UNIT II DYEING

Textile Colouration

The term coloration means to add colour. Textiles are usually coloured to make them attractive for
aesthetic appeal. They are also coloured for functional reasons, e.g. military camouflage and
fluorescent jackets for traffic or police personnel. Life would be more hazardous and certainly dull if
textiles were used only in their natural colours.
There are two ways of adding colour to a textile substrate dyeing and printing. Dyeing completely
covers the textile with colour whereas printing adds colour to the fabric surface in discrete or distinct
places.

Dyes and Pigments

The substances used to colour textiles can be classified as dyes or pigments, the differences between
which are listed in the table below.
Pigments

Dyes

1 Pigments are not water-soluble.

Dyes are water-soluble some are directly

soluble by themselves, while others are
soluble in the presence of assisting chemicals.
They possess no specific attraction for any Dyes have specific attraction for fibres.
particular fibre type.
Certain dyes are attracted to certain fibre
types.
Pigments generally have a larger particle size.
Dyes have a comparatively smaller size.

3
4 They are usually caused to adhere to the surface All dyes are usually absorbed into the fibre.

of the fibre. (Note the cross-section of the fibre Note the small dye molecules in the fibre, as
below.)
seen in the section, and hardly any on the
Fibre
fibre surface.
molecules

[Pigment particles are much

larger than dye
Pigment particles
molecules and irregular in shape;
here
they
(larger size than
dyes)are shown
circular only for ease in drawing.]

Fibre molecules

Dye molecules

[Dye molecules also vary in size and shape from

class to class. They are shown circular in the figure
only for convenience.]

5 Most modern pigments used on textiles are Although textile dyes were originally of natural
organically based synthetic colorants, though
inorganic salts such as the oxides of iron and
lead have also been traditionally used to colour
textiles and, in fact, titanium dioxide is still used
as a basis for pigment whites.

extraction, being derived from a number of

vegetable and animal sources, modern dyes
are synthetic organic colorants. Dyes can be
classified in a number of ways depending
upon their ionic character, chemical type or
application method.

Classification of Dyes

There are basically two ways of classifying various dyestuffs.

1.

According to application, and

2.

According to chemical constitution.

The general term for a dyestuff is colouring matter. The application-wise classification of dyestuffs is
more important from a practical point of view and is given below.
Synthetic dyes

Water - soluble dyes

Insoluble dyes

Dyestuffs
Vat dyes

Direct
dyes
Colouring
matter

Reactive
dyes

Sulphur dyes

Acid
dyes

Disperse dyes

Basic
dyes

Optical
whiteners

Natural dyes

Ingrain dyes

Azoic
dyes

Oxidation
colours

Mineral
colours

Pigments

Vat

Azoic

Mineral

Phthalocyanine

The term synthetic dyes is used for all dyes that are available in coloured form as readymade dyes.
Natural dyes are also included in the above classification as the extracts of a vast number of plants
and some from animal origin are used for dyeing silk, wool and cotton.
Some vat and azoic pigments, and mineral and pthalocyanine pigments are available in insoluble form
to the textile chemist. These are used without converting them into their soluble forms, generally for
textile printing. Hence such colorants are classified under pigments. The differences between pigments
and dyes have already been above. A few common dyes and pigments are described later.
The inclusion of optical brightening agents (optical whiteners) may be specially noted as these are
regarded as colourless dyes having a fluorescent system.

Affinity of Dyes for Fibres

As fibres vary considerably in chemical structure and as dyes too have different chemical groups that
are characteristic of them, it can be easily understood that all dyes will not have the same affinity for all
fibres. The disperse dyes, for example, have excellent affinity for the commonly dyed synthetic fibres
like nylon, polyester and acrylic but none for the cellulose or protein fibres. Similarly, azoic and vat
dyes are applicable only to the cellulose fibres but not to the other common fibres. The following table
presents the affinities of different dyes for different fibres, an asterisk representing affinity and a blank
space no affinity.

P o ly e s te r
fib r e s

F ib r e

A c r y lic
fib r e s

D ye
D ire c t

R e a c tiv e

*
*
*
*
*

A z o ic
Vat
S o lu b ilis e d V a t
S u lp h u r

*
*
*
*
*

A c id
M e ta l - c o m p le x
C h ro m e
B a s ic (C a t io n ic )

D is p e r s e

*
*
*
*

*
*
*
*

*
*

Direct dyes

i) Direct dyes are mainly applied to cellulose fibres such as cotton, viscose, cuprammonium rayon, etc.
The cellulose fibres have a good substantivity (affinity) for direct dyes so they can be dyed directly
from an aqueous solution; hence these dyes are called direct cotton dyes. As these dyes have
excellent substantivity for cellulose, they are also called substantive dyes.
ii) The direct dyes are attached to the fibre mainly by hydrogen bonding and van der Waals forces.
iii) The direct dyes have poor light and washing fastness but they are used extensively due to their low
cost and simplicity of the dyeing process.

i)

Reactive dyes

Since very strong covalent chemical linkages fix the dyes in the fibre these dyes are called
reactive dyes. The reactive dyes are soluble in water and are predominantly applied to the cellulose
fibres. The dye-fibre reaction takes place only when alkali is added to the dye bath.
A schematic representation of the covalent bond between the chlorine atom in a reactive dye and
the hydroxyl group in a cellulose fibre is shown below.

