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ADVANCES IN REACTIVE DYEING
OF CELLULOSE TEXTILES

By
Dr. Awais Khatri
Dr. Rafique Ahmed Jhatial

Department of Textile Engineering

Mehran University of Engineering and Technology
Jamshoro – 76060 Sindh Pakistan

HIGHER EDUCATION COMMISSION

ISLAMABAD
 Copyrights @ Higher Education Commission
Islamabad
Lahore Karachi Peshawar Quetta

All rights are reserved. No part of this publication may be reproduced, or transmitted, in any
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Project: “Textbook and Monograph Writing Scheme” aims to develop a culture of writing and to
develop authorship cadre among teaching and researcher community of higher education
institutions in the country. For information, please visit www.hec.gov.pk.

HEC – Cataloging in Publication (CIP Data):

Awais Khatri, Dr.
Advances in Reactive Dyeing of Cellulose Textiles
I. Textile Coloration / Textile Dyeing
677.21 – dc23 2015
ISBN: 978-969-417-184-5
First Edition: 2015
Copies Printed: 500
Published By: Higher Education Commission – Pakistan
Printed at HEC – Printing Press
Disclaimer: The publisher has used its best efforts for this publication through a rigorous system
of evaluation and quality standards, but does not assume, and hereby disclaims, any liability to
any person for any loss or damage caused by the errors or omissions in this publication, whether
such errors or omissions result from negligence, accident, or any other cause.

ii
 DEDICATION

This work is dedicated to

Mehran University of Engineering and Technology Pakistan
&
RMIT University Australia

iii
BLANK
 CONTENTS

1. INTRODUCTION ...................................................................................................................... 1
2. CELLULOSE AND COTTON TEXTILES ................................................................................ 2
2.1. Cotton Fibre ..................................................................................................................... 2
2.2. Cotton Polymer and Fibre Polymer System .................................................................... 3
2.3. Properties of Cotton Fibre ............................................................................................... 4
2.3.1. Hygroscopic properties ............................................................................................ 4
2.3.2. Chemical properties ................................................................................................. 4
2.3.3. Thermal properties................................................................................................... 5
2.3.4. Mechanical properties.............................................................................................. 5
3. dye classes for dyeing cellulose .......................................................................................... 5
3.1. Dyeing Cellulose with Anionic Dyes ................................................................................ 5
3.2. Significance of Reactive Dyes ......................................................................................... 6
3.3. Historical Development of Reactive Dyes ....................................................................... 6
4. ENVIRONMENTAL ISSUES .................................................................................................... 7
5. reactive dyes, Dyeing and advancements ........................................................................... 9
5.1. Chemistry of Reactive Dyes and Advancements ............................................................ 9
5.1.1. Bifunctional dyes .................................................................................................... 10
5.1.2. Poly-functional dyes ..................................................................................................... 11
5.1.3. Other developments .............................................................................................. 11
5.2. Dyeing Reaction Mechanisms ....................................................................................... 13
5.2.1. Nucleophilic substitution ........................................................................................ 13
5.2.2. Nucleophilic addition .............................................................................................. 13
5.3. Dye Reactivity ................................................................................................................ 13
5.4. Dye Substantivity ........................................................................................................... 14
5.5. Dye Exhaustion.............................................................................................................. 14
5.6. Dye Diffusion ................................................................................................................. 14
5.7. Dye Migration ................................................................................................................. 14
5.8. Dye Fixation ................................................................................................................... 14
6. Application methods for reactive dyes AND Advancements .......................................... 15
6.1. Batchwise Dyeing .......................................................................................................... 15
6.1.1. Low liquor-ratio dyeing machines .......................................................................... 16
6.2. Pad Dyeing .................................................................................................................... 17
6.2.1. Padders with low padding trough volume .............................................................. 18

v
 6.3. Pad Fixation Processes ................................................................................................. 19
6.3.1. Batching ................................................................................................................. 19
6.3.2. Baking .................................................................................................................... 20
6.3.3. Steaming ................................................................................................................ 21
6.3.4. Eco-control dyeing machine .................................................................................. 21
7. industrial / technical problems AND POSSIBLE SOLUTIONS ......................................... 22
8. future trends in reactive dyeing .......................................................................................... 28
8.1. Developments in Dyebath Chemicals............................................................................ 28
8.2. Chemical Modification of Cellulose ................................................................................ 29
8.3. Emerging Technologies ................................................................................................. 29
9. References ............................................................................................................................ 29

vi
 LIST OF FIGURES

Figure 2.1: The chemical structure of cellulose……………………………………………..…………….2

Figure 2.2: A morphological diagram of the cotton fibre…………………………………………...….....2
Figure 2.3: Scanning electron micrographs of raw cotton fibres…………………………....…………..3
Figure 2.4: The dissociation of cellulose……………………………………………………………...……4
Figure 5.1: Molecular structure of CI Reactive Red 1…………………………………………………...10
Figure 5.2: Molecular structure of CI Reactive Black 5 containing bis(sulphatoethylsulphone)
reactive group…………………………………………………………………………………..11
Figure 5.3: Nucleophilic substitution mechanism……………………………………………………......13
Figure 5.4: Nucleophilic addition mechanism…………………………………………………..……......13
Figure 6.1: Illustration of typical winch and jigger dyeing machines………………………………......16
Figure 6.2: Illustration of a typical ultra-low liquor ratio dyeing machine………………………...……17
Figure 6.3: Illustration of a typical dyeing padder……………………...………………………………...17
Figure 6.4: U-trough and nip dye liquor pad application systems……………………………………...19
Figure 6.5: Küsters trough shapes and sizes with liquor capacity in volume per unit……………….19
Figure 6.6: Illustration of Küsters cold-pad-batch range……………...…………………………………20
Figure 6.7: Diagram of a Monforts continuous dyeing range for drying and baking…………....……20
Figure 6.8: Illustration of a Benninger continuous pad-steam dyeing range …………………...…….21
Figure 6.9: Illustration of a MonfortsEcontrol dyeing range……………………………………….……22

vii
BLANK
 LIST OF TABLES

Table 3.1: Summary of history of leading commercial reactive dyes……………………………………8

Table 4.1: Typical composition of cotton dyehouse effluent……………………………………….........9
Table 5.1: Common reactive groups in order of increasing reactivity…………………………...…….12
Table 5.2: Typical fixation percentages of cotton dyes………………………………………...…….....15
Table 7.1: Industrial / technical problems & their solutions of reactive dyeing
of cellulose fabrics……………………………………………………………………………...22

ix
BLANK
 ABBREVIATIONS AND SYMBOLS

α Alpha
BASF Badische Anilin und Soda Fabrik
BOD Biochemical Oxygen Demand
COD Chemical Oxygen Demand
CI Colour Index
–
Cl Chlorine ion
Co Initial concentration of dye in the dyebath
Cs Concentration of dye in the dyebath sometime later during the process
o
C Degree celsius
D Dye chromophore
g/L grams per litre
h hours
H2O Hydrogen peroxide
–
HSO4 Bisulphate ion
ICI Imperial Chemical Industries
i.e. That is to say
kg kilograms
L Litres
m metres
min minutes
+
Na Sodium ion
–
OH Hydroxide ion
-OH Hydroxyl group
–
O Oxygen ion
-ONa Sodiumoxyl group
pH The power of Hydrogen
% Per cent
: Ratio
s seconds
-SO3Na Sodium sulphonate group
TDS Total Dissolved Solids

xi
BLANK
 PREFACE

Pakistan’s textile manufacturing and processing industry is mainly based on cotton. Therefore,
contents of cotton and other cellulose textiles manufacturing and processing have always been
the major part of the curricula of bachelor and master degree programs of textile engineering and
technology. Moreover, the growth and market sustainability of such processing industry depends
on continuous engineering and technological developments. This monograph focuses specifically
on the fundamental knowledge and recent developments in the dyeing of cotton textiles with
reactive dyes. The studies presented in the monograph will be suitable to be included in the
curricula of any graduate program in the discipline of textile engineering and technology taught at
any university/institute. Moreover, the monograph may be useful for postgraduate studies and
research more as a reference. The commercial aspects of the research presented in the
proposed monograph will also be beneficial for textile processors and industrialists.
Thanks to the Textbook and Monograph Writing Scheme of the Higher Education
Commission Pakistan for making our plan, on publishing a book on the title of this monograph,
successful after a peer-review process. It was a valuable learning experience for us in terms of
drafting a text book, peer-review feedback and advancement of self-knowledge.

Dr. Awais Khatri

Dr. Rafique Ahmed Jhatial

xiii
BLANK
1. INTRODUCTION
Globally, cellulose textiles are the most widely used among textiles made of various natural and
man-made fibers, especially for apparels. Therefore, the manufacturing, processing, coloration
and finishing of cellulose especially cotton textiles are always the key subjects in every textile
graduate program. Almost all textiles are coloured by various methods in order to make them
aesthetically more important and useful. Cellulose textiles are always preferred to be dyed with
reactive dyes due to their wide range of bright colours with excellent colour-fastness results.
However, there have been some efficiency and ecology related issues with such dyeings.
Therefore, there have been a number of developments and advancements into the dyeing of
cellulose textiles with reactive dyes over the past few decades. The proposed monograph will be
addressing such advancements and developments along with the fundamental knowledge. It will
assist in building an understanding of improving dyeing efficiency and reducing environmental
load.

Per capita demand for apparel textiles is projected to grow continuously. Therefore, it
becomes important to find solutions for reducing water use and the discharge of polluting
chemicals. For apparel textiles, the predominant dye-fibre combination is that of reactive dyes
and cellulose [1]. However, of all the dye-fibre combinations, cellulose dyed with reactive dyes
consumes the highest volume of water per kg of the fibre. Moreover, this combination causes the
highest discharge of salts, alkalis, unfixed dye and other organic matter per unit fibre mass [2].
Thus, dyeing efficiency in terms of dye fixation and environment sustainability in terms of effluent
discharge are higher comparing to other dye-fibre combinations. Brief explanation to its reasons
is given in following paragraphs.

