the reaction. For example, hexamethyldiamine has two amino groups
and an approximate molecular weight of 116.2. The equivalent weight in
terms of its reaction with acid is 116.2/2 or 58.1. Alternately, 1 gram will be
the equivalent of 1/58.1 amino group, which may be expressed as 1/58.1 i.e.
-3 -1 -1 2 -1 3
17.2 x 10 eq g or 17.2 milli eq g or 17.2 x 10 mili eq kg or 17.2 x 10
-1
eq ton .
For textile-grade, regular dyeing nylon 6 yarn, the quantity of amino and
-1
carboxyl end groups is about 60 eq ton . The amino end groups in nylon 6
have a predominant effect on dye pick-up when dyed with acid dyes, as
shown in Table 10.5 [25].
Table 10.5 The Relationship between Pick-up of Acid Dyes and Amino
End Groups Content in Nylon 6
-1
Amino end group content (eq ton ) Dyeability with acid dyes
10-15 Light
35-45 Regular
80-90 Deep
95-100 Ultra deep
115-120 Super ultra deep
With today’s nylons, barré due to variation in amine end groups or dye
sites is rare. Most dye-related problems are now due to differences in fibre
742
porosity, which determines accessibility of the dye sites. Porosity is

determined by the total tension-temperature history of the fibre – during fibre
manufacturing, texturising, heat-setting, dyeing and finishing. The variation
in porosity determines the rate of dyeability with dyes, especially those of
high molecular weight, namely milling acid, metal-complex and direct dyes.
Because of the increasing demand for higher wash-fastness, the dyer is
often forced to use rate-sensitive dyes.
Water has pronounced effects on the processing and performance of
nylon. For instance, nylon fabrics can be set with moist heat at 93-121ºC, far
below the temperature of 196-210ºC necessary to set the same fabric with
dry heat. In sharp contrast, water or moisture has very little effect on the
heat setting of polyester, which is dry-set at 180ºC or more. Furthermore,
once set, nylon, for all practical purposes cannot be reset, while polyester
can be set repeatedly by using successively higher temperatures. Thus,
nylon 6,6 and polyester differ dramatically in their response to moisture and
heat setting, though their softening (235ºC) and melting points (250ºC) are
virtually very similar. Nylon, of course, has moisture sensitive hydrogen
bonds, which are absent in polyester.
The potent carrier activity of water on nylon had been studied [26]. The
concept of water as a carrier for nylon is not, in itself, new. However, it is
often overlooked because carriers are generally considered chemical
compounds like phenols, chlorinated hydrocarbons, esters, etc. whereas we
cannot even think of water as a chemical. Carriers can be considered as
compounds, which provide chemical energy to supplement and/or replace
thermal energy in the dyeing and finishing of thermoplastic fibres. Water
provides chemical energy equivalent to about 100ºC of dry thermal energy
in its effects on a variety of fibre properties of nylon. The Tg of nylon 6,6 at
0% RH is about 80ºC based on measurement of films. At 100% RH, Tg is –
10 to – 20ºC, i.e. lowered by about 90-100ºC. Water has much less effect on
polyester, generally equivalent to about 20ºC of thermal energy. The
concept of chemical energy/molecular lubrication effect of water on nylon
helps to better explain the overall behaviour of nylon and the differences
between the responses of nylon and polyester.
The following hypothesises regarding the effect of water on nylon are
made [26]:
1. The carrier effects of water during dyeing of nylon, causes structural

changes which are reversible below about 75ºC and irreversible
above about 95ºC.
2. The effects of water and steam on nylon structure and dyeability are
analogous to those of dimethylformamide (DMF) on polyester. The
dye rate increases markedly in spite of drastic increases in
crystallinity.
743
3. Carrier (solvent) interactions are a general reaction of thermoplastic

fibres. The heat-setting of any fibre in 100% of an appropriate carrier
or carrier-saturated vapour should increase both crystallinity and
dyeing rate.
4. The dye uptake capacity of nylon is surprisingly constant over a wide
range of crystallinity. Therefore, crystallinity is not a primary factor in
determining dye uptake capacity.
5. Orientation or dye-rate barré is caused primarily by differences in
accessibility and not by differences in crystallinity or capacity.
6. Nylon is dyed by a hybrid mechanism. Works with crimper box barré
(CTB) induced in stuffer box texturising and false twist barré (FTB)
induced in false twist texturising showed that all types of dyes –
disperse, levelling acid and high molecular milling dyes are sensitive
to the same structural features. This evidence led to the conclusion
that the initial attachment of all types of dyes on nylon is by disperse
dye mechanism. Acid dyes subsequently exchange ions with end
amino groups and then transfer or level, if possible. The end amino
groups are necessary primarily to provide good wet fastness.
7. Acid dyeing of nylon is analogous to precipitation reaction. The
formation of slightly soluble precipitate of disperse and levelling acid
dyes or insoluble precipitates of milling acid dyes, drives the reaction
to equilibrium.
8. An essential role of pH in this hypothesis is to convert acid dyes to the
unionised disperse species which are insoluble in water but soluble in
organic solvents such as nylon.
9. End amino groups are not essential for acid dyeing of nylon, provided
the dyes used have adequate fastness. They are necessary only to
prevent the precipitate (on dyed nylon) from redissolving.
Nylon fibres contain both amine and carboxylic acid terminal groups, and
by selecting the appropriate dyeing conditions, the uptake of both anionic
and cationic dyes may be favoured. Nylon can also be readily dyed with
disperse dyes. Thus, virtually all the major classes of dyes are substantive
to nylon and there is an extremely wide range of dyes available for their
coloration.
An important factor in the ready acceptance of nylon by dyers was the fact
that it could be dyed with the ranges of acid dyes already available for wool
and silk. The majority of shades could be matched using relatively simple
dyeing techniques.
It is widely presumed that, under acidic conditions, the dyeing of
polyamide fibres with anionic mono or polysulphonated dyes (acid dyes) is
described by an electrostatic attraction between the anionic dye and the
protonated, hence cationic, fibre. Dyeing of wool or nylon, for example, is
744
normally achieved by applying these dyes from weakly acid solution at the
boil; however, colour chemists quickly realised that anionic dye molecules
were not absorbed solely by ionic interactions, but that solvophobic or
hydrophobic interactions were also important. Hydrophobic interactions were
employed to describe the phenomenon of nylon overdyeing. Analysis
showed that highest overdyeing was observed with monosulphonate dyes,
followed by disulphonate and trisulphonate. The tetrasulphonate dye, C.I.
Acid Red 41, showed no tendency to overdye. However, hydrophobic
interactions break down above 60°C. As all the above dyeing were carried
out at boil, it is, therefore, proposed that aromatic or π-π electrostatic
interactions are largely responsible for these effects. In case of nylon 6 and
nylon 6,6, it has to be noted that there are no aryl groups present in the fibre
and thus, at first sight, π-π interactions of the dye with the fibre is not
possible. However, dyed fibre is a different substrate, as absorbed dye
possesses aryl groups capable of undergoing π-π interactions with newly
absorbed dyes [27].
The variations in draw ratio or temperature during texturising do not affect
the number of accessible amine end-groups in the polyamide fibres.
Barriness effects in the dyeing of polyamide are dependent only on the
kinetics of diffusion and not on interaction of the dye with the fibre. If the
drawing is increased, the apparent diffusion coefficient decreases, whereas
it increases with increase in texturising temperature. The influence of
diffusion decreases as the dyeing temperature rises. The higher the
temperature, the lower is the difference in the apparent diffusion coefficient.
For level dyeing, normally the temperature of dyeing is raised slowly.
However, it appears that it will be more effective to increase temperature
quickly. The best technique will be to add dye in the dyebath after dyeing
temperature is reached, when the fibre is in swollen state [28].
10.4.1 Anionic Dyes on Nylon

Acid dyes are now widely used in the dyeing of nylon and it has been
suggested [29] that as rough guidelines, adequate wash fastness and level
dyeing on this fibre will be achieved if the molecular weight does not fall
below 400−500 for monosulphonated, and about 800 for disulphonated
dyes. If the molecular weight is raised above these values, unlevel dyeing
behaviour ensues, whereas if the molecular weight is lowered, the wash
fastness properties suffer. In a series of monosulphonated alkylarylamino
anthraquinone dyes, a similar linear relationship exists between the
standard affinity for nylon and the number of carbon atoms in the alkyl group
up to a value of four [27].
Acid dyes exhibit significantly better wet fastness on nylon than on wool
and it is found convenient to modify the classification system for acid dyes,
745
which was earlier based on wool. Considering the dyeing behaviour and
affinity of acid dyes for nylon, the dyes may be divided into three sub-groups
[10] − groups I, II and III.
Group I: Dyes with low affinity under neutral or weakly acidic conditions, but
exhaust well on nylon under strong acidic conditions.
Group II: The largest group of acid dyes, which exhaust well on nylon within
pH range 3.0-5.0.
Group III: Dyes, which exhibit high affinity for nylon under neutral or weakly
acidic conditions (pH 5.0-7.0).
The two most important commercial nylon fibres are nylon 6,6 and nylon
6. Although they exhibit many similarities, there are significant differences in
their physical and to a lesser extent, chemical characteristics, which are to
be considered while selecting dyes and processing techniques. Due to more
crystallinity, nylon 6,6 shows slower rate of dyeing and slightly superior
fastness in comparison with that of nylon 6 dyed with the same dye in
equivalent depth. The dyes build up more readily on nylon 6 and show
superior levelling properties.
The more compact structure of nylon 6,6 restricts migration and levelling
of dye molecules – the dyes should be more carefully selected and better
controls are to be exercised in the dyeing process. Generally dyes of larger
molecular size are selected for nylon 6 for better fastness. Although the
presence of antioxidants, delustrants, ultraviolet stabilisers and fibre
lubricants may influence light fastness of dyes, but the effects are same on
both fibres. A specific dye at a given depth on both fibres shows identical
light fastness.
It is preferable to dye nylon with dyes of moderate affinity i.e. Group II
dyes. These dyes exhibit good levelling and migration properties and
reasonable coverage of structural variations. These less complex dyes
provide combinations of good light fastness (5-6, 6) and also good wet
fastness (ISO Washing Test No. 3) in pale and medium depths on nylon 6,6.
However, on nylon 6 it is often necessary to after-treat medium depth dyeing
with synthetic tanning agents (syntan) in order to achieve comparable
fastness. For heavy depths, it is frequently necessary to use large-molecular
weight neutral dyeing (Group III) dyes and in most cases to employ a
synthetic or full back-tanning after-treatment. Though a wide range of acid
dyes are available, it is not easy to find dye combinations, the individual
components of which are truly compatible with respect to their dyeing rates,
migration, light and wet fastness. Only a limited number of red dyes of
neutral affinity (Group III) have good light fastness (≥ 5). In order to achieve
746
high light fastness (6-7 or 7) as in case of upholstery, it is often necessary to

supplement the range of acid dyes with metal-complex dyes.
Typical trichromatic combinations of weakly acidic (Group II) and neutral
affinity (Group III) dyes are:
Group II: C.I. Acid Yellow 25, C.I. Acid Red 57 and C.I. Acid Blue 72
Group III: C.I. Acid Orange 127, C.I. Acid Red 299 and C.I. Acid Blue 138
The steps to be followed in order to have level dyeing on nylon materials
expected to have some structural differences:
1. Where the presence of gross affinity variations is suspected, nylon is

treated before dyeing with an anionic blocking agent (3-4%) under
acidic conditions (pH 3.0 to 5.0) for 30 minutes at the elevated
temperature. For less severe variations, the pre-treatment may be
made for 20 minutes at 50ºC at normal dyebath pH. These are
preferentially absorbed on the fibres, which have more readily
accessible amine end-groups. The material is then rinsed and dyed in
the usual manner. During dyeing, the majority of blocking agents is
gradually displaced by the acid dyes, which have higher affinity for the
fibre. Products with good neutral affinity and suitable for simultaneous
(during dyeing) application are also developed.
2. Affinity variations can be minimised by dyeing at high temperature –
110-115ºC for nylon 6 and 110-120ºC for nylon 6,6. This is due to
swelling and increased accessibility in the crystalline region. The rate
of dye uptake and migration are significantly higher and the coverage
of strippiness is often significantly improved.
3. Dyes of low molecular weight are to be selected, if the required wet
fastness is achievable.
4. Affinity variations can be minimised by selecting less critical dyes.
The steps to be taken to achieve level dyeing on fibres having no

structural variations:
1. Selection of dyes of low affinity and good migration properties will

favour level dyeing. However, for better wet fastness, the use of more
complex high-affinity dyes may be necessary.
2. Heat-setting under tension increases crystallinity and reduces the rate
of dye uptake, whereas steam-setting has opposite effect on dyeing. A
pre-treatment with an anionic blocking agent reduces dye uptake of
most acid dyes.
3. The rate of dye uptake may be decreased by reducing the rate of
temperature rise. For dyes of low to moderate affinity, the temperature
may be raised at 2ºC/min from cold to maximum temperature
747
(85−100ºC). For dyes of high affinity, the rate may be reduced to

1−1½ºC/min. In fact, dyes do not exhaust uniformly over the whole
temperature range and maximum affinity is exhibited within a small
band (50−70ºC). The temperature may be increased rapidly below the
critical zone and then the temperature is raised slowly (1ºC/min) in the
critical zone.
4. The choice of dyebath pH is governed by the affinity of the specific
acid dye, but higher the pH, lower is the dye uptake rate and final
dyebath exhaustion. For high-affinity dyes, it is preferable to use acid-
liberating salt instead of free acids. The salts enable lower exhaustion
rates in the critical zone. At higher temperature, the pH progressively
decreases. Sometimes, buffered dye-liquors are preferred to ensure
reproducibility.
5. In addition to blocking agent, the use of levelling agents may be
necessary. In the presence of such levelling agents, shading additions
may be done even at high temperature. However, the performance of
a specific levelling agent depends on several factors. Some levelling
agents are also effective in correcting unlevel dye batches by treating
at boil in 2 g/l levelling agent at pH between 9.0-11.0. Under these
conditions most acid dyes are partially stripped from the fibre and can
then be exhausted more uniformly, by gradual reduction of the pH of
the dyebath, or by redyeing in a fresh bath.
Direct dyes can be applied on nylon in a manner similar to acid dyes.

However, most direct dyes are of limited value for nylon, owing to either their
sensitivity to structural variations or they offer no significant advantages over
acid dyes. Nevertheless, selected direct dyes are economically more
attractive to produce full bright reds, scarlets, dark browns, greens and
blacks. They exhibit good affinity for nylon under neutral or weakly acidic
conditions. The dyeing may be carried out with acid-liberating salts or in
heavy depths with acetic acid added gradually to reduce pH. Wet fastness
can be improved by after-treatment. Light fastness varies from moderate (3-
4) to very good (6-7). A few typical direct dyes of value on nylon are:
C.I. Direct Yellow 19
C.I. Direct Red 75
C.I. Direct Blues 74, 189
C.I. Direct Brown 58
Chrome dyes can be used to produce economical heavy dyeing on nylon

with excellent wet fastness and good to very good fastness to light.
Generally they give good coverage of physical variations, but are sensitive
to differences in chemical affinity. The colour matching is difficult as the
shade changes after metallisation. Moreover, residual chromium may cause
748
skin irritation. Therefore, these dyes are gradually being replaced by milling
acid dyes, which possess adequate fastness.
1:2 metal-complex dyes have proved particularly attractive for dyeing
nylon due to high saturation values (excellent build-up properties), freedom
from blocking effects (good compatibility in combination shades) and very
good fastness properties (washing and light). However, their dyeing
characteristics and coverage for affinity variations vary significantly and
depend on the molecular size and shape and the number of solubilising
groups. Indeed, some 1:2 metal-complex dyes have no solubilising groups
and are applied in dispersed form. Due to high-molecular complex structure,
1:2 metal-complex dyes accentuate physical affinity variations in nylon.
Nevertheless, the rate of uptake of dye can be controlled by temperature
and pH of the dyebath, and by the use of suitable levelling or retarding
agents. High temperature dyeing is advantageous for improving the
coverage of affinity variations. The shades are relatively dull, particularly in
the red and blue region. A number of acid, metal-complex and disperse dyes
enhance the resistance of nylon to thermal and photo-degradation. Very
marked protection is given by the following dyes:
C.I. Acid Yellow 119
C.I. Acid Red 228
C.I. Acid Green 43
C.I. Acid Brown 19
Whereas harmful effects are observed with the following dyes:

C.I. Acid Orange 92
C.I. Acid Reds 211, 225, 226
C.I. Disperse Black 1
The 1:2 metal-complex dyes exhibit good wash and light fastness
properties, which can be further improved by an after-treatment. During
dyeing, strongly cationic auxiliaries are to be avoided as they form low-
solubility complexes. There is a wide choice of 1:2 metal-complex dyes
offered by several manufacturers differing in the optimum pH range over
which they are applied.
1:1 metal-complex dyes are applied to wool under strongly acid conditions
for satisfactory migration properties. Such conditions can cause degradation
of polyamide, thereby limiting the use of 1:1 metal-complex dyes for dyeing
of nylons. Nevertheless, selected such dyes can be applied on nylon at pH
between 4.0 and 6.0, whenever depth of colour and washing fastness are of
major importance. Ideally, the dyes should be applied as self-colour on
nylon as compatibility between the members of this group is poor. A few 1:1
metal-complex dyes attain good wash-fastness in medium to heavy depths
749
2
and are fast to steam treatment up to 15 lb/in (121ºC), hence can be
applied for garments and half-hose.
Dyeing Methods
The general procedure for exhaust dyeing is to adjust the pH of the dyebath
between 3 and 5, according to the depth of shade and the nature of the dye.
It is often advantageous to add a levelling agent. The addition of an anionic
levelling agent like Lyogen PA 66 (anionic sulphonated oil derivative,
Clariant) gives satisfactory level dyeing on barré material with levelling type
acid dyes. The method may be used for other classes of dyes on non-barré
material. Lyogen PA 66 has affinity for nylon, hence they saturate active
sites in the fibre. It can, therefore, be termed as anionic blocking agent. The
dyebath is set at 50ºC with 4-2% Lyogen PA 66 Iiq. and depending on dye-
class mentioned below:
1. 1-3% acetic acid (80%), or
2. 2-4% ammonium acetate, or
3. 1-2% formic acid.
(The amounts are o.w.m., the lowest and highest amounts are for lighter
and darker shades respectively.)
1. For weakly acid-dyeing dyestuff, e.g. Nylosan E and F (F = better
wash-fast) (Clariant) in medium and dark shades.
2. For neutral-dyeing milling acid dyes (e.g. Nylosan N, Clariant), 1:2
metal-complex dyes (e.g. Lanasyn, Clariant), Solar (light-fast direct
dyes, Clariant) or for light shades of Nylosan E and F.
3. For strong acid dyes like C.I. Acid Yellow 17, Red 1, etc.
The goods are worked at this temperature for 15 minutes. If the barréness
is pronounced, the temperature may be raised and kept at boil for 20
minutes followed by cooling to 50ºC. The dye is dissolved with hot water,
boiled for short time, if necessary, filtered and added in the dyebath. The
temperature is raised to boil in 30 minutes and the dyeing is continued at
boil for 60-90 minutes. The dyestuff for shading and further acid, if required,
may be added without cooling, with prior addition of 0.5-1.0% Lyogen PA 66.
With higher barréness and especially with high-affinity high-molecular
weight acid and metal-complex dyes, the above process may not give
satisfactory results. It may be necessary to pre-treat the material with 3%
anionic blocking agent and 1% acetic acid (pH 5) for 30 minutes at boil
followed by rinsing prior to dyeing.
The dyebath is then set with:
Anionic blocking agent − 1%
Amphoteric levelling/retarding agent − 2-3%
Ammonium acetate − 3%
750
Dye − x%
and if necessary,
Sequestering agent, e.g. EDTA − 0.5%
and/or
Antifoaming agent − 0.2%
Thiourea (antioxidant) − 0.2%
The temperature is raised to boil over 30 minutes and treated at boil for 60
minutes.
For economical reasons, separate pre-treatment with anionic blocking
agent is omitted in most of the cases. Instead, the concentration of anionic
blocking agent in the bath may be increased to 2-3% and the material is pre-
treated in the bath for 20 minutes at 40ºC before the addition of dye and
levelling/retarding agent. If acetic acid is added along with the blocking
agent, it is to be subsequently neutralised and pH is to be raised to 6-7
using ammonia (25%). The pre-treatment enables the blocking agent to be
adsorbed on to areas of high affinity and to reduce the effect of affinity
variations. The dyeing is then continued in the usual manner. The
simultaneous addition of anionic blocking agent and cationic levelling or
retarding agent should be avoided since they form complex with each other.
The cationic agents should not be added until the fibre has adsorbed the
anionic blocking agents.
Clariant offers a weakly cationic retarding agent, Sandogen NH. The
compound has no affinity for the fibre, but it can form temporary complex
with the dye thereby retarding dye uptake.
For levelling type of acid dyes such as Nylosan E (Clariant) dyes, the bath
is set at 50ºC with 2-4% anionic blocking agent, e.g. Lyogen PA 66 liq. and
sufficient acetic acid to bring pH at 5. The temperature is raised to boil and
maintained at boil for 30 minutes. The steam is turned off and 1-4%
retarding agent, Sandogen NH Liq. is added. (The higher amounts of both
the auxiliaries are required for higher barré material or for lighter shades).
After circulating the material in the bath for 10 minutes at boil, the dye
solution is added and dyeing is carried out in the usual manner maintaining
pH at 5. For adequate coverage of barré, the temperature may be raised to
110-120ºC.
The milling acid dyes (e.g. Nylosan N) and 1:2 metal-complex dyes (e.g.
Lanasyn) are applied in near neutral bath using ammonium sulphate. For
these dyes, the pre-treatment with anionic blocking agent is carried out at
the minimum liquor ratio at boil for 30 minutes followed by addition of cold
water to lower the temperature at 65-70ºC and pH is raised from 5 to 6-7 by
addition of liquor ammonia (25%). Then Sandogen NH and dye are
successively added as above.
Nylon absorbs dye at relatively low temperature because of the potent
carrier action of water on the fibre structure. Selected levelling type of acid
751
dyes can be exhausted to deep shades and have acceptable barré

coverage at temperatures as low as 65ºC with an appropriate anionic
blocking agent. Some of the dyes suitable for low-temperature dyeing of
nylon are:
C.I. Acid Yellows 49, 116, 128, 159, 174, 198
C.I. Acid Reds 151, 266, 299, 337
C.I. Acid Blues 25, 40, 78
At this temperature, nylon fabrics do not hydroset and heat-setting may be
carried out under controlled conditions after dyeing.
Since low-temperature dyeing of nylon is a non-levelling system, it
requires more care than boiling dyebath methods including the use of best
levelling dyes and the optimum retarder.
Chrome dyes are normally applied on nylon by afterchrome method using
acid-liberating salts (ammonium sulphate or acetate) at boil. After dyeing for
one hour at boil, formic acid is added gradually to reduce pH to ensure high
degree of exhaustion. The dyed material is then rinsed thoroughly and
treated in a separate bath containing appropriate amount of formic acid and
sodium (or potassium) dichromate for 45 minutes at boil. Unlike wool, nylon
fibre cannot reduce dichromate ions into chromous ions. Hence a reducing
agent like sodium thiosulphate is added in the bath and the treatment is
continued for a further 20-30 minutes.
Selected 1:1 metal-complex dyes can be applied on nylon. The dye-liquor
is set with:
Dye − x%
Weakly cationic or pseudo cationic retarding agent − 1 g/l
Ammonium acetate − 3%
Acetic acid (30%) − 0.5%
(All percentages are o.w.m.)
The goods are entered and the temperature is raised to the boil at the rate
of 1ºC/min and maintained at this temperature for 45 minutes. The goods
are then cooled, rinsed and softened. Normally these dyes are used for
bright shades and are not normally after-treated with tannic acid or syntan.
After-treatments
Nylon 6,6 fabrics show better wet fastness with acid dyes as compared to
that on wool. When it is always preferable to select dyes of good fastness,
the choice is often restricted by the unlevelness due to structural variations
or by economical considerations. It was then observed that the washing
fastness of many existing anionic dyes on nylon can be improved by after-
treating with tannic acid, which was earlier used for mordanting silk and
cotton. To achieve optimum improvement in wet fastness, it is necessary to
form a skin around the outer surfaces of the fibre during the above full back-
752
tanning treatment. This is dependent on the concentration of tannic acid, the

time and temperature of treatment. For nylon 6,6, the optimum temperature
range is 85-95ºC, whereas for nylon 6, the range is between 55 and 75ºC.
The acid dyes should be fully exhausted and well rinsed before the
treatment which is carried out in a fresh bath containing (% o.w.m.) 2%
tannic acid and 2% formic acid (85%).
The temperature is raised slowly to 90ºC for nylon 6,6 or 70ºC for nylon 6
and the goods are treated for 30 minutes. 2% tartar emitic (potassium
antimony tartrate) is added to the liquor and the treatment is continued for a
further 20 minutes at the specified temperature. The fabric is thoroughly
rinsed and dried.
Pure tannic acid is costly. The yellow impurities present in it may stain the
fibre by absorption. During alkaline washing also, the material may become
yellowish due to oxidation of tannic acid. Full back-tanning treatment is
therefore restricted to heavy, dull colours such as brown, navy and black.
The after-treatment may be carried out on any material dyed with anionic
dyes. However, the application is mostly restricted to acid and metal-
complex dyes. When applied correctly the full back-tanning treatment results
in marked improvement in wet fastness of dyes.
The time-consuming and relatively expensive full back-tanning process
can be substituted by a simpler after-treatment using synthetic tanning
agents or syntans. These are essentially based on sulphonated phenol-
formaldehyde condensation products, water-soluble, anionic in nature and
substantive to nylon under acidic conditions. Although less effective than full
back-tanning treatment, the products improve the washing fastness of nylon
dyed with most anionic dyes. With careful selection of dyes, good fastness
can be attained even in heavy depths. The washing fastness is reduced
during subsequent dry-heat or steam-setting treatment, but the drop is less
significant in case of syntans as compared to that during full back-tanning
treatment. Syntan-treated materials exhibit slightly lower light fastness. Most
syntans are applied to the dyed and rinsed material in the presence of
formic or acetic acid (pH 3.0−5.0). For example, the dyed material may be
treated at 60−70ºC for 20−30 minutes with 3-5% (o.w.m.) Nylofixan PI liq.
(Clariant) and 1−2% (o.w.m.) formic acid (85%), followed by rinsing and
drying.
The compound can also be used to reserve nylon in blends. 0.1-0.25%
and 1-1.5% Nylofixan PI liq. may be used in the dyebath to prevent staining
of nylon 6,6 and nylon 6 respectively with direct dyes while dyeing nylon-
cellulosic blends. Similarly, 1-3% Nylofixan PI liq. may be used to prevent
staining of nylon with acid and metal-complex dyes while dyeing nylon-wool
blends.
It is not clear whether syntans form a skin on the fibre or form a complex
with the dye. It is often desirable to apply a softening agent to counteract the
753
stiffening effect of the back-tanning agent. The softening agent may be

nonionic such as Ceranine WNI (Clariant) or cationic such as Ceranine HCS
(Clariant). But it is important to avoid the use of very strong cationic
products, as they can have adverse effect on wet fastness due to complex
formation with the dye.
Stripping of Dyes
In some cases, it may be necessary to correct unlevel or excessively heavy
dye-lots and redye to the original shade. Before stripping, syntan-treated
material is to be treated for 30-45 minutes at 85ºC in 2 g/l caustic soda (4 g/l
for full back-tanned) and 1 g/l of a nonionic auxiliary. The treatment not only
removes the tanning agent, but also reduces depth sufficiently to allow
redyeing without chemical stripping.
Partial stripping is possible by treating with 20-30 ml/l ammonia, 1-2 g/l
anionic wetting agent at boil for 30-45 minutes. A treatment with 10-20 g/l
sodium hydrosulphite at 70ºC prior to ammonia treatment is helpful in
complete stripping. Stripping is also possible by treating with a suitable
auxiliary (cationic or amphoteric auxiliary or a nonionic vinyl polymer)
adjusted to pH 9-11 at as high temperature as possible for about 60
minutes.
For gross unlevelness, it is necessary to strip the fabric chemically in a
fresh bath containing stabilised hydrosulphite, acetic acid and a weakly
cationic auxiliary. This is followed by rinsing and redyeing. Oxidative
stripping (such as acidified sodium chlorite) is avoided due to degradation of
the fibre and less colour build-up in redyeing.
10.4.2 Reactive Dyes on Nylon