OH

OH

+ ClReactive
+ HC
OReactive Dye
OH
Dye
l
(A molecule of cellulose with (A reactive chlorine
(A covalent bond between
the cellulose
accessible of
OH
groups)
atom in reactive
molecule
ii) The application
these
dyes to cotton materials
involvesdye)
two distinct steps:
andDyeing
the reactive
dye)dye in the presence of common salt to effect as much exhaustion as possible.
a)
with the
b) Chemically reacting the dye with the fibre in the presence of an alkali like soda ash, caustic

soda, sodium silicate, etc.

iii) Reactive dyes are mostly applied to cellulose fibres; they also dye silk and nylon.
iv) The reactive dyes in general have good washing and light fastness, but suffer from poor
hypochlorite bleaching fastness.

Vat dyes

i) Vat dyes are the most important dyes for the coloration of cotton and other cellulose fibres.
ii) The washing, light, perspiration, rubbing, etc fastness properties of vat dyes are excellent.

iii) The vat dyes are insoluble in water and have to be dissolved by using sodium hydroxide and
sodium hydrosulphite (a reducing agent), usually at 50C, the treatment lasting for 15 to 20
minutes. The solubilisation process is referred to as vatting.
In the vatting process, the dye is reduced by the sodium hydrosulphite to the leuco-vat dye, which
in turn is converted into the water-soluble sodium salt in the presence of the sodium hydroxide. The
solubilised dye is taken up by the fibre and then brought back to the insoluble state in the fibre by
oxidation.
The steps in the dissolution of a vat dye, its take up by the fibre and the reversion of the dye back to
its insoluble form in the fibre can be listed as follows.
1. Vat dye dispersion in water + Sodium hydrosulphite
2. Leuco-vat dye + Sodium hydroxide

Leuco-vat dye

Sodium salt of the leuco-vat dye

3. Sodium salt of the leuco-vat dye dissolves in the aqueous bath.

4. The fibre takes up the dissolved leuco-vat dye molecules during the dyeing process.
5. The absorbed leuco-vat dye is oxidised back to the original insoluble vat dye inside the fibre.

Disperse dyes

i) Disperse dyes are nonionic in nature, insoluble in water and relatively much smaller in size
compared with other dye classes.
ii) These dyes are mechanically ground to a very small particle size and with the help of dispersing
agents, they can be dispersed in the dye bath.
iii) The dispersed dyes were originally developed for cellulose acetate fibre. The disperse dyes of today
are used to colour the synthetic fibres like nylon, polyester and acrylic fibres. The disperse dyeing of
polyester fibres is carried out at high temperature (135 C in the regular dyeing process and even at
200C using a special process called the thermosol process).
iv) Disperse dyes in general have fairly good all-round colour fastness.

Pigments

i) Pigments are insoluble in water.

ii) They have no substantivity (affinity) for any fibre and do not have any fibre reactive groups that can
form chemical bonds with fibres.
iii) Pigment particles are much larger in molecular size compared with dyes. Therefore they are not
capable of penetrating fibres; they are held mechanically on the fibre surface by means of special
chemicals. Dyes, on the other hand, are much smaller in size and therefore they penetrate the fibre
structure and get fixed inside the fibre, as stated earlier.
iv) On account of point No. (iii), pigments are applicable to all fibres and are used mostly in textile
printing rather than dyeing.
v) Pigments have moderate to good fastness to wet treatments if they have been properly fixed to the
substrate surface by binders.
Common Terms Used in Textile Chemical Processing

Dye or dyestuff

Dye molecules are organic molecules, which can be classified into the following three types.
1. Anionic in which the colour is caused by the anionic part of the dye molecule