Since 1950s, when ICI introduced the first commercial reactive dyes for cotton cellulose,
this dyeclass has become increasingly popular [3]. That is mainly due to high levels of washing
fastness, a wide gamut of bright colours, and versatility for different application methods. The
high fastness to washing of reactive dyes is due to their unique reactive group(s), which form(s)
covalent bonds with the hydroxyl groups of the cellulose under alkaline pH conditions.

The dyes also react with hydroxide ions present in the aqueous dyebath under alkaline
pH conditions. This produces nonreactive hydrolysed dye which remains in the dyebath as well
as in the fibre. In order to obtain the required levels of washing fastness, it is necessary to
remove all unreacted and hydrolysed (unfixed) dye from the cellulose fibre. It is achieved by
‘washing-off’; a series of thorough rinsing and ‘soaping’ steps. Around 50% of the dyeing cost is
related to the washing-off and effluent treatment [4]. The dye remained on the fibre after washing-
off is considered as dye fixed on the fibre. The dye fixation efficiency is typically in the range of
50–80% [2]; i.e. 20 to 50% of the dye necessary to achieve the desired depth of colour is
discharged to the environment.

Reactive dyes are soluble anionic dyes which, in solution, are repelled by the negatively
charged surface of the cellulose fibre. A salt such as sodium chloride or sodium sulphate is added
as an electrolyte to promote the dye transfer (exhaustion) to the fibre[5]. It also supports dye
penetration into the fibre interior (diffusion) which leads to better dye fixation [6]. The amount of
the salt can vary up to 2 kg per kg of the fibre depending on the dye structure, depth of shade and
dyeing method. Once sufficient dye is on the fibre, either by exhaustion (batchwise dyeing
methods) or padding (pad dyeing methods), alkali such as sodium carbonate, sodium bicarbonate
or sodium hydroxide is added to the dyebath to initiate the dye-fibre reaction. The quantities and
composition of the alkali depend on the pH required for the particular type of reactive group of the
dye and the dyeing method.

1
2. CELLULOSE AND COTTON TEXTILES
Cellulose is a polymer made of repeating cellobiose units, each consisting of two glucose
molecules attached end to end. A cellulose polymer may contain a several hundred to over
10,000 glucose molecules (Figure 2.1). Cellulose formation is similar to carbohydrates and
polysaccharides. The difference between cellulose and other complex carbohydrate molecules is
how the glucose molecules are linked together. Cellulose is a straight chain, long and rod-like
polymer, which is usually stable toward degradation into its glucose molecules even by any
enzymatic treatments.

Figure 2.1: The chemical structure of cellulose (source: [7])

Cellulose based textile fibres are the richest class of fibres of naturally occurring
polymers. These include natural cotton, flax, hemp, ramie and jute fibres and regenerated
viscose, cuprammonium, modal, lyocell and bamboo fibres. However, the worldwide total
consumption of cotton fibres is more than 80% among all cellulose fibres. Due to very high
consumption of cotton among all cellulose fibres, an account of the cotton textiles, fibre structure
and properties is presented below.

Cotton fabrics are known to have been in use at least for 7000 years [8]. Although,
numerous synthetic fibres such as polyesters, acrylics, polyamides and polypropylenes have
entered the market over the past 50 years, cotton has still maintained its strong consumer
demand worldwide. Today, cotton textiles represent more than half of the global textile market [5],
and the demand is expected to continue [9, 10]. This dominance of cotton fibre is mainly due to
its natural comfort, performance and appearance.

2.1. Cotton Fibre

Cotton is the purest form of the natural cellulose polymers. The fibre is a single plant cell found as
the seed hair of a genus of the plants called ‘gossypium’ [11]. Like all plant cells, a mature cotton
fibre has a distinct cuticle, well developed primary and secondary walls and a lumen (Figure 2.2)
[12].

Figure 2.2: A morphological diagram of the cotton fibre (source: [12])

2
 The cuticle is the very outside or ‘skin’ of the fibre. It is composed of pectins, protein and
waxes. Therefore, it makes the fibre hydrophobic unless a wetting agent is used. The primary
cell wall is immediately underneath the cuticle. The secondary wall, beneath the primary wall,
forms the bulk of the fibre. Inadequate development of the secondary wall during the growth of
cotton fibres on the plant creates ‘immature’ fibres. If there is no development of the secondary
wall, then the fibre is referred to as a ‘dead’ cotton fibre. The immature and dead fibres tend to
become entangled into small fibrous bundles, called neps, during the mechanical processes for
producing yarns [7, 13]. The immature fibres cannot be dyed to shades as dark as mature fibres
and the dead fibres remain undyed. Therefore, neps can be instantly see on the surface of the
dyed fabrics appearing as white and light spots. The colour contrast between the dyed neps and
mature fibres can be reduced by swelling of immature fibres by mercerising. The primary and
secondary walls are composed of cellulose ‘fibrils’. The fibrils occur in the spiral form at certain
angles to the fibre axis. The lumen is a longitudinally hollow canal in the centre of the fibre.

Micrographs of the raw cotton fibres are shown in Figure 2.3. Mature cotton fibres are
flattened tubes and are highly convoluted. The surface of such fibre enables inter-fibre friction
(cohesiveness) which is helpful in producing fine spun yarns of adequate strength. The
appearance of the cross-section of cotton fibre is bean- or kidney-shaped. The convolutions and
bean-shaped cross-section of the cotton fibre enable cotton apparel to be more comfortable. This
is because the particular structure of cotton fibre is more compatible with human skin and makes
apparel more moisture absorbent [12].

Cross-section Longitudinal view

Figure 2.3: Scanning electron micrographs of raw cotton fibres

(source: BTTG-Shirley Manchester [11])
2.2. Cotton Polymer and Fibre Polymer System
Cotton fibres are composed of cellulose polymers, mostly α-cellulose [13]. The basic molecular
structure of cotton cellulose is shown in Figure 2.1. Its repeating unit is cellobiose. The degree of
polymerisation of cotton cellulose is about 5000 based on cellobiose units [12].

Cotton polymer system is highly crystalline and oriented. Important groups on cotton
polymer (cellulose) are hydroxyl and methylol groups. The presence of abundant hydroxyl groups
and the polymer chain conformation cause intermolecular and intra-molecular hydrogen bonding
that enhances the rigidity of the fibre structure. The existence of van der Waal’s forces is of little
significance.

3
2.3. Properties of Cotton Fibre
2.3.1. Hygroscopic properties
The cotton fibre is hydrophilic and water absorbent [7]. This is because the polar hydroxyl groups
of cellulose polymer attract the polar water molecules. Its porous structure allows ready
penetration of water molecules between the fibrils and into the amorphous regions of the fibre
where they can easily form hydrogen bonds with free cellulose hydroxyl groups. Even the typical
cotton dyes, being quite large molecules, easily penetrate into the accessible inter-fibrillar and
amorphous regions.

The standard moisture regain of cotton fibre is about 8% and rises to around 25–30% at
100% relative humidity, at ambient temperature [7]. Cotton fibre swells with water absorption
because of the swelling of the secondary wall. It is one of the few fibres which gains strength
when wet [12]. This may be due to a temporary improvement in polymer alignment in the
amorphous regions.

2.3.2. Chemical properties

The chemical reactions with cotton cellulose occur mainly due to the activity of hydroxyl groups
and depend on the super-molecular structure. Any reaction is initiated in the more accessible
amorphous regions and at the surfaces of crystalline regions [13]. The reactions can be broadly
classified into two categories: esterification and etherification. Esterification is usually carried out
under acidic conditions. These reactions include nitration, acetylation, phosphorylation, and
sulphation. Acidic conditions hydrolyse the cotton cellulose at the glucoside oxygen atom which
links the two glucose units to form the cellobiose unit (Figure 2.1) [12]. Stronger acids hydrolyse
the cellulose more rapidly. A cotton fibre dissolves completely in a 70% aqueous sulphuric acid
[14]. Etherification, on the other hand, is favoured in an alkaline medium. This reaction is
important for dyeing cotton with reactive dyes. In the presence of even dilute base, cellulose
behaves as a weak acid and ionises to form a cellulosate anion according to the chemical
equation given in Figure 2.4 [15]. This anion is capable of reacting with suitable dyes by
nucleophilic substitution or addition to form covalent bonds [16]. Vickerstaff provided the evidence
–
for reactive dyes forming covalent bond with the cellulosate anion (Cellulose-O )[17].
– –
Cellulose-OH + OH (alkali) Cellulose-O + H2O

Figure 2.4: The dissociation of cellulose

Mercerising is a treatment of cotton with strongly alkaline solutions where fibre lustre,
tensile strength and dye uptake are improved [12, 18]. Such improvements are principally due to
the swelling of cotton fibre and the alignment of poorly oriented fibre polymers during this
treatment. The swelling is fundamentally due to the imbibition of water as a consequence of the
sorption of alkali by the cellulose [11].

Cellulose is readily attacked by oxidising agents, such as hypochlorites, chlorous, chloric,

and perchloric acids, peroxides, dichromates, permanganates, periodic acid, periodate salts, and
nitrogen tetroxide [13]. Oxidation of cellulose can lead to two products: reducing and acidic
oxycellulose. In reducing oxycellulose, the hydroxyl groups are converted to carbonyl groups or
aldehydes, whereas in acidic oxycellulose, the hydroxyl groups are oxidised to carboxyl groups or
acids.

