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EFFECT OF USING NATURAL AND SYNTHETIC ANTI

MIGRANTS IN CONTINUOUS DYEING OF COTTON


WITH REACTIVE DYES.

by

ASAD JAMIL

A Thesis Submitted in Partial Fulfillment of the Requirements for the


Degree of
Bachelor of Science in Textile Engineering

Department of Textile Chemistry


National Textile University, Faisalabad
March 2011

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EFFECT OF USING NATURAL AND SYNTHETIC ANTI
MIGRANTS IN CONTINUOUS DYEING OF COTTON
WITH REACTIVE DYES.

by

ASAD JAMIL

06-NTU-107

A Thesis Submitted in Partial Fulfillment of the Requirements for the


Degree of
Bachelor of Science in Textile Engineering

Department of Textile Chemistry


National Textile University, Faisalabad
March 2011
This copy of the thesis has been supplied on condition that anyone who consults it is understood
to recognize that the copyright rests with its author and that no quotation from the thesis and no
information derived from it may be published without the prior written consent of the author or
of the University (as may be appropriate).”

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Contents
ABSTRACT...........................................................................................12
Chapter 1...............................................................................................13
1.1. Background:..............................................................................13
1.1.1. Cotton...................................................................................13
1.1.2 Growth of Cotton Plant:........................................................14
1.1.3 Fiber Structure and Formation..............................................15
1.1.4 Physical Properties of Cotton................................................16
1.1.4.1 Color..................................................................................16
1.1.4.2 Heat...................................................................................16
1.1.4.3 Light...................................................................................16
1.1.4.4 Electrical............................................................................16
1.1.4.5 Shrinkage...........................................................................16
1.1.4.6 Absorbency........................................................................17
1.1.4.7 Solvents.............................................................................17
1.1.4.8 Resistance to Mildew.........................................................17
1.1.5 Chemical Properties of Cotton..............................................17
1.1.5.1 Effect of Alkalis..................................................................17
1.1.5.2 Effect of Acids....................................................................17
1.1.5.3 Reaction to Bleach.............................................................18
1.1.5.4 Affinity for dyes.................................................................18
1.1.5.5 Resistance to Perspiration:................................................18
1.1.6 Composition of cotton...........................................................19
1.1.7 Uses......................................................................................19
1.1.8 Introduction to Reactive Dyes:.............................................20
1.1.9 Reactive Dyeing....................................................................23
1.1.10 Selection of Reactive dyes....................................................23
1.1.11 Diffusion of dye in the application of Reactive dyes.............23
1.1.12 Factors that influence the Absorption and Reaction.............23
1.1.12.1 Adsorption.........................................................................24
1.1.12.2 Absorption.........................................................................24
1.1.12.3 Fixation..............................................................................24
1.1.13 Removal of Hydrolyzed dye..................................................25
1.1.14 Reactivity and Affinity of the dyes:.......................................25
1.1.15 Importance:..........................................................................26

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1.1.16 Migration..............................................................................27
1.1.16.1 Factors of Migration:..........................................................27
1.1.16.2 Solutions:...........................................................................27
1.1.17 Migration Inhibitors:..............................................................28
1.1.18 Synthetic Migration Inhibitors:..............................................28
1.1.18.1 Thermaco MIN[10]:............................................................29
1.1.18.2 Thermacol MP[10]:.............................................................30
1.1.18.3 Primasol FFAM[10]:............................................................31
1.1.19 Natural Migration Inhibitor:...................................................32
1.1.19.1 Sodium Alginate:...............................................................32
1.1.19.2 Guar Gum:.........................................................................33
1.1.19.3 Carboxy methyl cellulose:.................................................34
1.1.20 Dyeing Processes:.................................................................35
1.1.20.1 Exhaust dyeing..................................................................35
1.1.20.2 Semi continuous dyeing.....................................................36
1.1.20.3 Continuous dyeing:............................................................38
1.2 Significance of Problem:..........................................................39
1.3 Literature Review....................................................................41
1.4 Objectives of the Experiment:.................................................42
Chapter 2...............................................................................................43
2.1 Material...................................................................................43
2.1.1 Fabric specifications:............................................................43
2.1.2 Chemicals and auxiliaries:....................................................44
2.2 Machinery and Equipments:....................................................44
2.2.1 Application Equipments:.......................................................44
2.2.2 Testing Equipment:...............................................................45
2.3 Methods...................................................................................45
2.3.1 Application method:.............................................................45
2.3.2 Recipes:........................................................................................46
2.3.3 Testing methods...................................................................46
2.3.3.1 Migration test.....................................................................46
2.3.3.2 Tensile strength:................................................................48
2.3.3.3 Tear strength:....................................................................48
2.3.3.4 Crock fastness test method:..............................................49
2.3.3.5 Washing Fastness test method:.........................................50
2.3.3.6 Spectrophotometer:...........................................................51
Chapter 3...............................................................................................52

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3.1 Effects of migration inhibitors:................................................52
3.2 Effect of migration inhibitors on Tensile and Tear strength [24]:
55
3.2.1 Tensile strength:...................................................................55
3.2.2 Tear strength:.......................................................................56
3.3 Effect of migration inhibitors on crock fastness [25]:..............58
3.4 Effect of migration inhibitors on wash fastness [26]:..............60
3.5 Effect of migration inhibitors on CV-SUM:................................62
3.6 Effect of migration inhibitors on % strength:...........................63
3.7 Effect of migration inhibitors on Bending Length:...................65
Chapter 4...............................................................................................67
4.1 Key Findings of the Project......................................................67
4.2 Implication of the project:.......................................................67
4.3 Suggestions for Future Work:..................................................68
5 References:................................................................................69
References:

List of Figures:

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Figure 1. 1 Structure of Monoazo Type and Anthraquinone Dyes....................................21
Figure 1. 2 Structure of Pyrimidine and Quinoxaline Type Dye......................................22
Figure 1. 3 Structure of Quaternary Ammonium Dyes..................................................22
Figure 1. 4 Relative reactivity’s of reactive dyes for cellulose fibers.............................26
Figure 1. 5 Sodium alginate structure...................................................................32
Figure 1. 6 Structure of Guar Gum..........................................................................33
Figure 1. 7 Structure of Carboxy Methyl cellulose...................................................34
Figure 1. 8 Semi Continuous Process......................................................................37
Figure 1. 9 Continuous Process...........................................................................39

Figure2. 1 Layout of Migration Test Apparatus..........................................................47


Figure2. 2 Grey scale for color change.....................................................................47
Figure2. 3 Tensile Strength Tester..........................................................................48
Figure2. 4 Crock meter........................................................................................49
Figure2. 5 HT Dyeing Machine..............................................................................50
Figure2. 6 Spectrophotometer............................................................................51
Figure2. 6 Spectrophotometer

Figure3. 1 Natural Migration Inhibitors When Used.................................................52


Figure3. 2 Synthetic Migration Inhibitors When Used..................................................53
Figure3. 3 Migration Inhibitors..............................................................................54
Figure3. 4 Effect of Migration Inhibitors on Tensile Strength......................................55
Figure3. 5 Effect of Migration Inhibitors on Tear Strength.............................................57
Figure3. 6 Grey Scale for Color Change...................................................................58
Figure3. 7 Effect of Migration Inhibitors on Crock Fastness...........................................59
Figure3. 8 Grey Scale for Staining.......................................................................60
Figure3. 9 Effect of Migration Inhibitors on Wash Fastness........................................61
Figure3. 10 Effect of Migration Inhibitors on CV-SUM............................................62
Figure3. 11 Effect of Migration Inhibitors on % Strength...........................................64
Figure3. 12 Effect of migration inhibitors on Bending Length.....................................66
Figure3. 12 Effect of migration inhibitors on Bending Length.

List of Tables:
Table1. 1Composition of Cotton.............................................................................19

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Table1. 2 Characteristics of Thermaco MIN..............................................................29
Table1. 3Characteristics of Thermacol MP................................................................30
Table1. 4 Characteristics of Primasol FFAM.............................................................31

Table2. 1 Chemicals............................................................................................44
Table2. 2Major Equipment used in the Experiment:.....................................................44
Table2. 3Testing Equipment..................................................................................45
Table2. 4Recipes................................................................................................46
Table2. 4Recipes
Table3. 1Effect of Natural Migration Inhibitor...........................................................52
Table3. 2Effect of Synthetic Migration Inhibitor.........................................................53
Table3. 3Effect of Migration Inhibitor on Tensile Strength............................................55
Table3. 4Effect of Migration Inhibitor on Tear Strength...............................................56
Table3. 5 Effect of migration inhibitors on crock fastness.............................................58
Table3. 6Effect of migration inhibitors on wash fastness...............................................60
Table3. 7Effect of migration inhibitors on CV-SUM:...................................................62
Table3. 8Effect of migration inhibitors on % strength:..................................................63
Table3. 9 Effect of migration inhibitors on Bending Length...........................................65
Table3. 9 Effect of migration inhibitors on Bending Length

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DEDICATION

Those who live in our heart,

Throughout the whole span of our life,

Whose devotion and prayers make us

able and nearest,

Dearest and deepest to us.