Reactive dyes have been considered to be of potential interest for dyeing
nylon due to their brightness and high wet-fastness properties. Some of the
reactive dyes developed for cellulosic and wool fibres can be applied at boil
on both nylon 6 and nylon 6,6 under weakly acidic conditions (pH 4.0 to 6.0).
The covalent bonds form between the dye and amino-end groups, without
an alkaline fixation step [9]. Dyeing of nylon with reactive dyes leads to
lower fixation levels in medium to deep shades than similar dyeing produced
on wool. This problem stems from a paucity of nucleophilic end-of-chain
amino groups. The average amino group content of nylon 6,6 is about 0.036
moles per kg of fibre. The dyes that contain an activated double bond and
that react by a nucleophilic addition mechanism are capable of double
addition at the end-of-chain amino group (-NH2 + D- Æ -NHD- + D- Æ
-N(D-)D-). Double addition means that the maximum depth achievable with
a mono-functional vinyl sulphone dye of molecular mass 500 is 3.6 %
(o.w.m.) pure dye. In practice, lower values will be recorded due to the build
754
up of negative charge from the sulphonate groups on the fixed dye

molecules, giving rise to strong electrostatic repulsion effects. Development
of disperse vinyl sulphone reactive dyes and cationic vinyl sulphone dyes
will thus be worthwhile. Other common reactive dye systems based on
haloginated nitrogen heterocycles (e.g. MCT) will not give even moderate
build up since they are capable of only single reaction with a primary amine
group. A MCT dye with molecular mass 500 will maximally give a fixed
dyeing of 1.8% (o.w.m.) pure dye, actual amount will be much less for the
reason mentioned above. [27]
Mono-functional reactive dyes can be exhausted to nylon in medium and
heavy depth, but only a portion of the total dye exhausted forms covalent
bonds, the remaining portion is held by ionic bonds and Van der Waals'
forces. The dyes exhibit excellent wet fastness up to 0.7 to 1.0% (o.w.m.)
for regular nylon, which is the limit for their reaction. The limit depends on
the number and accessibility of free amine end-groups in the substrate and
will obviously be higher for deep and ultra-deep nylons. When the
concentration of dye exceeds the reaction limit, wet fastness will be
dependent on the molecular weight and substituent groups in the dye
molecule. Below reaction limit, they are very susceptible to variations of
amine groups. The coverage improves at higher depth. The coverage of
physical variation is generally quite good. A wide range of mono-functional
reactive dyes is available, but the dyes are to be carefully selected to
achieve good wash and light fastness.
Bi-functional reactive dyes are of considerable potential interest for nylon.
The reaction limit is higher and is about 2% (o.w.m.) on regular nylon.
Hence, medium to heavy shades can be produced, with all the dyes
covalently linked to amine end-groups. These dyes can also be applied
under weakly acidic conditions without an alkaline fixing treatment, when
very high fastness to washing can be attended. Heavy depths can be
achieved on deep and ultra deep-dyeing nylons. While good fastness to
washing can be achieved with these dyes, it is more difficult to achieve good
fastness to light on regular nylon.
In spite of the fact that bright and wash-fast shades can be achieved with
reactive dyes, they are not widely used because of the following reasons:
1. Poor migration properties, when applied below their reaction limits.

2. High sensitivity to chemical variations in the substrate.
3. Difficulty in correcting or stripping a faulty dyeing.
Because of the above problems, reactive dyes, particularly bi-functional

types are to be very carefully applied. Though stripping may be possible by
breaking the azo groups or the covalent bonds, the residual portions of the
dye remain fixed with the amine groups. Consequently, it is difficult to redye
755
the stripped material further with reactive or acid dyes. Obviously, redyeing
may be done with disperse dyes, the substantivity of which does not depend
on the available amine groups, but wash-fastness will be poor.
Nevertheless, selected reactive dyes can be successfully applied on
nylon. For mono-functional dyes, dye concentration may be exceeded the
reaction limit, but high fastness in those cases can only be achieved by
after-treating with selected synthetic tanning agents. With bi-functional dyes,
no dye will be taken up above reaction limit. Clearing treatment removes
unfixed dyes and results in high wet-fastness.
The general method of dyeing nylon with reactive dyes is to set the
dyebath with:
Dye − x % (o.w.m.)
Acid liberating salt (ammonium acetate) − 3% (o.w.m.)
Weakly cationic levelling agent − 1 g/l
The liquor or material is circulated at 40ºC for 10 minutes, the temperature

is raised at the rate of 1ºC/min up to boil, and the dyeing is continued for
one hour. For medium and heavy shades, the pH is to be lowered to about
4.0 for adequate exhaustion. When desired depth is achieved, the liquor is
slowly cooled and the goods are thoroughly rinsed, hydro-extracted and
dried. For bi-functional dyes, it is advantageous to after-scour the dyed
material at 60ºC for 20 minutes.
Procinyl (ICI) reactive-disperse dyes can be applied under neutral or
alkaline conditions, when dyes can form covalent bonds with the amine or
amide groups of the fibre. Initially the dyes are applied at slightly acidic
conditions at 85−100ºC for 30-60 minutes, when very well levelled
exhaustion occurs with high coverage of affinity variations. The dyebath is
set at 40ºC with 1 g/l nonionic auxiliary and 2 g/l acetic acid (30%) to bring
at pH 3.5-4.0.
The previously dispersed and sieved Procinyl dyes are added and the
material is run for 5-10 minutes. The temperature is raised at the rate of
1ºC/min up to boil and the dyeing is continued for 30 minutes. Up to this
stage, the dyes behave like normal disperse dyes and give very level
dyeing. Then the dye-liquor is made alkaline with soda ash to bring pH to
10-10.5 when the fixation is initiated. The dyeing is continued at boil for a
further 45-60 minutes. Once the desired colour is attained, the goods are
rinsed and soaped with 2 g/l nonionic detergent and 2 g/l soda ash at 65ºC
for 20 minutes. After final rinsing, the material is dried.
Under atmospheric dyeing conditions, the reaction limit of Procinyl dyes is
low. Consequently, the wet fastness in heavy depths is largely dependent on
the fastness of the unreacted dyes. Procinyl dyes can also be dyed at 100-
120ºC, when dye fixation occurs at any pH. However, for better levelling, the
dye should be initially exhausted below 100ºC.
756
The dyes in Procinyl range are compatible. On nylon, they produce

shades having moderate to good fastness to light, good sublimation
fastness and depending on depth, good fastness to washing. The shades
are stable and fixation increases under the high temperature conditions of
heat-setting.
No single reactive system is common to all members of the Procinyl
range. Some of dyes are monochlorotriazine, while others contain β-
chloroethyl sulphomoyl, epoxy, γ-chloro-β-hydroxypropyl, halogenpyrimidine,
and halogen-alkyl substituents on azo and anthraquinone chromophores
[30].
10.4.3 Dyeing of Modified Nylons

A number of modifications in nylon have been made in order to alter its
dyeability. Deep-dyeing nylons are produced in which the number of amine
end-groups is significantly increased over that of regular nylon by
introducing products like N-(2-aminoethyl) piperazine, phenyl phosphinic
acid derivatives or p-toluene sulphonic acid derivatives. In due course, ultra
deep-dyeing polymers are produced by further increasing the ratio of amine
to carboxyl acid end-groups. Tone-in-tone, reserve or cross-dyed effects
can be achieved on a mixture of regular and deep-dyeing (or ultra-deep)
nylons by dyeing with selected anionic dyes under controlled conditions.
Another modification was to decrease the number of amine end-groups in
the fibre in order to decrease affinity for anionic dyes by introducing groups
like carboxylic, sulphonic or typically sulpho-isophthalic groups. This also
increases the affinity of the fibre for cationic dyes. The so-called basic-
dyeable nylon is particularly prone to oxidative degradation. Oxidative
bleaches should be avoided and it is advisable to add a small amount of
anti-oxidant (e.g. 0.2% thiourea) while treating the fibre above boil. It can be
mixed with regular nylon to produce contrast effect by simultaneous dyeing
with anionic and cationic dyes. Reserve effects can be achieved by using a
single class of dye. Multiple colour effects can be achieved in fabrics made
of mixtures of regular, deep-dyeing and basic-dyeing nylons. However,
during production of these fibres, fugitive tints are to be applied in order to
distinguish each other.
For the production of differentially dyeable nylons, an important criterion is
to have an optimum balance between the number of anionic groups (-SO3H,
-COOH) and end amine groups. It has been observed that fibres containing
-1
about 0.06 to 0.1 eq kg of anionic groups have good affinity for cationic
dyes. If the amount is less than 0.06, the affinity will be poor, whereas above
0.1 streaky dyeing will result. For deep dyeing with cationic dyes and
negligible staining with anionic dyes, the optimum anionic group and amine
-1
group contents should be about 0.07 and 0.02 eq kg respectively. The
757
-1
amine group content of about 0.075 eq kg gives deep-dyeing nylon, while
-1 -1
fibres with 0.05 eq kg of anionic groups and 0.045 eq kg of amino groups
have almost equal affinity for cationic and acid dyes [31].
The dyeing characteristics of various differential-dyeing nylons can be
listed as follows:
1. Regular-dyeing or normal nylon – normal affinity for anionic dyes and
little or no affinity for cationic dyes.
2. Low-dyeing nylon – very low affinity for anionic and no affinity for
cationic dyes.
3. Deep-dyeing nylon – high affinity for anionic dyes and no affinity for
cationic dyes.
4. Ultra deep-dyeing nylon – very high affinity for anionic dyes and no
affinity for cationic dyes.
5. Basic-dyeable nylon - little or no affinity for anionic dyes and high
affinity for cationic dyes.
Anionic dyes reserve basic-dyeable nylon and give three tone effects on
three acid-dyeable nylons, whereas cationic dyes reserve all but basic-
dyeable nylon. Disperse dyes have approximately equal substantivity for all
types of nylons.
There is a risk of complex formation and precipitation when anionic and
cationic dyes are present simultaneously in the dyebath. Hence, blends of
differential-dyeing nylons may be dyed by a two-bath or two-stage process,
when the dyes of two dye-classes are added separately. However, the
process is uneconomical and usually an auxiliary (either nonionic or
amphoteric) called anti-precipitant is added for simultaneous application of
acid and basic dyes. Some commercial anti-precipitants are Alkanol CNR
(Dupont), Lyogene MS (Clariant), Dispersol CWL and VL (ICI).
Cationic dyes selected for the purpose should give minimum staining on
the deep- and regular-dyeing nylons.
For dyeing fabrics containing regular-dyeing, deep-dyeing and basic-
dyeable nylons, first the tints are removed with 1-2 g/l sodium hydrosulphite
at 80ºC for 20 minutes and scoured, if necessary. The material is rinsed and
entered in a dyebath containing:
Anionic dye − x g/l
Thiourea (antioxidant) − 0.2 g/l
Anti-precipitant − 1 g/l
Required amount of mixture (1:1) monosodium phosphate and disodium
phosphate to bring pH 5.
The liquor or material is circulated and the temperature is raised to 50ºC.

The required amount of pre-dissolved cationic dye is added. The
temperature is raised to boil over 30 minutes and the dyeing is continued at
758
boil. For addition of dyes, the temperature should be lowered to 80ºC and
anionic and cationic dyes are to be added separately. The temperature is
then again raised to boil. The material is cooled and rinsed. The wet
fastness can be improved by syntan or full back-tanning treatment.
10.5 DYEING OF ACRYLIC FIBRES
Regular acrylic fibres are produced from polymers containing 85% or more
of acrylonitrile monomer, the other co-monomers usually being methacrylic
acid, methylmethacrylate, vinyl acetate or a similar vinyl compound which
are incorporated in order to improve dyeability and mechanical properties.
They bring about a decrease in glass transition temperature enabling dyeing
at lower temperature. In modacrylics, the acrylonitrile content is less than
85%.
The acrylic fibre has become the third largest produced synthetic fibre in
the world. The production of acrylic fibres considerably exceeds the
production of modacrylic fibres and the annual production in 1981 was 4,627
million pounds [32].
Kidney or dog-bone shaped dry-spun fibres have better cover, good lustre,
softer handle and better soil-hiding capacity. But due to limited internal
surface, dye uptake is low. Micro-voids produced in wet spinning are
considered to be an important factor for its better dyeability. Significant
differences in dyeability occur between the dry- and wet-spun fibres as the
surface area is measured to be in the range of 200-300 m²/g for wet-spun
fibres, whereas that for dry-spun is less than 1 m²/g [32].
Commercial acrylic fibres contain acidic sites to the extent of 30-35 milli eq
-1
kg which impart dyeability with cationic dyes. The dye sites may be
sulphonic or carboxylic groups; the dyeing behaviour in the latter case
strongly depends upon the pH.
The polyacrylonitrile are hydrophobic and, therefore, do not as a rule,
possess marked affinity for water-soluble dyes, although there are
exceptions. The fibres can be dyed with disperse dyes at 95-100ºC, but the
exhaustion is slow and there is no good build-up for heavier shades. The
saturation values are much lower and only pale to medium shades can be
obtained. Better exhaustion can be obtained at high temperature, but above
110ºC, there will be excessive shrinkage of the fibres. Because of lower
substantivity, disperse dyes can give very level dyeing of good wet and light
fastness. However, as penetration is poor, only low-molecular weight dyes
can be used, which have poor sublimation fastness causing staining of
adjacent fabrics during pleating and hot-pressing. In heavier shades, the
rubbing fastness may not be very good. The fibres get yellowed on boiling
under alkaline conditions. The pH should be acidic during dyeing. The
759
dyeing with disperse dyes may be carried out in a liquor containing 1 g/l
sodium dihydrogen phosphate or 0.5 mg/l acetic acid (80%) together with 1
g/l nonionic dispersing agent at boil for 90 minutes.
Acrylic fibres are very delicate and are in semi-plastic state at boil. The
material should be cooled very slowly till the temperature falls below 75ºC
and restricted movement of the material should be maintained during the
time in order to prevent formation of permanent creases and distortion.
Residual dye in the dyebath, if any, may be deposited on the material during
cooling, which can be removed by boiling with 1 g/l acetic acid and 1 g/l
emulsifier.
10.5.1 Basic Dyes

The basic or cationic dyes are historically interesting as the first synthetic
dye, Perkin’s Mauve belongs to this class. Basic dyes like Magenta and
Malachite Green are also amongst the earliest synthetic dyes.
The basic dyes are so-named because they are derived from organic
bases. They are also called cationic dyes as they ionise in water producing
coloured cations. They are capable of salt-formation as shown in (10.4).
HO-R NH2 + HCl Æ R NH2Cl + H2O (10.4)
The base containing no chromophore, is colourless and the colour

appears only on salt-formation. Cationic dyes are generally sold in salt form,
usually chlorides, but sometimes as oxalates or even double salts with zinc
chloride.
The outstanding characteristics of basic dyes are the brilliance and
intensity of colour. The clarity of hue obtained with some basic dyes cannot
be matched with any other dye-class. Acid magenta, which is obtained by
sulphonation of basic magenta, requires double the quantity of the latter to
produce a full shade on wool. The basic dyes are not easily soluble in water
and may form a sticky mass, which is difficult to bring into solution. Some of
them are decomposed by boiling water and should be applied at
temperatures of 60 to 65ºC. They are readily soluble in alcohol or
methylated spirit. With alkali, basic dyes are decomposed into colourless
bases. Hard water or alkaline water should be avoided.
Basic dyes get precipitated, under certain conditions, when mixed with
anionic dyes like direct or acid dyes. Consequently, they cannot be used
together, except in the presence of anti-precipitants or at low concentrations.
The direct dyed material may be after-treated with basic dyes for brightening
of shades by mutual precipitation. The conventional basic dyes have poor
light fastness and poor to moderate washing fastness on wool and silk.
760
Modified basic dyes with improved light fastness are now widely used for
acrylics.
The conventional basic dyes belong to several chemical classes, such as:
1. Diphenylmethane or ketone imine (presence of C=NH group), e.g. C.I.

Basic Yellow 1
2. Triphenylmethane, e.g.
C.I. Basic Green 4
C.I. Basic Blue 5
C.I. Basic Violets 3 and 14
3. Thiazine (nitrogen and sulphur atoms forming a ring with benzene
carbons), e.g.
C.I. Basic Blue 9
C.I. Basic Green 5
4. Oxazine (similar to thiazine, but sulphur atom is replaced by oxygen),
e.g.
C.I. Basic Blue 12
5. Azine (similar to thiazine, but both atoms are nitrogen), e.g.
C.I. Basic Red 5
6. Xanthene (two benzene rings are linked by oxygen atom and
methylene bridge) derivatives, e.g.
C.I. Basic Violet 10
7. Acridine (two benzene rings are linked by a nitrogen atom and –CH=
group) derivatives, e.g.
C.I. Basic Orange 14
8. Azo groups, e.g.
C.I. Basic Brown 1
The conventional basic dyes, mainly because of poor light fastness, have
virtually fallen into disuse on natural fibres. With the invention of
polyacrylonitrile fibres, difficulty in dyeing was encountered due to very
compact structure of the fibre. Fortunately, a number of modified varieties of
the fibre were commercialised on which cationic dyes are substantive.
Moreover, the basic dyes showed much better fastness on these
hydrophobic fibres as compared to those on natural wool and silk. The
photo-fading of dyes is faster in the presence of water and oxygen, which
can not gain access in the hydrophobic polyacrylonitrile fibres.
Though the light fastness of conventional basic dyes is better on acrylics,
further improvements in dye structure lead to modified basic dyes. They
belong to three classes:
761
1. Cationic dyes containing a pendent cation with a non-resonating

positive charge as in C.I. Basic Blue 49 and C.I. Basic Red 18
(10−16).
Cl
C2H5
O2N -N=N- -N + −
CH2CH2N(CH3)2X
(10−16)
2. Cationic dyes with a delocalised positive charge as in C.I. Basic Violet
7 (10−17) and C.I. Basic Blue 5.
3. Cationic dyes with a heterocyclic ring containing a quaternary nitrogen
atom, which does not form an integral part of chromogen as in
(10−18).
CH3 CH3
C2H5
-
+ C-CH=CH- -N X
N C2H5
(10−17)
CH3
R
D=N=N- -N + -
C2H4 - N-CH3 X
(10−18)
In addition to efforts to improve light fastness, particularly important work

has been done, relating to production of dyes having specific affinity for
acrylic fibres. Above a certain minimum concentration of dye in the liquor,
the rate of adsorption, dc/dt, is, to a first approximation, proportional to the
rate of diffusion of the dye into the fibre and can well be considerably higher
with dyes that have a high compatibility (K-value) than those that have a
lower value. However, it is not the rate of adsorption that is the decisive
factor for compatibility, but the combined effect of affinity and rate of
diffusion. The physical significance of affinity is that the hydrophilic
substituents will increase the affinity of dye towards water or dye-liquor, or
conversely decrease its affinity for hydrophobic fibres. On the other hand,
hydrophobic substituents increase the affinity of the dye for acrylic fibres and
reduce its affinity for water. Very bulky hydrophobic substituents can restrict
diffusion of the dye and the two effects may cancel each other [33].
762
Some of the ranges of cationic dyes manufactured for acrylic fibres by

various manufacturers are Maxilon (Ciba), Astrazon (DyStar), Sevron,
Yoracryl (YCL) and Sandocryl B (Clariant).
New dye structures called migrating cationic dyes are synthesised to
overcome levelling problem. Work is essentially concentrated on hydrophilic
dyes of large molecules and dyes of small molecular size.
The introduction of hydrophilic groups lowers affinity of basic dyes to
acrylic fibres, improving migration properties. However, the gain in migration
is remarkably low, the degree of exhaustion decreases and the dyeing
equilibrium is shifted in favour of the dyebath.
+
The large molecules (roughly dye cation, I > 450) diffuse slowly and a
slow rate of uptake favours level dyeing. Some commercial dye ranges have
been developed with larger dye molecules. Although the rate of uptake
matters, the temperature dependence of dye uptake is more important,
which is, at least as high with large molecules as with small. A disadvantage
of using large molecules is that a long time is required to produce deep
dyeing. On the other hand, the rate of exhaustion is too rapid in pale dyeing.
As a whole, there is no appreciable advantage of larger molecules
compared to conventional dyes.
The better migration properties of small molecular dyes in both natural and
synthetic polymer fibres had been known for a long time. Small molecular
Calcozine basic dyes were developed by Cyanamid in 1957-58. In spite of
good migration properties, these dyes failed to get established. Migration, at
that time, was regarded as impossible for realisation in the dyeing of acrylic
fibres with basic dyes.
Maxilon M dyes (Ciba) launched in 1975, discarded the old belief that the
small molecules of dye will invariably result in poor wet-fastness. The glass
transition temperature, Tg of acrylic is above 100ºC in dry state and around
70ºC in wet state. The dyeing is carried out above Tg. In household
laundering of acrylic material, the temperature is kept below 70ºC to avoid
fabric deformation. If this precaution is observed, the dye stays locked inside
the fibre and good fastness is shown, even by dyes of small molecular size.
Later, Hoechst launched Remacryl E migrating cationic dyes.
However, with decreasing ionic weight, it becomes harder to meet
predetermined product requirements. The smaller the resonance system, it
is more difficult to produce a blue dye or a dye with adequate intensity of
colour, adequate light fastness or good stability to hydrolysis. The difficulties
in getting suitable small molecular dyes is apparent from the fact that out of
1,000 such dyes tested in Ciba-Geigy laboratory, only 5 met the desired
product requirements [34].
Any dividing line between non-migrating (NM) and migrating (M) types of
dyes is purely arbitrary and makes sense only with respect to practical
763
needs. The name M dyes is therefore, reserved for products, which fulfil
given minimum requirements.
Migration M% (i.e. levelness) can be expressed as follows:
Amount migrated after time t

M% =  x 100 (10.5)
Amount migrated after time ∝
For usual measurement, t = 60 (minutes).