4
2.3.3. Thermal properties
Cotton fibres are heat conductive [12]. Excessive application of heat energy causes the cotton
fibre to char and burn. Heating the fibre generally causes dehydration and decomposition of
cellulose [13]. At temperatures above 150°C, the extent of browning and hardening of the fibres
increases [7]. If processing requires higher temperatures, shorter treatment times are set to avoid
thermal damage.

2.3.4. Mechanical properties

Cotton fibres possess good mechanical properties such as tensile strength and cohesiveness.
This is because they have high molecular weight, crystallinity, the countless, regular, hydrogen
bonds formed between adjacent polymers within the fibre, and fibre surface structure [7, 12].

3. DYE CLASSES FOR DYEING CELLULOSE

Prior to the development of synthetic dyes, natural colourants were only the means of dyeing
textile fabrics. Today, natural dyes are basically only used in handcrafted fabrics. Some niche
boutique fashion ranges also use natural dyes as part of their theme. The volume of such fabrics
is extremely low. Natural colourants have four key weaknesses; they can only provide a limited
range of colours, shades are difficult to reproduce, they have poor fastness to laundering and
have very poor fastness to light.

The synthetic dyes used today provide reproducible and consistent dyeing with broad
shade ranges and light and wash fastness performance values between satisfactory to
outstanding. The manufacture of dyes is almost entirely the domain of major and ethical global
suppliers. In the mid 1900’s some azo-chromogen based colourants were found to be
carcinogenic. Although now banned they have recently reappeared in apparel wear as a result of
supply from illegal or unethical manufacturers. Sustainability audits should include examination of
supplier records.

Today, the available synthetic dye classes for dyeing cellulosic fibres are direct dye,
reactive dye, vat dye, sulphur dye and azoic dye. All of these dye classes have some advantages
(such as shade range, brightness, cost and ease of application but also some limitations (such as
limited shade range, lack of brightness, difficult to reproduce shades from batch to batch and
wash and light fastness) [19]. They may be categorised in two ways: ionic character, and the
main way with which the dye molecules attach to the fibre. The vat, sulphur and azoic dyes can
generally be categorised as nonionic dyes as they are generally water-insoluble in their original
form. The whole molecules of these dyes are mechanically retained within the fibre polymer
system. Direct and reactive dyes are water soluble anionic dyes as their anions are the colour
constituents.

3.1. Dyeing Cellulose with Anionic Dyes

Dyeing of textiles is fundamentally a process of transferring dye species onto the fibre through an
aqueous medium (dye exhaustion) followed by dye penetration into the fibres (dye diffusion).
When cotton fibres are immersed in an aqueous dyebath, the fibre surface acquires an initial
negative charge that is referred to as zeta potential [20]. This is due to a rearrangement of charge
groups at the interface between the fibre and the aqueous environment. Anionic dyes are usually
sulphonated to provide aqueous solubility and possess a negative charge in the aqueous
dyebath. Therefore, there is an electrostatic repellency for the dyes to diffuse through the fibre-
water interface. The only widely used method of overcoming this barrier is the addition of large
quantities of inorganic electrolyte, such as sodium chloride or sodium sulphate.

5
 When an electrolyte is added to the dyebath, it dissociates completely into its cations and
+ –
anions, for example sodium ions (Na ) and chlorine ions (Cl ) in the case of sodium chloride. The
negatively-charged surface of the fibre is suppressed by cations enabling the dye anion to enter
the fibre more readily. The presence of electrolyte anions also assists the dye anion to leave the
dyebath and enter the fibre polymer system due to the repulsion effect [12].

Direct dyes have inherent substantivity for cellulosic fibres. This is attributed to their large
co-planner molecular structure. The dyes are normally applied from an aqueous dyebath
containing an electrolyte. The fibre is immersed into the dyebath containing the dissolved dyes.
The bath is then gradually heated, usually to the boil, and the electrolyte is added for promoting
dye exhaustion and diffusion. The most attractive feature is the simplicity of the dyeing process.
However, a separate cationic after-treatment is necessary for most direct dyeings to enhance
washing fastness of the dyed fibre [21, 22].

The washing fastness standard, even when given a conventional after-treatment, does
not meet the demands for most cellulosic apparel and furnishing materials. Consequently, direct
dyes have been replaced by reactive dyes to a great extent due to better washing fastness of
reactive dyed cotton. The reactive dyes also provide exceptionally bright colours in many hues.
The very good washing fastness of reactive dyes is because they form covalent bonds with the
fibre.

3.2. Significance of Reactive Dyes

Vat dyes have very specific applications especially for industrial apparel fabrics where very high
levels of fastness and resistance to bleaching during laundering are required. Sulphur dyes
present the opportunity for low cost dyeing of a limited colour range particularly for high volume
mass apparel merchandise. The vat and sulphur dyes are insoluble in water. Their application
requires conversion to a soluble form before application. After the dye has been applied a
chemical reaction is used to convert the dye back to its insoluble form. Direct and reactive dyes
are water soluble anionic dyes. Direct dyes are low cost but suffer from lack of brightness and
poor wash fastness when used in dark shades. Their primary use in apparel wear is for pastel
and some medium depth shades. The dominant dye class for apparel is the reactive dyes. This is
mainly due to wide range of bright colours and the dyes are fixed to the fibre by covalent bonding
leading to excellent washing fastness. There are a number of different classes of reactive dye.
The classes are based on the type of the reactive group as well as the number of functional
groups present on the dye molecule. The early reactive dyes were based on mono-functional
dyes. Since then, di- and tri- functional reactive dyes have been developed.

3.3. Historical Development of Reactive Dyes

A variety of attempts have been made in the struggle to obtain the covalent bond formation
between a dye and a fibre. There are two general approaches in this respect: producing a dye
within the fibre, and producing a dye that is reactive towards the fibre. In 1895, Cross and Bevan
achieved a covalent dye-cellulose bond with respect to the first approach [23]. They showed that
cellulose (Cellulose-OH) treated with strong alkali was changed into ‘soda cellulose’ (Cellulose-
ONa). The soda cellulose could be treated with benzoyl chloride to form benzoyl cellulose. The
resultant benzoyl cellulose was nitrated where the nitro group was reduced and the amino group
was diazotised. Coupling the diazo group with N,N-dimethylaniline gave ‘dyed’ fibres [24].

The idea of covalent bond formation between the reactive group of a dye molecule and a
fibre polymer was initiated in the early 1900s [25]. Various reactive entities were found which
could react with the hydroxyl groups of cellulose and eventually be converted into coloured
cellulose. In 1954, Rattee and Stephen developed the reactive dyes for cotton fibre containing

6
highly reactive dichloro-s-triazine groups with a dyeing procedure [26]. They established that
dyeing cotton with these dyes under mild alkaline conditions resulted in a reactive chlorine atom
on the triazine ring of the dye being substituted by an oxygen atom from a cellulose hydroxyl
group (Figure 5.3). The role of the alkali was to cause dissociation of some of the hydroxyl groups
in the cellulose (Figure 2.4) to obtain cellulosate anion that reacts with the dye. This discovery led
to the introduction of the first commercial reactive dyeclass for cellulose that was marketed by ICI
in 1956 under the trade name of Procion M [16, 26, 27]. These dyes were introduced for the
production of fast bright colours on cellulosic fibres using continuous dyeing methods [28].
Procion Brilliant Red M-2B (CI Reactive Red 1) is one of the early dyes of this range [23].

The major factor contributing to the long delay in producing the first reactive dye for
cellulose was the belief that cellulose was a relatively inert fibre. Further was the fear that the
conditions required to effect a chemical reaction would cause serious fibre degradation [23, 27].
Therefore, in early studies, dyestuff chemists were led astray in thinking that they needed to
convert cellulose to the more reactive soda cellulose which could make fibre reactivity possible
[27, 29]. No one expected that any reactive group would prefer to react with a hydroxyl group of
cellulose when cotton is immersed in an aqueous dyebath containing numerous competitive
hydroxide ions of water [25]. However, a large number of reactive dyes with a variety of reactive
groups have been developed. Today, the fibre-reactive dyes are the largest single dyeclass used
for dyeing cotton. A summary of the industrial history of commercial reactive dyes for cellulosic
fibres is shown in Table 3.1 [23, 30, 31].

The development of commercial reactive dyes has essentially been based on improving
dye fixation efficiency, colour yields, colourfastness specifically light fastness and shade gamut.
th
Later, in late 20 century, reducing effluent pollution became an additional reason for such
development. Today, the leading reactive dye manufacturers are Archroma, DyStar and
Huntsman with their brand names Drimaren, Remazol / Levafix and Novacron respectively. There
are many others from China, Korea and India, selling their dyes mostly to small and medium
enterprises. The bifunctional reactive dyes such as DrimarenK/HF/CL, Novacron C/LS,
RemazolB/RB/RGB and Levafix EA/CA are the most successful dyes used in the large
enterprises.

4. ENVIRONMENTAL ISSUES
Textile dyeing processes are complex and numerous. Each fiber type has its own specific group
of dye classes. Typically, there are three to four different chemical classes of dye for two major
apparel fibers: wool and cotton. Other apparel fibers such as nylon, acrylic, polyester, rayon, silk,
and polypropylene have fewer dye classes available. Each dye class has its own “chemistry,”
water usage, energy requirements, and effluent discharge volumes and characteristics.

Effluent is a key environmental issue for all dyehouses. Dyehouse effluents are
multicolored discharge streams comprising non-biodegradable inorganic salts and alkali along
with organic matter such as surfactants, starches, and other process aids (Babu et al, 2007;
Phillips, 1996; Smith, 2003; Ibrahim et al., 2008). Color in a discharge is undesirable because the
reduced penetration of sunlight into the water decreases photosynthetic activity and lowers
dissolved oxygen levels (Cooper, 1995). Salts, alkalies, detergents, and other processing
chemicals cause high levels of BOD, COD, and TDS (for total dissolved solids) and hence
present a threat to aquatic life. Heavy metals, especially chromium, can be present depending on
the product profile of the dyehouse. They are unacceptable in their own right and can also
interfere with effluent treatment processes.