To my beloved parents.

Acknowledgment

I feel great pleasure in acknowledging my indebtedness to all those who have been of
substantial help and support to me during the preparation of this manuscript.

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The work presented in this manuscript was accomplished under the inspiring guidance
and enlightened supervision of Dr. Rashid Masood, Head of Department of Textile
Chemistry, National Textile University, Faisalabad. His efforts towards the inculcation
of the spirit of constant work and maintenance of professional integrity besides other
valuable words of advice encouraged me to keep on fighting against all over whelming
odds till success was ensured. I avail this opportunity to express my deepest sense of
gratitude and thankfulness to him.

I deem it utmost pleasure to express my heartiest gratitude and deep sense of obligation
to Dr. Tanveer Husain, Quality Assurance Department Dean, National Textile
University, Faisalabad fir his guidance, encouragement and invaluable suggestions
throughout the course of the project.

I thank all the staff of the chemistry lab for their cooperation and assistance during the
performance of my experimental work.

The completion of this project is a long term task and needs an ideal atmosphere for its
completion. I pay tribute to all my well wishers and class fellows for their cooperation
and sincere help.

ABSTRACT

In this project both natural and synthetic migration inhibitors were applied using
different concentrations i-e 10g/L, 20g/L and 30g/L. After dyeing of fabric the dyed
samples were test for:

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1. Migration test
2. Color depth
3. Tensile/ Tear strength
4. Bending length
5. Wash fastness

The results showed that synthetic migration inhibitors efficiently restrict dye particles
movement as compared to natural migration inhibitors. The result also shows that
natural migration inhibitors make fabric stiff as compared to synthetic migration
inhibitors. But on the other hand natural migration inhibitors as compared to synthetic
show good color depth and do not affect tensile and tear strength of fabric.

Chapter 1

INTRODUCTION

1.1. Background:
Migration is the shifting of the color to the surrounding areas. It is the unwanted reaction
between the dye and the fiber. Migration is a serious problem encountered both
in dyeing and printing. Dye migration is generally more on 100 per cent
polyester fabrics. It results in the coloring of unintended areas. Hence, any

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fabric containing the polyester is vulnerable to dye migration and bleeding.
Migration ceases when the fabric has dried to the point where the coherence
of the liquid phase is interrupted. Migration ceases when the fabric has dried
to the point where the coherence of the liquid phase is interrupted. In the
case of cellulose fibers this point is reached at about 30 percent moisture
content. Dye migration is also known as bleeding or dye sublimation.
Migration is a serious problem in pigment dyeing, particularly when an improvement in
handle (softening) is aimed at during dyeing. This phenomenon can be observed to a
greater or lesser extent with all dyes and all types of fibers. It is particularly serious
however when using pigment dyes.
Limiting moisture values below which the dye no longer migrates can be determined for
a given type of fabric and a given dye, although the phenomenon of migration is
extremely complex.

It may be stated that the most important measures for preventing migration are:
decreasing the liquor take-up (the mobile phase has to be decreased), increasing the
viscosity of the padding liquor, agglomerating the pigment upon drying, using special
pigment formulations which have low tendency to migrate and, not least, adding special
anti migration agents which arrest the dye particles on the fiber [1].

1.1.1.Cotton
Cotton is one of the vegetable fibers occurring in the nature. Cotton is a soft fiber and
grows on the seeds of cotton plant (Gossipium). The fiber most often is spun into yarn or
thread and used to make a soft, breathable textile, which is the most widely, used
natural-fiber cloth in clothing today. The English name derives from the Arabic Al-qutn
(which also comes from the Spanish word algodon) meaning cotton fiber.

Cotton fiber has also impurities in it. When it is being processed then it is almost pure
cellulose (C6H12O5).It is one of the most economical fibers. It is said that Pakistan is one
of the top most countries in the world with respect to growth of cotton. Its production is
economical because 10 % or less is being lost in the subsequent processing to convert
raw cotton into pure form. The cellulose is arranged in the way that gives cotton high
degree of strength, durability and absorbency. Each fiber is made up of 20-30 layers of
cellulose coiled in a neat series of natural springs. When the cotton boll (seed case) is
opened, the fibers dry into flat, twisted, ribbon like shapes and become linked together
and interlocked. This helps in the spinning of cotton fiber.

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In Pakistan, the best –considered cotton is available from Multan, Khanpur, Lodhran,
Hasilpur, Shujaabad, Bahawalpur, Fort Abbas and Rahim Yar Khan. Cotton produced in
these regions is normally purchased from August to December but I can vary according
to the weather conditions [2].

1.1.2Growth of Cotton Plant:


Cotton plants have a general time frame in which they grow and produce after planting
(introducing the seed to moist soil). With ideal conditions, the planted cotton seed will
germinate (to begin to grow) or sprout and emerge in about five to ten days. The first 2
leaves that are visible on the young cotton plant are seedling leaves called cotyledons
(cot-a-lee-dons). They are useful for absorbing sunlight into the plant. The sunlight is
then converted through a process known as photosynthesis, into nourishing
carbohydrates that will help the plant grow.

In about two to four weeks they turn over the photosynthetic task to true leaves (leaves
produced subsequent to the cotyledons) which continue the feeding process for the
duration of the plants life. The plant continues to grow, adding leaves and height, and in
approximately five to seven weeks, small flower buds called squares (a small flower bud
covered with fringed leaf-like parts called bracts) will appear on the cotton plant. As this
square develops, the bud swells and begins to push through the bracts until it opens into
an attractive flower. Within three days, the flower will pollinate (the transfer of pollen
from the anther to the stigma of the same or another flower) itself, change from a
creamy white or yellow color to a pinkish red, and then wither and fall, exposing a
small, green, immature cotton boll (a segmented pod containing 32 immature seeds from
which the cotton fibers will grow). This boll is considered a fruit because it contains
seeds. As the fibers continue to grow and thicken within the segmented boll, it enlarges
until it becomes approximately the size of a small fig. Now, the cotton fibers have
become mature and thickened with their primary growth substance, cellulose (a
carbohydrate, the chief component of the cell wall in most plants). An average boll will
contain nearly 500,000 fibers of cotton and each plant may bear up to 100 bolls.

In about 140 days after planting or 45 days after bolls appear, the cotton boll will begin
to naturally split open along the bolls segments or carpel’s and dry out, exposing the
underlying cotton segments called locks. These dried carpels are known as the bur, and
it's the bur that will hold the locks of cotton in place when fully dried and fluffed, ready
for picking.

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The growth cycle of the various cotton species vary in length, but the sequence of fruit
production remain the same. Weather, insects and moisture can adversely affect
optimum conditions for plant growth and it is the farmer's responsibility to adjust to
these conditions to optimize yield [2]

1.1.3 Fiber Structure and Formation


Each cotton fiber is composed of concentric layers. The cuticle layer on the fiber itself is
separable from the fiber and consists of wax and pectin materials. The primary wall, the
most peripheral layer of the fiber, is composed of cellulosic crystalline fibrils. The
secondary wall of the fiber consists of three distinct layers. All three layers of the
secondary wall include closely packed parallel fibrils with spiral winding of 25-35° and
represent the majority of cellulose within the fiber. The innermost part of cotton fiber-
the lumen- is composed of the remains of the cell contents. Before boll opening, the
lumen is filled with liquid containing the cell nucleus and protoplasm. The twists and
convolutions of the dried fiber are due to the removal of this liquid. The cross section of
the fiber is bean-shaped, swelling almost round when moisture absorption takes place
[3].

1.1.4 Physical Properties of Cotton


1.1.4.1 Color
Usually cotton fibers are cream white. Most Egyptian cotton has yellowish brown color
due to a pigment transferred from the soil. A certain variety of cotton grown in southern
states of United States of America has a bluish tinge, which is very difficult to bleach
[3].

1.1.4.2 Heat
Prolonged drying below 100°C can depolymerise cellulose by generally natural fibers
can withstand moderate temperatures. Exposure to heat does not produce any visible
change until a temperature of 120° C is reached. At this temperature, cotton becomes
yellow after 5 hours exposure, but show little change in strength. At 140°C, a distinct
brown color develops and serious loss of strength results. When heated for a few hours
at 240°C, almost complete loss of strength is noted [3].