Experience has shown that under standard conditions and given adequate
circulation, the whole migration process over a prolonged period can be
described by the Eqn. (10.6) [34]:
M% = tan γ √t (10.6)
The term tan γ represents the slope of the migration curve plotted against
√t. This is, however, an approximation, since with increasing √t, M tends to
assume infinite value. The tan γ is termed as migration value for a given
fibre, temperature and sodium ion concentration. It has also termed as rate
of migration, actually representing rate of equalising or levelling. It is largely
independent of concentration.
When applying conventional and migrating dyes to Orlon 72 at 100ºC in
+
the presence of 0.01 M Na and measuring the time in seconds, the
following dividing line may be drawn [34]:
tan γ %M (1 hour)
Conventional dyes (NM) <1.1 <65
Migrating dyes (M) >1.1 >65
Theory of Dyeing
Fundamentally, there are two ways to achieve level dyeing, namely:
1. Controlled, level uptake is ensured from the start of dyeing so that

subsequent correction is unnecessary.
2. Uncontrolled uptake, i.e. uptake accompanied by a greater or lesser
degree of unlevelness, followed by a migration stage in which the
unlevelness is corrected.
This classification is valid for all fibres and dye-classes. Due to non-
migrating nature, conventional basic dyes for acrylic fibres belong to (a),
which means they have to be applied by a closely controlled exhaust
process. The factors affecting the rate of uptake of basic dyes on acrylic
764
fibres have long been recognised and the recommendations for controlling
dye uptake are:
1. Careful control of temperature

2. Use of compatible dyes
3. Appropriate addition of retarders
The temperature has a marked effect on dye uptake of acrylic fibres as

compared to other fibres.
Another important aspect, relating especially to pale dyeing, is that even in
the cold, an appreciable amount of dye is unevenly adsorbed by ion
exchange on the fibre surface, which is almost impossible to correct later.
Over the years, efforts have been made to optimise the dyeing process for
acrylics by controlling dye uptake. Both the fibres and the basic dyes were
characterised by several technical parameters and the dyeing procedures
have been refined based on such knowledge.
For better levelling, migration i.e. mobility of the dye within the fibre can be
increased by raising the temperature to about 120ºC, but damage to the
fibre is inevitable. Secondly, the glass transition temperature of the fibre can
be reduced by using carriers. Neither of the two proposals has been
accepted commercially. A quite different idea was to add cations of low ionic
+ +
weight such as Na , N(CH3)4 and small-molecule cationic retarders.
Migration promoters such as these are intended to displace the dye from the
dye sites, thus promoting desorption and migration.
The theory of dyeing acrylic and modacrylic has been discussed
exhaustively by Beckmann [10]. Dyeing with cationic dyes occurs by an ion
exchange mechanism or a simple ion distribution. The three steps involved
in dyeing are:
1. Adsorption of dye cations at the fibre surface

2. Diffusion into the fibre
3. Occupying dye sites within the fibre
The first two steps determine the rate of dyeing, while the last influences
the dyeing equilibrium. Adsorption of cationic dyes on the surface of acrylic
fibres can be described by a Langmuir isotherm with saturation occurring at
low concentrations of dye in the bath. Within the range of concentration
used in practice, the fibre surface is saturated with dye. The rate of dyeing is
almost independent of liquor ratio.
During dyeing, sodium or hydrogen ions originally present in the fibre, are
replaced by dye cations. At equilibrium, the dye concentrations, CF in the in
the fibre and CS in the dyebath, closely follow a Langmuir isotherm with
pronounced saturation and high affinity. The maximum number of dye
765
cations, which can be taken up, is equal to the number of accessible anionic
dye sites in the fibre. This stoichiometric relationship enables the status of
the dye-fibre system, relative to saturation, can be calculated. Some
constants, characteristics of dyes and fibres, have been introduced. The
Society of Dyers and Colourists defined fibre saturation value A,
representing the number of dye sites available in the fibre, as that quantity
(in % fibre weight) of pure hypothetical dye of molecular weight 400 which
gives 90% exhaustion of the original dyebath when applied for 4 hours at
100ºC at M:L ratio of 1:100 and at pH 4.5.
Fibre saturation value, SF is defined as quantity of dye in the fibre and not
at the starting dyebath and as such, A = 1.1 SF.
Dye saturation factor, f, transforms quantities p of commercial dyes (in %
fibre weight) into molar units of A i.e. equimolecular quantity of pure
hypothetical dye of molecular weight 400. f decreases for a given dye as the
diluent-content increases.
At saturation, psat x f = A (10.7)
If p x f > A, the surplus dye (p - psat) will remain in the dyebath.
If p x f < A, then at equilibrium, almost all dye in the system will be taken
up by the fibre. For a combination of dyes, the equation becomes,
p1 x f + p2 x f + ···· < A or ∑pi x f < A (10.8)
Cationic retarders having affinity similar to those of the dyes are included
in the term ∑pi x f.
These conditions are independent of the M:L ratio within practical range of
1:10-1:40. The dyeing temperature does not affect equilibrium exhaustion
appreciably since the range of maximum temperatures used is narrow, the
affinities are high and heats of dyeing are normal, and A does not depend
significantly on temperature. For most acrylic fibres, A increases slightly with
increasing pH within the practical range, but the increase is significant only
for fibres having weakly acidic (carboxylic) dye sites.
A quantity of practical significance, relative saturation value, Srel is the
ratio of the number of dye cations in the system and that of dye sites in the
fibre as shown in Eqn. (10.9)
Srel = ∑pi x f/A (10.9)
If Srel is kept constant and certain other conditions (like compatibility of
dyes and retarders, control of temperature consistent with fibre dyeing-rate
constant) are maintained, the dyeing of different dyes on varying acrylic
fibres will be similar. A higher value of Srel leads to more level results, but
according to the definition or Eqn. 10.8, the value of Srel must be less than
one for good equilibrium exhaustion. Therefore, Srel should be balanced by
using rapid dyeing techniques or by careful controls on dyeing.
766
The safe levelness is obtained whenever the saturation of the fibre

reaches a certain value, which depends on the working conditions. It was
found that good results could be obtained with a relative saturation of about
0.9 when dyeing bulk yarns made from wet spun fibres and 0.6-0.7 from
Orlon 42 or Dralon. It follows that the relative saturation should be different,
depending on the kind of fibres used. The important factors are fibre
saturation value, SF and the rate of dyeing [35]. Different dyestuffs will
require different relative saturation value, Srel. The required relative
saturation is adjusted by adding an adequate amount of cationic retarder.
High-affinity dyes with low migration capacity will require a higher relative
saturation (means need more carrier) than low-affinity dyes of marked
migrating capacity under the influence of cationic retarders or electrolytes.
Affinity is important in relation to:
1. Equilibrium exhaustion when the amount of dye is near to or above

the saturation limit.
2. Blocking effect in dyeing with a mixture of dyes.
3. The effects of electrolytes and retarders.
4. Migration and levelling properties.
A few dyes have been developed recently which have extremely low
affinity and high diffusion coefficients. These dyes have better migration
properties than those of normal cationic dyes as mono-sulphonated acid
dyes on nylon.
As absolute affinity is difficult to measure, relative affinity Ar is determined
from equilibrium exhaustion of the dye in presence of a standard dye or
cationic auxiliary (colourless and does not interfere with photometric
measurements) for which Ar has been assumed to be unity.
Ar indicates migration power of the dye, the higher value meaning less
migration. It is closely related to compatibility. Dyes of high Ar values are
less influenced by electrolytes, cationic retarders or other cationic dyes, and
are more strongly influenced by anionic retarders than are dyes of lower Ar
value. It appears that it has no relationship with the rate of dyeing. Ar values
quoted by different manufacturers are based on different scales (e.g.
logarithmic or linear) and different standards, and as such are not
comparable.
The adsorption of individual cationic dyes is influenced by the presence of
others in the dyebath. In mixed or compound shades, if all the dyes used
exhaust at the same rate, the depth and not the hue changes with time. The
dyes are said to be compatible in that particular combination under the
above dyeing conditions. Since very little migration of cationic dyes occurs
on acrylic fibre, the dyeing should be very level from the start. Any
unlevelness must be corrected during the exhaustion stage. This is virtually
767
impossible in case of combination of incompatible dyes. Combination of

compatible dyes requires less dyeing time and less levelling agent assuring
better reproducibility and levelling.
The cationic dyes may be characterised according to compatibility by a
value called compatibility value K (between 1 and 5), which can be
measured by a standard test method proposed by The Society of Dyers and
colourists, UK [36]. Dyes of equal K value are compatible in combination on
each acrylic fibre under all practical exhaust dyeing conditions except in the
presence of anionic dyes or auxiliaries.
Theoretically, K is determined by affinity and diffusion coefficient, the latter
plays a minor role. In combinations, the dyes of lower K value will exhaust
more rapidly. However, K does not itself indicate rate of dyeing. The actual
rate of exhaustion of a dye depends on the presence of other dyes or
retarder. A combination of dyes, all having K = 5, might exhaust more
rapidly than the one in which all dyes have K = 3. The effect of cationic
retarders and electrolytes is more pronounced with dyes of higher K value,
because K is determined mainly by affinity.
Cationic retarders are mostly quaternary amine compounds with long
aliphatic chains and also aromatic groups, which determine their affinity.
Some of the commercial cationic retarders are Levagal PAN (DyStar,
formerly Bayer), Retargal AN (Clariant), Tinegal CRA (Ciba) and Basacryl
Salt G (BASF). They form colourless cations in water, which compete with
dye cations at the surface and inside the fibre. They replace some dye
cations from the fibre surface reducing dye concentration gradient effective
for diffusion. They also increase the total number of cations effective for
relative saturation, Srel. The effect of cationic retarders is, therefore, two
folds, in that they decrease the rate of exhaustion and increase Srel value.
Consequently levelness is improved, but there is a danger of oversaturation
or blocking. The decrease in the rate of exhaustion can also be achieved by
temperature control. However, the temperature influences the rate of dyeing
by changing the diffusion coefficient, not the concentration gradient. The
temperature also does not affect Srel. The retarder does not affect diffusion
coefficient. The difference between the effects of temperature and retarder
is especially apparent in pale dyeing. The small amount of dye present in
the dyebath can be fully accommodated on the fibre at the fibre surface. The
adsorption is rapid and cannot be controlled by temperature. The
unlevelness is almost certain, especially on poorly prepared material. This
adsorption strike is more pronounced when the Srel is lower. Thus, the
addition of a cationic retarder will improve the situation.
The knowledge of saturation factor, f is essential to prevent blocking. The
quantity of retarder should be small enough to satisfy the Eqn. 10.8.
Optimum exhaustion and levelling properties require the Compatibility Value
768
K of the retarder to be about equal or slightly higher than that of the dye,
because the retarder and dye should exhaust at the same rate.
In addition to the normal cationic retarders, Glauber’s salt is often used as
a weak, but inexpensive retarder or migration aid. Its effect is greater with
dyes of higher K value. The concentration of Glauber’s salt should be less
than 2.5 g/l. It may adversely affect the action of other levelling agents. In a
few cases, Glauber’s salt gives a better levelling effect, but only at higher
concentration (above 2.5 g/l) which is not recommended. Common salt may
be used, but should be free from contaminants like iron. It may, however,
corrode the dye vessel made of certain types of stainless steel.
The work showed that the nature of the cation caused a marked change in
dyeing kinetics, whereas the anions of the electrolytes exert little influence.
The retarding effect of various cations on the adsorption of purified C.I.
Basic Red 29 followed the order given below [32]:
+ + + + + +
Li < Na < K < Rb < Cs < (C4H9)4N
Both the dyeing rate and the equilibrium adsorption were found to be
significantly affected, when the ionic volume is greater, but the effect of
(C4H9)4NCl was noticeably higher than all others studied. It was suggested
that the effect of the cation in modifying the physicochemical properties of
the aqueous solutions and the water-structure breaking effect which
+ +
increase with increasing radius of the cation from Li to Cs were important
factors. The retarding effect produced by electrolytes was lower at higher
dyeing temperature and this may reflect the lower hydration of the cation at
high temperatures.
Low-affinity retarders usually have smaller molecules and do not show
serious blocking. Their effect on migration is between that of sodium
sulphate and cationic retarders having affinity similar to dyes. They are
called migration aids or migrators. In addition to normal retarders, they can
be used in larger quantities to affect migration. Due to low-affinity (high K
value), they exhaust after the dye and exert little influence in the exhaustion
stage of dyeing. However, they can be applied prior to dye, when they can
prevent excessive and uneven strike of the dye. They can also be used as a
levelling agent during shading in order to match a shade.
Some retarders are unstable and slowly become ineffective during dyeing
due to chemical reactions like hydrolysis of esters. They give less or no
blocking and are recommended for use when shading at high temperature.
Cationic polymeric retarders with up to a few hundred cationic groups per
molecule can be used for controlling the rate of dyeing. They give superior
coverage of two components of varying dyeability in bicomponent fibres.
Since they do not penetrate the fibre, they do not truly increase Srel and have
little or no positive effect on migration.
769
Methods of Dyeing
Cationic dyes show excellent build-up and fastness and many give brilliant
shades on acrylics. They are usually less expensive than disperse dyes.
However, their migration properties are, in general, poor. The dyeing should
be carried out very carefully so that the dye uptake is uniform from the
beginning. The effects of dyeing conditions should be known and are to be
carefully controlled. Material to liquor ratio does not exert much influence.
The temperature range of dyeing should extend to about 30ºC above Tg,
i.e. between 75 and 105ºC. Migration and levelness are better at higher
temperature. But different acrylic fibres show varying degrees of mechanical
unstability at high temperature. There may be flattening of fibres resulting in
loss of bulk and handle. Maximum permissible temperature depends on fibre
type, physical variables like tension, package density, etc. and the
characteristic of the dyeing machine.
The normal range of pH for dyeing of acrylic fibres is 3.5-6.0, in which both
cationic and disperse dyes are very stable. At lower pH, levelling is better
and for cationic dyes, the rate of dyeing and the equilibrium exhaustion are
lower. Most acrylic fibres show an increase of 10-20% in Fibre Saturation
Value A and rate of dyeing for one unit increase in pH within the said range.
This can be utilised to cope with saturation problems, e.g. for very deep
colours on fibres with low A value or while shading or redyeing. The
evaporation of acetic acid may not be of much problem, until pH increases
above 6 when dyes become unstable. It is better to use acetic acid-sodium
acetate buffer system to maintain pH of 4.5-5.5. For deep dyeing, pH may
be higher and retarder is not used. Sulphuric acid (pH 2.0-3.5) is sometimes
recommended for level-dyeing of wool-acrylic blends, but many cationic
dyes are unstable in this pH range.
Addition of 0.5−2% (o.w.m.) (or higher amount for deeper shades)
polyglycol type nonionic detergent may be added in the dyebath to keep the
dye vessel clean and after-scouring may not be necessary. They also
prevent precipitation of dye due to anionic residues in the material. 0.1 g/l
+ ++
potassium dichromate may be added when reducing metal ions (Cu , Fe )
are present in water, if permissible from effluent point of view.
The dye is dissolved by pasting with equal quantity of acetic acid (30%)
followed by addition of 20-50 times boiling water. Some dyes require special
methods and some require warm water. A typical recipe for dyeing is as
follows:
Cationic dye − x%
Acetic acid (30%) to bring pH 3.5-4.0 − 1-2 g/l
Glauber’s salt or common salt − 0-2.5 g/l
Nonionic detergent − 0.25-0.5%
770
Cationic retarder − y%
(All percentages are o.w.m.).
The value of y should be chosen according to depth of colour, the type of

dyes and the fibre. Saturation should be avoided considering requirements
expressed in Eqn. 10.8. There is very little adsorption below 75ºC and the
critical temperature is 80 to 100ºC. It is, therefore, advisable to raise the
temperature rapidly to 75ºC and then allow one hour for the liquor to reach
at boil. The bath should be kept at the maximum temperature for 10-15
minutes after complete exhaustion (after there is no visible change in the
colour of dye liquor) for sufficient penetration and to avoid ring dyeing.
When dyeing is carried out in an open vessel, the highest obtainable
temperature should be maintained and the temperature should not be
allowed to fall, because levelness of dyeing is very sensitive to temperature
variations. The dyeing, if possible, may be carried out at 105-107ºC because
exhaustion is more rapid and the migration is better.
At boiling temperature there is very little migration. It is, therefore, of
greatest importance that the adsorption by material should be uniform
throughout the dye vessel and that the control is exercised over the critical
temperature range. Because of poor migration properties, dyes of similar K
values should be chosen in the mixture.
Cooling after dyeing should be slow (about 1ºC/min) to avoid undesirable
handle, crease marks, etc. especially in fabrics.
Well-exhausted dyeing requires only a brief rinse in water. Soaping may
be necessary with some heavy depths and may be carried out at 60ºC with
soap and 1 g/l sodium hydrosulphite.
Constant Temperature Dyeing
The adsorption of cationic dyes is influenced by even a few degrees of
difference of temperature. It was found that dyeing at constant temperature
(85−90ºC) would give rise to an adsorption curve with a gradual and uniform
profile. The temperature chosen depends on the type and amount of dyes
and retarders, and also on the fibre. It is to be carefully calculated using
appropriate tables and charts. BASF has recommended Defitherm Process.
The main feature of the process is that the goods are dyed at a temperature,
which is defined by means of bath exhaustion time. A quaternary ammonium
compound, Defithermol TR, is recommended as retarder-cum-thermo-
regulator. Like cationic dyes, the compound has definite exhaustion on
each type of acrylic fibre. The percentage of dye is expressed as equivalent
to Defithermol TR and is called Defitherm Value. Normally dyeing is
recommended to be carried out at a temperature, T60 at which the bath
exhausts in 60 minutes. The use of Defithermol TR is required only if the
771
dyeing is carried out at a temperature higher than T60. Defitherm Tables

provide the following data:
1. Saturation values of various acrylic fibres.

2. Defithermol TR equivalent of cationic dyes.
3. Total % cationic product expressed as Defithermol TR by adding
multiplication product of % dye and Defithermol TR equivalent of each
dye in a combination.
4. Initial dyeing temperature, Ti.
5. Actual dyeing temperature, T60 on the basis of total % cationic
product.
The dyebath is raised to the initial dyeing temperature, Ti and pH is

adjusted to 4-4.5 with acetic acid. The goods are entered and circulated for
15 minutes to wet out and to achieve uniform temperature. The temperature
is rapidly raised to the desired dyeing temperature (T60 or higher) and
circulated for 5 minutes. The previously dissolved dye and Defithermol TR
are added in as highly concentrated form as possible. The bath is held at
selected temperature (± 1ºC) until exhaustion is complete requiring about
60-90 minutes. If adsorption is incomplete, the temperature may be raised
by 2 to 4ºC for complete exhaustion. The shading dyes, if necessary, should
be added without raising temperature. When the match is satisfactory,
temperature is raised to boil over a period of 10-15 minutes, after which
dyeing is continued for 20 minutes for complete fixation of dyes. During
cooling, a pause of 15 minutes is given at the dyeing temperature followed
by cooling to 60ºC.
The advantage of this method is that temperature variations within the
dyeing system, a major cause of unlevelness, are less likely to occur. There
are two disadvantages. Firstly, the exhaustion curve at constant temperature
has a shape, which may not be truly optimum. Secondly, the rate of dyeing
strongly depends on temperature, constant temperatures are to be correctly
calculated and maintained to within ± 0.5ºC, which is difficult to achieve.
The difficulties can be partially overcome by approaching the constant
dyeing temperature slowly. This is similar to stopping at a temperature
below the maximum temperature.
In constant-temperature dyeing methods, only a minimum amount of
retarder is recommended to prevent excessive adsorption strike and to
reduce the cost of retarder. Here, dyeing is mostly regulated by temperature
control and not by control of relative saturation, Srel. There are great
differences in Srel values for pale and deep dyeing. The probability of
unevenness will vary and will be higher for pale dyeing.
772
Rapid Dyeing methods

Several rapid-dyeing methods have been reported for acrylic fibres. Most of
the methods are based on dyeing in optimised conditions achieving level
dyeing from the start of the process, eliminating the need of time of
migration or dead time prior to exhaustion stage. Rapid dyeing method
based on migration and use of migrating cationic dyes has also been
proposed. The temperature control is simple – only the end temperature is
controlled and not the rate of increase of temperature.
However, the degree of unlevelness introduced is unpredictable when the
exhaustion is not controlled by temperature. Hence, actual migration time
required is unknown and sufficient time must be given for the worst degree
of unlevelness possible. The dyeing time will be longer than that for dyeing
level from the beginning. During optimisation of process, a few important
points are to be considered such as:
1. The compatibility of dyes and retarders.

2. The amount of cationic retarder used should bring the relative
saturation, Srel to a standard value, which may depend on the nature
of the fibre and dyes, for each recipe.
3. The rise of temperature should be adjusted to give a steady and
uniform increase of exhaustion with dyeing time. The optimum rate of
dyeing depends on the machine (e.g. liquor flow) and the standard of
levelness required for the goods. The rate of temperature rise is
generally linear with time.
The Astrazon Rapid dyeing Method [35] was derived as follows. First, the
relative saturation value, which gave the best results, was determined. Then
the correct way of varying the temperature was calculated for the above
relative saturation Value and for the required rate of adsorption (considering
necessary fibre and dyestuff data). From practical experience, the rate of
adsorption should normally be selected in such a way that not more than
15−20% of the dyestuff should go on the fibre for every 10 minutes of dyeing
time. If the dye goes on the fibre too quickly, there is a risk of unlevel dyeing.
On the other hand, if the rate is too slow, there will be a certain amount of
dead time. However, this is most preferred by the dyers, because uneven
dyeing is considered most undesirable.
The best possible curve is approached by selecting the initial temperature
properly (i.e. the temperature at which the dye has not gone into the fibre
appreciably) and also the best possible way of increasing temperature. The
temperature rise can always remain same – approximately 1ºC for every
2.5−3 minutes. However, it is necessary to determine the initial temperature
773
for each dyeing. The following figures must be known to determine the
optimum amount of retarder and the initial dyeing temperature:
Dyestuff data: concentration (p%)

combination index (K)
saturation factor (f)
Fibre data: rate of dyeing (V)
fibre saturation value (SF)
Bayer (presently DyStar), in the form of 5 tables, provides the necessary

data [35]. Tables 1 and 2 provide Astrazon dyestuff data (f and K) and fibre
data (V and SF values of various commercial acrylic fibres) respectively.
The fibre saturation value (SF) and rate of dyeing (V) of an unknown
acrylic fibre can be measured by comparative dyeing with a fibre having
known SF and V values.
For measuring SF value, the fibre under investigation is dyed in various
concentrations of a standard dye, say in four separate baths containing 1%
acetic acid (60%) in M:L ratio of 1:40 with 4, 5, 7 and 9% Astrazon Blue FRR
(DyStar, formerly Bayer), i.e. C.I. Basic Blue 69. A control dyeing is made
simultaneously with 7% Astrazon Blue FRR on Dralon or another acrylic
fibre with a saturation value of 2.1. After dyeing for 3-4 hours at boil, dyebath
exhaustion is determined by carrying exhaust dyeing on the same but
undyed material. The saturation value of the unknown fibre is found by
comparing the four exhaust dyeing with that of the control dye and selecting
the one which most closely resembles that of control. SF of the unknown
fibre will be 1.2, 1.5, 2.1 or 2.7 when the matched test dyeing is 4%, 5%, 7%
or 9% respectively.
The rate of dyeing can be determined by dyeing equal parts by weight of
the fibre under examination and of a fibre of known dyeing rate (e.g. Dralon
with V = 1.7) in a single bath with 2% Astrazon Blue FRR, i.e. C.I. Basic
Blue 69, with 1% acetic acid (60%) until the dye is exhausted. Equal depth
of shade on both fibres indicates equal dyeing rate. If the unknown fibre is
paler or deeper than the control, its dyeing rate is correspondingly lower or
higher. If the strength difference is more than 20%, the test should be
repeated with another control fibre with a lower or higher dyeing rate.
First, the individual dyestuff concentration value is determined from Table
3 [35] for every dyestuff, using % depth (p%) of each dye and f value for the
particular dye. These concentration values for all dyes used in the
combination shade are added to give the total dyestuff concentration value,
RF. It is a measure for the number of dyestuff cations, which occupy the
fibre. The total concentration value RG, is noted from Table 4 [35] using fibre
data namely SF, V and dyestuff data, K. If the formulation contains dyestuff
having different K values, the lowest one is chosen.
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%Retarder (Astragal PAN) = RG - RF (10.10)

The initial dyeing temperature is noted from Table 5 [35] for the total
concentration value, RG and for the V value of the fibre. The temperature
provided by the Table is for K value 3-5. For dyestuff having K value of 1
and 2, the initial temperature should be 4ºC and 2ºC lower than that
deduced from Table 5. The recommended dyeing recipe is as follows:
Astrazol dye − x%
Retarder (Levegal PAN) − y%
Acetic acid (60%) to give pH 4.0 − 3%
Sodium sulphate − 10 g/l
The dyeing is started at the calculated initial temperature. The goods are
placed in the bath containing dyes and others. The temperature is held for a
short while (say 5 minutes) followed by raising temperature at the rate of
about 1ºC every 2.5 minutes to the boiling point or preferably to 105ºC.
Dyeing is continued for 60 minutes, after which the matching is checked.
When desired shade is achieved, the liquor is cooled to 55ºC at a rate of
1.5ºC/min and dropped.
The method can be used for high bulk acrylic yarn in hank dyeing machine
in which goods are shrunk at the same time. If the dyeing is done below boil,
the hanks of yarn are to be steam-set before dyeing. The method can also
be used for loose stock, tops, wound packages, warp yarns and piece goods
on machines where the entire bath is prepared in the stock vessel and
heated to the necessary initial temperature. It is usual to dye acrylic
packages with one-way flow only – in to out. With high level of exhaustion of
basic dyes on acrylic fibres, high degree of reproducibility can be achieved.
With good control of the dyeing process, it is possible to achieve 85-95%
blind, i.e. no-addition dyeing. An empirical relation exists between package
density, flow rate and constant rate of temperature rise (CRTR) with regard
to the levelness of the dyeing obtained. As flow rate increases with constant
density, the CRTR can also be increased. For acrylic dyeing, the satisfactory
level for the parameters are:
Package density – 350-400 g/l
Flow rate – 40 l/kg/min
CRTR – 0.25ºC/min
If the dyeing machine does not have a separate stock vessel, the dyebath
may be set at about 10ºC below the initial dyeing temperature and then the
dyebath may be quickly heated to the initial dyeing temperature. In winch, it
is best to hold the temperature for 15-20 minutes so that the temperature is
uniform throughout the machine.
775
A large range of shades of high level of wet fastness can be obtained with
a three-colour combination of K = 3 dyes, namely:
C.I. Basic Yellow 28