7
 Table 3.1: Summary of history of leading commercial reactive dyes
Year Commercial name Company

1956 Procion M ICI

1957 Procion H ICI
1957 Cibacron Ciba (now Novacron from Huntsman)
1958 Remazol Hoechst (now from DyStar)
1959 Levafix Bayer (now from DyStar)
1959 Reacton Geigy
1959 Drimarene Sandoz
1961 Levafix E Bayer (now from DyStar)
1963 Elisiane Francolour
1964 Primazin P BASF
1964 Solidazol Cassella
1964 Procilan ICI
1966 LevafixEA, Levafix P Bayer (now from DyStar)
1966 Lanasol Ciba (now from Huntsman)
1968 Reactofil Geigy
1970 Verofix Bayer
1970 Drimarene R / DrimareneK Sandoz
1970 Procion HE, Procion Supra ICI
1977 Procion T ICI
1978 Cibacron F Ciba (now Novacron F from Huntsman)
1979 Sumifix Supra Sumitomo
1984 Kayacelon Nippon Kayaku
1987 Procilene ICI
1988 Cibacron C Ciba (now Novacron C from Huntsman)
1995 Drimaren Clariant (now from Archroma)
1996 Drimaren CL Clariant (now from Archroma)
1996 Cibacron LS Ciba (now Novacron LS from Huntsman)
1999 Procion XL+ BASF
1999 Levafix CA DyStar
1999 Drimaren HF Clariant (now from Archroma)
2001 Remazol Ultra RGB DyStar
2006 Novacron Huntsman
2011 Avitera SE Huntsman
2014 Remazol SAM DyStar

8
 Effluents from cotton processing are generally the most polluted. A typical composition of
the effluent from a cotton dyeing and finishing house is given in Table 4.1[32]. The most common
form of disposal is through the sewer and then to a central treatment plant. In some rare
instances, some plants still discharge directly to streams or the ocean. Dyehouses are typically
charged a volume fee plus separate fees for alkalinity, TDS, BOD, and heavy metals. The
increasing regulation of discharges from municipal plants, including demands for potable water
output, has resulted in higher charges to textile companies. This has placed dyehouses under
pressure to reduce both the volume output and the mass of dye, salts, and other processing
chemicals discharged in their effluent. Dyehouses have a number of options for reducing water
usage, for recycling, and for reducing discharge loads.

Table 4.1: Typical composition of cotton dyehouse effluent

Characteristics Values

pH 9.8 – 11.8

Total Alkalinity 17 – 22 mg/L

BOD 760 – 900 mg/L

COD 1400 – 1700 mg/L

Total Dissolved Solids 6000 – 7000 mg/L

Total Chromium 10 – 13 mg/L

Irrespective of the dyeing method and the type of reactive group(s), almost all of the
potentially toxic non-biodegradable inorganic salt [33], inorganic alkali and unfixed dye are
discharged to dyeing effluent. This leads to the environmental problem of a highly-coloured
effluent with high levels of dissolved solids [34] and oxygen demand [35]. Urea, which is often
used in pad dyeing methods [36] and in reactive printing [37] to increase dye solubility and yield
of the dye-fibre reaction, is another environmentally undesirable chemical [38]. Urea, when used
in the baking processes, decomposes and increases the nitrogen content of the effluent [39].

In recent decades, a number of techniques and technologies have been developed for
effluent treatments and recycling [32]. However, a better approach would obviously be to modify
the coloration technologies and chemistry to reduce the environmental discharge load. There
have been a number of such developments for improving the quality of effluent for cellulose
dyeing systems with reactive dyes [40]. This monograph presents those advancements in the
following sections. The presentation has started at fundamental level and leading to address how
to improve dyeing efficiency and to reduce the discharge amounts of inorganic chemicals (salt,
alkali and urea) and unfixed dye.

5. REACTIVE DYES, DYEING AND ADVANCEMENTS

5.1. Chemistry of Reactive Dyes and Advancements
The four characteristic features of a typical reactive dye molecule are the chromophoric group,
the water solubilising group(s) usually sulphonate (-SO3Na), the reactive group, and the bridging
group that attaches the reactive group either directly to the chromophore or to some other part of
the dye molecule (Figure 5.1). Each of these structural groups has an effect on the physical
properties of the dye molecule. The properties include colour, molecular size, solubility,
substantivity, ability to diffuse into fibres, migration within the fibre(s), colour-fastness, and so

9
on.Typical reactive dye chromophores include the azo, triphenodioxazine, phthalocyanine,
formazan and anthraquinone [25, 41]. Most commercial ranges of reactive dyes have a
comprehensive colour gamut, many of which are particularly bright.

Figure 5.1: Molecular structure of CI Reactive Red 1 (source: [42])

Reactive dyes possess their ability to form covalent bonds with the fibre due to the
presence of the reactive groups in their structure. A wide range of possible reactive groups has
been studied and evaluated by researchers and dyestuff manufacturers [25]. However, the
production of the dyes of commercial interest is limited by a number of factors such as adequate
reactivity towards cotton but lower reactivity towards water (Figures 5.3 and 5.4), adequate dye-
fibre bond stability, ease of manufacture, dye stability during storage and cost of the final reactive
dye. Table 5.1 shows some typical reactive groups. The reactive groups can be divided into two
distinct categories depending on the mechanism of formation of the dye-fibre bond, and the
stability of this bond to subsequent treatments. They are the carbon-nitrogen (heterocyclic) ring
structures such as triazinyl and pyrimidinyl, and the masked vinyl sulphones usually in the form of
sulphatoethylsulphone precursor group.

5.1.1. Bifunctional dyes

The early reactive dyes had only one reactive group in the dye molecule. Such dyes are referred
to as monofunctional reactive dyes. Many of the reactive dyes available today are bifunctional
with molecules having two identical or different reactive groups. Dyes with two identical reactive
groups are known as homo-bifunctional reactive dyes and those with different groups as hetero-
bifunctional. Technically, the bifunctional dyes have increased probability of reaction with the
fibre. Thus, they give higher fixation yields and thus leave less colour in the dyehouse effluent.
The CI Reactive Black 5 (Figure 5.2, source: [42]) is a dye containing two sulphatoethylsulphone
precursor groups. This dye has long been successful and known to produce a high degree of
fixation. The CI Reactive Blue 250 has a similar reactive system and was used in this study. The
idea of two reactive groups in a dye molecule then led to the introduction of the first commercial
range of homo-bifunctional dyes, based on two aminochloro-s-triazine reactive groups in the
same molecule. They were calledProcion HE (Table 3.1). The Kayacelon React and most of the
Cibacron LS (the low-salt) reactive dyes are homo-bifunctional.

A hetero-bifunctional dye possesses two different reactive groups and thus has two
different extents of reactivity towards the cotton and two possible optimal temperature and pH
conditions for dye-fibre reaction. Therefore, such a dye can give a more uniform degree of fixation
over a wider range of fixation temperature and pH conditions than a homo-bifunctional dye.
Amongst the earliest hetero-bifunctional reactive dyes were those capable of reacting with
cellulose via both mechanisms, nucleophilic substitution and nucleophilic addition. This is
because they contained a halogenotriazine and a sulphatoethylsulphone precursor groups. The
typical examples are the Sumifix Supra (monofluorotriazine and sulphatoethylsulphone) and

10
Cibacron C (monochlorotriazine and sulphatoethylsulphone) mentioned in Table 3.1. Many such
hetero combinations have been described, but not all have achieved commercial success [30-32,
42]. However, most reactive dye manufacturers today market at least one range of hetero-
bifunctional dyes.

Figure 5.2: Molecular structure of CI Reactive Black 5 containing bis

(sulphatoethylsulphone) reactive group
5.1.2. Poly-functional dyes
Some bifunctional dyes are claimed to provide a fixation efficiency of up to 95% when applied on
cotton by the pad-batch dyeing method [43, 44]. Incorporating more than two reactive groups into
the dye molecule should theoretically increase the fixation efficiency. However, these additional
reactive groups can have an impact on important dyeing properties such as substantivity and
migration because they change the molecular size and alter the extent and mode of reactivity.
Therefore, the idea of additional reactive group(s) have been more of patenting interest [30, 45].
Several tri-, tetra- and penta-functional dyes have been developed. Some have been introduced
to the market. [30, 46]. Ongoing improvements from further research and development in this
area are expected. DyStar disclosed a dye containing the monochlorotriazine, monofluorotriazine
and vinylsulphone combinations [45]. A few of these dyes have successfully been marketed such
as Cibacron Red C-2G and Remazol Red BS (CI Reactive Red 181) [30, 45, 46]. Some
commercial polyfunctionalreactive dyes are claimed to be ‘low salt’ dyes. The requirement of
reduced amount of salt may be due to the high affinity and have high fixation efficiencies. The use
of commercially available bi- or poly-functional reactive dyes have been recommended as the
best available technique for increasing the dye fixation efficiency [47, 48]. Moreover,
tertafunctional and pentafunctional dyes have also been discovered by researchers and dye
manufacturers [45]. However, none of these has advanced to the level of being commercialised.

5.1.3. Other developments

Reactive dyes based on a nicotinic acid residue allow dye-fibre reaction at a neutral pH of 7–7.5
[49]. These dyes are particularly suitable for neutral, high temperature exhaust dyeing, and for
one-bath dyeing of polyester/cotton blended fabrics [50]. This continues to be an active area for
research and development [51, 52]. Eliminating the need for salt by developing a reactive dye
with cationic features has also been successfully demonstrated in the laboratory [53]. Though
cationic reactives are yet to be commercially developed they remain an active area of research.
Lewis has recently presented a comprehensive review on developments in the chemistry of
reactive dyes [31]. In there, he has presented history of available dyes, commercial developments
during the period 1999-2014, dyes of research interest, neutral fixing dyes, cationic dyes, acid-
fixing dyes, and reactive dyes for non-cellulosic fibres.