1.1.4.3 Light

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Cotton fabrics are affected by ordinary light and more particularly by ultraviolet light.
They oxidize, turning yellow and losing strength from exposure to sunlight over a
protected period. Cotton fabrics should therefore fade from direct sunlight [3].

1.1.4.4 Electrical
Cellulose when dry is a poor conductor. This causes it to become charged with static
electricity. Static electricity can cause many processing problems for textile materials.
This electrical charge can cause fibers and yarns to repel each other, leading to
ballooning [3].

1.1.4.5 Shrinkage
When cotton fiber is wet, it tends to contract or shrink as it dries. As a result, cotton
yarns and fabrics can shrink considerably, particularly those that are loosely constructed.
However, preshrinking finishing processes minimize shrinkage that a fabric or garment
has and care instructions should be followed to retain the required size and shape [3].

1.1.4.6 Absorbency
The ease and extent to which moisture can penetrate into a fiber determines its
absorbency. Once the outer protective cuticle of the cotton in finishing process, such as
kiering and mercerizing breaks down fiber, then fiber becomes very absorbent. Its
hallowing centre, or lumen, aids in conveying moisture. In addition to it, yarn and fabric
construction plays an important role in absorbency [3].

1.1.4.7 Solvents
Cellulose does not dissolve in common organic solvents. Strong solutions of certain
acids first swell and then dissolve it [3].

1.1.4.8 Resistance to Mildew


Cotton fabrics, especially sized fabrics mildew readily when permitted to remain in a
damp condition. Small greenish black or rust spots caused by mildew fungus develop
and a musty odor can be detected. Therefore, cotton material should be kept in a dry
atmosphere or mildew inhibitor should be used [3].

1.1.5 Chemical Properties of Cotton


1.1.5.1 Effect of Alkalis
At low and high pH in the absence of air, alkalis have no affect on cotton. However, in
the presence of oxygen or some metals at high temperature, oxy cellulose is formed. As
a result, cotton turns yellow and loses strength slightly. With cold dilute sodium

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hydroxide, (25-30 %) cotton fiber swells and natural convolutions present in cotton are
removed. This phenomenon is called mercerization, and is used to impart strength,
smoothness and luster to treated fabrics [4].

1.1.5.2 Effect of Acids


Strong acids like nitric acids attack cotton, generally, these acids disintegrate cotton.
Higher the concentration of acid or higher the temperature, more rapid is the destruction
of the fiber. Dilute solutions of acids, if washed immediately, cause no harm, but when
they are allowed to concentrate by evaporation of water, cloth loses strength and
crumbles to powder. Acids are used in a process called carbonization to disintegrate
cellulose portion of wool and cellulose mixtures. Volatile organic acids, like acetic
acids, do not harm cotton fibers [4].

1.1.5.3 Reaction to Bleach


Bleaches are chemical solutions designed to remove discoloration (and some time
color). While hydrogen peroxide may be used, the more common household bleaches for
cotton are solutions of sodium hypochlorite. These bleaches used as directed, will
effectively bleach cotton fabrics. Labels on wash and wear fabrics should be observed
since some of these finishes are chlorine retentive. Such cotton clothes turn yellow when
subjected to sodium hypochlorite bleaches [4].

1.1.5.4 Affinity for dyes


Cotton has a good affinity for dyes. It is dyes with vat dyes, but oxidation bases, azoic
and reactive dyes may also be effectively used. Colorfastness is generally good, but
specific conditions should be considered. Washing a sample in hot water can test
fastness of dyes to washing [4].

1.1.5.5 Resistance to Perspiration:


Perspiration may be alkaline or acidic, depending upon the individual’s metabolism.
Since cotton is resistance to alkali, alkali perspiration does not deteriorate cotton.
However, acid perspiration has a slightly deteriorating effect. In either case,
discoloration may occur [4].

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1.1.6 Composition of cotton
Cotton fibers mainly consist of cellulose and small amounts of other compounds varying
in different samples. The raw cotton contains the following ingredients:

Table1. 1Composition of Cotton

COMPONENTS PERCENT

Cellulose 94.0

Protein 1.3

Ash 1.2

Wax 0.6

Sugars 0.3

Pigments Traces

Others 2.6

1.1.7 Uses
There are some of the products where cotton is being used:

1. Terry cloth
2. Absorbent bath towels
3. Seersuckers
4. Bed sheets
5. Yarn manufacturing
6. Making blends with other fibers
7. Fish nets
8. Denim
9. Cotton seed is used in the production of vegetable oils [4].

1.1.2Introduction to Reactive Dyes:


Reactive dyes consist of a chromophore attached to a reactive group through a

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-NH- group. The chromophore is responsible for the color of the molecule. The reactive
group provides capability for the dye to react with the fiber and has little or no influence
on the color.
CHROMOPHORE-NH-GROUP
Since the dye is fixed to fiber by covalent bonds, the chromophore can be a small,
simple structure with limited reaction to the fiber. Small molecular structures in reactive
dyes provide advantages such as high solubility in water, easy removal of hydrolysed
and bright colors. Therefore the chromophore is usually a relatively small structure
containing sulfonate groups to make the dye soluble in water. Typically chromophores
in reactive dye structures are mono azo, anthraquinone, pthalocyanine (for bright
turquoise hue), triphenodioxazine and formazan. The azo group is sometimes metalized
with copper, cobalt, or chromium to produce a bathochromic shift.
Several types of reactive groups are found in reactive dyes. The first reactive dyes
contained triazine reactive groups. This type of reactive group is important in reactive
dyes today. The dyes are made by attaching a chromophore to trichlorotriazine (cyanuric
chloride).

Figure 1. 1 Structure of Monoazo Type and Anthraquinone Dyes

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Dichlorotriazine type reactive dyes contain two displaceable (reactive) chlorine groups.
Monochlorotriazine type reactive dyes are made by substituting one of the remaining
chlorine atoms with an unreactive group leaving only one reactive group on the dye
molecule. Dichlorotriazine reactive dyes are more reactive and are usually applied at
lower temperatures then monochlorotriazine reactive dyes. Both types are widely used.
Cyanuric chloride is a chromophoric blocking group. Attachment of two chromophores
through the triazine ring structure produce a dye with the color that would be produced
by physically mixing two chromophores. Thus attachment of a blue and a yellow
chromophore through a triazine ring produces a green dye. Although the structure
produced by this method are too large to be reactive dyes, the technique used in making
direct dyes, CI direct green 26 is an example of a dye produced by this method.

Diazine reactive groups are also used in reactive dye molecules. Pyrimidine and
quinoxaline are the most important of the diazines in commercial reactive dyes.

Figure 1. 2 Structure of Pyrimidine and Quinoxaline Type Dye

The leaving groups (chlorine of other) on diazines rings are less reactive then those on
triazine rings. The quinoxaline dyes are less reactive then Dichlorotriazine reactive dyes.
Even though they may contain more than one halogen atom, the reactivity of the other
Diazine types is similar to that of the monochlorotriazine types.
Although chlorine is the most common leaving group on reactive dye molecules, many
other leaving atoms and groups have been described in patent literature. Three leaving

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groups other then chlorine that are found on commercial dyes are fluorine, quaternary
ammonium, and methyl sulfonyl. Following are the examples of dyes with these leaving
groups.

Figure 1. 3 Structure of Quaternary Ammonium Dyes

All three of these groups are effective leaving group which makes the dye more reactive
then dyes with reactive molecules containing chlorine leaving groups. The nicotinic acid
leaving group shown in the quaternary ammonium example above produces dyes which
react with cellulose under neutral conditions. This allows them to be applied
simultaneously in the same dye bath with disperse dyes on polyester cotton blend fabrics
[5].

1.1.3 Reactive Dyeing


In previous section, the general nature, historical background and chemistry of reactive
dyes were discussed. Here the principle of dyeing with reactive dyes and their behavior
in the dye bath will be considered [5].

1.1.4 Selection of Reactive dyes


Many reactive dyes are now commercially available, with a variety of reactive groups.
Their simplicity of application and broad spread of reactivity and substantivity makes
them very versatile in application. But as with other classes of dye, the quality of their
dyeing depends upon careful dye selection. Appropriate levels of reactivity,
substantivity and rate of diffusion are needed for the method of application best suited to
the goods in hand. Indeed the dyeing of reactive dyes may be described quantitatively in

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thee terms, but usually a simpler empirical representation is more appropriate on the
shop floor [5].