C.I. Basic Red 46
C.I. Basic Blue 41
The dyes with K = 1 may be useful for low-affinity fibres and for production
of dark shades. A wide gamut of shades can be obtained with trichromatic
combination of K = 1 dyes, namely:

C.I. Basic Red 45
C.I. Basic Blue 69
When high level of light fastness is required, such as for furnishing fabrics
or carpets, the following dyes can be used on dry-spun fibres to obtain
adequate light fastness:
*
C.I. Basic Yellows 28 , 63
*
C.I. Basic Reds 18 , 24, 25, 78
*.
C.I. Basic Blues 45, 47
*
(The dyes with may be used in mixture for black shade).
The dyeing process of migrating cationic dyes (e.g. Maxilon M, Ciba-

Geigy) can be broken down into an exhaustion phase followed by migration
phase. It is not necessary to pay much attention to the exhaustion phase
because any unevenness occurring can be corrected later. However, if
major corrections are to be carried out, long migration times will be required.
The migrating cationic dyes must be compatible and are normally applied
using electrolyte together with a migrating cationic retarder with a similar K
value to that of dyes and a similar migration value (tan γ). The use of
conventional cationic dyes and retarders are not recommended to be used
with migration cationic dyes.
Stripping of Cationic Dyes
Depending on the dyes used, partial stripping, to remove about 30% of the
dye present, can be achieved by treating the goods in a fresh boiling bath
containing either 1−10% (o.w.m.) anionic retarder and 1 g/l acetic acid
(60%) or 1-5 g/l Merseilles soap.
High temperature enhances stripping. The effect may vary for different
dyes and consequently, the hue of compound shade may change
776
drastically. The treatment removes cationic retarder substantially and may

therefore be used prior to redyeing.
Stripping may be carried out with oxidative bleaching agents, e.g. free
chlorine or chlorine dioxide. Complete stripping is not possible with all dyes.
The best method is to treat with in an acidified hypochlorite bath such as:
Sodium hypochlorite (15 g/l active chlorine) − 5-8 g/l

Acetic acid (pH 5.5-6) − 2-3 ml/l
Sodium nitrate (to prevent corrosion) − 1-4 g/l
The goods are boiled in the bath for 30 minutes, rinsed in hot water and
antichlored for 20-30 minutes at 85ºC with 1-1.5 g/l sodium bisulphite or
1−1.5 g/l sodium dithionite.
A final scouring may be done with a nonionic detergent.
The result may improve by pre-treatment for 60 minutes at boil before
stripping with:
Monoethanolamine − 5 g/l
Common salt − 5 g/l
Redyeing to change hue or depth may be difficult due to oversaturation. If
Srel exceeds 0.95 for the total quantity of dye and cationic retarder already
on the fibre and to be applied in redyeing, the high-affinity dyes are to be
used in redyeing using pH 1-2 unit higher than that used in the previous
dyeing up to a maximum pH of 6. High-affinity (low K value) displaces low-
affinity dyes and retarder.
10.6 DYEING OF BLENDED MATERIALS

The term blending is used by the yarn manufacturers to describe specifically
the sequence of processes required to convert two or more kinds of staple
fibres into a single yarn composed of an intimate mixture of the component
fibres. To the dyer, however, the important type of staple-fibre blend is that
in which components are two different fibrous polymers, each with its own
characteristic dyeing properties. Three reasons are put forward to justify the
replacement of a homogeneous by a blend:
1. Economy by blending with a cheaper fibre.
2. Advantage of desirable performance characteristics (dictated by
physical properties) contributed by both fibre components.
3. Attractive appearance and tactile qualities by development of fabric
designs incorporating multicolour effects or combinations of yarns of
different lustre, crimp or denier.
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Blends of synthetic-polymer with natural fibres offer the most valuable

possibilities for combining desirable physical properties, because the two
components are very dissimilar. In blends of polyester or acrylic fibres with
cotton or viscose, the synthetic fibres provide crease recovery, dimensional
stability, tensile strength, abrasion resistance and easy-care properties,
whilst the cellulosic fibres contribute moisture absorption, antistatic
characteristics and reduced pilling.
Blended staple yarns of synthetic staple (i.e. short-length fibres) with
cellulose (cotton or viscose) are produced in large quantities so that
continuous dyeing methods for such blends are as important as for the
parent cellulosic fibres. Polyester-wool blends have gained a considerable
share in suiting fabric. Wool yarns for woven carpets have been largely
replaced by nylon-wool blends, sometimes containing viscose staple as third
component. Staple blends of acetate-wool, acetate-nylon and polyester-
nylon have been introduced for hand-knitting yarns. The development of
wholly synthetic blended fabrics, such as texturised polyester-acrylic fibre
dress-wear, polyester-nylon shirting or nylon-acrylic half-hose has increased
the scope for differential dyeing apart from differential dyeing varieties of
individual fibres. Ternary blends of normal and basic-dyeable polyester with
nylon, wool or cellulosic fibres have become popular in the apparel sector.
Staple blended yarns are widely established in woven fabrics, but a large
variety of woven and knitted fabrics are also made from two or more types of
homogeneous yarns. Such types of fabrics are known as union fabrics.
However, from dyer’s point of view, the broader term blended fabric may be
used to describe all types of fabric containing two or more fibrous fabrics
differing in dyeing characteristics.
Pile fabrics, popular in the upholstery and furnishing sector, consists of a
nylon or cellulosic backing fabric with a resilient pile made from wool or
acrylic staple. Cotton pile in a nylon support is widely used in lightweight
towelling and children-wear. The carpet industry is a long-established outlet
for fibre blends.
With recent developments in polymer extrusion methods, the number of
possible continuous mixed filament yarns available is now at least as great
as that of staple-fibre blends. Mixed-filament yarns, in which two or more
discrete types of filament are present in the same yarn, may be either
mixed-ply (or twisted) or actual multifilament yarns, formed by the
intermingling of two or more types of filament by extrusion from special type
of spinneret to give a random distribution of the individual filaments within a
single yarn. Filaments made from two different synthetic polymers fused
together within the filament are known as bicomponent (or conjugate)
filaments.
Bicomponent filament structures are of the following three types:
1. Bilateral or side-by-side
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2. Concentric or core-sheath
3. Bi-constituent or matrix-fibril
Estimates of the relative proportions of different fibre types and blends for
coloration in 1996 [37] are:
Cotton – 39%
Viscose and other rayons – 6.8%
Linen and other bast fibres – 1.2%
Wool and hair fibres – 5.2%
Silk – 0.2%
Polyester – 9.5%
Nylon (including spandex) – 10.4%
Acrylics and modacrylics – 7.4%
Cellulose acetates – 1.0%
Polyester-cellulosic blends – 15.2%
Other blends – 4.1%
The dyeing of blended materials has been extensively discussed by Shore
[10].
The kinds of coloured effects achieved by dyeing a blend of two fibres can
be categorised as:
1. Solid shades, i.e. both fibres are dyed as closely as possible to the
same hue, depth and brightness. This is most popular as the blends
are mainly developed for the reason of economy or improvement of
physical properties and not for multicolour effects. Solid shades are
difficult to obtain on blends of fibres having similar chemical
composition but varying dyeability − the same dye-class gives different
build-up on such varieties of fibres depending on their relative affinity.
2. Reserved effects, i.e. only one fibre is dyed while the other is retained
white or undyed.
3. Shadow effect or tone in tone is obtained when two fibres are dyed to
the same hue and brightness but of different depths. It may be
considered as intermediate stage between solid and reserve effects.
The effect may be obtained by using two substrates (e.g. nylon-wool
or acetate-polyester) or differential dyeing variants of a substrate
having similar dyeability but of varying affinities.
4. Contrast or two-colour effects or cross-dye, i.e. the two fibres are dyed
in contrast hues. The contrast may be sharp or subtle. In either case,
optimum brightness on both component fibres enhances the pleasing
appearance of the contrast effect. Cross-staining reduces the
sharpness of contrast. The best contrast effect is obtained on blends
of acid-dyeable and basic-dyeable synthetic fibres, since the freedom
from significant cross-staining under optimum dyeing conditions
779
permits the contrast of complementary pairs, e.g. red-green, blue-

orange or violet-yellow.
Reserve, shadow and contrast effects are mainly of interest for mixed-ply
hand-knitted yarns, union fabrics and tufted carpets from differential-dyeing
fibres. It is difficult to obtain satisfactory reserve of acid-dyeable fibres like
wool and nylon. Acrylic fibres cannot be reserved in the presence of
disperse-dyeable polyester fibres.
In order to dye large varieties of blends, it is necessary to classify the
textile fibres according to the dye-classes, which can exhaust on them in full
depths, namely [10]:
1. Dyeable with disperse dye, e.g. acetates and polyester (D-class
fibres).
2. Dyeable with anionic dyes, e.g. cellulosic fibres, nylon, wool and silk
(A-class fibres).
3. Dyeable with basic dyes, e.g. acrylic and modacrylic fibres, basic-
dyeable nylon, basic-dyeable polyester (B-class fibres).
Most important binary blends are as follows:
D-blends
Acetate-polyester.
A-blends
Wool-silk, wool-cellulose, silk-cellulose, nylon-wool, nylon-cellulose, normal
and deep-dyeing nylons.
DA-blends
Polyester-cellulose, polyester-wool, polyester-nylon, acetate-nylon and
acetate-wool.
DB-blends
Normal and basic-dyeable polyesters, polyester-acrylic and acetate-acrylic.
AB-blends
Wool-acrylic, cellulose-acrylic, nylon-acrylic, basic-dyeable polyester-nylon
(or wool), deep-dyeable and basic-dyeable nylons.
The examples of ternary blends are:

A-blends
Nylon-wool-cellulose, low-dyeing-normal-deep (or ultra-deep)-dyeing nylons,
normal nylon-deep-dyeing nylons-cellulose.
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DA-blends
Polyester (or acetate)-nylon-cellulose, acetate-polyester-nylon and acetate-
nylon-wool.
AB-blends
Normal, deep and basic-dyeable nylons and acrylic-modacrylic-wool (or
cellulose).
DBA-blends
Polyester-acrylic-cellulose and normal polyester-basic-dyeable polyester-
nylon (or wool, or cellulose).
Except a few AB-blends, ternary blends have not been accepted
commercially.
The dyeing possibilities of the most important blends are discussed below.
10.6.1 Dyeing of D-blends

Though all synthetic-polymer fibres are readily dyeable with disperse dyes,
the dyeability of secondary acetate, triacetate and polyester differs greatly at
a given temperature. The rates of dyeing on acetates are much higher and it
is difficult to obtain solid shades in acetate-polyester blends.
10.6.2 Dyeing of A-blends

These blends are usually developed because of a desirable balance of
physical characteristics, and the attainment of solid effects is, therefore,
necessary.
Cotton-viscose Blends
Due to limited supply of cotton, man-made viscose or rayon is blended with
cotton to produce cheaper fabrics, but with higher lustre. Cotton-viscose
blends require careful treatment, as rayon fibres are more susceptible to
chemical attack than cotton.
It is difficult to obtain identical shades on both fibres when they are
together in a fabric, because the regenerated cellulose has a greater portion
of amorphous region resulting in higher dye uptake. It is easier to obtain
solid dark shades on blends of viscose with mercerised cotton by dyeing
direct dyes at boil with salt, but in light shades, greater dye is adsorbed on
the latter.
In case of direct dyes, the solidity of shades obtained on cotton-viscose
blends vary considerably with individual dyes and can be controlled by
dyebath temperature and salt addition. Light shades present little difficulty in
the absence of salt. For medium and dark shades, salt is necessary and
781
solid shades can be obtained at lower dyeing temperature, e.g. 60ºC. But
this results in reduced penetration and poor fastness. Some direct dyes,
which are best for yielding uniform shades, are:
C.I. Direct Yellows 28, 44, 50

C.I. Direct Oranges 26, 34, 37
C.I. Direct Reds 81, 82
C.I. Direct Blue 78
C.I. Direct Blacks 51, 59
The problem of dyeing solid shades also applies in case of vat and
sulphur dyes.
Procion MX brand (cold brand) dyes are found to give better solidity of
shades on such blends compared to other types of Procion dyes when dyed
by batch methods.
As solidity of shades is more likely to be achieved in a short time dyeing
process, padding process is expected to give more solidity in case of both
vat and reactive dyes.
Wool-silk Blends
Wool-silk blends are becoming important for high quality apparel, though the
use is still limited. Natural silk is sometimes blended in equal proportions
with wool to improve lustre and strength. Wool-silk blends are important for
goods like kimonos, dress fabrics and knitwear. Silk yarns are also used as
effect threads in worsted fabrics.
Dyeing of wool-silk blend is normally carried out on yarn, and to a lesser
extent on woven fabric, when a solid shade is required. Degumming of silk is
to be carried out prior to blending to avoid alkaline damage to wool.
Alternately, partial degumming in the blended form may be carried out by
boiling with sulphuric acid and magnesium sulphate (or soap) as in the case
of scappe or supple silk. This is done when silk is blended with fine wool
worsted yarns or high-quality animal fibres, such as alpaca, cashmere,
mohair, angora etc. Blends may be produced by the following two ways:
1. Making intimate blends, mainly for hand-knitting yarns and knitted
goods.
2. Using warp and weft of separate fibres during weaving of fabrics
(union fabrics).
Both wool and silk can be dyed simultaneously in a single dyebath using
milling acid dyes and 1:2 metal-complex dyes. From the technical
standpoint, the main problem in dyeing such blends is the distribution of the
dye between the two fibres. Silk fibre lacks the impervious structure of wool
and the dyes are more readily adsorbed and desorbed by silk. At low
782
temperatures, dye is taken up preferentially by silk and later migrates to the

wool-hair at higher temperatures. Under normal wool-dyeing conditions,
more acid dye is adsorbed by wool than by silk. Hence, the dyeing
temperature is a decisive parameter in the control of dye distribution.
Since the same class of dye must be used for the two fibre components, it
is hardly possible to achieve two-tone effects during dyeing. Consequently,
plain dyeing is mostly produced in commercial practice.
The use of strongly acidic dyebath favours dyeing of silk, although an
acceptable partitioning between the two fibres to yield a solid shade may be
obtained. The fastness to wet treatment is lower with silk. The tensile
strength and lustre are adversely affected while dyeing close to boiling
temperature.
Improved washing fastness on silk may be obtained by reactive dyes, but
the dyeing requires alkaline conditions. Silk is less susceptible to alkaline
damage than wool. Mild alkaline conditions are to be maintained to minimise
damage of wool.
The combination of Isolan S, Alizarin Brilliant and Supranol Fast dyes
(acid dyes, DyStar) are recommended to be used for 50:50 wool-silk blend.
The pH of dyebath is set at 4.5−5 and the temperature is raised to 70ºC,
when silk is dyed in preference to wool. The dyebath is then raised to 90ºC
and held for sufficient time to obtain a solid shade by gradual transfer of dye
from silk to wool.
It has been observed that the pH and dyeing temperature of various
nonreactive dye-classes manufactured by Clariant for optimum distribution
between wool and silk are:
Sandolan N – pH 4.5-5.5 and 70-80ºC

Sandolan Milling N – pH 4.5-6.5 and 80- 85ºC
Lanasyn S – pH 4.5-6.5 and 85-90ºC
Sandolan MF dyes are used for pale to medium shades on piece goods
because of better levelling, but the wet fastness is somewhat poor on silk.
Glauber’s salt improves levelling of such dyes. The recipe is as follows:
Sandolan MF dye −x%

Lyogen MF − 1%
Sodium acetate and acetic acid to maintain pH 4.5-5.5
Sandolan Milling N and Lanasyn S dyes are used for medium and heavy
shades. The recipe is as follows:
Sandolan Milling N or Lanasyn S dye − x %
Lyogen SU − 1%
783
Sodium acetate and acetic acid to maintain pH 4.5-5.5
In two-bath reactive dyeing process of Ciba-Geigy, the silk is first dyed

with Cibacron F dyes at pH 8.5 with 1-2 g/l soda ash in presence of 20-80 g/l
Glauber’s salt or common salt at 60ºC. After rinsing and soaping to remove
unfixed dye and souring, the wool portion is dyed with Lanasol dyes.
In a different approach by Clariant, Drimalan F or Drimarene K dyes are
applied on both fibres either
- at 90ºC and pH 7 with 20-60 g/l salt

- at 70ºC and pH 4.5-5.5 with 5 g/l salt.
After dyeing, the temperature is reduced to 40ºC and 2−5 g/l sodium
bicarbonate is added and held for 30 minutes for fixation. A levelling agent,
such as 1% Lyogen FN, may be added in the dyebath. The material is
soaped with 0.5 Sandopan DTC (nonionic detergent, Clariant) for 10-20
minutes at 70ºC.
BASF recommended that wool should first dyed with Acidol M acid dyes
and then the silk component with Basilen M reactive dyes at pH 8-8.5 for 60
minutes at 30ºC.
Wool-cellulose Blends
The blends containing similar proportions of wool and cotton are of
considerable importance over many years. Union fabrics made from cotton
warp and woollen weft have enjoyed some popularity for shirting and other
apparels, but are now being largely replaced by lighter synthetic blends.
Another outlet has been blazers and coating.
Wool-cotton blends are currently used for articles such as shirts, blouses,
knitting yarns, women’s outwear and sportswear. For blends containing
more than 30% wool, a shrink-resist treatment is usually necessary to impart
sufficient stability to washing of the final product.
The normal alkaline conditions for cotton goods cannot be adopted for
wool-cotton blends. Scouring and setting operations are to be carried out as
those in the case of wool.
Direct dyes alone or admixed with milling and/or 1:2 metal-complex dyes
can be used. A slightly acidic condition facilitates exhaustion of wool dyes. If
the dyeing with direct dyes is started under neutral or slightly alkaline
condition, the pH may be lowered by adding acetic acid after 15-20 minutes
at maximum dyeing temperature (92-95ºC). Cooling of dyebath to 60ºC prior
to rinsing can improve exhaustion of direct dyes. When levelling acid or
mordant acid dyes are applied, it is extremely important to rinse out mineral
acid after dyeing and neutralise with little soda ash in order to avoid the
784
formation of hydrocellulose. Mineral acids may be substituted with formic or

acetic acid.
There are a number of acid dyes which dye wool and leave cellulose
unstained when applied with ammonium sulphate or acetate, such as C.I.
Acid Yellow 71, Reds 129, 130, 499, Blue 138 and Green 27. Most of the
direct dyes stain wool slightly from neutral bath. Under acidic conditions, the
protein fibres develop strong affinity for them. The staining on wool may be
reduced by dyeing direct dyes at 40-60ºC adding 1% (o.w.m.) soda ash.
However, at such low temperature the wet fastness of direct dyes is not
good. In order to minimise cross-staining of wool by direct dyes, blocking
agents like Mesitol HWS (Bayer, presently DyStar), Cibatex RN (Ciba-
Geigy) and Nylofixan PI (Clariant) are used. These aromatic sulphonates
exhaust on wool and restrict uptake of direct dyes. Good results can be
obtained with a greater range of dyes at 40-60ºC or even with a few at 80ºC.
After-treatment with a cationic dye-fixing agent may be done in order to
improve wash-fastness.
For generating bright shades on wool-cotton blends, the cotton can be
dyed with reactive dyes and the wool with reactive or selected non-reactive
dyes in two stages.
While dyeing the cotton portion, the maximum permissible alkali is 10 g/l
soda ash and the maximum temperature permissible under such alkaline
condition is 40ºC. Selected Remazol, Drimarene K, Levafix E-A, Procion
MX and Basilen M dyes can be applied under such condition.
Cibacron F (MFT) can be applied with 2 g/l soda ash (pH 9-10) at 60ºC.
The dyeing time and the concentration of electrolyte can be reduced for all
dyes. At the end of dyeing, the pH is adjusted to 6-7 and the temperature is
raised to 93ºC when the hydrolysed dye exhaust to wool as acid dyes.
Similar procedures may be adopted for Drimarene K and Levafix E-A dyes.
By careful selection of the diazo and coupling components, both fibres can
be dyed in azoic colours to the same shade and depth. The minimum alkali
concentration is 2 g/l caustic soda for application of coupling component to
a 50:50 wool-cellulose blend. When the concentration is 4 g/l, the wool is
dyed in heavier depth, which is advantageous for some coupling
components. When naphtholation is done above 20-25ºC, the wool is deeply
dyed and cotton is lightly dyed, resulting in a reduction in solidity of shade.
Fast bases give heavier shades than fast colour salts. Both naphtholation
and coupling may be done in jigger. Alternately, the coupling component
may be applied by padding and then developed in a jigger. Thorough
soaping is necessary to remove surface deposition of the pigments. The
preferred coupling and diazo components are:
- C.I. Azoic Coupling Components 4, 7, 8, 12, 13

- C.I. Azoic Diazo Components 2, 5, 6, 10, 13, 32, 36
785
Selected vat dyes can be applied on 50:50 wool-cotton blends, the

optimum dyeing conditions being 4 g/l caustic soda and 4 g/l sodium
hydrosulphite at 40ºC for 45 minutes. The choice of vat dyes is, therefore,
limited, as many of the commonly used vat dyes require larger quantities of
caustic soda and higher dyeing temperature. The following vat dyes can dye
both wool and cotton to the same shade:
C.I. Vat Red 10
C.I. Vat Violets 14 and 17
C.I. Vat Blues 14 and 16
C.I. Vat Greens 1 and 3
C.I. Vat Browns 3, 38 and 49
C.I. Vat Black 27
The various problems of exhaust dyeing of wool-cotton blends are:

1. Cotton requires strong alkaline conditions and high temperatures for
scouring as well as for fixation of reactive dyes. Such severe
conditions cannot be maintained during blend dyeing, the dyeability of
cotton is, therefore, less than optimum. If union fabric is made with
separate yarns of two fibres, the cotton yarn can be scoured
thoroughly and optionally mercerised to achieve optimum
performance.
2. As compared to wool, the exhaustion of dyes, especially direct and
reactive, on cotton is often poor. The exhaustion is still further less in
blends as the liquor ratio is decided on the total weight of blended
material and the effective M:L ratio against cotton portion is much
higher depending on the blend ratio.
3. Cross-staining of wool is inevitable, to more or less extent, by cotton
dyes even in the presence of anionic blocking agents.
It is possible to dye cotton portion in wool-cotton blends by pad-batch
process using Procion MX, Drimarene K, Remazol and Cibacron F dyes.
The padding may be done along with caustic soda (70º Tw, maximum 12
ml/l + sodium silicate, 60 ml/l) or soda ash (maximum of 30 g/l). This is
followed by cold batching for 24 hours (4 hours for MX brand). After
thorough washing-off to remove alkali and unfixed dye, the wool portion is
dyed by usual exhaust method.
Clariant recommended a pad-roll method using a mixture of solar (direct)
and Sandolan MF dyes or a mixture of Indosol SF and Lanasyn S dyes to
dye both fibres. The fabric is padded at 20-50ºC according to depth of shade
and pH 5.5-6.5. The fixation is done by batching in a chamber for 3 hours at
85ºC. The fabric is then washed off and optionally after-treated with cationic
agents.
786
Silk-cellulose Blends
Blends of silk with cellulosic fibres are widely used for various materials,
such as:
- upholstery fabrics
- furnishing fabrics
- hand-knitting yarns
- shirting fabrics
- women’s outwear apparels.
Mercerised cotton, linen, ramie and especially lustrous viscose are

blended with silk. Mostly jacquard woven fabric is produced with patterns
often dyed with two-colour effect.
The two ways of processing are:
- One-bath one-stage dyeing with direct and acid or metal-complex dyes

with a reserving agent such as Nylofixan PI (Clariant).
- Two-bath dyeing with reactive dyes on cellulosic portion followed by
dyeing of silk with acid and metal-complex dyes.
The problems are:

1. Very few direct dyes exhibit sufficient reserve of silk.
2. The reactive dyes dye silk virtually in the same depth as the cellulosic
fibres, but often the dyeing is off-shade. Hence, with reactive dyes
only two-tone effects are produced. In the first phase, when the dye
strikes both the fibres in about the same depth. In the second phase,
the silk is overdyed.
The milling acid dyes and strongly polar 1:2 metal-complex dyes show good
reserve of cellulosic fibres up to deep shades.
The recipe (% o.w.m.) for one-bath process is:
Direct dyes, e.g. Solar Dyes (Clariant) − x%
Sandolan N or Lanasyn S dye − y%
Nylofixan PI − 0.5-2%
The dyes and Nylofixan PI are added at 20-30ºC and pH is set at 7.0-5.5
with sodium acetate-acetic acid. The material is run for 20 minutes and salt
is added. The temperature is then slowly raised to 70-80ºC and the dyeing is
continued for 60 minutes followed by soaping. Glauber’s salt increases
787
uptake of direct dyes on cellulosic fibres, but may stain silk heavily. The use
of fibre-substantive levelling agents may cancel the effect of Nylofixan PI.
In two-bath process, the cellulosic portion is first dyed with Drimarene K
dyes at 40-50ºC using 30-50 g/l Glauber's salt and 5-15 g/l soda ash. This is
followed by second stage dyeing of silk with Sandolan N or Lanasyn S dyes
with a levelling agent, 0.5-1.5% Lyogen MF/SU at pH 7-5.5 at 70-80ºC.
Intermediate soaping is not required. The dyed material may be after-treated
with a cationic fixing agent, at 20-25ºC for 20-30 minutes for improvement of
fastness properties on both fibres.
Blends of Differential-dyeable nylons
The distribution of acid dyes between normal, low- and deep-dyeable nylons
depends on the dyeing conditions and the molecular structure of the dye,
especially the degree of sulphonation. Greater differentiation and better
reservation of the less-dyeable component are achieved at higher pH.
However, total exhaustion will be lower at higher pH and the chance for
economic exhaustion of the more-dyeable variant is limited.
At a given pH in the neutral region, the dye exhaustion decreases with the
increase of sulphonic groups in the dye molecule, the effect is more
prominent with fibres having more basic groups as in the case of deep-
dyeing variety. Consequently, highly sulphonated dyes give higher
differentiation between the fibres of varying dyeability at a given pH. For
shadow effects, dyes of lower sulphonation are applied carefully at pH 5−6,
while for sharper differentiation, more sulphonated dyes are used at pH 6−7.
Some examples of monosulphonated monoazo or anthraquinone dyes
showing moderate differentiation are C.I. Acid Red 57, Blue 40 and Blue 72.
Sharper differentiation can be achieved with most disulphonated monoazo,
disazo or anthraquinone types of acid dyes and selected disazo
trisulphonates and tetrasulphonates. Trichromatic combinations can be
obtained using C.I. Acid Yellow 17, Red 37 and Blue 23 (disuphonated).
Suitable buffer, such as a mixture of sodium dihydrogen phosphate and
disodium hydrogen phosphate, may be used to ensure reproducibility of
shadow and contrast effects from batch to batch. The dyeing is started at
40ºC with suitable buffer and 1 g/l dispersing agent. The temperature is
raised to boil within 45-60 minutes and dyeing continued for another 30-60
minutes depending on the depth and the degree of differentiation required.
The blends may be after-treated with syntan to improve wet fastness.
Low-energy A or B class disperse dyes, particularly B class anthraquinone
dyes are recommended for solid shades on these blends.
The anionic levelling agents used to minimise barréness are preferentially
adsorbed by the deep-dye variant, thereby reducing the degree of
differentiation. Weakly cationic levelling agents, on the other hand, control
the rate of dyeing without suppressing the differentiation.
788
In case of differential-dyeing nylon tufted carpets based on jute backing,

low pH should be avoided during dyeing as lignin is transferred to the nylon
pile, especially on deep-dyeing variants. The yellow-brown stains cause
dulling of bright shades and lower light fastness. Staining will be negligible at
pH 6-8 and will be only on deep-dyeing variants, which are generally dyed in
deep shades. Much of the jute impurities are removed by pre-scouring with
2 g/l soda ash and 2 g/l nonionic detergent for 20 minutes at 80ºC.
Ternary blends of acid-dyeable nylon variants are less important than
binary blends. Levelling acid dyes for these blends differ in selectivity
according to structural type. The differentiation at pH 4 to 7 tends to
increase with degree of sulphonation – monsulphonate levelling acid dyes
give marked differences only in full depths at pH 7-8. Milling acid and metal-
complex dyes are not popular for these blends because of poor
differentiation.
Nylon-wool Blends
Nylon-wool blended materials may be dyed in solid shades using levelling
and milling type of acid dyes and metal-complex dyes. Solid shades may be
easily obtained on staple-fibre blends, but is difficult to obtain on union
fabrics made from crimped nylon warp and wool staple weft. The distribution
of dye between nylon and wool depends on dye structure, applied depth,
pH, blend ratio and quality of the component fibres. A good selection of
monosulphonated acid dyes for giving solid shades over a wide range is C.I.
Acid Yellow 29, Red 57 and Blue 71. The range may be supplemented with
C.I. Acid Violet 41 and Blues 40, 67.
Acid dyes show saturation problem with nylon but not with wool. The rate
of dyeing and exhaustion is higher on nylon than on wool, particularly at 60-
80ºC, which is noticeable in pale dyeing. Solidity is obtained at a critical
depth, which is specific for the dye and is higher for monosulphonated dyes.
Above the critical depth, the nylon becomes progressively difficult to dye and
exhaustion is more on wool. The saturation limit is higher on nylon 6 fibres
and more economical disulphonate combination is often preferred for nylon
6 and wool blends. Synthetic tannins such as Nylofixan PI liquid are used to
control even distribution on both wool and nylon components. The reserving
action is impaired by simultaneous use of nonionic dye-substantive dyeing
chemicals. Sandolan MF dyes (Clariant) are highly suitable for dyeing nylon-
wool blends due to higher migration properties. For trichromatic dyeing, the
following dyes may be used in combinations:
Sandolan Golden Yellow MF-RL

Sandolan Red MF-GRL
Sandolan Blue MF-GL
789
Suitable shading dyes for perfect on-tone dyeing are as follows:
- For dyeing wool component to red with Sandolan Scarlet N-GL

- For dyeing nylon component to blue with Nylosan Blue N-GL.
Disulphonated acid dyes and 1:1 metal-complex dyes having lower

substantivity for nylon can be dyed in a bath containing 2-4% formic or
sulphuric acid and 5-10% sodium sulphate at pH 2-3. The dyeing is started
at 50ºC and raised to boil over 30-45 minutes and continued for 60-90
minutes. Monosulphonated acid and 1:2 metal-complex dyes dye nylon
more readily. The dyeing method is similar to the above. The initial pH of the
bath is set at 5-6 with 3% ammonium acetate and acetic acid. For better
levelness in pale shades, pH is set at 6 while more acid is required for
higher depths. Solid shades are difficult to obtain with chrome mordant dyes
as both dye and chromium are preferentially adsorbed on wool.
Polyamide/cellulosic blends can be economically dyed with high-quality
Indanthren vat dyes by conventional pad-dry-pad-steam process [38].
Nylon-cellulose Blends
Nylon-cotton staple blends containing 10-50% nylon are used in dress-wear
and leisure shirts, while nylon filament base and cotton pile are used for
weft-knitted towelling. Bright shades with good wash and light fastness are
obtained with reactive dyes and acid or metal-complex dyes. A wide range
of reactive dyes can also be used satisfactorily on both fibres, if the
proportion of nylon is not too high.
Solid shades are difficult to achieve on nylon-cellulose staple blends and
more difficult on union fabrics. Reserve, shadow and limited contrast effects
are practicable on these blends, but seldom required in practice. The nylon
component may be reserved by applying selected salt-controllable (Class-B)
direct dyes to the cellulosic fibre at 80-90ºC, salt and syntan are added to
protect nylon from cross-staining. The suitable direct dyes include C.I. Direct
Yellow 50, Red 80 and Blue 71 or 78. Good levelling Class-A direct dyes
can be applied in pale and medium shades. There are a few direct dyes,
which give solid shades on the two fibres at pH 4-5.
There are a number of direct dyes having very little affinity for nylon,
especially in a slightly alkaline bath, which can be used for correction of
shades on the cellulosic component, e.g. C.I. Direct Yellow 50, Red 81,
Black 71, etc.
Acid dyes, which under neutral conditions, do not stain cellulose, can be
used for shade correction of nylon component such as C.I. Acid Yellows 36,
72, Red 88, Blues 25, 67, 78, 138 and Black 48.
Solid shades can be obtained on nylon-cellulosic blends using direct and
disperse dyes by one bath method. The dyebath is set at 40ºC and pH 8
790
with trisodium phosphate, alkanol polyoxyethylene (as dispersing and

levelling agent) and 2% syntan to minimise uptake of direct dyes on nylon.
Disperse dyes are added at 40ºC and direct dyes at 70ºC. 20% salt is added
after 30 minutes and dyeing is carried out at boil.
Neutral dyeing acid and 1:2 metal-complex dyes give good reserve on
cellulosic fibres. The dyebath is set at 40ºC with 0.5-2% syntan, the
optimum pH ranges from 7-8 (ammonia) for pale depth to 5-6 (ammonium
acetate and acetic acid) for full depths with metal-complex dyes. Anionic
dyes are added with 0.5-1% cationic retarder and 1% dispersing agent to
solubilise dye-retarder complex. Direct dyes are added at 60-70ºC and
dyeing is continued at boil adding 20% salt and lowering the temperature to
80ºC to promote exhaustion of direct dyes.
For solid shades on nylon-cellulosic blends with vat dyes, the optimum
dyeing temperature varies from 60-115ºC, depending on dye structure,
applied depth and liquor ratio. The distribution favours nylon preferentially at
higher dyeing temperature. Semi-pigmentation method is preferred.
Bright hues with excellent fastness can be achieved on nylon-cellulosic
using reactive dyes. Like vat dyes, reactive dyes are also sensitive to the
type of nylon present. In one-bath, three-stage method, the steps are:
1. The reactive dyes are first exhausted on nylon from weakly acidic
solution in the absence of salt.
2. Salt is then added for exhaustion into the cellulosic fibre.
3. Finally alkali is added for fixation on cellulosic fibres.
The distribution of dye on both fibres may be controlled by the selection of

dyebath pH, temperature and electrolyte concentration.
Many 1:2 metal-complex and several acid milling dyes are fast to soda
boiling and can be applied with reactive dyes in one-bath two-stage method.
Reactive dyes and metal-complex dyes can be applied in the presence of
alkali, followed by neutralisation with acid and raising temperature to boil to
dye the nylon component.
Continuous dyeing of A-blends
Nylon-wool and nylon-cellulosic (blend or pile and backing) are popular in
the carpet industry and continuous dyeing methods have become popular in
the field in recent years. Tufted carpets containing acid-dyeable variants can
be dyed by wetting at ambient temperature with suitable wetting agent at pH
7, followed by padding with a thickened solution of dye, acetic acid,
thiodiglycol (swelling agent) and penetrating-cum-wetting agent and finally
steaming for 8-10 minutes at 100ºC. The problem of staining by lignin of
jute-backing fabrics is negligible, but the differentiation of the variant yarns is
also less. Nylon-wool carpet or upholstery fabrics may be dyed by similar
791
pad-steam method with acid or metal-complex dyes. The padding is done

with dye, 5-10 ml/l acetic acid, a mixture of anionic and nonionic agent (30-
40 g/l) for stability of pad-liquor and thickener.
Viscose carpets containing 10-20% nylon can be dyed continuously with
direct dyes when acceptable solid effect can be obtained on both the fibres.
Nylon 6 is dyed more heavily than nylon 6,6 in such blends. Reactive dyes
may be applied for cellulosic component and disperse dyes can be applied
for nylon component satisfactorily for pale shades.
10.6.3 Dyeing of DA-blends

The blends of polyester with natural fibres are most successful examples of
achieving the benefits of blend. The dyeing of DA-blends is usually directed
towards solidity rather than differential effects, but unfortunately the most
troublesome problem is the staining of wool with disperse dyes. Cellulosic
fibres are less sensitive to cross-staining by these dyes.
Acetate-nylon blends
Solidarity is not easy to obtain on acetate-nylon because most disperse
dyes show a marked bathochromic shift on nylon compared with their hues
on the acetate (yellows appear bluer, reds bluer and blues greener on
nylon). The hues on nylon are duller and the blends look skittery, if a
substantial proportion of nylon is present. A good reserve is obtained on
acetate using 1:2 metal-complex dyes.
Polyester-nylon blends
The affinity of disperse dyes is lower but the rate of diffusion is much more
rapid in case of nylon as compared to those of polyester. In the absence of
carrier at boil, nylon is dyed heavily with disperse dyes, while at high
temperature or in the presence of 3-4 g/l carrier, the polyester is favoured.
The popular trichromatic combination of C.I. Disperse Yellow 42, Red 60
and Blue 56 gives approximately similar depths on the two fibres under
carrier dyeing conditions at boil. Many acid dyes give good reserve of
polyester when applied with up to 3% acetic acid and levelling agent at boil.
Good reserve may also be obtained by applying 1:2 metal-complex dyes at
pH 7-8 and polysulphonated reactive dyes with 4% formic acid at pH 3-4.
Shadow or dependent contrast effects can be obtained with disperse and
acid or metal-complex dyes by one-bath two-stage method. The dyebath is
set at 20-40ºC with anionic dyes, 0-2% acetic acid and up to 5% ammonium
acetate or sulphate to give required pH. The temperature is raised slowly to
60-80ºC. 2-4 g/l carrier and disperse dyes are added. The temperature is
raised to boil and dyeing is continued for 60-90 minutes.
792
Polyester-wool blends
Polyester-wool blends have been established in woven suiting for many
years. Whilst various blend ratios have been used, by far the most popular
blend is 55% polyester and 45% wool as the blend gives the best
combination of wear and easy-care properties from the consumer’s
viewpoint. It is common practice to dye them by a one-bath technique. For
better aesthetic appeal, wool-rich blends are in great demand in recent
years. In such blends, polyester component may account for only 20 to 30%
and conventional one-bath dyeing methods often failed to give good shade
solidity. Recently deep- and basic-dyeable polyester yarns have widened
the possibilities of fabric design. Unlike all-wool jersey, polyester-wool
fabrics can be dyed on the beam.
Polyester, but not acetate fibres, will withstand normal preparatory
processes of wool, namely carbonising and milling. Crabbing and pre-setting
for 25-30 seconds at 170-180ºC protects fabric against winch creasing or
shrinkage in beam dyeing. But heat-setting may aggravate wool staining.
The biggest problem of dyeing polyester-wool blends is the staining of
wool with disperse dyes. The stain on wool is dull and exhibits poor wash
and light fastness. Though the terms stain or cross-stain are frequently
used, the wool is actually dyed by disperse dyes, but with low levels of
fastness. Accordingly, the process is governed by laws of equilibrium and
depends on several factors, such as:
1. Dye structure, i.e. molecular size, number, type and distribution of

polar groups
2. Depth of shade.
3. pH of the dyebath.
4. Liquor ratio.
5. Dyeing temperature.
6. Presence of other substances.
7. Condition of the fibres.
The first factor has less influence on the initial level of staining than
dyebath conditions and the quality of dye dispersion. Mechanical retention in
yarn crevices plays an important part and low-twist wool stains more readily
than fine, high-twist yarns. Particle size and stability of dye dispersion are
also very important. Staining decreases with increase in concentration and
anionic charge of the stabilising agent present in the dispersion. Carriers
also exert a marginal influence. In spite of more staining, o-phenylphenol is
widely used for polyester-wool due to lower cost. Good carrier-dyeing
properties and low staining or ease of clearing from wool are given by
disperse dyes of Class B and C e.g. nitro (C.I. Yellow 42), monoazo (C.I.
Orange 25 and Red 82) and especially anthraquinone (C.I. Reds 11, 59, 60
793
and Blue 56, 72 or 87) dyes. Below boil, wool is stained preferentially. At or
above boil, migration from wool to polyester occurs on prolonged dyeing, but
there may be damage to the wool. At low pH, the uptake of dispersing
agents and disperse dyes are more, on the other hand a dyebath pH higher
than 7 may cause poor dispersion of disperse dyes and damage of wool.
The one-bath method gives satisfactory fastness in pale to medium
depths, but two-bath sequence gives more reproducible solidity or brighter
contrast effects as well as optimum fastness in full depths.
In one-bath process, disperse and acid dyes are added at 50-60ºC with
3−5% ammonium acetate or sulphate and acetic acid to give pH 5-6, 0.5−1
g/l sodium dinaphthylmethane disulphonate and 3-5 g/l carrier. The
temperature is raised to boil or 105ºC slowly and dyeing is continued for 60-
120 minutes depending on depth. If dyeing is done above 110°C and
outside isoelectric range of wool (pH 4.5-5.2), a fibre-protecting agent, or
suitable auxiliary should be added.
After one-bath dyeing, the stain on wool may be cleared by scouring with
1-2 g/l nonionic detergent and 0.5-1 ml/l acetic acid (pH 4-5) for 20-30
minutes at 50-70ºC. In one-bath process, staining will be more if the affinity
of disperse dye on polyester is lower (as in the case of C.I. Disperse Violet
27) than that when the affinity is higher (as in the case of C.I. Disperse
Orange 30 or Blue 73). Full depths are usually dyed by a two-bath
sequence, as follows:
In two bath process, the polyester component may be first dyed with
disperse dyes, anionic dispersing agent and carrier at pH 5-6 with acetic
acid. The surface deposition on the polyester and the stain on wool are
removed by an intermediate clearing with nonionic detergent along with:
3 g/l sodium dithionite and 2-3 ml/l ammonia for 15 minutes at 60ºC,
or
1 g/l zinc sulphoxalate-formaldehyde and 1 ml/l formic acid for 15 minutes
at 50-70ºC.
In the next stage, the wool is cross-dyed with acid or 1:2 metal-complex
dyes from ammonium acetate and acetic acid with 1-2 g/l levelling agent.
The temperature is raised from 50ºC to boil slowly and dyeing is continued
for 45-60 minutes.
However, wool suffers some loss in strength and elastic properties. In the
wool dyeing stage, cross-staining of polyester by acid dyes especially with
levelling type is much less. The milling and 1:2 metal-complex dyes are
preferred. 1:1 metal-complex and levelling acid dyes require lower pH when
staining on polyester is more severe. Oxidative treatment during chrome
dyeing may damage wool and change the hue. When dyeing is carried out
at 105ºC in enclosed dyeing conditions, wool may degrade and disperse
794
dyes may be reduced by the degradation products. A reduction inhibitor may

be added.
Partition of disperse dyes goes strongly in favour of wool when its
proportion of the blend is increased. This change in partition is greatly
exaggerated, if equilibrium exhaustion is not achieved. Dyeing by a two-bath
method will give better shade partition than a one-bath method and the
dyeing of polyester in the first stage gives best results. Because disperse
dyes are taken up by wool rapidly at low temperature, the dyeing of
polyester is to be started at a temperature higher than normal (maximum
80°C). The carrier increases the rate of exhaustion on polyester, but the
equilibrium uptake will be reduced. This means more dye in the bath, which
will be taken up by wool. The effect is more pronounced in pale shades, but
the degree varies from dye to dye. The carrier is to be removed as much as
possible during intermediate reduction-clear. For all but heaviest shades
(black, navy, etc.), the ideal polyester dyeing conditions are 45 minutes at
110°C with carrier. The temperature of wool dyebath should be 20°C lower
for minimum wool stain, i.e. maximum 90°C. However, heavy shades on
wool should be dyed at boil to achieve desired depth and fastness. This
necessitates dyeing of polyester at 120°C. Prolonged treatment during
disperse dyeing may increase reduction of dyes in wool-rich blends [39].
Deep- or easy-dyeable polyester, especially developed for blending with
wool, can be dyed at boil without carrier.
To avoid all the problems of dyeing polyester-wool, the industries prefer
separate dyeing of both fibres before spinning. Polyester is dyed in tow or
top form, with sublimation-fast disperse dyes. Wool is dyed separately in top
form, either in spools or in cages, using fast wool dyes like Lanasyn,
Lanasyn N or Sandolan Milling N dyes to attain the similar fastness level as
on polyester. The problems involved in blend are solved, but separate
dyeing of each component entails higher dyeing time, higher labour cost and
pre-planning. The system cannot always be flexibly adapted to rapidly
changing market requirements.
Polyester-cellulose
An advantage of incorporating polyester in cotton from dyer’s point of view is
that it can withstand relatively severe preparation necessary for cotton
before dyeing. Viscose fibres, especially polynosic, are more suitable than
cotton due to higher lustre and softness. On polyester-cellulose, the degree
of staining is less, prolonged boiling favours migration of disperse dyes to
polyester without severe attack on cellulose and the stain can be removed
by reduction-clearing. Reactive dyes give negligible staining on polyester.
Direct dyes give good reserve, but insoluble vat, sulphur and azoic dyes
show moderate to severe cross-staining on polyester. Sometimes vat dyes
are used to dye both the components.
795
Woven staple 67:33 polyester-cotton and 50:50 polyester-viscose blends

are very popular and are produced in sufficient quantities allowing
continuous dyeing feasible. For knitted fabrics, higher production can be
achieved using pressure jet and rapid jet machines. Pre-setting can be
avoided without creasing in jet dyeing. The other advantages include shorter
dyeing circle, lower liquor ratio, higher turbulence and vigorous washing.
Lower dimensional stability is a barrier for continuous dyeing of knitted
fabric.
Thorough preparation of polyester-cotton woven fabrics is essential to
successful dyeing. Cotton is usually the minor component in a polyester-
cotton blend so that alkaline scouring, bleaching and mercerising usually
provide adequate preparation. For optimum absorbency, the cotton waxes
can be removed with solvent scour in boiling trichloroethylene.
Polyester-cellulose blends may be scoured in winch using 1-2 g/l anionic
detergent and 2-5 g/l soda ash for 45-60 minutes at 70-80ºC. In jig dyeing,
higher concentrations are required and 1-2 g/l caustic soda may be used
instead of soda ash. The dyeability of polyester-cotton (but not polyester-
viscose) can be improved by cold mercerisation or treatment with 60 g/l
caustic soda for 2-3 minutes at cold followed by rinsing. Heat-setting is done
on stenter for 30-40 seconds at 180-200ºC or at higher temperature for
closely woven poplins or similar constructions.
Several possible batchwise dyeing methods for polyester-cellulose are
based on the use of disperse dyes and various classes of dye for cellulosic
fibres, depending on the requirements of hue, depth and fastness of the
shades and cost considerations. For high temperature dyeing machines like
jet dyeing, D-class disperse dyes (e.g. C.I Disperse Yellow 63, Orange 32,
Red 72 and Blue 27) and even C-class dyes may be used. B-class disperse
dyes may be used for low-cost one-bath processes based on carrier dyeing
with direct or sulphur dyes for the cellulosic fibres.
Disperse and direct dyes can be applied in a cheap, simple, one-bath
process, but fastness is inadequate. Clariant recommended one-bath
application of Foron RD disperse dyes and Indosol direct dyes from single
bath as both require identical fixation conditions (about 15 minutes at
130ºC). The fastness of Indosol dyes can be improved significantly by a
reactant fixing agent, Indosol CR liquid or Indosol E-50 Pdr., which still
results in home laundering fastness.
Economical one-bath process may also be used with disperse and
reactive dyes for bright and fast shades, but two-bath sequence with
intermediate clearing is necessary to achieve optimum fastness.
Many of the hot-dyeing reactive dyes (e.g. HE-brand) are sufficiently
stable to withstand the conditions of high-temperature dyeing and they can
be dyed by one-bath two-step sequence. Carrier method is not
recommended as the carriers have restraining action on the exhaustion and
796
fixation of reactive dyes. The reactive and disperse dyes are added at 60ºC
with 0.5 g/l sodium dihydrogen phosphate (pH 5-6), 1 g/l dispersing agent, 5
g/l sodium-m-nitro-benzene sulphonate (to prevent reduction of reactive
dyes at high temperature). The temperature is raised quickly to 95ºC and
then over 30-40 minutes to 130ºC. The dyeing is continued for
45-60 minutes. The temperature is reduced to 80ºC and required quantity of
common salt (50-80 g/l) is added. After 15-20 minutes, soda ash (15-20 g/l)
(pH 11) is added and fixation is completed in 40-60 minutes at 80ºC.
Ciba recommends one bath LS Superfast method using disperse (Terasil)
dyes and low-salt reactive (Cibacron LS) dyes. The use of lower amount of
electrolyte assures higher dispersion-stability of disperse dyes. On
polyester-cellulosic blends, the washing fastness of disperse dyes may be
lower due to poor cotton reserve. Terasil W (Ciba) dyes claimed to have
higher fastness to meet Oeko-Tex 100 standard.
The cold-brand reactive dyes may be applied with disperse dyes from
single bath or can be applied separately by pad-batch method before dyeing
polyester component. The former is added first at 20-30°C with salt,
reduction inhibitor and phosphate buffer to set pH at 8.5. The temperature is
raised to 80°C over 45 minutes and held for 15 minutes. Acetic acid is
added to bring pH to 6-6.5. The disperse dyes and dispersing agent is
added and polyester is dyed at boil or at 130°C with and without carriers
respectively. The method is suitable for piece dyeing, but in package dyeing,
the polyester component is to be dyed first as disperse dyes may be
precipitated in the presence of electrolyte.
Medium to full depths can be obtained with disperse and vat dyes in one-
bath two-stage sequence, but instability of vat dyes at high temperature may
create a problem. For dyes like indanthrone blues and some carbazole
browns and olive greens, 2-3 g/l sodium nitrite should be added to prevent
over-reduction. Owing to rapid consumption of sodium dithionite, vat dyes
are best applied in machines fully filled with liquor (e.g. beam and fully-
flooded jet machines) rather than H.T. Winch, partly-flooded jet or overflow
machines. In one-bath method, the dyebath is set at pH 5-6 with 1-2 g/l
dispersing agent, disperse and selected vat dyes. Dyeing is done at 130°C
for 45-60 minutes in the usual way. The temperature is reduced to 85°C. 30
g/l caustic soda and 10 g/l sodium dithionite are added and dyeing is
continued for 30 minutes at 85°C. This is followed by oxidation at 50°C and
soaping. Colour matching is a problem as some vat dyes may stain
polyester component. It is advisable to add vat dyes after cooling to 85°C
and 15 minutes after the addition of reducing system.
The problem of dye-instability can be avoided and best all-round fastness
can be achieved by two-bath application when the second bath of vat dyeing
may act as reduction clearing bath for disperse dyes. Some duller hue may
be achieved economically by two-bath application of disperse and sulphur
797
dyes. Intermediate clearing is necessary and wet fastness may be only

moderate. Caustic soda and sodium dithionite should be used to solubilise
sulphur dyes as sodium sulphide may damage polyester.
Continuous Dyeing of DA-blends
Among DA-blends, pad-thermofix continuous method of dyeing is very
popular for polyester-cotton blends. For longer runs to a given colour, the
process ensures high tinctorial yields, reproducibility and uniformity more
economically than batchwise methods. Simultaneous dyeing and heat-
setting without creasing, better coverage of dye-affinity variations, rapid and
uniform penetration of high-energy (D-class) dyes, are some of the
advantages of pad-thermofix method. However, thorough preparation
(preferably by continuous methods) is important before continuous dyeing.
The blends containing more than 60% polyester can be dyed in solid pale
shades with disperse dyes only. The sequence is:
Pad with disperse dyes and migration inhibitor Æ Dry Æ Thermofix.
For heavier shades, the material may be reduction-cleared and the
cellulosic portion dyed by continuous or batch methods with direct, vat or
reactive dyes.
Reactive and vat dyes are the main alternatives for the cellulosic
component. Reactive dyes give very good reserve of the polyester. One-
bath and two-bath processes based on disperse and reactive dyes give very
good fastness up to medium depth, especially on polyester-viscose fabrics.
Severe fastness requirements can be attained by disperse and vat dyes
combinations.
Selected disperse and reactive dyes can be fixed simultaneously by
simple and economical one-bath pad-thermofix method. The dyes are to be
selected carefully to avoid interactions of reactive dyes and instability of
disperse dyes under alkaline conditions. Polyester-cellulose fabrics are
padded with selected disperse and reactive dyes along with 10 g/l sodium
bicarbonate, 50 g/l urea and 10-20 g/l sodium alginate or
carboxymethylcellulose (migration inhibitor). After passing through a infra-
red pre-dryer, the drying can be completed in a hot-flue machine or cylinder
dryer without appreciable migration. The thermofixation is usually carried out
for 60 seconds at 200-220ºC. Staining on cellulosic component is greater
than batchwise processes and can be removed by subsequent reduction-
clearing and soaping. During thermofixation, the transfer of disperse dyes
from cellulose to polyester proceeds through vapour phase. Some dye is
also lost by vaporisation. A critical combination of fixation time and
temperature gives optimum yield for a particular dye. High-energy disperse
dyes are most widely used for pad-thermofix methods, especially in full
depths.
798
The presence of urea promotes excessive staining of cellulose, poor

fastness and yield on polyester. Instability of disperse dyes in alkaline
condition may be avoided by applying mixture of both dyes from a neutral
bath containing migration and reduction inhibitor.
Pad with disperse and reactive dyes and migration inhibitor Æ dry Æ
thermofix Æ pad with alkali (10 g/l sodium bicarbonate) and salt (10 g/l to
minimise migration) Æ dry at 90ºC for 60-90 seconds Æ steam for 10-20
seconds at 100-105ºC Æ soap at boil Æ rinse Æ dry.
Selected vat dyes can dye both components in pale-to-medium depths. At
fuller depths, the cellulose is dyed more deeply and skittery effect is
obtained. The best solidity is obtained by selected indigoid and thioindigoid
dyes, but these have limited fastness. Better fastness is obtained in the
yellow to orange region by derivatives of polycyclic quinones. Suitable dyes
are padded at 30-40ºC with 2-5 g/l T.R.Oil and 10-20 g/l migration inhibitor.
The padded fabric is dried and thermofixed for 60 seconds at 200-220ºC.
The fabric is cooled and padded with 40 g/l caustic soda and 40 g/l sodium
dithionite. It is then steamed for 20-40 seconds at 100-105ºC, oxidised and
soaped. The same method may be used for a mixture of selected disperse
and vat dyes.
Pad with disperse dyes, vat pigment and migration inhibitor Æ dry Æ
thermofix Æ pad with caustic soda and sodium dithionite Æ steam Æ rinse
Æ oxidise with peroxy compound Æ soap Æ rinse Æ dry.
Disperse dyes used should be stable to reducing conditions.