11
 Table 5.1: Common reactive groups in order of increasing reactivity
*
Reactive group Typical commercial name(s) Reactivity

Drimarene X (Clariant) Low

D
Trichloropyrimidine

Procion H (DyStar)
Basilen (BASF) Low
Cibacron (Ciba)
D
Aminochloro-s-triazine
D SO2CH2CH2OSO3Na
Remazol (DyStar) Moderate
Sulphatoethylsulphone

D Levafix E (DyStar) Moderate

Dichloroquinoxaline

Cibacron F (Ciba) Moderate

D
Aminofluoro-s-triazine

Drimarene K (Clariant) Moderate to high

D Levafix E-A (DyStar)

Difluorochloropyrimide

Procion MX (DyStar) High

D
Dichloro-s-triazine

*
D = Dye chromophore

12
5.2. Dyeing Reaction Mechanisms
5.2.1. Nucleophilic substitution
Reactive groups based on carbon-nitrogen ring structures undergo nucleophilic substitution
(Figure 5.3) [42]. They react with cellulose by the substitution of a labile chlorine, fluorine, methyl
sulphone or nicotinyl leaving group. The adjacent nitrogen atom in a heterocyclic ring activates
the system for nucleophilic attack. The attacking nucleophile can be either a cellulosate anion or
a hydroxide ion of water. The reaction with cellulosate anion leads to ‘fixation’ of the dye on the
fibre and that with hydroxide ion results in ‘hydrolysis’ of the reactive dye.. Note that the
– - -
cellulosate anion (Cellulose-O ) and hydroxide ion (OH ) are represented by :X generally in the
following Figures 5.3 and 5.4.

Dichloro-s-triazine dye Transient species Partly-hydrolysed dye (X = OH)

(D = Dye chromophore) or dyed fibre (x = O-Cellulose)

Figure 5.3: Nucleophilic substitution mechanism (source: [42])

5.2.2. Nucleophilic addition
Reactive groups based on masked vinyl sulphone structures undergo nucleophilic addition
(Figure 5.4). They react with cellulose by addition to a carbon–carbon double bond, usually
activated by an adjacent electron-attracting sulphone group. This type of group is usually
generated in the dyebath by elimination of sulphate ion from a sulphatoethylsulphone precursor
group in the presence of alkali. Again, the nucleophilic addition of hydroxide ion of water leads to
dye hydrolysis.

Alkali –
+ HSO4

Sulphatoethylsulphone dye Vinylsulphone dye

(D = dye chromophore)

Vinylsulphone dye Transient species Hydrolysed dye (X = OH)

or dyed fibre (x = O-Cellulose)
Figure 5.4: Nucleophilic addition mechanism (source: [42])
5.3. Dye Reactivity
Dye reactivity refers to the rate at which a reactive group tends to undergo a nucleophilic
substitution or addition reaction with the fibre polymer. The reactive groups of various types
possess a wide range of reactivities. The dyes of high reactivity, such as dichloro-s-triazine

13
reactive dyes, are applied to cotton at lower temperatures and only require a weak alkali such as
sodium bicarbonate or sodium carbonate for fixation. The less reactive types, such as
aminochloro-s-triazine dyes, need higher temperatures and stronger alkalis such as sodium
carbonate and/or sodium hydroxide. Table 5.1 gives the typical reactive groups commercially
popular with reference to their relative reactivity.

5.4. Dye Substantivity

The term ‘substantivity’ was originally derived from popular substantive dyes (Direct dyes) and
refers to the ability of a dye to uptake from a liquid medium onto a textile fibre and to set [54]. The
quantitative measurement of the force with which the dye is captured by the fibre is determined
as ‘affinity’. However, substantivity is often used as a qualitative description of the affinity of a dye
for a particular fibre.

The substantivity of a dye generally depends on the extent of its solubility, and on its
molecular size and structure. Substantivity is favoured by the formation of multiple dye-fibre
bonds [1]. In reactive dyeing of cotton, these bonds are hydrogen bonds and covalent bonds.
Thus, reactive groups also exert a significant effect on the substantivity.

5.5. Dye Exhaustion

In exhaust dyeing, the fibre starts absorbing the dye as soon as it is immersed into the dye liquor.
As a result, the concentration of dye in the dyebath decreases gradually [55]. This shift of dyes
towards the fibre is generally referred to as exhaustion. The degree of dyebath exhaustion as a
function of time describes the rate and extent of the dyeing process. For a single dye, the
exhaustion is expressed as the mass of dye taken up by the fibre divided by the total mass of the
dye originally used in the dyebath of constant volume [54] (Equation 5.1).

%Exhaustion = [(Co – Cs) / Co] x 100 (5.1)

Where, Coand Csare the concentrations of dye in the dyebath initially and at sometime
later during the process, respectively.

5.6. Dye Diffusion

The penetration of a dye into the fibre polymer system from the dye-fibre interface is known as
dye diffusion. Fick’s second law states that the rate at which the dye diffuses across a unit area in
the fibre is proportional to the concentration gradient across that area, the proportionality constant
being the diffusion coefficient [56]. The coefficient of diffusion is a parameter used in most
fundamental studies on dye diffusion.

5.7. Dye Migration

The mobility of dye molecules within the fibre is referred to as dye migration. The extent of this
mobility depends mainly on dye substantivity and dye-fibre bonding. In the case of dyeing cotton
with reactive dyes, covalently-fixed dyes cannot migrate during the dyeing process. Accordingly,
the dye cannot diffuse into the fibre when it is fixed on the surface of the fibre[57].

5.8. Dye Fixation

There are three main ways in which dye molecules can become attached (fixed) to the cotton
fibre: mechanical retention, physical bonding and chemical reaction [15]. Vat, sulphur and azoic
dyes are fixed principally with mechanical retention, i.e. the dye molecules are trapped in an
insoluble pigmentary form within the fibre polymer system. Direct dyes are fixed with physical
hydrogen bonding and van der Waal’s forces. Reactive dyes are fixed mainly by reaction with the
fibre polymer leading to the formation of covalent bonds.

14
 Dye fixation is generally determined as an estimate of the average proportion of dye
actually fixed on a textile fibre [54]. The typical fixation percentages of cotton dyes are given in
Table 5.2 [58]. The lower fixation levels of reactive dyes are essentially due to unavoidable dye
hydrolysis during dyeing. There have been various analytical ways for estimating the extent of
dye fixation and dye hydrolysis. Today, the percentage of dye fixation is usually determined by
using absorbance measurements of dyebath solution and/or colour strength measurements of the
fabric during dyeing [51, 59, 60].

Table 5.2: Typical fixation percentages of cotton dyes

Dyeclass Fixation (%)

Azoic 83–93

Direct 70–95

Reactive 50–80

Sulphur 60–70

Vat 80–95

6. APPLICATION METHODS FOR REACTIVE DYES AND ADVANCEMENTS

6.1. Batchwise Dyeing
Batchwise dyeing is a process of immersion of the fabric in the dyebath, transfer of the dye to,
and its gradual diffusion into, the fibre, so that the dyebath concentration decreases. In the typical
batchwise dyeing of cotton with reactive dyes, the first phase of dyeing is carried out under
neutral pH conditions to allow dye exhaustion and diffusion [25]. This promotes uniform
coloration. Sodium chloride or sodium sulphate is often present initially, or added gradually to the
dyebath during this phase, to promote exhaustion. The temperature of the dyebath may also be
gradually increased to aid penetration of dye into the fibres, and to assist uniform migration.
Fixation of the dye is then achieved by adding a suitable alkali to the dyebath, either completely
or gradually, to activate the cellulosate anions. The reaction phase of the dyeing occurs over 30–
o
60 min with typical dyeing temperatures within the range from 30 to 90 C, depending upon the
type of reactive group and its reactivity. The fixation process results in additional dye transfer to
the fibre which is often referred to as secondary exhaustion [61, 62]. The secondary dye
exhaustion and dye-fibre reaction then progress until no further dye is taken by the fibre. The
important parameters in exhaustive reactive dyeing are the liquor-to-fibre ratio, temperature, pH
and time.

After completion of the dye exhaustion and dye-fibre reaction phases, the fabric contains
covalently-bonded dye, absorbed but unreacted dye, and the hydrolysed dye. The unreacted and
hydrolysed dyes are generally referred to as unfixed dyes. The fabric also contains the residual
electrolyte and alkali which should be removed. The unfixed dye is weakly trapped within the fibre
through hydrogen bonds and van der Waal’s forces which can desorb easily during washings by
the consumer of the dyed cotton textiles. In other words, the presence of unfixed dye in a reactive
dyed fabric gives poor washing fastness. Thorough washing-off after dyeing of reactive dyed
cotton is therefore essential to remove all of the unfixed dye, residual electrolyte and alkali. This
washing-off is a series of thorough rinsings including boiling with a detergent. This needs large
amounts of good quality water [58]. In traditional reactive dyeings, around three quarters of the

15
total water consumed is required for washing-off phase [63]. The typical exhaust dyeing machines
for cotton goods are Winch and Jigger; their schematics are shown in Fig. 6.1.