2. Cationic in which the colour is caused by the cationic part of the dye molecule
3. Disperse in which the colour is caused by the whole molecule (i.e.non-ionic dyes).
Anionic and cationic dyes are applied from an aqueous solution i.e. a solution of the dye in water. The
non-ionic type is applied from an aqueous dispersion. (An aqueous dispersion consists of a finely
divided solid material, like a water-insoluble dye, uniformly distributed or dispersed- but not dissolved in water.)
A dyestuff is a substance that is capable of colouring a textile material in such a manner that it
associates closely with the fibre, i.e., it is not removable by simple physical means (e.g. rubbing or mild
detergent). It must be soluble in water, or capable of going into solution by chemical means. A highly
dispersed condition may be regarded as a form of solution (e.g. disperse dyes).
An essential feature of the dyeing process is that the dye molecule must be capable of entering the
fibre structure, the path for the dye molecules being provided by the intermolecular spaces (the
amorphous regions) in the fibre. Once the dye has entered the fibre structure it becomes firmly
attached to the surface of the fibre molecules either by purely physical forces (secondary valency
forces like van der Waals forces and hydrogen bonds) or by chemical combination.
Acetate fibre and the synthetic fibres in general resist the penetration of their fibre structure by dye
molecules, but certain dyes, like the disperse dyes, which have a great affinity for synthetic fibres, are
capable of forming a solid solution with the fibrous molecule; this means that one solid, the disperse
dye, dissolves into another solid, the synthetic fibre. Even with these dyes, some of the synthetic fibres,
like polyester, have to be swollen either with suitable swelling agents or by using high temperature and
high pressure dyeing techniques.
Swelling of the fibres appears to play a large part in the dyeing of all fibres, and is mainly caused in
general by water, or by solvents in the case of synthetic fibres, or by raising the temperature and
pressure of the dye bath.

Substantivity/Affinity

The substantivity of a dye for a fibre can be defined as an attraction between the fibre and the dye
under given dyeing conditions, whereby the dye is selectively extracted from an application medium by
the fibre. For quantitative work the term affinity is used as it is more clearly defined and can be given a
numerical value (usually in joules per mole).
Affinity is thus defined as the difference between the chemical potential of the dye in its standard state
in the fibre and the corresponding potential in the dye bath. In simple terms substantivity or affinity
indicates the preference of a dye to go from the solution phase to the fibre.

Exhaustion

This is a measure of the proportion of the dye absorbed by the fibre in relation to that remaining in the
dye bath. Thus, it indicates the amount of dye that has moved from the solution into the fibre under
given dyeing conditions. It is also a measure of the substantivity of the dye for the fibre. Exhaustion is
expressed in terms of percentage.
For example, if the exhaustion of a dye bath is 75%, it means that 75% of the dye in the dye bath has
moved from the dye solution or dye liquor into the fibre. The term exhaustion is mainly applicable to
batch-wise dyeing which is also called exhaust dyeing. Textile yarn and fabric are often dyed by the
exhaust dyeing technique.

Material-to-Liquor Ratio

This expression refers to the weight-to-volume relationship between the fibre to be dyed and the total
volume of dye bath. It is normally abbreviated as MLR and sometimes written as M:L ratio. An M:L ratio
of 1:10 means that a dye bath volume of 10 litres is required to dye 1 kg of dry fibre.
The material-to-liquor ratio is also sometimes referred to as an inverse ratio and called the liquor-togoods ratio or simply the liquor-ratio and this ratio is given by the following expression.
Liquor-to-goods ratio =

Total volume of dye liquor used in ml

Dry weight of material dyed in grams

Thus 5 g of material dyed at a liquor-to-goods ratio of 5:1 would use 5 5 = 25 ml dye liquor.
Similarly, 3 g of material dyed in a dye bath of 60 ml has a liquor/goods ratio of 60/3 = 20/1 or 20:1.
Typical liquor ratios used in different types of machine

i) In all the liquor circulating machines like kier, jet dyeing and cheese dyeing machines
the M:L ratio is 1:4 or 1:5.
ii) In a jigger it is 1:3 to 1:5.
iii) In a padding machine it is 1:1.
iv) In a winch it is in the range 1:15 to 1:25.
v) In an open beck the ratio would be 1:20 to 1:40.
The higher the M:L ratio, the larger is the volume of dye liquor, so lower is the concentration of dye, as
dyes are always taken in terms of a percentage of the weight of the textile to be dyed. The lower the
concentration of dye solution, the longer it will take to obtain a given level of dye absorption or shade.
See a subsequent section on Shade percentage for more information.