1.1.5 Diffusion of dye in the application of Reactive dyes


a) Diffusion of dye into the cellulose fiber. Varying the dyeing time, the dye bath
temperature and the salt concentration controls it.
b) Reaction between the dye and cellulose. It is achieved by the selection of an
appropriate alkalinity (pH).
The above mentioned stages very briefly describe the reactive dyeing procedure,
following is given all the phases and factors that play a vital role in reactive dyeing [5].

1.1.6 Factors that influence the Absorption and Reaction


Dyeing of cellulose fibers with reactive dyes takes place in three distinct phases:

• Adsorption
• Absorption
• Fixation
• Removal of hydrolyzed dye that is not fixed covalently to cellulose
The different factors affecting the above mentioned stated three phases of dyeing are as
follows

1.1.2.1 Adsorption
Factors affecting are:
• Nature of dye ( dye affinity )
• Liquor ratio
• Electrolyte concentration
• Temperature
• Nature of fiber

1.1.2.1 Absorption
Factors affecting are
• Nature of dye ( diffusion co-efficient of dye )
• Liquor ratio

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• Temperature
• Nature of fiber
• Particle size of fiber

1.1.2.1 Fixation
Factors affecting are:

• Reactivity of dye
• pH
• temperature

1.1.2 Removal of Hydrolyzed dye


Factors affecting are
• Affinity
• Electrolyte concentration
• Temperature

For continuous process of dyeing rapid washing-off is essential and this is favored by
using dyes of lower substantivity. This will also avoid premature exhaustion of dye from
the padding liquor during the time the fabric is passing through. If exhaustion was
allowed to happen too rapidly, the fabric would develop a deeper shade at one end than
at the other end, a phenomenon known as Tailing.

1.1.2 Reactivity and Affinity of the dyes:


If the reactivity of the dye is increased considerably, the rate of reaction with the fiber
increases. Therefore, the dyeing can be carried out in a short time. However, in this case
the rate of hydrolysis of the dye also increases, leading to deactivation of a part of the
dye. This will result in wastage of dye. If on the other hand, the reactivity of the dye is
decreased, the extent of hydrolysis can be reduced considerably. However, this results in
the slower rate of reaction with the fiber also.
The ultimate object of dyeing is to react as much of the dye as possible with the fiber
and minimize the hydrolysis of the dye. This is achieved in practice in two stages. The
dyeing is first started from the aqueous medium under neutral conditions when the dye
does not react either with the fiber or with water. Then Glauber’s salt or common salt is
added to exhaust the dye onto the fiber as much as possible. In this respect, this stage of
dyeing (exhaustion) resembles the dyeing of direct dyes on cotton. Then the second step

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(fixation or reaction with the fiber) is carried out by adding the alkali (i.e. soda ash).
Since the exhausted dye is already on the fiber, it is more likely that the exhausted dye
reacts with the fiber in preference to water. However, the dye present in the dye bath
(which contains a substantial amount of reactive dye) can now react with water since it
is under alkaline conditions. It is already stated that the hydrolyzed dye cannot further
react with the fiber but due to he affinity forces, it is absorbed by the fiber and is
retained in it. During the subsequent washing or soaping the substantively held
hydrolyzed dye gets stripped into the washing bath thereby reducing the washing
fastness of the dyeing [6].

1.1.3 Importance:
Current ranges of reactive dyes include many that have a broad spread in their level of
reactivity and substantivity. Some examples are shown in Figure, in which their
respective levels of reactivity are compared. Since their introduction these dyes have
played a dominant role in the dyeing of cellulosic fibers.

Figure 1. 4 Relative reactivity’s of reactive dyes for cellulose fibers


Many reactive dyes possess a resistance to daylight previously only associated with vat
dyes. This is reflected in their use for top-quality curtains, furnishings and awnings.
They also contribute to the color quality of many domestic goods that require frequent
washings, such as toweling, and are used extensively for shirting’s, tapes, ribbons, dress
goods and knitted sportswear; the last-named accounts for around 40% of the reactive
dye market [7].

2
1.1.4 Migration
In many continuous dyeing processes, it is necessary to give the padded fabric an
intermediate drying, during which some of the dye present on the goods may move to
the surface of the cloth. This movement of dye particles during the dyeing operations is
generally termed migration.

On the basis observations various types of faulty dyeing which are occurring in practice
due to migration can be readily explained. Cases of two-sided dyeing and listing are
caused by a vertical migration of the dye particles, where one side of the fabric receives
more or less heat then the other. Streaks which occur during drying may also be due to
uneven drying and vertical migration. If a difference in hue as well as depth is observed
where there is two-sidedness or listing, then selective migration has occurred. With
horizontal migration, the dye particles migrate over the surface of the textile material. A
faded or washed-out appearance of portions of the dyed fabric is traceable to horizontal
migration. When the dyes migrate in a horizontal direction at different rates, then
dichroism (two-color effect) is produced.

1.1.4.1 Factors of Migration:


Intermediate drying is one of the most important steps in the pad-dry-cure process where
the most common problem ‘migration’ can take place. Important factors on which
migration depends are as follows:

• Dye constitution,

• Dye formulation,

• Pick-up,

• Additives in the dye padder,

• Residues of wetting agents and lubricants on the fabric,

• Fabric structure, and

• Drying conditions

1.1.2.1 Solutions:

2
• Make sure to maintain consistent temperature, wind velocity, and wind pressure
while drying the fabric so that it gets dried evenly.
• Use dyestuffs and that are less likely to migrate.
• Dye the fabric as soon as possible after dyeing or padding
(so that the fabric does not hang around un-dried for a long time) [9].

1.1.3Migration Inhibitors:

A substance added to a dye to slow down its ability to spread or bleed into a fabric as it
is applied. Natural and synthetic migration inhibitors are used in the industry.

Anti migration agents used particularly for dyeing and printing include polyvinyl methyl
ethers of a mean molecular weight of about 100,000, alginates, low molecular weight
cellulose ethers, polyethylene glycols of mean molecular weights of from 8,000 to
10,000 and special polymers of poly vinyl caprolactam.

Migration-inhibiting agents which are to give useful results in dyeing and printing
followed by intermediate drying should neither disturb the dye neither finish nor cause
loss in brilliance. In addition, the agent should have adequate liquor stability, should not
cause any hardening of the handle and should have good solubility at room temperature.
The turbidity point of these compounds is also of special importance and should lie
within a range from about 35° to 55°C.

Migration inhibitor for continuous dyeing improves surface levelness of dyeing.


Migration inhibitors are necessary to control dye particle movement during the pre
drying phase.

1.1.4 Synthetic Migration Inhibitors:


Synthetic migration inhibitors have mostly chemical constitution of acrylic copolymer.
Their ionic character is anionic. They wash off easily hence no harshening of handle.
They are present in both colored and colorless forms but mostly yellowish in color.
Stable in hard water and to acids, alkalis and electrolytes in the usual amounts. They are
stable at 20°C and can be kept for a year or more then year but they should be tightly
reclosed after each withdrawal. The required amount of migration inhibitor depends on
dyestuff concentration. They reduce cleaning time hence shortened downtime and
increased productivity. They are applied in the continuous process and their application
is in the following processes:

2
• Pad-dry-cure
• Pad-steam
• Pad-jig
• Thermosol process
• Wet-in-wet dyeing
• Pad thermosol pad steam process

Synthetic migration inhibitors to be used in the experiment are:

• Thermacol MIN
• Thermacol MP
• Primasol FFAM

1.1.2.1 Thermaco MIN[10]:


Table1. 2 Characteristics of Thermaco MIN
Chemical Aqueous solution of an acrylic polymer
constitution
Ionic character Anionic

Physical form Colorless liquid

Specific gravity approx. 0.9

General stability Stable to hard water and pH values between 4 and 10.

Storage stability Stable for more then one year at 20°C in closed containers.
Should
not be stored at temperatures above 40 °C

Compatibility Compatible with anionic and nonionic auxiliaries.

Ecology/Toxicolog The usual hygiene and safety rules for handling chemicals
y should be observed in storage, handling and use. The
product must not be swallowed.

1.1.2.2 Thermacol MP[10]:


Table1. 3Characteristics of Thermacol MP
Chemical Aqueous solution of an acrylic polymer
constitution
Ionic character Anionic

1
Specific gravity approx. 1

pH about 6

General stability Stable in hard water and to acids, alkalis and electrolytes in
the usual amounts.

Storage stability Stable for more then one year at 20°C in closed containers.
Solidifies at temperatures below freezing but after reverting
to room temperature it is fully effective again.
Compatibility Compatible with anionic and nonionic auxiliaries.