(A) (B)
Figure 6.1: Illustrations of typical winch (A) and jigger (B) dyeing machines (source:[64])
6.1.1. Low liquor-ratio dyeing machines
The concentration of dyeing chemicals and auxiliaries is determined by the fabric mass per unit
volume of dyeing liquor. Thus, the total consumption of chemicals can be reduced by reducing
the volume of liquor [65]. On this basis, a wide number of forms of low liquor-to-fibre ratio jet
dyeing machines have been commercially introduced [66, 67]. Different machinery manufacturers
offer specific equipment for particular fabric styles and weights; for example jet airflow assist,
special jets for sensitive fabrics and driving creels to aid rotation of fabric in the dye machine. As
a result of these new technologies the apparel dyeing industry has moved from a 20:1 liquor ratio
(litres of water per kilo of fabric) in the 1970’s and 1980’s down to ratios as low as 6-8:1 in the
1990’s. Ultra-low liquor ratio jet dyeing machines (Fig. 6.2) now offer the opportunity to dye at
ratios as low as 3:1. The reduction in liquor ratio also increases the driving force for the dye to
move from solution into the fibre [68]. Thus, a lower concentration of salt is needed for dye
exhaustion. The lower volume of water also results in less hydrolysis of the reactive dye thereby
increasing the dye yield. Other advantages of low liquor dyeing machinery are reduced dye liquor
wastage and lower steam consumption to heat the dyebath. The developments in low liquor
dyeing machinery over the past 50 years have resulted in major improvements to sustainability;
lower water and energy use, lower dye and salt use and hence reduced disposal to the
environment. Such dyeing machines are highly recommended as the best available technology
for batchwise dyeing [47].

16
 Figure 6.2: Illustration of a typical ultra-low liquor ratio dyeing machine
6.2. Pad Dyeing
Continuous pad impregnation is a process where a fabric is passed in open-width form through a
small bath (trough) containing dye solution and through the pressure squeezing rollers to remove
the excess liquid evenly. The amount of dye solution taken as the percentage of mass of the
fabric is the per cent pickup. The impregnation and uniform squeezing together are called
padding and the device is known as a padder. For continuous pad dyeing, fixation must be rapid
(30–120s) and usually involves heating (by baking or steaming) the impregnated fabric. The
exception to this is the cold pad-batch process, where the fabric is padded with dye and alkali and
then batched at ambient temperature for 6–24h. The cold pad-batch dyeing is also referred to as
a semi-continuous dyeing because of such a prolonged fixation time. As discussed in previous
section, the fabric is finally subjected to a thorough washing-off after the dye fixation step. This is
usually done on the continuous washing range. Padding is the most important process of
continuous and semi-continuous dyeings [69]. Dye build-up, levelness and evenness on the fabric
largely depend on this step. Factors of concern being the wetting of the fabric, the dwell time in
the padder, the type of fibre and the construction of the fabric, per cent pickup, preferential
adsorption of dyebath components because of substantivity of dyes, reaction of reactive dyes in
the dyebath, dye aggregation, and the transfer of impurities in the fabric from a pretreatment step
into the padder. An illustration of a typical dyeing padderis shown in Fig. 6.3.

Figure 6.3: Illustration of a typical dyeing padder

17
 From a sustainability perspective, padding based dyeing methods for cotton fabrics are the
most preferred coloration pathway [70]. Moreover, The European Commission [47] recommends
padding as the best available technology for reducing the dyeing liquor wastages. Relative to
batchwise dyeing pad-based dyeing methods offer [69];

- Lower liquor-to-fibre ratio in the dyebath

- Lower amounts of left-over dyebath solution
- Faster dye application
- Easier control on dye levelness on the fabric
- No electrolyte required for exhaustion

The lowest possible liquor-to-fibre ratio in batchwise dyeing is 3:1 using ultra-low-liquor-ratio
dyeing machines. Pad dyeing reduces this to between 1:1 and 0.5:1. Such low liquor ratios
further increase dye take-up. As a result further reductions in quantities of dye and water are
discharged as effluent at the end of the process. However, these methods are normally avoided
on knitted fabrics and small lots due to certain limitations [2] such as dimensional instability and
higher pollution load [47].

In continuous pad dyeing processes the uniformity of dye applied across and along the fabric
is critical to the final shade and acceptability of the dyed fabric. Key factors in achieving this are
the dwell time in the padder, the type of fibre and the construction of the fabric, per cent pickup,
whether there is any preferential adsorption of dyebath components (this can produce tailing of
the shade), reaction of reactive dyes in the dyebath, dye aggregation, and the transfer of
impurities in the fabric from a pretreatment step into the padder. It is also important that the dye
fixation is achieved within a short time frame (30–120s) after padding. Fixation of the dyes in the
impregnated fabric is achieved by baking or steaming in specialised continuous ranges.

6.2.1. Padders with low padding trough volume

In pad dyeing methods, the dyeing liquor left in the padding trough, pipes and pumps is drained to
the effluent in its concentrated form at the end of a dyeing process [47]. However, under certain
circumstances, it may be drained to a sealable drum for later use. The volume of the liquor left
depends on the padding trough capacity. A number of machinery manufacturers have developed
trough volumes down as low as 10–15L. This has provided meaningful improvements to dye
utilisation and disposal to waste (Phillips, 1996). Fig. 6.4 (A) shows a padder with a low volume
trough. Note the fabric moves upwards into the squeeze rollers which allows surplus liquor to be
returned to the trough. An alternative approach is to form a trough between the two squeeze
rollers (Fig. 6.4 (B)). Küsters trough shapes and sizes with their liquor volume capacity are
illustrated in Fig. 6.5.

18
 (A) (B)

Figure 6.4: U-trough (A) and nip (B) dye liquor pad application systems (source: [40])

Figure 6.5: Küsters trough shapes and sizes with liquor capacity in volume per unit width
in metre (source: [71])
6.3. Pad Fixation Processes
A range of fixation technologies have been developed to take advantage of pad dyeing. Some
have been evolutionary whereas others have been developed specifically for a particular dye-
fibre product. A summary of the key features of the various fixation technologies and their
sustainability issues is given in the following sections.

6.3.1. Batching
A typical pad-batch dyeing machine is shown in Fig. 6.6. Pad-batch dyeing processes are the
most economical of all pad dyeing processes for the reactive dyeing of cotton [72]. In fact, for
small lots of around 1000–10,000m, this process is more economical than batchwise dyeing,
mainly due to lower energy requirements. This process, also referred to as cold-pad-batch,
involves padding the fabric with a dye solution containing a suitable alkali system and then
winding the fabric onto a roller before batching for 6-24h [25, 42]. In order to avoid evaporation
from the exposed edges of the roll, the fabric is wrapped with winder end-cloth and then sealed
with a plastic film. For dye fixation at ambient temperature, the dyes must have a high reactivity.
During batching, the roller rotates slowly to avoid welling of the liquor within the batch. After
batching, the fabric is washed to remove unfixed dye and residual chemicals. This is done either
on a continuous washing range or on a batch dyeing machine. Relative to jet dyeing, cold pad
batch dyed fabrics are claimed to have an improved handle and cleaner surface appearance.
Prominent water and energy savings [73], reduced consumption of dyes and chemicals, and less

19
space and labour requirements, of pad-batch dyeing process [74], make it economical and
ecologically sustainable [75].

Figure 6.6: Illustration of a Küsters cold-pad-batch range (source: [71])

6.3.2. Baking
A typical pad-dry-bake dyeing machine is illustrated in Fig. 6.7. Pad-dry-bake dyeing of cotton
with reactive dyes, as its name implies, involves padding, intermediate drying and then dye
o
fixation by baking at high temperatures up to 160 C for 60–120s[22]. Dye selection based on the
level of reactivity is important. The process is completed by washing-off. The padding solution
comprises the dye, an alkali (usually sodium carbonate), urea and an antimigrant (usually an
alginate based thickener). A high concentration of urea, in the range from 50–200g/L is used to
help the cotton retain water during drying and subsequent baking [72]. The hot, dry environment
provides a suitable medium for dye diffusion within the fibre. It also improves dye fixation and
colour yield [42, 76-78]. Sometimes, urea is also used in pad dyeing to improve dye solubility.
Urea is removed during washing-off but poses pollution issues as it is a source of nitrogen [25].

Figure 6.7: Diagram of a Monforts continuous dyeing range for drying and baking
(source: Monforts brochure)
Intermediate drying is a critical step in any continuous dyeing sequence. Excessive evaporation
and dye migration are the key problems. An antimigrant is used in the padding liquor to avoid dye
migration which causes shade changes on both sides of the fabric. Pre-drying using hot cylinders
or infrared heating are also used to minimise this problem [64].

20
6.3.3. Steaming
A typical pad-steam dyeing machine is illustrated in Fig. 6.8. Pad-steam dyeing with selected
reactives is the simplest and most economical process for producing pale to medium shade
depths on cotton apparel fabrics [25, 72, 79]. Fabric is padded with a reactive dye solution
containing inorganic electrolyte (for diffusion and subsequent levelness of the dyes into the fibre)
and the appropriate alkali (to initiate the dye-fibre reaction) followed by 60–90s steaming for dye
fixation. Steamers used for fixation transport the fabric, as deep loops, on moving rollers. They
provide an air-free environment by means of a water exit seal (as a ‘water-lock’). Each
commercial range of dyes requires a particular set of steaming conditions. For reactive dyes on
o
cotton steam fixation is achieved using saturated steam at 101–102 C and 100% humidity. Dye
class selection is important; bifunctional reactive dyes tend to be more reproducible than
monofunctional systems [80, 81]. Finally, the fabric is washed-off to remove unfixed dye and
residual chemicals.

Figure 6.8: Illustration of a Benninger continuous pad-steam dyeing range

(source: Benninger brochure)

Early steam fixation processes for reactive dyeing of cotton followed the sequence: pad
(with neutral dye solution) – dry – pad (alkali and salt) – steam – wash. This sequence is often
referred to as pad-dry-chemical pad-steam process. This process sequence is quite similar to the
continuous vat dyeing of cotton fabrics. The fabric is first padded in a neutral reactive dye solution
and dried in a hot chamber. After intermediate drying, the fabric is padded with a dilute solution of
sodium hydroxide in saturated brine followed by steaming to complete the dye-fibre reaction. High
concentrations of electrolyte are required to minimise colour bleeding during the second alkali
padding. Vacuum extraction of the padded fabric, in lieu of an intermediate drying, can be used
to restrict dye bleeding into the chemical pad solution [82].