Expression

The term expression indicates the percentage increase in the weight of dry fabric after padding.
For example, let us assume that the dry weight of a length of fabric is 1 kg. Let this fabric be saturated
with dye liquor and padded between the rolls of a padding mangle to squeeze out the excess liquor. If
the weight of the wet fabric coming out of the padding mangle is 1.8 kg, it means that there is an
increase in weight of fabric by 0.8 kg. The weight of dye solution in the padded fabric is 80% of the dry
weight of the fabric. The expression in this case is said to be 80%.
The higher the expression in a fabric being padded, the lower is the squeezing pressure in the padding
mangle and vice versa. A fabric padded to an expression of 110% will contain more dye liquor than one
padded to 90% expression, and so on. The former fabric has greater pick-up than the latter case.
A useful formula for padding is,
Grams of dye liquor
in
100 ml of pad liquor

Percentage of dye needed on fabric

100
Percentage of pick-up

Shade Percentage

Shade percentage refers to the quantity of dye taken for a dyeing expressed as a percentage of the
dry weight of the fibre to be dyed.
For example, if 1 g of a dye is taken for dyeing 100 g of a textile material, the shade percentage is
referred to as 1% shade. And with reference to the dyed material, it is said to be dyed to a 1% shade.

Similarly, if a kilogram of fibre is required to be dyed to a 3.5% shade, the amount of dye to be taken
would be (1000 3.5)/100 = 35 grams.
Percentage depth of shade can thus be defined as parts by weight of dyestuff to be added to a dye
bath per 100 parts by weight of material. Thus a 2% depth of shade would require the addition of,
2 g of dye in order to dye 100 g of material
or 1 g of dye in order to dye 50 g of material
or 0.1 g of dye in order to dye 5 g of material.
When the weight of the dye to be added is small, it is common to prepare a concentrated solution of
the dye and add a part of it to the dye bath. In such cases, the volume of stock solution to be added is
often calculated from the following formula.
ml of dye solution
required or added

% of depth of shade Weight of fibre to be dyed in g

Concentration of stock dye solution in g/100 ml

For example, if a 3% shade is required to be dyed on 4 grams of cotton yarn using a solution of one
gram of dye in 200 ml of water (i.e. 0.5 g in 100 ml water), the volume of the stock dye solution
required would be given by,
ml of dye solution required or added =

3
0.5

= 24 ml

Dyeing Assistants

Dyeing assistants are chemicals that facilitate, in one way or another, the production of the required
shades in dyeing. They are also called dyeing auxiliaries. Some typical dyeing assistants are briefly
discussed below.
Water Softening/Sequestering Agents
These compounds are used basically where hard water is used in dyeing process. They react with
metallic ions in such a way that they become part of a complex ion. Commonly used softening agents
are
Calgon
(sodium
hexa-metaphosphate)
and
ethylene-diamine-tetra-acetic
acid,
(COOH.CH2)2N.CH2.CH2.N(CH2.COOH)2, often abbreviated as EDTA. The formation of complexes is
referred to as chelation and is manifested by what are called chelating compounds. Calgon reacts with
calcium or magnesium in the following way:

N a 2[N a 2(P O 3)6] + C a ++

N a 2[C a (P O 3)6] + 2 N a ++

Exhausting Agents
Exhausting agents are important from the point of view of economical dyeing because they facilitate
the movement of the dye molecules to the fibre and thereby exhaust the dye bath. Common salt or
Glaubers salt (sodium sulphate) is predominantly used as an exhausting agent in the dyeing of
cellulose fibres with direct, azoic, vat, solubilised-vat and reactive dyes.
In all these cases, the dyes act as anionic dyes (splitting up into dye anions and sodium or other metal
cations in water). When a cellulose fibre is immersed in water it acquires a negative electrical charge
called zeta potential. As a result, the negatively charged fibre surface repels the negatively charged
anions present in the water (i.e. during dyeing of cellulose fibre from an aqueous solution of the anionic
dye).
When common salt or Glaubers salt is added to the dye bath the sodium ions released by it try to
neutralise or reduce the negative charge of the fibre surface, thereby reducing the repulsion of the dyeanion at the fibre surface. As a result, the approach of the dye anions towards the fibre surface is