Ecology/Toxicolog The usual hygiene and safety rules for handling chemicals
y should be observed in storage, handling and use. The
product must not be swallowed.

1.1.2.3 Primasol FFAM[10]:


Table1. 4 Characteristics of Primasol FFAM
Chemical Acrylic Copolymer.
constitution
No surfactant No foaming; freely miscible with water.

Physical form Yellowish viscous liquid.

pH 6.5 - 7.5.

Density 1.09 g/cm3 at 20 °C

1
General stability Stable in hard water and to acids, alkalis and electrolytes in
the usual amounts.

Storage Primasol FF-AM can be kept for at least 12 months in the


original sealed.
Containers at temperatures between 5°C and 25°C. Once the
containers have been opened, their contents should be used
up as rapidly as possible, and they should be tightly reclosed
after each withdrawal.

Safety When using this product, the information and advice given in
our Safety.
Date sheet should be observed. Due attention should also be
given to the precautions necessary for handling chemicals.

Ecology/Toxicolog The usual hygiene and safety rules for handling chemicals
y should be observed in storage, handling and use. The
product must not be swallowed.

1.1.3 Natural Migration Inhibitor:


Natural migration inhibitor used in the industry:

• Sodium alginate
• Guar gum
• Carboxy methyl cellulose (CMC).

But the most commonly used is sodium alginate.

1.1.2.1 Sodium Alginate:


Sodium Alginate is the purified carbohydrate product extracted from brown seaweeds by
the use of dilute alkali. It consists chiefly of the sodium salt of Alginic Acid, a
polyuronic acid composed of b-D-mannuronic acid residues linked so that the carboxyl

1
group of each unit is free while the aldehyde group is shielded by a glycosidic linkage.
Molecular Formula: C5H7O4COONa

Figure 1. 5 Sodium alginate structure

In Dyeing, Printing and Textile Industry:

It has been a long history since sodium alginate has been used in warp sizing, packing,
dyeing and printing. In dyeing and printing, it is an ideal kind of material with wide
applications in the cotton, wool, silk and synthetic fiber. Especially since active dyestuff
came into the world, there has been many years' history of application.

In textile dyeing and printing, alginates are used as migration inhibitors and thickeners.
Alginates became important with the advent of reactive dyes. These combine chemically
with cellulose in the fabric. Many of the usual thickeners, such as starch, react with the
reactive dyes, and this leads to lower color yields and sometimes by-products that are
not easily washed out. Alginates do not react with the dyes; they easily wash out of the
finished textile and are the best migration inhibitors and thickeners for reactive dyes.
Alginates are more expensive than starch and recently starch manufacturers have made
efforts to produce modified starches that do not react with the reactive dyes, so it is
becoming a more competitive market. This use of alginate represents a large market, but
it is affected by economic recessions when there is often a fall in demand for clothing
and textiles. The types of alginate required vary from medium-to-high viscosity. Textile
accounts for about 50 percent of the global alginate market [11].

1.1.2.2 Guar Gum:

2
Guar gum is a natural hydrocolloid that is obtained from the ground endosperm of the
guar plant. This plant is basically an annual plant that grows in huge number in the arid
regions. Guar gum is basically a polysaccharide (a long chain of sugars) made of the
sugars, galactose and mannose. Guar gum is white to off white powder and odorless.

Figure 1. 6 Structure of Guar Gum

Guar Gum mainly consists of hydro colloidal polysaccharide with a high molecular
weight, which consists of galactopyranose- and mannopyranose- units in glycoside
linkage which can be chemically described as galactomannan. The most important
property of guar gum is its ability to hydrate rapidly in cold water to attain uniform and
very high viscosity at relatively low concentrations. Another advantage associated with
guar gum is that it is a soluble in hot & cold water and provides full viscosity in even
cold water. Apart from being the most cost-effective stabilizer and emulsifier it provides
texture improvement, and water-binding; enhances mouth feel; and controls crystal
formation. It is inert in nature. It is resistant to oil, greases, and solvents.

In Dyeing, Printing and Textile Industry:

Guar Gum gives excellent film forming and thickening properties when used for textile
sizing, finishing and dyeing and printing. It reduces warp breakage, reduces dusting
while sizing and gives better efficiency in production.

Guar gum provides very good transfer of dyestuff to the fiber by conventional fixation
process. Color shades are not impaired. To improve the color yield, Guar gum can be
blended with other thickener such as starch based products. The thickener can be washed
off easily. The handle of the fabric is not affected. The viscosity of the guar gum and
stock migration inhibitors shows good stability over along period

2
Good storage stability when kept in the unopened packaging in a cool and dry place
[12].

1.1.2.3 Carboxy methyl cellulose:


Carboxy Methyl cellulose (CMC) is a cellulose derivative with carboxymethyl groups
(-CH2-COOH) bound to some of the hydroxyl groups of the glucopyranose monomers
that make up the cellulose backbone. It is often used as its sodium salt, sodium
carboxymethyl cellulose.

Figure 1. 7 Structure of Carboxy Methyl cellulose

Most CMCs dissolve rapidly in cold water and are mainly used for controlling viscosity
without gelling (CMC, at typical concentrations, does not gel even in the presence of
calcium ions). Its control of viscosity allows use as thickener, phase and emulsion
stabilizer and suspending agent. CMC can be also used for its water-holding capacity as
this is high even at low viscosity; particularly when used as the Ca 2+ salt. CMC is non-
toxic, and is non-allergenic.

In Dyeing, Printing and Textile Industry:


Its good water solubility, excellent film-forming characteristics and stable solution
viscosity make it an efficient agent used in textile. CMC does not cause hardening of the
handle of the substrate in textile dyeing and printing with reactive dyes. Such a CMC
may be used as an alternative to alginate thickeners. Textile Sizing is the most
important textile application for CMC.

Printing & dyeing grade CMC features:

• Good stability of viscosity.


• Good distribution uniformity of degree of substitution.
• Good fluidity of solution.

2
• High water scrubbing rate [13].

1.1.2 Dyeing Processes:


There are three types of processes in dyeing.

1) Exhaust dyeing
2) Semi continuous dyeing
3) Continuous dyeing

1.1.2.1 Exhaust dyeing


In exhaust dyeing (also called batch dyeing) a certain amount of textile material is
loaded into a dyeing machine and brought to equilibrium with a solution containing the
dye and the auxiliaries over a period of minutes to hours.

The dyeing process starts with the absorption of the colorant onto the external surface of
the fiber, then the diffusion and migration of the colorant through the fiber takes place.
The use of chemicals and controlled temperatures accelerates and optimizes exhaustion
and fixation (rate/level) of the dye. When the dyeing is judged to be the right shade, the
spent dye bath is drained and the textile material is washed to remove unfixed dyes and
chemicals. Washing is usually carried out in the same equipment. However, separate
washing machines can also be used.

All these operations can be carried out with different degrees of automatisation. In fully
automated dye houses all steps going from the preparation of recipes and laboratory
trials to dyestuffs and chemicals feeding, material transportation, loading and unloading
of the machines and control of dyeing parameters (e.g. level, heating, injection at
selected speed, pH, temperature, etc.) are performed under computer guidance. Small to
medium size batches can be dyed using this method.

The method of dyeing may include the following machines:

• Jet dyeing machine


• Jigger dyeing machine
• Beam dyeing machine [14].

1.1.2.1 Semi continuous dyeing


In this type of dyeing the material may be padded with the dye solution on mangle and
finished off on a jig.
In the process of semi-continuous dyeing that consists of pad-batch, pad-jig, pad-roll the
fabric is first impregnated with the dye-liquor in, what is called a padding machine.
1
Then it is subjected to batch wise treatment in a jigger. It could also be stored with a
slow rotation for many hours. In the pad-batch this treatment is done at room
temperature while in pad-roll it is done at increased temperature by employing a heating
chamber. This helps in fixation of the dyes on to the fiber. After this fixation process,
the material in full width is thoroughly cleansed and rinsed in continuous washing
machines. There is only one point of difference between Continuous and semi-
continuous dyeing process is that in semi-continuous dyeing, the dye is applied
continuously by padding.The fixation and washing remaining discontinuous. Liquor
Ratio in semi-continuous dyeing is not of much importance and is not taken as a
parameter. One of the widely used techniques for semi-continuous dyeing process is the
Pad Batch Dyeing a schematic diagram is given here for the semi-continuous dyeing
process.