In recent decades, simpler and more environmentally sustainable dyeing sequences such
as pad-dry-steam and pad-steam have been introduced by the major machinery manufacturers in
collaboration with dye suppliers. The new sequences and machinery minimise bleeding and
migration problems associated with pad-dye pad-chemical methods [83].

6.3.4. Eco-control dyeing machine

Urea is used in the pad-dry-bake dyeing process to improve the extent of the dye-fibre reaction.
Inorganic salt is used in pad-steam dyeing to improve dye levelness into the fibre. Salt is also
used in pad-dry-chemical pad-steam process to minimise dye bleeding during chemical padding.
Although considerable progress has been made in improving the sustainability of continuous
dyeing processes from the 1970’s to the 1990’s there remained problems with the need to
continue to use urea and inorganic salts. In the late 1990’s a joint machinery and process

21
development by BASF and Monforts provided industry with a continuous cotton dyeing process
which did not require urea and salt [84]. The machine (shown in Fig. 6.9), known as the ‘Eco-
Control’ range, is based on the injection of moisture vapour into the hot fixation chamber. Typical
o
fixation conditions for a dichloro-s-triazine dye have been reported as 120 C temperature and 20–
25% relative humidity. Only small concentrations of alkali (sodium bicarbonate) are required for
these dyes. This development has been commended as the best technology for improving
ecological and economic impact of the pad dyeing processes [47].

1. Feedding section 2. Pad mangle 3. Wetting unit

4. Thermex hot-flue 5. Chamber atmosphere measuring and control unit,
6. Steam injection unit 7. Outlet section

Figure 6.9: Illustration of a MonfortsEcontrol dyeing range

(Source: Monforts brochure)
7. INDUSTRIAL / TECHNICAL PROBLEMS AND POSSIBLE SOLUTIONS
Various industrialists and researchers have reported practical problems of reactive dyeing of
cellulose fabrics and their solutions [85-88]. Following table presents a compilation of the
industrial/technical problems and their solutions based on previous reports and our experience.

Table 7.1: Industrial / technical problems and their solutions of reactive dyeing of cellulose
fabrics
Problem Possible cause Possible solutions Dyeing
machine(s)
Streak marks 1. From looms during 1. Ensuring streak-free fabric at Winch, Soft-flow,
weaving the weavers’ end Jigger,
2. Roller marks from 2. Ensuring streak-free fabric Pad-Thermosol,
continuous during pre-inspection Pad-Steam,
pretreatment 3. Proper maintenance and Pad-batch
cleaning of all rollers of fabric
contact
Colour spots / 1. Poor pretreatment 1. Good pretreatment Winch, Soft-flow,
dark coloured 2. Residual 2. Good pretreatment, good Jigger,
areas / stains / contamination on the washing after pretreatment Pad-Thermosol,
blotches / resist substrate Pad-Steam,
spots / filtering 3. Water contamination 3. Purification of water and/or use Pad-batch
of sequestering agents
4. Contaminated salt, 4. Good quality control of
alkali, other chemicals commodity chemicals

22
 5. Staining of material 5. Proper housekeeping, use of
by flying particles of liquid dyes whenever possible
powder dyes
6. Incompatible dyebath 6. Using compatible dyebath
ingredients ingredients
7. Improper dyes 7. Dissolving dyes properly
dissolving
8. Dyebath foaming 8. Using anti-foaming assistant
9. Improper machine 9. Proper machine cleaning
cleaning before dyeing before dyeing
10. Too high rate of dye 10. Optimum dyeing process
exhaustion and/or rate control
of reaction
11. Shorter liquor ratio 11. Optimum liquor ratio
12. Areas of denser / 12. Good quality control and
more compact yarn proper pre-inspection of the
appearing darker due to substrate
lesser light scattering
13. Improper post 13. Optimum post dyeing
dyeing washing-off / washing-off / rinsing
rinsing
14. Aggregation of dyes 14. Refer below for causes and
solutions of the ‘Dye aggregation’
problem
Light coloured Presence of immature 1. Good quality control and Winch, Soft-flow,
areas / spots and damaged fibres on proper pre-inspection of the Jigger,
on the surface of the substrate substrate Pad-Thermosol,
substrate causes stronger light 2. Proper singeing Pad-Steam,
scattering resulting 3. Mercerisation Pad-batch
them to appear lighter
Dark dyed Improper winding Proper edge-to-edge winding Jigger and Pad
selvedges Dyeing
Machines
Low dye 1. High substantive 1. Using dyes of adequate Winch, Soft-flow,
solubility dyes substantivity Jigger,
2. Low dyebath 2. Optimum dyebath preparation Pad-Thermosol,
preparation temperature Pad-Steam,
temperature Pad-batch
3. High salt 3. Optimum salt concentration
concentration
4. Dissolving dye before other
chemicals and auxiliaries
Dye 1. Too high dye 1. Optimum dye concentration Winch, Soft-flow,
aggregation concentration Jigger,
2. Too high salt 2. Optimum electrolyte Pad-Thermosol,
concentration concentration Pad-Steam,
3. Too low temperature 3. Optimum temperature Pad-batch
4. Poor dye solubility 4. Good dye solubility
5. High substantive 5. Using dyes of adequate
dyes substantivity
Slow rate of 1. High dye solubility 1. Optimum dye solubility Winch, Soft-flow,
exhaustion 2. Low dyeing 2. Optimum dyeing temperature Jigger
temperature

23
 3. Low salt 3. Optimum salt concentration
concentration
4. Low dye substantivity 4. Using dyes of adequate
substantivity
Poor dye 1. Poor solubility of 1. Using dyes of good solubility Winch, Soft-flow,
leveling / dyes Jigger,
uneven dyeing 2. Low dye diffusion 2. Using dyes of smaller Pad-Thermosol,
molecular size and optimum Pad-Steam,
substantivity Pad-batch
3. High dye 3. Using dyes of adequate
substantivity substantivity
4. Dyes of poor 4a. Using dyes of good migration
migration 4b. Using dyes of smaller
molecular size and optimum
substantivity
5. High salt 5. Optimum salt concentration
concentration
6. Too high rate of dye 6. Optimum dye exhaustion rate
exhaustion
7. Rapid increase of 7. Optimum rate of temperature
temperature rise
8. Rapid shift of 8. Proper pH control
dyebath pH
9. Low rate of liquor 9. Optimum rate of liquor flow
flow
10. Low mechanical / 10. Optimum mechanical /
agitating action agitating action
11. Addition of alkali too 11. Addition of alkali after proper
early dye exhaustion and leveling
12. Using Metal 12. Using alternative dyes;
complex or optimum dyeing conditions
Phthalocyanine dyes
13. Presence of metal 13. Using appropriate complexing
particles such as iron agents; using metal particles free
and copper water
14. Using improper 14. Using compatible surfactants
surfactants
15. Variation in padder 15. Even padder pressure
pressure during the throughout the dyeing process
dyeing process
Low dye 1. Poor pretreatment 1. Good pretreatment Winch, Soft-flow,
penetration / 2. Too high dye 2. Using dyes of optimum Jigger,
diffusion substantivity substantivity Pad-Thermosol,
3. Poor dye solubility 3. Using dyes of good solubility Pad-Steam,
4. Dyes of poor 4. Using dyes of good migration Pad-batch
diffusion coefficient and good diffusion coefficient
5. Improper salt 5. Optimum salt concentration
concentration
6. Using optimum dyeing
conditions
Poor dye 1. Lower or too high 1. Optimum alkali concentration Winch, Soft-flow,
fixation alkali concentration or or pH Jigger,
pH Pad-Thermosol,
Pad-Steam,

24
 2. Lower or too high 2. Optimum fixation temperature Pad-batch
fixation temperature
3. Shorter or prolonged 3. optimum dyeing time
dyeing time
Poor washing 1. Too high dye 1. Using dyes of adequate Winch, Soft-flow,
off substantivity substantivity Jigger,
2. Dyes of poor 2. Using dyes of adequate Continuous
migration and low migration and diffusion coefficient washing range
diffusion coefficient
3. Low liquor ratio of 3. Optimum liquor ratio of
washing bath(s) washing bath(s)
4. Improper 4. Optimum temperatures of the
temperatures of the washing-off steps
washing-off steps
5. High salt 5a. Using low salt dyes
concentration in the 5b. Optimum rinsing cycle /
washing bath sequence
6. Water hardness 6. Using soft water and / or
sequestering agents
7. Inadequate washing 7. Optimum washing time
time
8. Inadequate number 8. Optimum number of wash
of wash cycles / wash baths
cycles / wash baths
9. Low mechanical / 9. Optimum mechanical / agitating
agitating action action
10. Improper use of
dyebath chemicals and 10. Compatible dyebath
auxiliaries chemicals and auxiliaries
11. Use of Disazo,
Metal Complex, 11a. Using alternative dyes if
and Phthalocyanine possible or
dyes 11b. Using more severe washing-
12. Improper water off conditions
current, water level and 12. Optimum water current, water
padder pressures in the level and padder pressures in the
continuous washing continuous washing tanks
tanks
Foaming 1. Too high mechanical 1. Optimum mechanical / agitating Winch, Soft-flow,
/ agitating action action Jigger,
2. Improper surfactant Pad-Thermosol,
3. Too high surfactant 2. Using low foaming surfactant Pad-Steam,
concentration 3. Optimum surfactant Pad-batch
4. Air entrapping into concentration
the dyeing machine / 4. Prevention of air entry into the
dyebath stock tanks dyeing machine / dyebath tanks
Inconsistent 1. Residual peroxide 1. Ensuring contamination-free Winch, Soft-flow,
shade / shade content, alkalinity substrate before dyeing Jigger,
change and/or other Pad-Thermosol,
contaminantion in the Pad-Steam,
substrate Pad-batch
2. Water hardness 2. Using soft water and if needed
appropriate sequestering agents