facilitated. In other words, the fibre takes up more dye in the presence of salt than in its absence.
However, the extent of increase in exhaustion brought about by salts varies from dye to dye. Also, with
other dye-fibre combinations, other chemicals are used as exhausting agents.
Dispersing Agents
Dispersing agents are described as sodium salts of any of the following.
i) a naphthalene sulphonic acid condensation product
ii) an aromatic sulphonic acid condensation product
iii) highly condensed NS acid
iv) disodium salt of methylene dinaphthalene disulphonic acid, etc.
These are available in the form of yellowish brown powder, light beige coloured powder, dark brown
mobile liquid, and so on.
The powder brand is a non-hygroscopic powder that is,
i) readily soluble in water with any degree of hardness (it is stable to hard water),
ii) resistant to alkalis, acids and salts and has dispersing and protective colloid properties.
It finds use in the dyeing of vat dyes by the vat-acid process; also in dyeing with disperse dyes,
solubilised vat dyes and azoic (naphthol) colours.
In the dyeing of polyester and polyamide with disperse dyes, the use of a dispersing agent leads to the
production of a fine dispersion of the dye. Because of its non-foaming nature, it is recommended for
the high temperature dyeing of piece goods or yarn under pressure.
Levelling Agents
Levelling agents are used to produce uniform, even dyeing on textile material. Some dyes have the
tendency to rush on to the fibre due to their high affinities for the fibre. In such cases it is difficult to
produce an even dyeing under normal circumstances. The use of levelling agents results in uniform
uptake of dye by the fibre by bringing about retardation in the movement of the dye to and into the
fibre.
The degree of retardation effected by the levelling agent varies from dye to dye and hence a
concentration of levelling agent that is suitable for one dye may not be so for another. The quantity of
the levelling agent should not exceed about 0.5 g/l of the dye liquor and should not be added
immediately before the material to be dyed is entered. The dye liquor should be as dilute as possible
before adding the levelling agent.
Retarding Agents
These agents are used as levelling agents to retard the sudden rushing of dye to and into the fibre. In
some cases where the dyeing rate is very high because of high affinity of the dye for the fibre, retarding
agents are used for slowing down the dyeing process. Retarding agents act in one of two ways:
i) They have some affinity for the fibre. Though this affinity is less than that of the dye for the fibre,
they also compete with the dye to enter the fibre. So, fewer dye sites are initially available for the
dye and even dye uptake results.
As the dyeing progresses and the temperature increases, the more substantive dye molecules
replace the retarding agents at dye sites to complete the dyeing with good exhaustion of the dye
bath.

ii) They form large complexes with the dye molecules at low temperatures in the dye bath. The largesized dye-agent complex finds it difficult to enter the fibre structure. When the temperature of the
dye bath is raised, the complex breaks up, releasing the retarding agent. The dye is now taken up
by the fibre.
Mechanism of Dyeing

The process of dyeing may be divided into three phases,

i) Adsorption of the dyestuff at the fibre surface,
ii) Diffusion of the dyestuff through the internal structure of the fibre, and
iii) Fixation or anchoring of the dye molecule at a suitable location or dye site.

Adsorption: In the first phase or step, the dye molecules in the dye bath move towards the fibre
and those that are nearest to the fibre get adsorbed on to the fibre surface. They form a very thin
layer of molecules on the fibre surface. Other dye molecules still in the dye bath can be adsorbed
only if this adsorbed layer moves further into the fibre. A schematic representation of a fibre
showing the adsorption of dye molecules on the surface of the fibre is shown in the figure below.

Fibre molecules
Dye molecules only
on fibre surface

Penetration: In the second step, the adsorbed dye molecules enter the fibre structure and
gradually penetrate or diffuse into the pores or canals in the structure. The rate of penetration and
the depth to which they get will depend upon the molecular characteristics of the dye, the molecular
arrangement in the fibre and the dyeing conditions. Diffusion or penetration of dye in the fibre
accounts for almost the whole of the dyeing time. The greater the penetration of dye into the fibre
the brighter and better is the dyeing. Good dye penetration is thus the key to quality dyeing. Poor
penetration results in dull, surfacial dyeing with unsatisfactory colour fastness properties. The
following figure shows schematic representations of dyed fibre, one with good dye penetration and
the other with poor penetration.

Cross-sections of an incompletely-penetrated or ringdyed fibre this fibre will appear dull. (The dots inside
the sections are the cut ends of fibre molecules.)

Cross-sections of a completely dyed fibre this fibre

will appear bright and attractive. (The dots inside the
sections are the cut ends of fibre molecules.)

Fixation: The final step is one where the dye molecules find suitable locations or dye sites, where
they get fixed or anchored. The forces by which the dye molecules are held thus inside the fibre
vary in nature and strength and depend upon the dye-fibre relationship.

The exact nature of the forces holding dye particles to fibre surface is not fully understood, but the
possibilities may be classified as follows:
i) van der Waals forces: Very weak forces of attraction are always present between the electrons of
one atom and the nucleus of another in close enough proximity. Individually these are very weak
forces, but collectively they are considered to be of sufficient strength to be the most important
attractive forces between dye and fibre. These forces of attraction are known as van der Waals
forces. Disperse dyes are held in a polyester fibre by means of van der Waals forces.

ii) Hydrogen bonds: These forces of attraction are weak forces set up between certain atoms in the
dyestuff molecule when they are close enough to other atoms in the fibre. One of these atoms is
the hydrogen atom, hence the term hydrogen bond. Some direct and vat dyes are hydrogen
bonded in cellulose fibres.
iii) Salt linkages: In aqueous solution, dyestuff molecules split up into positively and negatively charged
particles called ions, one of which is coloured. Depending upon the particular class of dyestuff
being considered, the coloured ion may be cationic (carrying a positive charge), or anionic (where
the charge is negative).