One-bath one-pass process for polyester-cellulose has major production
advantages. In RTN process, the polyester and cellulose portions of the
blend are dyed at the same time in a simple pad-dry-thermofix process. The
recipe combines the new generation of Dispersol disperse dyes with Procion
CX reactive dyes, sodium bicarbonate and the usual padding auxiliaries. An
auxiliary product Zetex FN-T aids fixation in the heaviest depths of shade.
The RTN wash-off sequence utilises the easy-clear properties of the
Dispersol dyes and involves a hot alkaline soaping at the beginning of the
washing sequence.
10.6.4 Dyeing of DB-blends

Blends of polyester and acrylic fibres or polyester containing acrylic effect
yarns are important in woven upholstery and furnishing, easy-care suiting,
outwear and dress-wear. Polyester-acrylic blends are usually piece-dyed.
Jersey fabrics knitted from normal and basic-dyeable polyester yarns can be
used for contrast effects.
799
Polyester-acrylic
Polyester-acrylic fabrics are scoured at pH 4 with 1-2 g/l nonionic detergent
and heat-set for 30-60 seconds at 190-185ºC before dyeing. Solid or
contrast effects in full depths should be dyed by a two-bath method for
improved fastness. The polyester component is dyed first (by carrier or high-
temperature method) as basic dye may bleed during disperse dyeing,
especially at high temperature. The polyester should be dyed slight heavily
to allow partial transfer of disperse dyes to acrylic during second stage of
basic colour dyeing. An intermediate scour with 0.5% nonionic detergent for
20 minutes at 80ºC removes stains of disperse dyes and residual carrier.
Reserve, shadow and contrast effects can be obtained by dyeing acrylic in
full depth. Excellent reserve of the polyester component can be obtained by
dyeing acrylic component with selected basic dyes at boil. On the other
hand, pale to medium depths of selected disperse dyes can be dyed on
polyester with satisfactory reserve of the acrylic fibre using a
methylnaphthalene carrier at boil.
10.6.5 Dyeing of AB-blends

Nylon-acrylic blends used for sportswear, blanket, etc. have wool-like handle
and appearance, but better tensile strength and abrasion resistance. Blends
of acrylic with wool are less durable, but more bulky than nylon-acrylic
blends. They have better dimensional stability and abrasion resistance than
all-wool fabrics. Acrylic-cellulosic blends are the most important of the
acrylic fibre blends.
Blends of AB type are of more interest for reserve and contrast effects
because both components are dyeable with ionic dyes and good solidity can
be obtained. Though either component may be reserved, it is usual to
reserve acrylic fibre using anionic dyes. A wide range of bright contrast can
be achieved as the fibre carrying opposite charge very selectively adsorbs
the ionic dyes. However, opposite charges of the two dyes leads to
incompatibility in one-bath dyeing and an appropriate anti-precipitant should
be used.
Nylon-acrylic Blends
Nylon-acrylic blended fabrics may be dyed with selected acid and basic
dyes, added separately with an appropriate anti-precipitant. The dyebath
contains 3% acetic acid and 5% Glauber’s salt. The temperature is raised
slowly to 80-85ºC and held for 15-30 minutes for exhaustion of acid dyes.
The temperature is raised to boil and dyeing is continued for 60-90 minutes
at boil. The dyebath is cooled to 70ºC before release.
In one-bath two-stage process, the acrylic component is dyed first with
basic dye at boil with 3% acetic acid. The fabric is slowly cooled to 70ºC and
800
pH is adjusted to 2-2.5 with sulphuric acid. The 1:1 metal-complex dyes are
then added with anti-precipitant (alkylamine polyoxyethylene) and the nylon
component is dyed at boil. For 1:2 metal-complex dye, the opposite
sequence is preferred. The dyebath is set with selected 1:2 metal-complex
dyes, ammonia and anionic type anti-precipitant. After exhaustion on nylon
at boil, the dyebath is cooled to 80ºC and the acrylic component is dyed in
the usual way.
For optimum fastness and to avoid the risk of precipitation, two-bath
method is preferred. The basic dye is applied first at boil and the nylon
component is dyed in a separate bath with 1:2 metal-complex or neutral-
dyeing acid dyes at 80-85ºC.
Wool-acrylic Blends
Wool-acrylic blends can also be dyed with selected anionic and basic dyes,
either at pH 2-2.5 for 1:1 metal-complex dyes or at higher pH for neutral-
dyeing acid and 1:2 metal-complex dyes. 1:1 metal-complex dyes are more
compatible with basic dyes due to their zwitterionic character at low pH.
Mild cationic alkylamine polyoxyethylene form water-soluble complexes with
anionic dyes preventing precipitation in the presence of basic dyes.
However, the alternate method of improving compatibility by complexing
basic dyes with anionic retarder gives better control of dyeing rate and
minimises staining on wool. The staining of wool by basic dyes is favoured
at the early stage of dyeing below 80ºC. As the boil is approached, transfer
of basic dyes from wool to acrylic proceeds, thereby wool exerts a retarding
action. The degree of wool staining depends on dyeing conditions and is
minimised by dyeing for at least one hour and at pH not higher than 5. Wool-
acrylic blends may be dyed in pale shades by setting dyebath at 50ºC with
2% acetic acid (pH 4.5), 5% salt, 1-2% anionic retarder and 0.5-1% alkanol
polyoxyethylene. The anionic and basic dyes are added at short interval.
The temperature is raised to 90ºC over 45 minutes, held for 15 minutes,
again raised to boil and continued for 60-90 minutes. Better compatibility
may be attained in medium depth by adding anionic dyes in the starting bath
and treating for 15-30 minutes at 80ºC. This is followed by addition of basic
dye, retarder, acid (pH 4.5). The temperature is raised to boil. After
completion of dyeing, the fabric is cooled to 70ºC and scoured with nonionic
detergent.
In the two-bath process, the acrylic is dyed first by adding basic dyes,
sufficient acetic acid to bring pH to 4.5-5 and a cationic retarding agent. The
temperature is raised to boil, taking care in the critical range of 80ºC-100ºC.
If the wool is heavily stained, it can be cleared in a bath containing 3 g/l
sodium dithionite at 60ºC followed by rinsing. Fresh liquor is then made up,
the wool is dyed in the normal manner with the appropriate dyes, and after
cooling to below 70ºC it is taken out.
801
High exhaustion, fixation and fastness on both wool and acrylic fibres
(50:50 blends) were obtained using reactive cationic dyes containing
monoflurotriazine group [40].
Acrylic-cellulose Blends
These blends may be dyed in two-bath method using basic dyes for acrylic
component and then vat or reactive dyes for cellulosic component. The
selected vat dyes should show minimum staining on acrylic. The vinyl
sulphone reactive dyes are stable to cross-dyeing with basic dyes at pH 5,
which can be utilised for one-bath two-stage process. The reactive dyes are
first applied and the alkaline fixation bath is then subsequently adjusted to
pH 5 with acetic acid. The acrylic component is then dyed with basic dyes in
the usual way.
Disperse dyes have limited fastness on acrylic. Acrylic-cellulosic fibres can
be dyed in pale depths most economically by one-bath application of
disperse and direct dyes. The direct dyes should show satisfactory
exhaustion under mild acidic conditions. The dyebath is set at 50ºC with 1
g/l anionic dispersing agent, 0.5 ml/l acetic acid, disperse and direct dyes.
The temperature is raised to boil over 30-45 minutes and dyeing is
continued for 30-60 minutes. The temperature is lowered to 70º-80ºC. 5-
10% (o.w.m.) Glauber’s salt is added and direct dye is exhausted at that
temperature.
The direct and basic dyes can be applied on acrylic-cellulose blends by
one-bath method. The dyebath is set at 40ºC with 1-2 g/l alkanol
polyoxyethylene (anti-precipitant), acetic acid and sodium acetate buffer (pH
5-6) and direct dyes. 5-10% (o.w.m.) Glauber’s salt is added and the
temperature is raised to 80ºC and held for 15 minutes. The basic dyes and
anionic retarder are added. The bath is heated to boil and continued for 60-
90 minutes.
Acrylic-cellulose blends can be dyed in medium to heavy depths with
lesser risk of incompatibility but by lengthy two-step procedure, first with
basic dyes in the usual way, then by direct dyes. After dyeing with basic
dyes, the temperature is lowered to 80ºC, the direct dyes and salt are added
and the dyeing is completed in 60 minutes at 80ºC. The two-bath sequence
is same, except pH during dyeing with basic and direct dyes are 5 and 7
respectively.
10.6.6 Union Dyes

Several dye manufacturers have produced mixed dye systems especially for
printing blended fabrics, but many of them can be used for dyeing also. The
main problem of such mixtures of different dye-classes is that they can give
solid shades on specific blend-ratios. When the relative quantities of two
802
components in a blend are changed, one component is deeply dyed and the
solidity of shade is hampered.
Some of the mixed disperse-reactive dyes introduced in the market were:
1. Resocoton dyes (Bayer), mixtures of Resolin disperse dyes and
Levafix P/PA reactive dyes marketed in 1973 [41].
2. Remaron dyes (Hoechst), mixtures of Samaron disperse dyes and
Remazol reactive dyes.
3. Naviron dyes (IDI)
4. Dispersol PC/Procion PC dyes (ICI) containing disperse dyes soluble
in mild caustic soda so that the unfixed dyes can be removed during
washing leaving no stain on cellulosic or polyester component.
5. Dispersol T/ Procion T dyes (ICI) containing disperse dyes similar to
Dispersol PC, but fixable by Thermofix method and acid-fixable
reactive dyes, Procion T.
6. Procilene dyes (ICI) are mixtures of to Dispersol PC and Procion T
dyes.
Some of the disperse-vat dyes mixtures introduced in the market were:
1. Cottestren dyes (BASF)

2. Teracoton dyes (Ciba-Geigy)
Some of the disperse-metal-complex/acid dyes mixtures introduced in the

market were:
1. Lanastren dyes (BASF)

2. Teralan dyes (Ciba-Geigy)
Union dyes have lost importance in the market as fabrics of various blend
ratios are simultaneously being used.
Being thermoplastic in nature, synthetic fibres require high temperature for
dyeing. Their dyeing methods are comparatively simple, but dyeability varies
considerably with their morphology which, in turn, depends on the previous
history of the materials. The materials from various batches of fibre shows
distinct differences in dyeability. The suitable dye-classes are also limited.
The commercially important synthetic fibres, polyester, nylon and acrylic
fibres require three distinctly different dye-classes, namely disperse, acid
and basic dyes respectively for successful dyeing. Another popular outlet for
synthetic fibres is blending with natural fibres. Nevertheless, blends of such
fibres of distinctly different physical and chemical properties have created
severe problems for the dyers. Each blend is to be carefully judged and
suitable dyeing processes are to be adopted. A number of alternate
processes are suggested, but complete satisfaction may be difficult to
achieve.
803
The best way to solve the problems of dyeing of blended materials is to

develop a dye, which can be applied on fibres of different chemical
compositions. A universal disperse-reactive dye having dichlorotriazine
reactive group has been developed from a sequence of reactions using a
yellow acid dye (C.I. Acid Yellow 34). Under neutral condition, the dye can
be applied on polyester, nylon and wool fibres. When pH is adjusted to 9, it
can dye cotton, but in pale shades only. By adding dimethylethylenediamine
in the dyebath, acrylic fibres can be dyed at pH 5. Except on cotton and
acrylic, light and washing fastness properties, in general, were moderate to
good [42].
REFERENCES:
1. H.D. Jordan. 1969, Bayer Farben Revue, No. 15.
2. P. Ackroyd. 1974, Rev. Prog. Coloration, 5, 86-96.
3. Disperse dyes – sensitivity to metal ions in process water, Technical
Information Bulletin No. 13, (Mumbai, India: Jaysynth Dyechem).
4. Case of anomalous and abnormal fading with disperse dye
combinations, Technical Information Bulletin No. 23, (Mumbai, India:
Jaysynth Dyechem).
5. H. Leube and H. Uhrig. 1974, Canadian Textile Journal, March issue.
6. Report of the Committee on the dyeing of disperse dyes. 1964, JSDC,
80, 237.
7. Report of the Committee on the dyeing of disperse dyes. 1977, JSDC,
93, 228.
8. D. Blackburn and V.C. Gallagher. 1980, JSDC, 96, 237-245.
9. P.S. Collishaw, M.J. Bradbury, J.A. Bone and R.F. Hyde. 1998,
Colourage Annual, 117-125
10. D.M. Nunn (Eds.). 1979, The Dyeing of Synthetic-polymer and Acetate
Fibres (Bradford, UK: SDC).
11. J.F. Dawson. 1978, Rev. Prog. Coloration, 9, 25-34.
12. M. L. Williams, R. F. Landel and J. D. Ferry. 1955, J. Amer. Chem. Soc.,
77, 3701.
13. W.C. Ingamells. 1980, JSDC, 96, 466-474.
14. E.I. Valko. 1972, Rev. Prog. Coloration, 3, 50-62.
15. A. S. Fern. 1955, JSDC, 71, 502.
16. S. Shakra, H.L. Hanna and A. Hebeish. 1979, Die Angewandte
Macromolekulare Chemie, 75, 53-62.
17. A.N. Derbyshire.1974, JSDC, 5, 273-280.
18. Terenix dyes on polyester, Technical Information Bulletin No. 02,
(Mumbai, India: Jaysynth Dyechem)
19. J W Gibson. 1979, Textile Chemist and colourist, 11, 241-245.
804
20. Application of Terenix dyes by Thermosol process on 100% PES fabric,

Technical Information Bulletin No. 19 (Mumbai, India: Jaysynth
Dyechem).
21. R.V.S. Subramanian. 1973, Silk and Rayon Industries of India, May
issue, 155.
22. D. Joshi. 1998, Colourage, November issue, 49-52.
23. New varieties of polyester in the Indian market, Technical Information
Bulletin No. 35, (Mumbai, India: Jaysynth Dyechem).
24. M.L. Gulrajani. 1975, Colourage, July issue, 23-36.
25. V.B. Gupta and V.K. Kothari (Eds.). 1997. Manufactured Fibre
Technology, (London, UK: Chapman & Hill).
26. W.T. Holfeld and M. S. Shepard. 1978, Textile Chem. and Colourist, 10
(2,3), 26-34, 50-58.
28. I. Razafimahefa, I. Vroman and P. Viallier. 2004, Coloration Technology,
120 (1), 61-71.
29. C.V. Stead. 1975, Rev. Prog. Coloration, 6, 1-6.
30. M.L. Gulrajani. 1974, Colourage, December issue, 25-32.
31. M.L. Gulrajani. 1974, Colourage, April issue, 25-30.
32. I. Holmes. 1983, Rev. Prog. Coloration, 13, 10-23.
33. U. Mayer, and E. Siepmann. 1974, Rev. Prog. Coloration, 5, 65-74.
34. W. Biedermann. 1979, Rev. Prog. Coloration, 10, 1-10.
35. W. Beckmann. 1969, Bayer Farben Revue No. 16, 1-16.
36. Basic dyes on acrylic fibre committee. 1972, JSDC, 88, 220.
37. J. Park and J. Shore. 2000, TCC & ADR, 32 (1), 46-50
38. W. Hiebach. 2005, International Dyer, 3, 33.
39. A.F. Doran. 1999, JSDC 115, 318-322.
40. K. Xie and A. Hou. 2004, Coloration Technology, 120 (6), 307.
41. R.M. Mittal, and S.S. Trivedi. 1983, Chemical Processing of
Polyester/cellulosic blends (Ahmedabad, India: ATIRA).
42. P. Suwanruji, H.S. Freeman. 2004, Coloration Technology, 120 (5), 220.
Chapter
Eco-friendly Textiles 11
11.1 INTRODUCTION
Having a fibre production of approximately 40 million tonnes (1990), the
textile industry is probably the only industry with its suppliers located
throughout the world. Up to 80% of the textiles sold in the market of some
western countries are imported from other countries. Any textile production -
from fibre to garment production - influences the environment to a higher or
lesser degree. Textile industry has responsibility for the impacts of their
activities to the environment. Ecology is the science of the relations of
human beings to their environment. The ecology in textile industry may be
divided into three steps, production ecology, ecology of use and ecology of
disposal of textiles [1].
Looking at 2000 AD and beyond, environmental requirements and related
legislation will be the major driving force for innovation in both the dye
manufacturing and dye application industries. The pressures for the
coloration industry, and the whole chemical industry, from environmentalists
are a disconcerting mix of good sense, passion and in some cases
downright nonsense. Out of this heady brew legislative requirements have
emerged with increasing regularity. The industry has been forced to become
increasingly innovative in order to develop products and processes, which
are more environmentally friendly than the existing ones.
In wet processing, one potential hazard presented by dyestuffs is the form
of dust. Inhaled dust can block the respiratory tract and certain dyes may
induce allergic reaction, which can severely restrict breathing. The problem
can be minimised by employing dust masks and downdraught booths in the
most affected areas, such as dye weighting and dissolving areas. Liquid and
granular forms are better as they do not cause dusting like powders. Liquids,
however, may settle in storage. The granular dyestuffs dissolve more readily
than powders and they flow like liquids. Many dyestuffs are now available in
granular form [2].
The only important mordant dyes are the chrome dyes for wool, almost
universally applied by the after-chrome process. They are still important in
806
the market place due to their extraordinary fastness properties and

economy, especially in full shades of navy and black. However, the release
of chromium is increasingly seen as a severe environmental problem. The
male workers occupationally exposed to Cr(IV), have been found to have
lower sperm count and decreased sperm mobility [3]. The draft regulations
indicate that very little chrome (<100 ppb) in dyehouse effluents will be
tolerated. This is unrealistic because a Cr(III) consumption of 10 mg per day
in food is normal for good health and the natural content of Cr(III) in soil is
about 200 mg/kg. Nevertheless, Cr(IV) is highly toxic, both to human and
aquatic life and steps should be taken to eliminate Cr(IV) from the dyeing
process. Efforts have been made to replace toxic dichromate with fibre
substantive Cr(III)-organic acid, anionic complexes. The oxidative damage
of wool with Cr(IV) will also be reduced. All chrome-dyed shades cannot be
reproduced with reactive dyes – in deep navy and black shades on wool,
reactive dyes cannot provide equivalent fastness because of lower degree
of fixation.
The premetallised dyes are important for wool and nylon, but have similar
problems as with chrome dyes. Many US mills have banned their use.
However, in their absence it is difficult to obtain muted shades of required
light fastness and levelness, especially on nylon [4].
The main objection against dyeing with reactive dyes is the use of large
quantities of inorganic salts to suppress the negative charge at the fibre
surface. Multifunctional reactive dyes are developed to achieve high
substantivity and reactivity. For low salt application, two ranges of reactive
dyes namely Cibacron LS (Ciba) and Remazol EF (EF = environmentally
friendly, Dystar) are developed. An alternative approach to enhance
substantivity is the modification of cellulose by amination, as discussed in
Section 8.4.8.
Although the dyes in general have low toxicity to aquatic life, the dyeing
industry remains under severe pressure to reduce coloured discharge, as a
very large quantity of dyes and pigments is discharged every day (Section
2.9). Table 2-6 shows the percentage loss of dye in the effluent during
dyeing with various classes of dyes. The wool and acrylic dyers tends to be
in the best situation in this respect, as high exhaustion (>90%) is normal
when wool is dyed with acid dyes and acrylic with cationic dyes. The biggest
problems relate to the dyeing of cotton with reactive and sulphur dyes. The
dyeing industry should move to total reuse of its water by several processes
described in Chapter 2. The recovery and reuse of unused dye will be
harder. However, constant efforts are being made and commercial systems
are available to recover and reuse indigo e.g. Romicon and Dorr-Oliver in
the USA [4].
The concept of AOX (Section 2.9) arose from a German drinking water
directive (DIN 38409414, 1987). The consent limit is likely to be as low as
807
2 ppm and as such compounds containing these are to be used carefully.

The products used in the textile industry falling in this category are:
1. Chlorine-containing bleaching agent.

2. Shrink-proofing of wool with chlorine, the most promising alternate
being permonosulphuric acid.
3. Insect-proofing agent for wool.
4. Some types of carriers used in dyeing with disperse dyes.
5. Certain chromophores.
6. Some classes of reactive dyes.
For reactive dyeing of cellulosic fibres, the demand for achieving virtually
100% dye uptake and fixation is urgent. The efforts are to be made to
replace halogen groups with other groups. Alternately, it is necessary to
develop after-treatments that liberate halogens from unfixed dye.
Interestingly, organo-fluorine does not fix in AOX classification as the
presence of fluorine is not detected in the test protocol due to formation of
water-soluble silver fluoride. The manufacturers are thus likely to
concentrate on reactive dyes containing vinyl sulphone and fluoro-
heterocycles.
Considering the increasing costs of using and disposing of water, attention
was moved towards non-aqueous dyeing systems. Unfortunately, most of
the organic solvents suitable for the purpose are chlorinated hydrocarbons,
which are now subjected to absorbable organohalogen (AOX) controls.
In ITMA 1991, the announcement and demonstration was shown for a
new method of dyeing from an environmentally safe solvent, supercritical
carbon dioxide. At the triple point (for carbon dioxide around -60°C and
0.5 MPa or 5 atmosphere) all three common forms, gas, liquid and solid,
may coexist. Above the triple point, an increase in temperature drives liquid
into the vapour phase, whilst an increase in pressure drives vapour back
into liquid, until the critical point (for carbon dioxide 31°C and a pressure of
7.3 MPa). At this point, if the gas is heated above its critical temperature, it
cannot be liquefied, whatever, high the applied pressure, it retains the free
mobility of the gaseous state, but with increasing pressure its density will
increase towards that of a liquid. This highly compressed gas is called a
supercritical fluid. A supercritical fluid can be defined as a substance above
its critical temperature and pressure. Under these conditions, the fluid has a
unique property, in that does not condense or evaporate to form a liquid or a
gas [5]. Solvating power is proportional to density, whilst viscosity is
comparable with that of a normal gas. Consequently, the fluid has
remarkable penetrating properties. Although several substances are useful
as supercritical fluids, carbon dioxide has been most widely used. As a
solvent, supercritical carbon dioxide shows ideal properties. In dyeing,
808
supercritical carbon dioxide gives the option of avoiding water discharge. It

is cheap, recyclable, non-toxic and non-flammable. Its production does not
add to the greenhouse effect, because it is obtained as a by-product from
fermentation and ammonia synthesis. Its high solvating power cause
dissolution of disperse dyes. Reduction clearing is not necessary after
disperse dyeing of polyester from supercritical carbon dioxide. The dyestuff,
which is not adsorbed by the substrate, can be collected and reused. No
other chemical is required for dyeing. However, the process demands
special vessel engineering as very high pressure is involved.
The advantages of supercritical carbon dioxide processing are [6]:
1. Reduce/eliminate water and auxiliaries.