25
 3. Dyebath 3. Using appropriate sequestering
contamination with agents
heavy metals such as
calcium, magnesium
and chlorine
4. Using improper 4. Optimum use of compatible
dyebath auxiliaries dyebath auxiliaries
such as surfactants,
sequestering,
exhaustion, fixation
agents and/or
lubricating agents
Dull shades Using metal complex Using alternative dyes of bright Winch, Soft-flow,
dyes such as shades Jigger,
containing copper or Pad-Thermosol,
many vat dyes possess Pad-Steam,
dull shades Pad-batch
Poor colour 1. Poor pretreatment 1. Good pretreatment Winch, Soft-flow,
yield 2. Residual peroxide on 2. Proper washing after Jigger, Pad-
the substrate pretreatment leaving no residual Thermosol, Pad-
chemical on the substrate Steam, Pad-
3. Reactive dye 3a. Careful storage of dyes batch
hydrolysis 3b. Using freshly prepared dye
solution
3c. Optimum dyeing conditions
including proper selection of dyes
and alkali
4. Too low dye 4. Using dyes of optimum
substantivity substantivity
5. Too low salt 5. Optimum salt concentration
concentration
6. Too low alkali 6. Optimum alkali concentration
concentration
7. Lower dye 7. Optimum dye concentration
concentration
8. Too low or high 8. Optimum liquor ratio
liquor ratio in batchwise
washing
9. Too short dyeing 9. Optimum dyeing time
time
10. Using improper 10. Optimum use of surfactants
surfactants
11. Loss of dye or 11. Careful weighing / dispensing
chemicals during of dyes and chemicals
weighing / dispensing
12. Water hardness 12. Using soft water and/or
appropriate sequestering agent
Poor washing 1. Inadequate washing- 1. Optimum washing off (See Winch, Soft-flow,
fastness off of unfixed reactive above the causes and solutions Jigger,
dyes of ‘Poor washing-off’ problem) Pad-Thermosol,
2. Inherently low 2. Using cationic fixing agents or Pad-Steam,
washing fastness any other fastness improving Pad-batch,
properties of the dyes aftertreatment Continuous
washing range

26
Poor rubbing 1. Dyes of inherently 1. Using dyes of good rubbing Winch, Soft-flow,
fastness poor rubbing fastness fastness Jigger,
2. Catalytic damage of 2. Preventing catalytic damage of Pad-Thermosol,
the substrate the substrate by ensuring soft Pad-Steam,
water and using sequestering Pad-batch
agent during dyeing process
3. Presence of 3. Using appropriate complexing
polyvalent ions agents
4. Too high moisture in 4. Proper conditioning of the test
the test material material
5. Using improper 5. Using proper finishing agents
finishing agents
6. Un-mercerised 6. Using mercerised cotton
cotton
7. Improper diffusion 7. Using optimum dyeing
and fixation conditions
8. Incomplete washing- 8. Optimum washing-off
off
Physical 1. Too long dyeing time 1. Optimum and right first time Winch, Soft-flow,
damage or re-handling / dyeing Jigger,
corrective procedures Pad-Thermosol,
2. Too high mechanical 2. Optimum mechanical or Pad-Steam,
or hydraulic action hydraulic action Pad-batch
3. Too high dyeing 3. Optimum dyeing temperature
temperature
(increases the
sensitivity of the
material to physical
damage)
Listing/ 1. High machine speed 1. Optimum speed Jigger,
Edge-to-edge or speed variation Pad-Thermosol,
or edge-to- 2. Edge-to-edge 2. Control of even widthwise Pad-Steam,
centreshade temperature variation temperature Pad-batch
variation
3. Improper dosing 3. Follow dye manufacturer’s and
lab recommendations for dosing
4. Variation in 4. Control of widthwise padder
widthwise padder pressure
pressure
5. Widthwise variation 5. Ensuring no variations coming
in pretreatment quality from back processes
or fabric mass
Ending / Tailing 1. Poor dye solubility 1. Proper dye dissolving Jigger,
2. Unsuitable dye 2. Suitable dye combination Pad-Thermosol,
combination specially in terms of dye affinity Pad-Steam,
3. Dyebath temperature 3. Constant and optimum dyebath Pad-batch
and pH variation temperature and pH
4. Lengthwise variation 4. Ensuring no variations coming
in pretreatment quality from back processes
Front-back 1. Improper fabric 1. Gradual increase in drying Pad-Thermosol
fabric shade drying temperature of drying chambers.
variation due to Use of pre-drying with IR is
dye migration recommended.

27
 2. Low viscosity of 2. Use of reasonable
dyebath solution concentration of solution
thickener (as anti-migrant)
8. FUTURE TRENDS IN REACTIVE DYEING
There is little doubt that the refinement of dyes, process paths, machine technology recycling and
effluent treatment that have resulted in significant improvements to sustainability over past
decades will continue. Some of these developments will be driven by the constant demand for
cost reductions along the supply chain. Others will be driven by tighter national environmental
regulations. Moves to more global uniformity of environmental regulations could have a profound
effect on the sustainability of the industry as a whole. So too could consumer advocacy and
pressure from brands and retail chains for more sustainable products.

The key pathways for improving the sustainability of the dyeing lie in the five areas;

- development of synthetic dyes with improved chemistries,

- development of dyeing machinery and processes,
- use of environmentally safer chemicals in dyebath formulations,
- chemical modification of fibre prior to dyeing, and
- emerging technologies

Much of these pathways remain the province of research departments of major suppliers and
to universities and research institutes. Developments into dye chemistry and dyeing
machinery/processes have been presented in sections 5 and 6 respectively; the other three areas
are discussed below.

8.1. Developments in Dyebath Chemicals

Biodegradable dyebath chemicals offer an interesting alternative to inorganic salts. The attraction
is lower effluent loads. Betaine, an organic compound, allows reductions in the amount of
inorganic salt [89]. Organic surfactants, as inorganic salt substitutes, also reduce the effluent load
[90]. Mixtures of magnesium-based organic compounds in the dyeing of cotton with direct or
reactive dyes has been patented [91]. However, commercialisation is problematic because
magnesium increases water hardness and creates problems with colour matching and dye
process control [92, 93].

Sodium salts of organic acids have been explored as alternatives to sodium chloride and
sodium sulphate. Trisodium citrate has been shown to be a viable alternative to traditional
inorganic salts for exhaust dyeing of cotton with reactive, direct and solubilised vat dyes [94].
Salts of polycarboxylic acids are also effective alternative to salt [95, 96]. Tetrasodium ethylene
diamine tetra-acetate and other alkaline polycarboxylic sodium salts, have also been reported as
an a replacement for both salt and alkali in exhaust and continuous pad-steam dyeing of cotton
with reactive dyes [33, 97]. Research is expected to continue into salt substitutes as they do
produce meaningful reductions in effluent load. The cost of the salt alternatives remains the
impediment to commercial use.

Alternatives to the use of urea in printing and some continuous reactive dyeing methods
is ongoing. Use of a dicyandiamide in the dyebath has been shown to reduce the amount of urea
required [66]. Caprolactam products can result in partial or complete substitution for urea in
reactive dyeing and printing of cotton fabrics [98].

28
8.2. Chemical Modification of Cellulose
Chemical modification of cellulose to improve dyeing with direct, reactive, sulphur or vat dyes, is
an emerging area. The research has focused on the introduction of cationic groups to the fibre
[99-103]. Such modifications, usually referred to as cationisation, are achieved by treating cotton
with low molecular weight cationic chemicals or with cationic polymers (resins). Most of the
cationic groups are quaternary, tertiary or secondary amino residues. In the reactive dyeing of
cationised cellulose substrate, the anionic dyes are attracted by the cationic charges on the fibre.
As a result, higher fixation efficiency and reduced (or no) use of salt can be achieved. Salt and
alkali free reactive dyeing of modified cotton have also been reported [104-106].

In reactive dyeing, cationisation of cotton has been shown to be capable of eliminating

the use of inorganic salt and alkali and leaving a reduced amount of unfixed dye. This offers
significant environmental benefits. However, the technique has yet to be adopted by industry.
That is mainly because cationisation is an additional process step and the treatment itself does
not guarantee nontoxic effluent. Natural polymers such as cationic starch and chitosan have been
explored as cationising agents [107-109]. These may make the cationisation process
environmentally safer. Mercerisation of cotton fabric is a usual practice of continuous dyehouses.
It is a pre-dyeing process that ensures the benefits of improved colour yield, tensile strength,
lustre and dimensional stability. Mercerisation is an expensive process in terms of capital,
maintenance, running and the caustic recovery costs. An experimental refinement into the
cationisation of cotton fabric has the potential of replacing the mercerization process, which can
be carried out on a stenter without any capital and much of the running costs.

8.3. Emerging Technologies

Ultrasonic energy offers the opportunity to increase the intensity and speed of reaction of many
wet textile processes. Past studies have demonstrated improvements to energy, water and
chemical consumption, improved colour yields and reduced effluent loads [110-112]. Recently,
Nadeeka et al. have reported a successful ultrasonic-assisted dyeing of cotton fabric with reactive
dyes, wherein improved dye uptake at lower temperatures has been claimed [113]. Thakore
constructed a specially mounted ultrasonic tube resonator and used it for exhaust and pad-batch
dyeings of cellulose based fabrics with reactive dyes on a production scale [114].

Microwave heating has been shown to improve the uptake and fixation of reactive dyes
on cotton [115, 116]. Research on potential applications is expected to continue. Plasma and
supercritical carbon dioxide have been explored as ways to eliminate the use of water in dyeing
[112, 117-122].

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