When strong electrostatic forces of attraction develop between the ions in a fibre and oppositely
charged dyestuff ions, salt linkages or ionic bonds are said to be formed. For example, when the

(anionic) SO3 groups in an acid dyestuff gets close enough to attract a (cationic) -NH 3 group in
wool, silk or nylon, the resulting bond is a salt linkage or an ionic bond or an electrostatic bond.
F ib r e

H y d ro g e n O
bond
H

NH

SO

+
E le c tr o s ta tic
bond

D y e a n io n w ith
p la n a r s tr u c tu r e
b o u n d w ith u n p o la r
v a n d e r W a a ls ' fo rc e s

_ SO 3

NH

E le c tr o s ta tic
bond

O
Cl

C o v a le n t
bond

iv) Covalent bonds: Bonds resulting in very strong chemical forces that are not easy to break except
under severe conditions are called covalent bonds. The classic example is that of the combination
of cellulose fibres with reactive dyestuffs, where the hydroxyl group in the cellulose is covalently
bonded to a suitable atom in the reactive dye.

The various types of bonds occurring for different dye-fibre combinations are illustrated in the above
figure. A comparison of the relative strengths of the bonds described above is indicated in the table
below.
Type of Bond

van der Waals force

Hydrogen bond

Salt linkage

Covalent bond

Bond strength, kJ

20

60

330-420

Relative strength

1.0

2.5

7.5

40-50

The types of bonds mainly found in various dye-fibre combinations are listed in the table below.

10

Fibre
Cellulosic: Cotton,
jute, flax, rayon, etc.

Dye class having affinity

Type of dye-fibre bonds

Direct, vat, solubilised

vat and sulphur

van der Waals' forces

and hydrogen bonding

Reactive

Covalent bonds

Direct, acid, metal

complex and basic

Ionic or electrostatic bonds

Reactive

Covalent bonds

Polyester

Disperse

van der Waals' forces

and hydrogen bonding

Cationic-dyeable
polyester (CDP)

Cationic

Ionic or electrostatic bonds

Disperse

van der Waals' forces

and hydrogen bonding

Acrylic

Cationic

Ionic or electrostatic bonds

Disperse

van der Waals' forces

and hydrogen bonding

Protein/polyamide:
Wool, silk, nylons

11

General Theory of Dyeing

There is no generally applicable theory of dyeing capable of explaining all dyeing phenomena
satisfactorily. However various models are available which provide a basis for the study of a range of
dye-fibre systems.
The theories of dyeing are concerned with the nature of dye diffusion in solid polymeric fibres.
Essentially, they are based on two important fundamentally different models for dyeing diffusion in
fibres namely the pore diffusion model and the free volume or mobile segment model.

The pore diffusion model

This model represents the fibre as a solid structure with a network of interconnected channels or pores
that are filled with dyeing liquid, which is normally water. The dissolved dye diffuses through these
pores, where it can be simultaneously adsorbed on the walls of the pores.
The pore model assumes that the pores are connected to each other as well as to the external dye
bath and that their diameter is sufficiently large for the dye molecules to find space in them. The
diffusion of the dye in cellulose fibres is generally based on the pore model. According to this, a
network of pores swollen and filled with water is present in the fibres and it is within this network that
dye diffusion and sorption take place.

In the case of reactive dyes, the diffusion is followed by chemical reactions between the dye and the
fibre. It is well known that the dyeing results on cellulose fibres are greatly influenced by the fibres
physical structure. This explains the different dyeability between cotton and rayon and that between the
various types of regenerated cellulose fibres.

Organised zones
Dye molecules or ions

Disorganised zones
Water or solvent
molecules

Schematic figure of the pore diffusion model

Organised zones
Dye molecules or ions

Disorganised zones
Water or solvent
molecules

Schematic figure of the free volume model

The free volume model

In contrast to the pore model, the free volume model describes the dyeing process as diffusion of the
dye through the less ordered or amorphous regions of the polymer structure. The rate of diffusion is
therefore determined by the mobility of the polymer chain segments in these regions. The most
important support for this theory comes from the observation that the temperature dependence of the
rates of dyeing for a particular type of fibre is less above a certain temperature.
The resistance of the solid structure of the fibre to the penetration of the dye is much lower above this
temperature. This temperature is referred to as the glass-transition temperature of the fibre in question