Figure 1. 8 Semi Continuous Process


The only difference between continuous and semi-continuous processes is the fact that
in semi-continuous dyeing the application of the dye is performed continuously by
padding, while fixation and washing are discontinuous.

Special Features of Semi continuous Process:

• Significant cost and waste reduction as compared to other conventional dyeing


processes.

2
• Total elimination of the need for salt and other specialty chemicals. For example
there is no need for anti-migrants, leveling agents and fixatives that are necessary
in conventional dye baths.

• Optimum utilization of dyes that eliminates specialty chemicals, cuts down


chemical costs and waste loads in the effluent. All this results in a formidable
reduction in wastewater treatment costs.

• Excellent wet fastness properties.

• Pad batch dyeing cuts energy and water consumption owing to low bath ratio
(dye: water) required for the process. This is because unlike other dyeing
processes it does not function at high temperatures.

• A uniform dye quality is achieved with even color absorbency and color
fastness.

• As compared to rope dyeing, Pad batch dyeing produces much lower defect
levels.

• In semi continuous dyeing, qualities like high shade reliability and repeatability
are common. This is because of high reactivity dyes with rapid fixation rate and
stability.

• Lastly semi continuous dyeing can also improve product quality. The fabric
undergoing the cold semi continuous dyeing process is able to retain an
uniformly colored appearance. It shows added luster and gives a gentle feel. The
fabric gives a brighter look in shades [15].

1.1.2.1 Continuous dyeing:

1
The textile substrates are feeded continuously into a dye range. The speeds can vary
between 50 to 250 meters per minute. According to Industry estimates Continuous
dyeing is a popular dyeing method and accounts for around 60% of total yardage of the
products that are dyed.

A Continuous dyeing process typically consists the following. Dye application, dye
fixation with heat or chemicals and finally washing. Continuous dyeing has been found
to be most suitable for woven fabrics. Mostly continuous dye ranges are designed for
dyeing blends of polyester and cotton. The step of padding plays a key role in the
operation of continuous dyeing.

Figure 1. 9 Continuous Process

A continuous dye range has been found useful and economically sustainable for dyeing
long runs of a given shade. One important factor that separates continuous dyeing from
batch dyeing is the tolerance factor for color variation. That is more for continuous
dyeing as compared to batch dyeing. This is so because of two reasons

a) The speed of the process.

b) Presence of a large number of process variables which affects dye application.

2
The problem of migration occurs in every process which involves intermediate drying of
fabric [16].

1.2 Significance of Problem:


A substance added to a dye to slow down its ability to spread or bleed into a fabric as it
is applied. Some examples are Sodium Alginate and Super clear.

As this problem occurs mostly in the dyeing of cotton and have no any explanation i-e
which migrating agent will affect to which extent and which will be cost effective in the
sense of quality and cost.

Fastness properties, shade depth, bending length, tear and tensile strength test will also
be performed after the application of anti migrants (Natural and Synthetic) in continuous
dyeing of cotton.

Migration test will be conducted on each sample and finally results will be concluded
which anti migrant is more effective [1].

3
1.3 Literature Review
F.Somm and R.Buser, Sandoz AG worked on migration problems during intermediate
drying of pad dyeing and concluded that many continuous dyeing faults are definitely
traceable to migration problem [17].

Nick j. Christle works on different natural and synthetic thickeners for the thermosol and
space dyeing processes in general. Essential properties of the gums used in thermosol
and space dyeing and some typical procedures of the gum preparation and techniques of
application are given [18].

Allan H. Lambert and Robert J. Harper, worked on a novel approach to restrict


migration of reagents during drying of cotton textiles is to add thermal gels such as
cellulose ethers. Methyl cellulose was applied along with a cross linker, but methyl
cellulose does not interfere with cross linker, nor does it completely restrict migration
[19].

Stanely P. Rowland, Noelie R. Bertoniere and Walter D. king worked on reagent


migration in fabric thickness in pad-dry-cure finishing. Migration of DMDHEU in the
thickness direction of fabric was examined under conditions of forced draft drying from
40oC to 160oC. The subsequent cured fabrics were subjected to de Boer migration
measure to clarify extents of migration of reagent residues to fabric surface. Unbalanced
and variable migrations observed for forced draft drying in laboratory oven [20].

P. Bajaj, R. B. Chavan and Manjeet Bhatia worked on cross linked acid based thickeners
their preparation and performance in reactive dyeing and printing. For economical and
technical reasons, low solid content thickeners are desirable for textile application with
reactive dyes on cotton. Cross linking of an acrylic acid based thickener (saponified
acrylonitrile) was attempted with multi valent metal salts and a bifunctional cross
linking agent. As the concentration of the aluminum sulphate is increased, a tremendous
increase in the viscosity occurred [21].

J. N. Etters worked on inducing and measuring particulate migration and reviewed a


recommended method for inducing and measuring particulate migration and refinements
to the method were suggested. Statistical analysis of experimental data shows that the
use of a watch glass migration chamber that is saturated with water vapor can lead to
slightly higher values of particulate migration than can the use of an unsaturated
chamber [22].

1
1.4 Objectives of the Experiment:
The objectives of the experiment are:

• To evaluate the different migration inhibitors


• To find out the migration
• To study the effect of different migration inhibitors on
○ Color depth (%)
○ Bending length
○ Wash fastness
○ Rubbing fastness
○ Tensile strength
○ Tear strength

Chapter 2

EXPERIMENTAL WORK:

2
1
1.1 Material
To proceed with the proposed project material and methods are selected. Methods were
performed in National Textile University, Faisalabad with the exception of migration
inhibitors which were acquired from CIBA and BASF chemicals.

The material and equipment used for the completion of the project are described below
in detail.

• Fabric
• Chemicals
• Equipments

2.1.1 Fabric specifications:


100% bleached cotton fabric was used in this work and its warp and weft count were 31s
and its end per inch were 90 and picks per inch were 59.

1.1.2Chemicals and auxiliaries:


The chemicals were used, are given below:

Table2. 1 Chemicals

Serial # Chemicals Commercial name Manufacturer

1 Migration inhibitor Thermacol MP Huntsman

2 Migration inhibitor Primasol FFAM BASF

2
3 Migration inhibitor Thermacol MIN Huntsman

4 Migration inhibitor Sodium alginate

5 Migration inhibitor Guar gum

6 Migration inhibitor Caroboxymethyl


cellulose

7 Reactive dye Sandal fix red 150% Sandal dyestuff

1.2 Machinery and Equipments:


2.2.1 Application Equipments:
Table2. 2Major Equipment used in the Experiment:
Equipment Type Manufacturer Model No
Padder Lab Tsujii Dyeing Machine
VFM 250-A
Manufacturing Co. Japan
scale
Thrmosol Lab Daiei kagaku aeiki seisakushu.Ltd Japan OPT – 1
scale

2.2.2 Testing Equipment:


Table2. 3Testing Equipment.

Type of Test Instrument used Manufacturer Test

Standard

Migration test Simple transparent glass, Self made AATCC

watch glass and grey Test

scale Method
140-2001

Washing fastness Launder- Meter DAIEI KAGAKV ISO 105

SEIKI CO3

MFG.CO.LTD

1
Colorfastness to Crock meter Shirley ISO105*12

crocking development
Manchester, UK

Color strength Spectrophotometer Color-Eye


Gretamacbeth

Tensile strength Tensile tester Daiei kagaku aeiki ASTM 14-

seisakushu.Ltd 32

Tear strength Elmendrof tear tester Daiei kagaku aeiki ASTM 14-

seisakushu.Ltd 22

CV-sum & % strength spectrophotometer Gretagmacbeth

2.3 Methods
2.3.1 Application method:
First of all 100% bleached cotton was taken. The bleached cotton was then dyed with
Sandal fix red 150% reactive dye for 10% shade using different migration inhibitors,
both synthetic and natural. The laboratory dyeing pad thermosol machine was used and
method of dyeing was pad-dry-cure. Padding was done in padder after padding, drying
and curing was done in thermosol. The drying temperature was 120°C for two minutes
and curing temperature was 180°C for two minutes.

2.3.2 Recipes:
Table2. 4Recipes

Sandal fix red 150% 10 g/L

Na2CO3 20g/ L

Urea 10g/ L

Migration inhibitor 10g/ L, 20g/ L and 30g/L

1
The same procedure was repeated by taking 10g/ L, 20g/ L and 30g/L of migration
inhibitors used i-e. Sodium alginate, Carboxymethyl cellulose, and Guar gum,
Thermacol MP, Primasol FFAM and Thermacol MIN. All other chemicals were
remaining same in the whole experiment except the concentration of migration
inhibitors. Migration test was performed on each sample after padding then fabric was
dried and cured.