2. Rapid processing.
3. Potential for reduced energy consumption.
4. Mild critical properties (PC = 73.8 bar, TC = 31.1°C).
5. Use of non-toxic and non-flammable carbon dioxide, which is also
cheap and abundant.
6. Carbon dioxide can be recycled.
The possible fields of application are scouring, bleaching and dyeing of

textile fibres. Most of the dyeing studies have been made on polyester
followed by nylon, wool and silk. The dyeing of cotton is most troublesome.
The study of synthesis of azoic dyes on cotton has showed that no mineral
acid or neutralisation is required and electrolyte requirement is very low.
This opens out the possibility of production of high purity dyes such as those
required for inkjet printing inks [6].
In the presently available machine, polyester can be dyed in package
form. The bath is set with pure disperse dye and is run in supercritical
carbon dioxide. The temperature is raised to 130°C and pressure to 30 MPa.
The pressure is gradually decreased to reduce the solubility of disperse
dyes in the supercritical fluid and carbon dioxide is recovered. The time
required is about 30-45 minutes and the levelness is controlled by pressure
reduction program. The dye uptake is about 100% and no reduction clearing
is necessary. However, the full breakthrough of such technology cannot be
achieved unless it could be applied to cellulosic fibres [4]. Dyeing of cotton
and other cellulosic materials with disperse dyes requires pre-treatment of
the natural fibres with a plasticising agent such as polyethylene glycol
(PEG), for enhancing their affinity. Most of the natural dyes are physically
similar to synthetic disperse dyes, in the sense that they are also sparingly
soluble in water. PEG treated cotton can be dyed with natural lipophilic
compounds, such as anthraquinones and their derivatives, in supercritical
carbon dioxide medium at a temperature less than 100°C and pressure 100-
250 bar (1 bar = 0.987 atmosphere) within 30 minutes [7].
809
The solubility of disperse dyes in supercritical carbon dioxide has been

measured to assist the design of the dyeing process. It was found that the
solubility increases with increased pressure, as well as by the addition of
polar co-solvent.
The study of dyeing polyester with C.I. Disperse Blue 27 in supercritical
carbon dioxide showed that the activation energy of dye on polyester is
considerably lower than that in conventional dyeing [8].
Using ammonium carboxylate perfluoropolyether to create reverse
milcellar system in supercritical carbon dioxide media, excellent dyeing of
acrylic fibre was obtained with C. I. Basic Blue 47, even in the absence of a
retardant and/or acid [9].
Tabata et al. [10] has proposed the possible dyeing mechanism for
supercritical fluid dyeing (SFD). Initially, the fibre is swollen in supercritical
carbon dioxide (the affinity of carbon dioxide affinity for PET and PP fibres is
high) and the Tg of the fibre decreases by the plasticisation effect of
absorbed carbon dioxide. The equilibrium sorption of carbon dioxide in the
fibre is achieved in a short time. On the other hand, the hydrophobic
dyestuffs have a relatively high dissolution in supercritical carbon dioxide
and the dissolved dye interacts with carbon dioxide molecules. These dye
molecules can diffuse relatively easily into the amorphous region of the
swollen fibres, and subsequently be adsorbed on the fibre molecules to a
high extent following the partition law. The diffusion inside the fibre may be a
rate-limiting process, but is faster due to higher swelling. The concentration
2 4
of the dye in the fibre amounts to 10 –10 times more than that in the
dyebath. This high affinity is completely different from that in solvent dyeing
systems.
A new type of PET fibre was developed via a high-speed spinning
technique (HSS) and the SFD behaviour was compared with fibre produced
by conventional methods. At lower temperature and pressure, the HSS PET
fibre, which had inherently larger crystallite sizes and lower birefringence,
showed a larger dye uptake. However, when the supercritical conditions
were elevated to 125°C and 230 bar, the dye uptake of both types increased
markedly and the difference in dye uptake between the fibres became small.
This suggests that the swelling of fibres in supercritical carbon dioxide
exceeded a certain degree and then the diffusion of dye molecules was
promoted. The swelling also promoted the rearrangement of molecular
chains. The HSS PET fibre showed slightly higher grades in sublimation
fastness tests [11].
The dyeing apparatus so far used are automatic supercritical extractor,
such as that of Hewlett Packard (model HP 7680T). A simple apparatus for
dyeing in supercritical carbon dioxide has been described [12] and is shown
in Figure 11.1. It consists of a temperature controller (1), a stainless steel
dyeing vessel (2) of 50 ml capacity with a quick-release cap (3), a heating
810
9
5
3
7
4
1 2 6
8
Fig. 11.1 Supercritical Fluid Dyeing Apparatus [8]
jacket (4), a manometer (5), a Varex HPLC carbon dioxide pump (6) and a
cooler for cooling the pump (7). There is a side arm (8) for convective
circulation and a vent (9). The apparatus works up to 100°C and 350 bar.
11.2 TOXICITY
Toxic substances are defined by different agencies as follows:

According to National Institute of Safety and Health, USA., a toxic substance
is any chemical or biological agent, which has the potential to result in short
or long term disease, bodily injury, affect health adversely or endanger the
life of man.
Department of Environment, Canada, says that a toxic substance is one,
which is capable of being disperse in the environment or being transferred
into matter capable of being dispersed, any element or free radical or
combination of elements in manufactured items or in effluents, emissions or
wastes, which can have an immediate or long term effect on environment or
danger to human life.
More specifically, toxicity is the ability of a substance to cause damage to
living tissue, impairment of the central nervous system, severe illness or in
extreme cases, death when ingested, inhaled or absorbed by the skin.
Toxicity is objectively evaluated based on test doses, made on experimental
animals (mice, guinea pigs, dogs, etc.) under controlled conditions. The
tests include exposure of the animals to:
1. Oral ingestion
2. Extended skin contact
3. Inhalation of the material under test
Certain terms are used in this evaluation:
811
1. LD50, the average lethal dose, is that dosage, that when administered
to animals, kills 50% of them. Usually, the exposure is in terms of mg
toxicant/kg of body weight (oral, intravenous or subcutaneous).
2. LC50, the average lethal concentration, is the concentration of a
toxicant in air, which when administered to test animals for a definite
period, kills 50% of them and is expressed as ppm toxicant in air.
3. Poison is any substance that is harmful to living tissues when applied
in relatively small doses.
4. Carcinogen is any substance that causes the development of
cancerous growths in a living tissue. These substances belong to two
classes:
(i) Those that are known to induce cancer in man or animals,
either by occupational exposure in the industry or by ingestion
in foodstuffs.
(ii) Experimental carcinogens are those that have been found to
cause cancer in animals under experimental conditions.
11.3 BANNING OF DYES AND INTERMEDIATES
Before 1970, bladder cancer was common among workers engaged in

handling benzidine in the production of benzidine dyes. In 1971, the major
German colorant manufacturers voluntarily agreed to cease production and
marketing of such azo dyes.
At the beginning of the 1990s, the German Senate Commission for testing
for harmful substances, recommended that the azo dyes should be treated
in the same way as the amines on which they are based, because the azo
dyes can be split under certain physiological conditions to form carcinogenic
amines. In a second amendment in 1994 to the Ordinance on Materials and
Articles, the use of certain azo dyes is prohibited in the manufacture of
materials and articles that are designed for more than temporary contact
with the human body. The specific azo dyestuffs include those, which are
known to be toxic or are suspected to release harmful aromatic amines.
Two German laws have been amended that apply specifically to textile
processing activities. These are the Fourth Federal Emission Protection
Ordinance and the ordinance on materials and articles. The German
Legislation came in force from 30th June, 1996.
The German ordinance on materials and articles has received worldwide
attention because of its fundamental importance for the textile supply chain
and probably the most widely discussed law in the textile sectors in the last
few years. Similar ordinances were adopted in various other countries.
812
Twenty aromatic amines are banned, which are listed below (source: Eco-
Tex Consortium, Germany):
Amines definitely carcinogenic in nature
1. Benzidine
2. 4-chloro-o-toluidine
3. 2-naphthylamine
4. 4-aminodiphenyl
Amines reasonably suspected to be carcinogenic are:
/
5. o-toluidine (3,3 dimethyl benzidine)
/
6. o-dianisidine (3,3 dimethoxy benzidine)
7. p-chloro-aniline
8. 4-chloro-o-toluidine
/
9. 3,3 -dichloro-benzidine
10. o-amino-azotoluene
11. 2-amino-4-nitrotoluene
12. 2,4-toluylendiamine(4-methyl 1-1,3 phenylenediamine)
Other prohibited amines are:
13. 2,4-diaminoanisole (4-methoxy-m-phenylenediamine)
/
14. 4,4 -diaminodiphenylmethane
/ /
15. 3,3 -dimethyl-4-4 -diaminodiphenylmethane
16. p-kresidine (2-methoxy 5-methylaniline)
/
17. 4,4 -methylene–bis-(2-chloroaniline)
/
18. 4,4 -oxydianiline
19. 2,4,5-trimethylaniline
/
20. 4,4 -thiodianiline
Dyes releasing following amines on decomposition are to be phased out:
21. p-amino-azobenzene
22. 2-methoxyaniline.
Textile industries are using a large number of chemicals, which include

various toxic and harmful substances during various processes; a few are
listed below:
1. Cotton growing – banned pesticides such as DDT, Dieldrin, Aldrin etc.

2. Sizing – pentachlorophenol as preservative.
3. Scouring – chlorinated products.
4. Bleaching – sodium and calcium hypochlorite.
5. Dyeing and printing – azo dyes containing/releasing banned amines,
dyes containing traces of heavy metals (e.g. arsenic, lead, cadmium,
813
mercury, nickel, copper, chromium, cobalt and zinc), formaldehyde-

based auxiliaries.
6. Finishing − formaldehyde-based finishes, stain removers containing
chlorinated products.
7. Packing – wooden boxes treated with insecticides.
Approximately 70% of all dyes (belonging to various dye-classes) used in

the textile industries are azo dyes. Due to the toxic nature or amine
(banned)-releasing properties, about 25% of the azo dyes are already
prohibited to manufacture and to use.
According to DIN 55493, pigments are colorants that are not bioavailable
because they are not soluble in the application medium. The Fifth
Amendment in November 1996, excludes poorly soluble pigments with a
molecular weight of over 700. The decision on whether a pigment is
prohibited is based on the official test method.
World-wide forbidden dyes belonging to various dye-classes are listed
below (without any guarantee of completeness).
Direct dyes (amine releasing, 82 dyes):
C.I. Direct Yellows 1 (22250), 24 (22010), 48 (23660).
C.I. Direct Oranges 1 (22370), 6 (23375), 7 (23380), 8 (22130), 10
(23370), 108 (29173).
C.I. Direct Reds 1 (22310), 2 (23500), 7 (24100), 10 (22145), 13 (22155),
17 (22150), 21 (23560), 22 (23565), 24 (29185), 26 (29190), 28
(22120), 37 (22240), 39 (23630), 44 (22500), 46 (23050), 62
(29175), 67 (23505), 72 (29200).
C.I. Direct Violets 1 (22570), 12 (22550), 21 (23520), 22 (22480).
C.I. Direct Blues 1 (24410), 2 (22590), 3 (23705), 6 (22610), 8 (24140), 9
(24155), 10 (24340), 14 (23850), 15 (24400), 22 (24280), 25
(23790), 35 (24145), 53 (23860), 64 (22595), 75 (24411), 76
(24411), 151 (24175), 160 (-), 173 (-), 192 (-). 201 ( -), 215 (24115),
295 (23820).
C.I. Direct Greens 1 (30280), 6 (30295), 8 (30315), 8:1 (-), 85 (30387).
C.I. Direct Browns 1 (30045), 1:2 (30110), 2 (22311), 6 (30140), 25
(36030), 27 (31725), 31 (35660), 33 (35520), 51 (31710), 59
(22345), 79 (30056), 95 (30145), 101 (31740), 154 (30120), 222
(30368).
C.I. Direct Blacks 4 (30245), 29 (22580), 38 (30235), 86 (24115), 91
(30400), 154 ( -).
Direct dyes (without C.I. No.): - (23820), - (30230).
Acid dyes (amine releasing, 24 dyes):
C.I. Acid Orange 45 (22195)
814
C.I. Acid Reds 4 (14710), 5 (14905), 24 (16140), 73 (27290), 85 (22245),

114 (23635), 115 (27200), 116 (26660), 128 (24125), 148 (26665),
150 (27190), 158 (20530), 167 (-), 264 (18133), 265 (18129),
420 (-).
C.I. Acid Violet 12 (18075), Brown 415 (-).
C.I. Acid Blacks 29 (-), 94 (30336), 131 ( -, 132 (-), 209 (-).
Acid dyes (poisonous, 2 dyes):
C.I. Acid Oranges 156 (26501), 165 (28682)
Acid dyes (carcinogenic, 4 dyes):
C.I. Acid Red 26 (16150), Violets 17 (42650), 49 (42640), (without C.I.
No.) - (16155).
Basic dyes (carcinogenic, 8 dyes):
C.I. Basic Yellows 2 (41000), 21 (48060).
C.I. Basic Reds 9 ( -), 12 (48070).
C.I. Basic Violet 16 (48013).
C.I. Basic Blues 3 (51004), 7 (42595), 81 (-).
Basic dyes (amine releasing, 3 dyes):
C.I. Basic Reds 42 ( -), 111 (-).
C.I. Basic Brown 4 (21010).
Azoic colours (poisonous, 3 Components):
C.I. Azoic Diazo Components 20 (37175, Blue BB), 24 (37155, Blue RR),
41 (37165, Violet B).
Azoic colours (amine releasing Components, 8 Nos.):
C.I. Azoic Blue 37.
C.I. Azoic Diazo Components 11 (37085, Red TR), 12 (37105, Scarlet
G), 17 (37270, Orange R), 29 (37255, Red GTR), 48 (37235, Blue
B), 112 (37225, Corinth B), 113 (37230, Dark Blue R).
Disperse dyes (carcinogenic, 1 dye):
C.I. Disperse Blue 1 (64500).
Disperse dyes (allergenic, 26 dyes):
C.I. Disperse Yellows 1 (10345), 3 (11855), 7 (26090), 9 (10375), 23
(26070), 39 (-), 49 (-), 54 (47020), 56 (-), 64 (47023).
C.I. Disperse Oranges 1 (11080), 3 (11005), 76 (-), 149 (-).
C.I. Disperse Reds 1 (11110), 11 (62015), 15 (60710), 17 (11210), 151 (-
).
815
C.I. Disperse Blues 3 (61505), 7 (62500), 26 (63305), 35 ( -), 102 ( -),

106 ( -), 124 (-).
Others:
C.I. Developer 14 (76035, Developer B)
C.I. Ingrain Blue 2/2(74160, Phthalogen Brill. Blue IF3G, Brill. Blue 3G)
11.4 TESTING METHOD

The most important steps of the textile test method for tracing the presence
of banned dyes/intermediates [13] are:
1. Take 1.0 g textile sample carefully. For a rich pattern sample, a

sample must be taken for each shade and each is analysed
separately.
2. Treat with sodium dithionite in citrate buffer (pH 6) in a closed vessel
at 70°C.
3. On completion of the reduction, extract solid phase with tert-
butylmethyl ether on Extrelut 20 (Kieselguhr, Merck).
4. Gently concentrate in a rotary evaporator.
5. Dissolve solvent-free residue in 2 ml methanol.
6. Qualitatively analyse by thin layer chromatography, gas
chromatography, high-pressure liquid chromatography or capillary
electrophoresis.
7. Quantitatively analyse by high-pressure liquid chromatography with a
diode array detector.
8. Prepare qualitative results by at least two independent
chromatographic separation techniques.
The existing limit value is not a legal one. It only exists for analytical
reasons and called recognition threshold value. It is defined as 30 ppm of
arylamine per kilogram of homogeneously coloured sample.
11.5 ECO-FRIENDLY PROCESSING
Legislation is an effective means of bringing the change in mindset.

However, it should be a tool at the last resort. To comply with regulations it
is desirable to take preventive measures that could minimise the
dependency on the end of pipe (effluent) treatment. Effluent treatment is not
a complete satisfactory solution as it converts the undesirable process
waste into some other form leading to problem of solid waste disposal,
816
landfills and contamination of ground water. It is more desirable to put

greater emphasis on reducing pollution through source reduction and clean
technology [14]. Some ways of reducing pollution at source are as follows:
1. Good housekeeping.
2. Substitution of highly dispersible, hazardous or toxic dyes and
chemicals with more eco-friendly products; proposed substitution of
some commonly used polluting chemicals are listed in Table 11.1.
However, most of them are less effective or costly compared to the
conventional ones.
Table 11.1 Some Textile Chemicals and Their Eco-friendly Substitutes [14]
Existing Chemicals Uses Proposed substitutes
Pentachlorophenol, Size preservative Sodium silicofluride
formaldehyde
Nonyl phenyl ethylene oxide Detergent, emulsifier Fatty alcohol ethylene
adducts (APEO) oxide adducts
Silicones and amino-silicones Softener Eco-friendly softeners,
+ APEO emulsifier wax emulsions
Calcium and sodium Bleaching Hydrogen peroxide
hypochlorite
Sodium silicate, phosphorous- Peroxide stabiliser Nitrogenous stabilisers
based compounds
Dichloro and trichloro benzene Carriers in dyeing Butyl benzoate, benzoic
acid
Kerosene Pigment printing Water-based thickeners
Formaldehyde Finishing, dye fixing Polycarboxylic acid, non-
formaldehyde products
Sodium dichromate Oxidation in dyeing Hydrogen peroxide
3. Optimisation of processes, dyes, chemicals and water by studies at

actual sites rather than blindly following manufacturers
recommendations.
4. Modification of machinery and equipment.
5. Effective maintenance.
6. Reuse, recover and recycle.
Adaptation of cleaner technologies using
1. Eco-friendly fibres.
2. High exhaustion dyes.
3. More effective processes like low liquor processing, Right-First-Time,
Right-on-Time and Right-Every-Time processing.
4. Dyes and auxiliaries having low metal (multivalent) content.
5. Low formaldehyde-releasing finishes.
6. Easily biodegradable sizes.
817
7. Enzyme processing.
8. Mechanical finishes.
The advantages of source reduction and cleaner technologies are

decreased waste liability, decreased waste collection, handling and
disposal costs, better economy due to decreased loss of material and
energy, and higher recovery values of wastes.
11.6 ECO-AUDITING
To assure production of eco-friendly textiles, the following precautions are to
be undertaken by the textile industries:
1. To procure dyestuffs and auxiliaries from reputed manufacturers and

to use their latest shade-cards, as they may have already withdrawn
the harmful dyes from their shade-cards and provided alternatives
wherever possible.
2. To insist on providing safety data sheets for the dyes and auxiliaries
procured. These will provide information whether the procured
materials are free from amines and the latest prohibited chemicals.
3. To check the commercial name, C.I. No. of each dye procured, and to
ensure that they do not figure in any red list or banned list.
4. To insist on a liability declaration, while procuring fibres/yarn/grey
fabric/finished fabrics, etc., that these are free from harmful and toxic
materials.
5. To go for eco-audit of the unit which will enable to assess eco-status.
Eco-auditing is a systematic, documented, periodic and objective review of

the facility, operation, practices and products related to meeting
environmental requirements. It is the assessment of the textile unit with
regard to their conformance with norms/criteria stipulated in respect of
certain eco-parameters. The criteria and parameter covered by Eco-Tex
Consortium, Germany, one of the eco-label issuing organisations,
supported, documented and guaranteed evidence covering:
1. The details of sizing and desizing processes.

2. The declarations that no use has been made of carcinogenic and/or
allergic dyestuffs, chloro-organic carriers or biocide finishes.
3. Perspiration, water and saliva (spit) fastness (for baby-wear) of dyed
material.
4. Absence of heavy metals and formaldehyde.
5. pH value.
818
6. No use of banned pesticides.

7. Recyclability and disposal.
The purpose of eco-audit is to establish a continuous chain of information

right from raw materials to the finished textile product. If the eco-auditing
conducted on the textile unit is not satisfactory, the testing of products is
taken up for various eco-parameters in order to ensure their conformance
with the criteria stipulated. The details of the equipment required for the
analysis of various eco-parameters are:
1. To detect dyestuffs releasing aromatic amines (carcinogenic) – High

performance Liquid Chromatography.
2. Presence of pentachlorophenol – Gas Chromatography with Mass
Spectrometer.
3. Presence of pesticides – Gas Chromatography with Mass
Spectrometer, Fourier Transforming Infrared Spectrometer.
4. Free formaldehyde content – UV-visual Spectrophotometer.
5. pH of aqueous extract – pH meter.
6. Fastness to water – Wash Wheel Machine.
7. Fastness to perspiration – Perspirometer.
8. Presence of Heavy Metals – Atomic Absorption Spectrometer and
accessories.
9. Biological Oxygen Demand and Chemical Oxygen Demand of the
effluent – BOD and COD monitors.
Criteria for environmentally hazardous textile dyes of today and more

important for the tomorrow are:
1. Heavy metal contents – zero or below legally prescribed minimum

hazardous substance content. Various eco standards quote maximum
permissible residual metal levels. These figures are a measure of the
amount of free metal that is extracted (by incubating for 1 hour at
40°C) in an acid perspiration solution or saliva solution (Section 6.9.5).
These standards apply not just to chrome afterchrome dyes, but also
to other metal complex dyes.
2. AOX (absorbable organic halogen) content – zero or below legally
prescribed minimum hazardous content.
3. Degree of fixation – maximum, at least equal to the state of art.
4. Wet/wash fastness - maximum, at least equal to the state of art.
Life cycle analysis (LCA) is becoming a common environmental

management tool and a good analytical method for assessing and
optimising the environmental quality of a system over the whole life cycle.
819
The LCA approach covers the whole manufacturing process, from the
product’s birth to the disposal of waste. It assures protected environment by
establishing an eco-balance overview of the inputs, processes and outputs.
11.7 ECO-LABELLING
The environmental labelling of products, as proposed by authorities and
consumer protection organisations, aims at the introduction of such a label
for all kinds of goods including textiles.
The first generation eco-labels and eco-claims, which tended to be
company-specific, were rarely backed up by specific toxicological data. In
view of this unsatisfactory state of affairs, various institutions and
professional associations have drawn up lists of criteria for assessing the
toxicological profile of textile materials as a basis for use of eco-labels.
Meaningful eco-labels of this sort give customers a legal assurance that the
goods purchased contain no toxic substance or that they do not exceed
specific limits, so that they do not represent a health hazard as far as
present knowledge is concerned.
Textile ecology is far too complicated to be covered by just one set simple
criterion. Secondly, a trustworthy label is based on testing and not on
declaration by the company. Thirdly, a proper textile labelling system is not a
barrier to trade. Lastly, it should be based on a set of written rules and
standards [1].
Of the existing many textile eco-labels, some are national labels, whereas
others are so-called private labels. Many countries have their own national
labels such as Blaue Engel in Germany, Öterreichisches Umweltzeichen in
Holland, Nordic Swan in Scandinavia and Eco-Mark in India. Such national
labels are only of some significance in the countries of origin. The important
private eco-labels are:
1. ECO-TEX (Eco-Tex Consortium, Germany), based on auditing and

analysis of products and processes.
2. OEKO-TEX, based on tests on the finished products.
3. GuT, essentially a life-cycle analysis protocol for carpets.
4. GUW, seal of eco-friendly Furnishing Fabrics Association.
5. UPF (Ultraviolet Protection Factor) label by TUV Rheinland for sun
protection materials.
Probably, the most widely used textile eco-label is the Oeko-Tex Standard
100, the label of the International Association for Research and Testing in
the field of Textile Ecology founded by Austrian Textile Research Institute.
The Oeko-Tex Association currently comprises test institutes from 12
820
European countries along with associated laboratories in the People’s

Republic of China, in Turkey and the USA. Each of the independept national
institutes has exclusive rights to award the Oeko-Tex label and to perform
related tests and inspections. These members follow one uniform testing
method worldwide. The label or mark states that the textile product or
accessory has been tested for harmful substances according to the
conditions specified in this standard. The standard is applicable to textile
and leather products. The objective is to market products, which do not
contain substances detrimental to health. The products have been classified
into four groups according to their contact with human skin, namely:
Class I: Products for babies upto the age of two years old.
Class II: Products having direct contact with skin, such as blouses, shirts
and underwear.
Class III: Products not having direct skin contact, such as skirts, trousers
and jackets.
Class IV: Furnishing and decorating materials.
One of the main features of the scheme is the test procedure for
chemicals associated with dyeing processes and for dyes themselves. Thus,
for each product group, there are limiting values of extractable heavy metals
(EHM). Limiting values and fastness properties in Oeko-Tex Standard 100
are shown in Table 11.2 [1].
Table 11.2. Oeko-Tex Standard 100 limits
Parameter/ compound Product class

I II III IV
pH value 4-7.5 4-7.5 4-9 4-9
Formaldehyde 20 75 300 300
Antimony 5.0 10.0
Arsenic 0.2 1.0
Lead 0.2 1.0
Cadmium 0.1 0.1
Chromium 1.0 2.0
Chromium (VI) Under detection limit1
Cobalt 1.0 4.0
Copper 25.0 50.0
Nickel 1.0 4.0
Mercury 0.02 0.02
Pesticides2 0.5 1.0
Contd.
821
Table 11.2. Contd.
Parameter/compound Product class