12

(Tg), or more precisely the glass-transition temperature of the fibre under dyeing conditions, since the
classical glass-temperature is a parameter that is normally measured in the dry state of the fibre.
The glass-transition temperature plays a significant role in dyeing. It corresponds, at a molecular level,
to the temperature at which the amorphous regions of a polymer are converted from a glassy state to a
rubbery, visco-elastic state. Above this temperature, segments of the polymer chain in the amorphous
regions are rubber-like and have increased mobility, and below it they are in a frozen or glassy state.
The segmental mobility causes changes in the arrangement of the chain molecules in these regions.
Due to the segmental mobility, holes or free spaces are formed above Tg and disappear again or
occur at neighbouring sites of the polymer chain segments involved.
In the visco-elastic state the polymer structure cannot be considered in static terms; the structure
changes constantly. However, as the relatively small dye molecule diffuse through such a structure
there is possibility of their absorption in the free volume of the fibre structure.
Absorption and desorption

When a fibre is placed in a solution of a dyestuff that has affinity for the fibre, the dyestuff will be
absorbed into the fibre. As more and more is transferred from the solution to the fibre a position of
equilibrium will develop and further transfer will cease.
The concentration of dyestuff in the bath and in the fibre at equilibrium will be in a definite ratio of the
one to the other.
The exact ratio depends on the particular dyestuff, the temperature of the bath and the concentration of
salt in the bath. If on the other hand, the dyed fabric is placed in a bath of clear water under similar
conditions, with or without salt, dyestuff will be desorbed from the fibre until eventually the same
balance is set up. At this point dye transfer will not have really ceased but the rates of change would be
the same in both directions, bath to fibre and fibre to bath.
In commercial dyeing it is not possible to prolong the dyeing time indefinitely and consequently a state
of true equilibrium is rarely reached. The rates of dyeing in practice are therefore quite as important as
the equilibrium effects. With all dyestuffs substantive to cellulose a few simple rules govern these
variables.
i)

With any given dye and dyeing conditions the higher the temperature the more rapid the
rate of dyeing.

ii)

The higher the temperature the more rapidly does levelling take place.

iii)

At equilibrium, the amount of dyestuff absorbed by the fibre is greater at low temperatures than
at higher temperature. The biggest difference is observed with those dyestuffs that possess low
affinity for the fibre. In practice, however, this effect is seen only with dyestuffs that dye most
rapidly. True equilibrium is established even more slowly at lower temperatures than that at the
higher temperatures normally used.
The effect of temperature on dye uptake

In general, as the temperature of the dye bath increases, the rate of dye up take also increases. This is
due to the fact that increase in thermal energy causes an increase in the kinetic energy or movement
of the dye molecules. The increase in temperature also results in the rapid movement of the segments
of molecules in the amorphous regions in the fibre. Both of these effects combine to increase the rate
at which the dye is taken up by the fibre. High temperature also brings about a greater degree of
levelling in most dye-fibre combinations.
This does not mean that all dyes are applied at high temperatures. That temperature is chosen for a
dye-fibre combination that gives optimum/maximum dye uptake within a practically reasonable period
of time. This is why the dyeing procedures of different dye-fibre combinations includes different
maximum dyeing temperatures.

13

For example, cotton is best dyed at the boil when direct dyes are used, but with reactive dyes, the
temperature depends upon the reactive dye brand used; the cold brand dyes are dyed at room
temperature and the hot-brand dyes at around 80C. Vat dyes are usually applied at 50-60C.
The dyeing of nylon and acrylic fibres are usually carried out at the boil, while polyester fibre is dyed at
135C in special dyeing equipment.

Direct Dyes on Cotton

Introduction
Direct dyes are also called substantive dyes because of their excellent substantivity (affinity or
attraction) for cellulose textile materials like cotton and viscose rayon. This class of dyes derives its
name from its property of having direct affinity for cellulose fibres when applied from an aqueous
solution.
Chemically, direct dyes are sodium salts of aromatic sulphonic acids and most of them contain an azo
group as the main chromophore. Various manufacturers market direct dyes under different trade
names. Some examples are given below.
Manufacturer
Indokem
Hindustan Ciba Geigy
Clariant
Atul Products
ICI

Trade Name
Incomine
Chlorantine, Solophenyl
Solar
Atul Direct
Chlorazol

However, there is a German ban on the use of certain azo dyes that has become effective since 1996.
Other countries in Europe now have similar legislations in force and thus the use of direct dyes is now
severely restricted. This is because many of the direct dyes are based on harmful amines such as
benzidine, etc. It is therefore absolutely essential that the eco-friendliness of direct dyes be ascertained
before using them in regular bulk dyeing of textiles. To facilitate this, official lists of the red-listed direct
dyes are available.
The structure of a direct dye predominantly contains the N=N (azo) and the SO3Na groups.
Properties of Direct Dyes
1. Direct dyes are soluble in water and have affinity for cellulose and protein fibres, especially wool.
2. Chemically the dyes are represented as sodium salts of sulphonic acid (DSO3Na), where D
represents the remaining part of the dye molecule.
3. When the dyes are dissolved in water, the dye molecules get dissociated into ions (DSO3 and
Na+). During dyeing, the textile material absorbs the coloured anions from the dye solution. This is
followed by diffusion of the molecules into the fibre where they are finally retained or anchored by
means of physical forces (hydrogen bonds and van der Waals forces).
4. Owing to their water solubility, the dyes possess poor wash fastness. Light fastness, however, is
poor to moderate, even good in some cases.
5. The fastness properties of these dyes can be improved slightly by means of certain aftertreatments.
Classification of Direct Dyes
The direct cotton dyes are classified into the following groups depending on the effect of electrolyte
and temperature.
Class A: Self-levelling dyes