• drying temperature 120 °C


• curing temperature 180°C

After dyeing hot washing and cold washing was done of each sample.

2.3.3Testing methods
2.3.3.1 Migration test
Fabric was impregnated with colorant and auxiliaries then fabric was padded and dried
partially covering with a watch glass and partial drying was done, and therefore
migration to occur. The degree of migration was evaluated by visual examination.
AATCC Test Method 140-2001 was followed [23].

Figure2. 1 Layout of Migration Test Apparatus.


Visual examination was observed on a gray scale of 1-5 by reference to the Gray Scale
for Color Change:
Grade5. No migration
Grade4. Slight migration
2
Grade3. Medium migration
Grade2. Severe migration
Grade1. Very severe migration

1 2 3 4 5

Figure2. 2 Grey scale for color change

2.3.3.2 Tensile strength:


Test Standard ASTM 14-32

Principle

➢ The specimens are cut both warp wise and weft wise.
➢ Then specimens are mounted in the clamps of tester with moderate tightening.
➢ Machine is operated and specimen is broken.
➢ Read the breaking force for the specimen.
➢ The test is performed for both warp wise and weft wise sample.

2
Figure2. 3 Tensile Strength Tester

2.3.3.1 Tear strength:


Test Standard ASTM 14-22

Principle

➢ The specimens are cut both warp wise and weft wise.
➢ Tester was leveled with the help of adjusting screws
➢ Pendulum was set up right with help of knob
➢ Sample was placed between fixed and moveable jaws and screw was tighten
➢ A cut was made on the fabric
➢ Knob was rotated in the clockwise direction to release the pendulum.
➢ Tearing of the fabric occurs as the pendulum was released.
➢ Record the reading from the scale.

2.3.3.1 Crock fastness test method:


Test Standard ISO105*12

Principle:

1
A colored test specimen is rubbed with white crock test cloth under controlled
conditions. Color transferred to the white test cloth is assessed by a comparison with the Gray
Scale for Staining or the Chromatic Transference Scale and a grade is assigned.

Figure2. 4 Crock meter

2.3.3.2 Washing Fastness test method:


Test Standard ISO 105 CO3

Principle:

A specimen of the textile in contact with one or two specified adjacent fabrics is mechanically
agitated under specified conditions of time and temperature in a soap, or soap and soda solution,
then rinsed and dried. The change in color of the specimen and the staining of the adjacent
fabric, or fabrics, are assessed
with reference to the original
fabric, either with the grey scales.

1
Figure2. 5 HT Dyeing Machine
2
2.3.3.3 Spectrophotometer:
Principle:

A spectrophotometer, one of the most useful physics lab equipments is the combination
of two devices, a spectrometer and a photometer. Spectrometer is used for producing
light of any selected wavelength or color while a photometer is used for measuring the
intensity of light. The two devices are placed at either side of a cavetti filled with a
liquid. Spectrometer produces the light of desired wavelength and it passes through the
tube and reaches photometer that measures its intensity. Then the photometer produces a
voltage signal to a display device, usually a galvanometer. As the amount of light
absorbed by the liquid changes the signal also changes. The concentration of a substance
in solution can be measured by calculating the amount of absorption of light at the
appropriate wavelength or a particular color

Figure2. 6 Spectrophotometer

Chapter 3
Results and discussion:
3

3
3.1 Effects of migration inhibitors:
Natural migration inhibitors when used rating obtained was:

Table3. 1Effect of Natural Migration Inhibitor

Migration 0g/L 10g/ L 20g/ L 30g/L


inhibitor

Sodium alginate 2 2.5 3 4

Guar gum 1.5 2 2.5 3

CMC 2 2.5 3 3.5

Figure3. 1 Natural Migration Inhibitors When Used

Synthetic migration inhibitors when used rating obtained was:

Table3. 2Effect of Synthetic Migration Inhibitor

Migration 0g/L 10g/L 20g/L 30g/L


inhibitor

Themacol MP 1.5 2 2.5 4

Thermacol MIN 1.5 2.5 3 3.5

Primasol FFAM 1.5 3 3.5 4

Figure3. 2 Synthetic Migration Inhibitors When Used

Figure3. 3 Migration Inhibitors

1
From the above results we observed as the concentration of migration inhibitor is
increased the migration is less, and it was also observed that synthetic migration
inhibitors do their job well then natural migration inhibitors. Synthetic migration
inhibitors also reduce cleaning time hence increased productivity. In natural migration
inhibitor, sodium alginate prevents dye migration better then other natural migration
inhibitors, while in synthetic migration inhibitors Primasol FFAM and Thermacol MP
prevents better dye migration.

3.2Effect of migration inhibitors on Tensile and Tear strength [24]:


3.2.1 Tensile strength:
Table3. 3Effect of Migration Inhibitor on Tensile Strength

3
Migration 0g/L 10g/L 20g/L 30g/L
inhibitor
War Weft Warp Weft Warp Weft Warp Weft
p (kg) (kg) (kg) (kg) (kg) (kg) (kg)
(kg)
FFAM 20 17 23 20 21 18 20 17
MIN 20 17 17 15 14 12 16 14
MP 20 17 16 11 14 12 13 16
Sodium 20 17 17 14 17 15 16 13
alginate
Guar gum 20 17 18 16 17 14 18 15
CMC 20 17 18 15 19 16 20 17

Figure3. 4 Effect of Migration Inhibitors on Tensile Strength.

The results shows that synthetic migration inhibitors effect on tensile strength is
negative as the tensile strength is decreasing with the increasing concentration of
migration inhibitor, due to acrylic acid component present in the polymer structure of
migration inhibitors causing degradation to some extent while natural migration
inhibitors do not affect the tensile strength of fabric too much.

3.2.2Tear strength:
Table3. 4Effect of Migration Inhibitor on Tear Strength

Migration Inhibitor 0g/L 10g/L 20g/L 30g/L


Warp Weft Warp Weft Warp Weft Warp Weft
(g) (g) (g) (g) (g) (g) (g) (g)
Primasol Ffam 850 220 880 170 820 160 780 130

Thermacol Min 850 220 640 280 590 250 520 190

2
Thermacol Mp 850 220 580 180 520 160 470 130

Sodium Alginate 850 220 580 260 540 220 480 190

Guar Gum 850 220 480 240 430 200 390 150

CMC 850 220 580 240 520 180 460 140

Figure3. 5 Effect of Migration Inhibitors on Tear Strength.

The results in table and figure show that as the concentration of migration inhibitor
increases the tear strength decreases. However, in case of synthetic migration inhibitors
more tear strength is lost as compare to migration inhibitors as the concentration of
migration inhibitor increases as migration inhibitors are thickeners so they increases
stiffness of fabric which becomes cause of decreasing tear strength.

3.3 Effect of migration inhibitors on crock fastness [25]:


Rating:

1 2 3 4 5

Poor excellent

2
Figure3. 6 Grey Scale for Color Change

Table3. 5 Effect of migration inhibitors on crock fastness

Migration 0g/L 10g/L 20g/L 30g/L


inhibitor
Wet Dry Wet Dry Wet Dry Wet dry

Primasol FFAM 4 4.5 3.5 4 4 4 3.5 4

Thermacol MIN 4 4.5 4 4.5 3.5 4 4.5 5

Thermacol MP 4 4.5 4 4.5 4 4.5 4 4.5

Sodium alginate 4 4.5 3.5 4.5 4 4.5 3.5 4.5

Guar Gum 4 4.5 3 4 3.5 4 3 4

CMC 4 4.5 3.5 4 4 4.5 3 4

Figure3. 7 Effect of Migration Inhibitors on Crock Fastness.

The results in table and figure shows that effect of migration inhibitors on crock fastness
is not seen and they do not affect the crocking properties of the fabric. Poor Crock
fastness is due to the poor fixation of dye, as migration inhibitors do not take any part in
the fixation of dye so they do not affect the crock fastness values of fabric.

3
3.4Effect of migration inhibitors on wash fastness [26]:
Effect of migration inhibitors on staining:

Rating

5 4 3 2 1

Excellent
Poor

Figure3. 8 Grey Scale for Staining

Table3. 6Effect of migration inhibitors on wash fastness.

Migration 0g/L 10g/L 20g/L 30g/L


inhibitor

PRIMASOL 4 3.5 4 3.5


FFAM

Thermacol MIN 4 4 3.5 4.5

Themracol MP 4 4 4 4

Sodium alginate 4 3.5 4 3.5

Guar gum 4 3 3.5 3

5
CMC 4 3.5 4 3

Figure3. 9 Effect of Migration Inhibitors on Wash Fastness.