I II III IV
PCP/TeCP 0.05 0.5
3
Banned dyes Not used
Chlorinated organic 1.0
carriers
Biocidic and flame
retardant finishes None
Colour fastness (Staining)
Water 3
Acidic perspiration 3-4
Alkaline perspiration 3-4
Rubbing, dry4 4 4 4 4
Rubbing, wet4 2-3 2-3 2-3 2-3
Emission of volatiles
Aromatic 0.3 0.3
hydrocarbons
Organic volatiles 0.5 0.5
Odour No abnormal odour5
Notes for Table 11-2:
Extractable quantities are in ppm., fastness in grades.
1
Detection limits, 0.5 ppm for Cr (VI), 20 ppm for arylamines, 0.006% for
allergeneous dyes (using TLC techniques).
2
Total pesticides incl. Pentachlorophenol (PCP)/2,3,5,6 tetrachlorophenol
(TeCP).
3
Cancerogenes, allergeneous dyes and dyes with cleavable arylamines.
4
For pigment, vat or sulphur dyes, rubbing fastness of 3 (dry) and 2 (wet)
acceptable.
5
No odour of mould, high-boiling fraction of petrol, fish, aromas or
perfumes.
To achieve a better environmental performance of a company and of

verifying and showing them to the public, an environmental auditing and
certification scheme, namely Öko-Tex Standard 1000 has been developed.
The aim of Standard 1000 is an evaluation of the environmental
performance of textile sites and products, and to document independently
822
that certain environmental measures are undertaken and a certain level is

achieved.
11.8 NATURAL DYES
The discussion about possible replacement of synthetic dyes by natural

dyes is often not based on scientific facts, but clouded with other
considerations about toxicity of synthetic dyes, particularly during
production, and the recent craze for using natural products. A systematic
study [15] showed that the large-scale use of natural dyes is not feasible
and the present processes of application of natural dyes need optimisation
from the point of view of economy and ecology. Considerable variations
occur from batch to batch and the recipe formulation and tone adjustments
are more difficult than synthetic dyes. Frequent redyeing adds to the cost.
Fustic, safflower, madder, and various other types of natural sources have
been known to be used to dye various natural fibres like wool, cotton, silk,
etc. since man first started colouring his clothes. By mid−19th century there
was a vast range of colours that could be obtained.
Gradually these dyes were replaced by synthetic dyes because of their
limited shades and poor fastness properties, and lack of information
regarding the methods to improve the fastness and colour value. On the
other hand, synthetic dyes were cheaper, readily available, had a wide array
of colours, easy to apply and better fastness properties.
Two hundred years or more ago, production of crops such as indigo (and
woad), weld and madder was based on labour-intensive agronomy and
time-consuming downstream manufacturing processes for preparing the dye
were necessary. The trade of natural dyes began to decline in the second
half of the 19th century and now 100 years later, many of the dyes that were
once commonplace are little known and difficult to obtain. Many of the plants
have not been cultivated for their dyes on any commercial scale for the last
100 years. Indeed, the original cultivation variety in Holland had been lost, a
new variety of similar characteristics has been recently developed.
Cochineal cultivation, which was discontinued in Central America, has
survived in Peru and Canary Islands. Despite this success, the re-
establishment of some of the old sources of these dyes is not possible and
many old dyes are rarely seen. Newer sources are gradually becoming
available. Biotechnological routes, like use of microorganisms and cell
cultures, are being utilised for manufacture of natural dyes like indigo,
alizarin, etc. Although such dyes as madder, cochineal, fustic, brazilwood,
sanderswood, cutch, indigo, logwood and weld are obtainable, they are
relatively expensive and retailed in small amounts.
823
The current worldwide awareness about environment has again revived

interests in natural dyes. Synthetic colorants have been cited as causing
skin complaints, illnesses and cancer. Some natural dyes have low level of
toxicity as well. Certain natural dyes may have detectable mutagenic effects.
Some traditional mordants used in dyeing of natural dyes, such as certain
salts of tin and chromium, may be objected on environmental grounds.
Aluminium and iron are relatively innocuous; they are naturally abundant
and can produce excellent results in dyeing.
What attracts people to textiles coloured with natural dyes may be one or
a combination of factors, including a preference for naturalness,
environmental friendliness, harmonising natural shades or just for novelty.
Natural dyestuffs, as the name indicates, refers to all those colouring
matter that are derived or extracted from nature, i.e. either animals or
vegetables (plant extract).
In recent years, considerable research work is being carried out in various
institutes, on the standardisation of the process for the extraction and
application of natural dyes. Efforts are also being made for simplifying and
modifying the existing dyeing techniques to improve the fastness properties,
particularly washing.
The advantages of natural dyes may be summarised as follow [16]:
1. Obtained from renewable resources.

2. No health hazard.
3. No or little chemical reactions are involved during dye preparation.
4. No disposal problems.
5. Harmonised with nature.
The drawbacks are:

1. Poor availability and colour yield.
2. Difficult to standardise and to blend.
3. Poor solubility in water and tedious extraction procedure may be
necessary.
4. Inadequate degree of fixation.
5. Poor brightness and fastness properties.
6. Limited number of suitable dyes.
7. Lengthy dyeing procedure.
8. Poor reproducibility of shade.
9. Water pollution by heavy metals and large amount of organic
substances.
Present requirement of natural dyes is about 10,000 tonnes, which is

equivalent to 1% of the world's synthetic dye consumption.
824
Natural dyes are classified into two groups, namely substantive and
adjective dyes. The substantive dyes require no pre-treatment to the fabric
(e.g. indigo, orchil, turmeric, etc.). The adjective dyes can only dye
mordanted material or with the addition of a mordant to the dyebath. (e.g.
logwood, madder, cochineal, fustic, alizarin, etc.)
Substantive dyes can further be classified as direct (for cotton, e.g.
turmeric, safflower; for wool and silk e.g. safflower), acid (for silk and wool,
e.g. saffron, lac), basic (for silk and wool, e.g. berberine).
Natural dyes can also be classified into monogenetic and polygenetic
dyes. The monogenetic type of dyes produce only one colour irrespective of
the mordant applied along with dye or present on the fibre, whereas the
polygenetic dyes produce different colours according to the mordant
employed (e.g. logwood, alizarin, fustic and cochineal).
Based on the chemical nature of these dyes, they can be classified as
follows:
1. Diarylol methane (turmeric).

2. Carotenoid (saffron, annato).
3. Alkaloids (barberry).
4. Quinonoid (dolu, henna).
5. Flavonoid (French marigold, sandal).
6. Benzoquinone (safflower).
7. Anthraquinone (alroot, moyam).
Natural dyes can further be divided based on their origin into dyestuffs of
animal origin and dyestuffs of vegetable origin. The dyestuffs obtained from
animals, such as cochineal and lac dyes, belong to the former category,
while dyes like indigo and logwood are of vegetable origin.
The major types of natural dyes and their origin have been tabulated by
Hill [17] as shown in Table 11.3.
The fixing agents recommended are alum, stannous chloride, tartaric acid,
copper sulphate, ferrous sulphate, T. R. Oil and potassium dichromate. They
produce different hues/tones with the same dye.
Tannins are used as the natural mordants in the natural dyeing process,
as they can enhance the affinity of different dyes. Tannins are naturally
occurring phenolic compounds and the ones having o-dihydroxy groups
form metal chelates after pretreatment or post treatments of the substrate
with metal salts. Tannin-metal salt combination, rather than the tannins
themselves, can be considered as the mordant for natural dyes. Some
important raw materials for tannins are oak bark and wood (Quercus
infactoria), pomegranate rind (Punica granatum), cutch (Acacia catechu),
etc.
825
Presently efforts are being made to apply natural dyes on various

synthetic fibres, but so far this has met with limited success [18].
Table 11.3 Major Types of Natural Dyes and Their Origin
Chemical class Colouring matter Origin Colour obtained
Vat dyes
Indole Indigotin Woad, indigo Blues
Quinone Juglone Walnut Browns
Mordant dyes
Anthraquinones Alizarin Madder roots Reds,
oranges, browns
Pseudopurpurin Madder roots Reds,
oranges, browns
Munjistin Munjeet stems Reds,
browns, maroons
Laccaic acids Lac insects Reds, purples,
Maroons
Flavoid tannins Catachin Cutch Browns, greys
Flavone Luteolin Weld Yellows, khaki
Flavonol Quercetin 50% of all plants Yellows, khaki
Anthocyanins Cyanidin Elderberries Purples
Neoflavanoidones Haematoxylin Logwood Violets, blacks
Brazilin Brazilwood Reds, purples
Isoflavanoid Pterocarpin Sanderswood Oranges
Direct dyes
Carotinoid Curcurmin Turmeric Yellows
Crocin Saffron, gardenia Yellows
Alkaloid Berberine Mahonia wood Yellows
Orinol Orcein Orchil Purples
Benzoquinone Carthamine Safflower Pinks
Reactive dyes
Depsides Atranorin Lichens Fawns
Despidones Salazinic acid Lichens Browns
826
REFERENCES:
1. E. Zippel. 1998, Oeko-Tex labelling of textiles In: Proceedings of
Ecotextile '98 - Sustainable Development, Bolton, UK, pp. 197-210.
2. K. Parton. 1998, JSDC, 114, 8-10.
3. V.A. Shenai. 2002, Colourage, XLIX (2), 31-36.
4. D. Lewis. 1997, JSDC, 113, 193-196.
5. M.A. McHugh and V.J. Krukonis. 1994, Supercritical Fluid Extraction:
nd
Principle and Practice, 2 Edn (Oxford, UK: Butterworth-Heinemann).
6. D. Hinks and N. Punrattanasin. 2004, In SDC Symoposium on Reactive
Dyes: A Celebration of 50 Years of Innovation at Manchester (UK) on
14-16 April.
7. M. Mukhopadhyay and N. Bhattacharya. 2001, Colourage, XLVIII (8),
21-28.
8. A. Hou and J. Dai, 2005, Coloration Technology, 121 (1) 18.
9. J.H. Jun, K. Sawada, T.Takagi, G.M. Kim, C.H. Park and M. Ueda.
2005, Coloration Technology, 121 (1), 25.
10. I. Tabata et al. 2001, Coloration Technology (formerly, JSDC), 117, 346-
351.
11. Y. Kawahara et al. 2001, Coloration Technology, 117, 266-269.
12. A.S. Özcan et al. 1998, JSDC, 114, 169-173.
13. A. Geisberger. 1997, JSDC, 113, 197-200.
14. Y.S. Asolekar (co-ordinator). 2000, Environmental Problems in
Chemical Processing of Textiles, NCUTE, I.I.T. Delhi, India.
15. U. Sewekov. 1995, Melliand Textilber., 76, 330.
16. M.L. Gulrajani, and D. Gupta. 2001, Dyeing and Printing with Natural
Dyes, NCUTE-workshop at I.I.T. Delhi, India, September 3-5.
17. D.J. Hill. 1997, Rev. Prog. Coloration, 27, 18-25.
18. U. Brückner et al. 1997, Textilveredlüng, 32 (5/6), 112.
Index
Absorbency test 187 Banned amines, chemicals, dyes

Acetate fibres 17 812
dyeing 723 Basic dyes … Cationic dyes
Acid dyes 375, 632 Barré 723, 741
classification 632, 744 Baume 170
application 634, 744 Beam dyeing machines 427, 445
chemical 632 Beer's law 337
equalising 634, 640 BEN-IMPACTA 279
fast 636 BEN-INJECTA 152
milling/supermilling 636, 641 Benzidine 498
Acrylic fibres 32 Benzenoids 331
dyeing 757 Bio-polishing 149
constant temperature Bleaching
methods 770 chlorite 286
rapid dyeing methods 771 combined 283
theory 764 combined scouring 285
Activated carbon 71 enzymatic 295
Activation energy of dyeing 397 flax 302
Adsorption isotherm 384 hydrogen peroxide 262
Affinity 359, 398 activators 270
Aniline black 598 batch 273
Antidiazotates 609 combined hypochlorite
Anti-precipitant 757 283, 296
AOX 57, 807 continuous 276
APEO 182, 816 stabilisers 263, 267
Aramid fibres 30 semicontinuous 275
Auxochrome 330, 333 strength 264
Azobenzene 334 hypochlorite 255
Azoic colours 376, 600 estimation 257
application methods 612 process 260
colour salt/double salts 609 jute 299
Azoic coupling components 603 knitted fabric 296
Azoic diazo components 606 peracetic acid 293
diazotisation 608 silk 309
Bast fibres 12 wool 303
retting of 12 bio-method 306
828
ferrous mordant 307 Lovibond 344

Blended materials 776 Colour index 372
dyeing of Colour
acetate-nylon 791 and chemical constitution 329
acrylic-cellulose 800 resonance and molecular
cotton-viscose 780 orbital theory 334, 335
nylon-acrylic 799 Colour order systems 355
nylon-cellulose 789 Combined preparatory processes
nylon-wool 788 191
polyester-acrylic 798 Combi-steamer 157, 278
polyester-cellulose 794 Copolymer 3
polyester-nylon 791 Copper number 188
polyester-wool 791 Cotton 9
silk-cellulose 785 impurities in 14, 132
wool-acrylic 800 Cuprammonium fluidity 188
wool-cellulose 783 Cyanuric chloride 521
wool-silk 781 Cylinder and conveyor dryers
Blue wool standards 367 483
Bluing 311
Defoamers/defoaming agents
Cationic dyes 375, 757 128
chemical class 759 Degree of polymerisation 2
compatibility value 766 Denim processing 579
dye saturation factor, 764 Desizing 150
fibre saturation value, 764 acid 154
migrating 761 chlorite 159
modified 760 bromite 159
Cationic fixing agents 512 efficiency of 163
Caustic boil 177 enzyme 155
Cellobiose 10 hypochlorite 158
Cellulose acetate fibres 17 peroxy 160
Centrifuge……hydroextractor rot 154
Chroma 354 Detergents 112
Chromaticity-coordinates 349 evaluation of 121
Chromaticity diagram 350 theory of 115
Chrome dyes 655 Diffusion coefficient 396
chemical classes 656 Diffusion models 388
dyeing methods Direct dyes 374, 495
afterchrome 661 chemistry 496
chrome mordant 659 classification 508
metachrome 660 dyeing
theory 662 after-treatments 510
Chromophore 330 methods 509
CIELAB/CIELUV 352 stripping 513
Colorimeters 343 substantivity 501
829
theory 506 anaerobic process 74

non-benzidine 498 biological 74
Disperse dyes 377, 701 coagulation 66
chemical structures 713 membrane separation 78
classification 707 oxidative processes 68
dyeing methods 724, 739 treatment plant 82
rapid 711 various effects of 56
theory 718 Emulsifier
v number 709 characteristics of 108
Dispersing agents 126, 720 selection of 107
Dominant wavelength 351 Emulsions 105
Donnan membrane effect 646 Enzymes
Dope dyeing… mass coloration advantages of 145
Dye-fixing agents 129 in carbonisation 228
Dyeing in degumming of silk 236
activation energy, chemical in denim processing 581
potential 397 in effluent treatment 76
adsorption isotherm 384 in bleaching 271, 295
affinity 398 in preparatory processes 148,
equilibrium and rate 394 155
fixation mechanism 391 types of, 147
models 388 Excitation purity 351
theory 383
Dyes 328 Fastness (colour) tests 360
bonds with fibre 392 bleaching 370
classification 371 dry-heat/sublimation 371
fastness of 360 laundering 364
identification of 378 light 366
properties of 329 perspiration 369
substantivity 359 rubbing 369
universal 802 saliva 370
washing 363
Eco-auditing 817 Fastran process 412
Eco-friendly processing 815 Fats and waxes 14
Eco-friendly substitutes 816 Fabric dyeing machines 429
Eco-labelling 819 Fibre dyeing machines
Ecosteam method 459 batch 408
Effluents continuous 411
biological effects of 60 Flax 12
BOD and COD 61 Float dryers 487
characteristics of (textile) 62 Fluorescent brightening agents
control of quality of 64 313
treatment methods 66 chemistry and properties 314
adsorption 71 Foam dyeing machines 469
aerobic process 74, 77 Foam applicators 471
830
Foaming agents 127, 470 127, 568, 632, 652, 767

Lightness 354
Garments dyeing machines 466 Lignin 14
Glass transition temperature 389, Longclose dyeing m/c 409
718 Lyocell fibres 17
Grey scales 361
Mangling 479
Hank dyeing machines 414 Mass coloration 16, 695
Hemp 13 acetate, 697
Hue 354 acrylic, nylon 698
Hussong hank dyeing m/c 414 polyester, polyolefins 700
Hydroextractors (centrifuge) 477 viscose 696
suction 481 Maximum application techniques
hydrogen bond 393 280
Hydrogen peroxide 161, 262, Membranes 78
573, 591 Mercerisation
strength of 264 ammonia 204
Hydrophobic bonding 393 barium activity number 206
Hydron blue 596 caustic 192
Hypochlorite of fabric 200
bleaching powder 256 of knitwear 203
estimation of 257 of yarn 198
sodium 256 effects of 194
hot 197
Ingrain dyes 377, 622 slack 203
Ion-exchange resins 46 Metameric objects 349
Ionic bond 394 Metal complex dyes 666
Isoelectric point 1:1 complex 668
silk 688 1:2 complex 672
surfactants 90 migration inhibitor 732
wool 642 Mineral colours 377, 619
Mineral khaki 619
J-box 173 Mordant dyes 375
Jet Dyeing Machines 438 Molar extinction coefficient 332,
fully flooded, softflow 441 338
Jigger 286, 429 Molecular orbital theory 335
Jute 13 Munsell system 356
Keratin - α, β 22 Natural dyes 821

Kier 169 NOBS 270
Kubelka-Munk function 341 Nylon 29
amino end groups 741
Lambert's law 337 differential-dyeing 756
Lanapad R.F. process 410 dyeing of 786
Levelling and retarding agents dyeing
831
acid dyes 744 application methods

disperse dyes 739 batchwise 540
of modified 756 continuous 548
reactive dyes 753 on nylon 753
on silk 690
Obermaier dyeing m/c 409 on wool 682
OECD 182 pad-batch 646
Optical density 338 bond stability 535
Oxidation colours 377, 597 bridge links 520
Oxycellulose 11 chlorotriazines 521
o.w.m. 178 chromophores 518
Package dyeing machines 418 classification 520, 533
Padding mangles 449 halopyrimidine 525
loop-transfer 456 high fixation 528
troughless 454 liquid brand 538
Pectic acid and pectin 14 low-salt 552
Peroxodisulfates/persulfates 160 neutral fixation 527
Phthalocyanines 333, 496, 519, vinyl sulphone 523
607, 622 Resonance theory 334
Pigments 328, 377 Retarders…. Levelling agents
dyeing 623 Reverse micellar system 184
Polyenes 332 Right-First-Time dyeing 530, 712
Polyamide Fibre…nylon
Polyester 31 Sancowad process 469
causticisation 248 Saturator 276
dyeing methods Scouring 134
carrier 724 changes during 168
high-temperature 727 efficiency of 186
of modified 736 of cotton 166
of texturised 735 bio 183
thermosol 730 recipe of 179
dyeing theory 718 solvent 182
EDP 738 of knitted fabric 180
micro 737 of wool 207
Polymer 3 back washing 220
Premetallised dyes…metal emulsion 214
complex dyes fabric 224
Preparatory processes, aims of freezing 219
133 grease recovery 216
machines for fibre 209
Radiation dryers (radio frequency solvent 219
and dielectric) 487 suint 218
Ramie 13 yarn 221
Rayons….viscose of synthetic material 246
Reactive dyes 376, 514 Sequestering agents 49,167
832
Serracant machine 412 amphoteric 95

Shearing and cropping 136 isoelectric point of 96
Silk 24 anionic 92
degumming of 231 biodegradability of 105
with detergent 235 cationic 94
with enzyme 236 cloud point of 103
with soap 233 critical micelle concentration of
dyeing 687, 690 102
weighting of 239 HLB value of 99
wild 25 and properties of 100
Singeing 138 hydrophiles of 96
gas 140 hydrophobes of 97
burner positions 142 nonionic 94
conditions of 143 Synthetic fibres 27
Soaps 110 Bleaching 292, 294
properties of 111 glass transition temperature
Sodium chlorite 286 28, 389, 718
estimation 288 heat-setting of 134, 241
Sodium dithionite/hydrosulphite scouring of 246
253, 307, 566 Synthetic tanning agents/syntans
Sodium hypochlorite 256 752
Sodium sulphide 589
Solubilised pigment colours.. TAED 269
Ingrain dyes TDS 42
Solubilised vat dyes 376, 582 Textile fibres 1
auto-degradation 584 burning tests of 35
dyeing method 584 chemical bonds in 4
Solubilising agents 126 classification of 6
Softeners 129 identification of 33
Space dyeing machines 473 impurities in 14
Speciality hair fibres 23 microscopic test 34
Spectrophotometer 345 properties of 3
forward and reverse optics solubility of 35
347 structure of 2
geometry 346 Thermosoling unit 461
Spiraloda/Autoloda 437 Thiourea/thiourea dioxide 254
Standard depths 362 Time of half-dyeing 395
Stenters 242, 484 Toxicity 810
Substantivity 359 Triphenodioxazine 332, 497, 518
Sulphur dyes 376, 585 Triphenylmethane 332
dyeing methods 593 Tristimulus values 349
solubilised 595 Trithiocyanuric acid (TTCA) 255
Supercritical fluid 807 Twaddell 169
Surfactants/surface active agents
90 Uniform colour scales 352
833
Union dyes 801 crabbing and blowing 223

Universal dyes 802 cuticle, cortex, medulla of 19
damage 649
V number 709 dyeing
Van der Waal’s forces 392 continuous 676
Vaporloc 176 low temperature 679
Vat dyes 376, 555 methods 640, 658, 670,
classification 675
chemical 557 theory 642
application 570 fat/wax in 20
dyeing method felting 228
exhaust 570 fulling/milling 229
pigmentation 570 processing sequence 629
semi-continuous and potting 224
continuous 575 scouring 207
semi-pigmentation 570, shrink-resist 627
575 suint 20
stripping 578
photo-degradation 538 Yoshida forces 508
Viscose 16
Zeolites 46
Warp dyeing machines 426
Washing ranges (continuous)
462
Water
carrier action 742
consumption norms of 53
demineralisation of 46, 48
effects of impurities 41
hardness of 43
estimation 44
removal 46
quality norms 55
Sources 40
Wetting and rewetting agents
123, 568
tests of 187
Winch 432
Whiteness 310
improvement of 311
instrumental assessment of
318
Wool fibres 18
back washing of 220
carbonisation 225

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About the book

Since colour makes textiles attractive, coloration or dyeing has been

About the author

Asim Kumar Roy Choudhury

copious quantity of water, combines it with chemicals and the wastewater is

for their valuable suggestions. I am thankful to my colleague, Dr. P.K.

Asim Kumar Roy Choudhury

CHEMISTRY OF TEXTILE MATERIALS 1

WATER REQUIREMENTS AND TREATMENTS 40

2.11 Textile Effluents 62

PREPARATORY PROCESSES I (CLEANING) 131

4.1 Introduction 131

5.1 Introduction 250

5.2 Reductive Bleaching Agents 252

6.1 introduction 326

7.1 Introduction 402

8.1 Fibre Structure 491

8.2 Dye-classes 493

9.1 Introduction 628

10.1 Introduction 693

ECO-FRIENDLY TEXTILES 805

11.1 Introduction 805

Chemistry of Textile Materials 1

1.2 TEXTILE FIBRES

1.3 FIBRE STRUCTURE

In general, all fibres that are useful in textile applications are

1.4 POLYMER SYSTEM

1.5 ESSENTIAL PROPERTIES OF FIBRE

Monomer 1 Monomer 2 Monomer 3

Symbolic structure of grafted

Fig. 1.1 Symbolic Structures of Different Types of Polymers

contributes to the strength of the fibre by holding crystalline regions

(iii) Strongest and chemically most stable covalent bonds or cross-

1.6 CLASSIFICATION OF FIBRE PROPERTIES

typical classification of such fibre properties with some examples is given

1.7 CLASSIFICATION OF TEXTILE FIBRES

1. Regenerated fibres are manufactured by dissolving natural fibre-

(truly continuous filament) by passing it through a fine orifice called

Figure 1.2 shows classification of textile fibres [3].

1.8 CELLULOSIC FIBRES

Vegetable Animal Mineral Natural polymers Refractory and

Polyamides Polyvinyl Polymerised Synthetic

Substituted Substituted with Substituted with Substituted with

Mono-substituted Di-substituted Mono- Di-substituted

Fig. 1.2 Classification of Textile Fibres

Table 1.1 Classification of Textile Fibres as per Chemical Constitution

1.8.1 Cotton Fibre

present in cellulose, consists of two β-d-glucose molecules joined in the 1:4

1.8.2 Bast Fibres

1.8.3 Impurities in Vegetable Fibres

emulsification with soap at high temperature. The melting point of cotton

Table 1.2 Chemical Constituents of Vegetable Fibres (% on dry wt.)

1.8.4 Rayon Fibres

blending with synthetic fibres. Rayons are resistant to common household

1.8.5 Cellulose Acetate Fibres

When examined under a microscope, acetate fibres show no longitudinal

1.9 PROTEIN FIBRES

Table 1.3 Average Composition (%) of Raw Wool Fibres [5]

increased as analytical techniques have been improved. Thus, the number

fibres show different X-ray diffraction diagrams, corresponding to two forms

subsequent processes. Initially epithelial scales are loosened giving access

1.9.2 Speciality Hair Fibres

Speciality Hair Fibres