The results in table and figure shows that effect on wash fastness by migration inhibitors
is not seen, because migration inhibitors have no any role in the fixation of dye as dye
fixation is the key factor in wash fastness, more the dye fixation better the wash fastness,
however synthetic migration treated fabric has better wash fastness as compared to
natural migration inhibitors.

3.5Effect of migration inhibitors on CV-SUM:


The results of application of different migration inhibitors are given below. The
following table shows the effect of migration inhibitors on the CV-SUM of the samples.

Table3. 7Effect of migration inhibitors on CV-SUM:

Migration inhibitor 0g/L CV- 10g/L CV- 20 g/L CV- 30 g/ L CV-


SUM SUM SUM SUM

Primasol FFAM 3.124 3.184 3.451 3.263

Thermacol MIN 3.124 2.914 2.469 2.776

Thermacol MP 3.124 3.100 3.032 2.949

3
Sodium Alginate 3.124 3.695 3.839 3.204

Guar Gum 3.124 3.077 3.142 3.212

CMC 3.124 3.660 3.252 3.536

Figure3. 10 Effect of Migration Inhibitors on CV-SUM.

The results in table and figure shows that migration inhibitors has no any significant
impact on CV-SUM, however, CV-SUM of natural migration inhibitors is
comparatively more then synthetic migration inhibitors due the fact that natural
migration inhibitors have cellulose components in its polymer structure, so dye is more
attracted to the cellulose component, resulting in better CV-SUM value of natural
migration inhibitors.

3.6Effect of migration inhibitors on % strength:


The results of application of different migration inhibitors are given below. The
following table shows the effect of migration inhibitors on the % strength of the
samples.

Table3. 8Effect of migration inhibitors on % strength:

Migration inhibitor 0g/L % strength 10g/L % strength 20g/L % strength 30g/L %strength

Primasol FFAM 110.54 105.45 114.30 108.08

Thermacol MIN 110.54 101.27 96.79 91.95

Thermacol MP 110.54 103.29 97.51 101.25

Sodium Alginate 110.54 122.39 127.16 106.12

Guar gum 110.54 106.39 101.75 104.09

CMC 110.54 117.11 145.26 107.73

2
Figure3. 11 Effect of Migration Inhibitors on % Strength.

The results in table and figure shows that natural migration inhibitors show good %
strength then synthetic migration inhibitors, due the fact that natural migration inhibitors
have cellulose components in its polymer structure, so dye is more attracted to the
cellulose component, resulting in better % Strength value of natural migration inhibitors.

3.7Effect of migration inhibitors on Bending Length:


Bending length of the dyed fabric was measured using cantilever test method.

Table3. 9 Effect of migration inhibitors on Bending Length

Migration 0g/L bending 10g/L bending 20 g/L 30 g/ L


inhibitor length (cm) length (cm) bending bending
length (cm ) length (cm)

Primasol FFAM 3.4 3.3 3.5 3.7

2
Thermacol MIN 3.4 3.4 3.6 3.8

Thermacol 3.4 3.4 3.6 3.9


MP

Sodium alginate 3.4 3.7 3.9 4

Guar gum 3.4 3.6 3.7 4

CMC 3.4 3.6 3.7 3.9

Figure3. 12 Effect of migration inhibitors on Bending Length.

From the above table and graph it is shown that bending length of fabric treated with
natural and synthetic migration inhibitors has increased, however natural migration
inhibitor treated fabric has more bending length as compared to synthetic migration
inhibitor treated fabric due to the fact that they give more stiffness to the fabric.

Chapter 4
SUMMARY AND FUTURE WORK

4.1Key Findings of the Project


Following conclusions are drawn after the project:

2
• Synthetic migration inhibitors efficiently restrict dye particle movement during
drying but along with the environmental concern.
• Natural migration inhibitors are environmental friendly but do not restrict dye
particles movement efficiently.
• Migration inhibitors have no any effect on wash fastness as they have no any role
in dye fixation.
• Migration inhibitors also not have any impact on crock fastness properties of
dyed fabric.
• Synthetic migration inhibitors do not cause stiffness in fabric while natural cause
to little extent.
• Synthetic migration inhibitors also effect on Tensile/ Tear strength of fabric
while natural migration inhibitors do not affect strength of fabric.
• CV-SUM and % strength of natural migration inhibitors is better then synthetic
migration inhibitors because cellulosic component in natural migration inhibitors
have more dye affinity then acrylic based synthetic migration inhibitors.

3.1Implication of the project:


During continuous dyeing of fabric intermediate step of drying is done due to which the
dye particles move either horizontally or vertically which causes various problems of
serious concern i.e. listing, two sidedness, and shade variation of fabric. In order to
overcome migration problem various migration inhibitors are being used in the industry
both natural and synthetic migration inhibitors. Now a day’s synthetic migration
inhibitors migration inhibitors are mostly used in the industry as they are easy to use,
storage and provide better hindrance to migration but they are not bio degrade able so
they are of environmental concern, this project will provide a detail study of migration
inhibitors effect on properties of fabric.

3.2Suggestions for Future Work:


Although I tried my best to achieve the goal of the project. I did this project on pad-dry-
cure method in future pad-dry-steam method could be used. In future research could be
done on the new generation of migration inhibitors which are now available in market
and desired properties obtained by new generation of migration inhibitors could be
compared with natural.

1
4 References:

[1] Derwin, Chambers , ‘’ Dye migration control with amine salt of poly(vinyl
methyl ether/maleic acid)’’ United States Patent 3940247

[2] Cottoninc. [Online]. ¬ http://www.cottoninc.com/cotton-nonwoven-techincal-


guide/images/strucureofcottonfiber.gif

[3] Cotton Missouri. [Online]. ¬ http://cotton.missouri.edu/images/chemicalcotton.gif

[4] The cotton fiber from textile fiber, by V.A. Shenai, page 150-179

[5] Chemical Finishing of Textiles by W.D. Schindler and PJ.Hauser., page


123-126

[6] fiber to fabric , Bernard B. Corbman. McGraw, chapter 13, page 460-470

[7] Cellulosic dyeing by john shore

[8] K. Hunger (Editor),”Industrial Dyes, chemistry, Properties, Applications”, wiley-vch,


Germany.

[9] Dye migration.[Online] ¬


http://catspitproductionsllc.com/dyemigration.aspx, December 26,2010

[10] Technical data sheet of migration inhibitors of CIBA, BASF Chemicals.

[11] Dennis J. McHugh, “Production, Properties and Uses of Alginates”, chapter: Production
and Utilization of Products from Commercial Seaweeds, Rome, Italy. © FAO 1987

[12]Guar gum, [Online] ¬ http://www.guargum.biz/index.html, January 22,


2011

[13]CMC [Online] ¬ http://www.rachada.co.th/5-1-2.html, January 26,2011

[14] Exhaust dyeing process,[Online] ¬


http://www.springsamsolutions.com/index.php?option=com_content&task=view&id=65
,February 2,2011

[15] Semi continuous process,[Online] ¬ httworldtextile.aimoo.com/Dyeing-


Laboratory/Continuous-dyeing-of-reactive-by-pad-dry-chemical .html. February
3,2011

[16] Continuous dyeing, [Online] ¬


http://www.scribd.com/doc/21333479/continous-dyeing-project january,22,2011

[17] F.Somm and R.Buser, Sandoz AG, worked on migration problems during
intermediate drying, December 1985 International dyer..

3
[18] Nick j. Christle works on different natural and synthetic thickeners for the
thermosol, July 1992, International Dyer.

[19] Allan H Lambert and Robert J, Harper use of cellulose ethers in migration control,
page 584.October 1989, Textile Research Journal.

[20] Stanely P. Rowland, Noelie R. Bertoniere and Walter D. king, reagent migration in
pad-dry cure finishing, page 318, September 1983, Textile Research Journal.

[21] P. Bajaj, R. B. Chavan and Manjeet Bhatia worked on cross linked acid based
thickeners, page 63, January 1986, Textile Research Journal.

[22] J. N. Etters worked on inducing and measuring particulate migration, page 274,
May 1987, Textile Research Journal.

[23] Dye and Pigment Migration in a Pad-Dry Process, AATCC test method 140-
2001manual, page 239-242

[24] Tensile Strength Test by Grab Method, ASTM 14-32, Tear Strength by Grab
Method, ASTM 14-22 Test Manual.

[25] Test Method for Crock Fastness, ISO105*12 Test Manual

[26] ISO test method for wash fastness, ISO 105 CO3 Test Manual

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