14

While using these dyes, the dyeing may be uneven in the initial stages but they get levelled on
prolonged dyeing because of better migration properties. These dyes do not require salt for their
exhaustion.
Class B: Salt-controllable dyes
These dyes do not migrate well and require salt addition for increased exhaustion. If uneven dyeing
takes place initially, it is very difficult to correct the dyeing.
Class C: Temperature-controllable dyes
Similar to the Class B dyes, the levelling properties of these dyes are poor. They are also sensitive to
salt and their exhaustion cannot be controlled with salt alone. These dyes require their exhaustion to
be effected by controlled rise of dye bath temperature.
When more than one dyestuff is required to match a given shade, dyes belonging to the same class
should be preferred.
Mechanism of Dyeing
When cotton is immersed in a solution of a direct dye, the following events take place.
1. Fibre swelling in the liquor
2. Adsorption of the dye at the fibre surface
3. Diffusion of dye molecules into the interior of the fibre
4. Fixation of the dye molecules at appropriate places in the fibre structure by means of weak van der
Waals forces and hydrogen bonds
The phenomenon of adsorption and diffusion can be illustrated by microscopic views at different stages
of dyeing of cotton as shown in the figure below. In the first few minutes of dyeing only adsorption
takes place as seen by the surface dyeing in the middle view. When the dyeing period is extended,
complete diffusion takes place and the dye fills the whole cross-section of the fibre.

Undyed cotton

Cotton dyed at 100 C

(for a few minutes)

Cotton dyed at 100 C

(for a day)

Why does a direct dye have great affinity for cellulose fibres?
The cause for the affinity of direct dyes to cellulose fibres results from the hydrogen bond like linkages
between the hydroxyl groups (proton donors) of the cellulose and the delocalisable -electron system
of the dye (proton acceptor).
It is also held that the affinity of the dye to cellulose is connected with the linear and coplanar nature of
the direct dye molecule. The affinity is also associated with a system of alternate single and double
bonds (conjugated double bonds). Other interactions such as van der Waals forces also play a part.
Effect of Electrolytes
It has been observed that the addition of an electrolyte, i.e. salt, in direct dyeing promotes exhaustion.
However the effect varies considerably from one dyestuff to another.
How does a salt bring about exhaustion of the dye bath?
a) When cellulose fibres are immersed in water, the fibre surface acquires a small negative charge
known as the zeta potential.

15

b) In an aqueous bath containing both fibre and direct dye, the latter being anionic will be repelled by
the negative surface charge on the fibre. Little exhaustion will therefore take place.
c) When an electrolyte such as sodium chloride is now added to the bath, it ionises into sodium
cations and chloride anions.
d) The sodium cations neutralise or reduce the negative charge on the fibre surface and the dye
anions in the bath, repelled by the chloride anions, move to the fibre where they are adsorbed.
e) The dye anions are much larger than the chloride anions, but they have a great substantivity for the
cellulose fibre and are therefore quickly absorbed by the almost neutral fibre surface.
f)

Once adsorption of dye has occurred, the other steps of dyeing, namely diffusion and fixation take
place subsequently with ease.

The action of electrolyte in helping to exhaust the dye bath is shown in the figure on Page 58. Thus, in
the dyeing of cellulose fibres, electrolytes enhance the exhaustion of direct dyes to a considerable
extent. However, the exhaustion effected by electrolytes varies from dye to dye, as stated above. The
variations in the extent of exhaustion of various dyestuffs in the presence of salt have been attributed
to the presence of the sulphonic acid groups in the dye molecule. The effectiveness of salt in promoting
exhaustion varies directly with the number of sulphonic acid groups. Thus the greater the number of
sulphonic acid groups in a dye, the greater is the effect of the electrolyte.
Effect of Temperature
The amount of dye taken up by the fibre (while dyeing a cellulose fibre with direct dye) depends on the
temperature of dyeing. The rate of dyeing increases with rise in temperature i.e. dyeing takes place
slowly at lower temperature and the dyestuff moves quickly on to the fibre with increase in
temperature. As the thermal energy of heat is increased, the kinetic energy of movement of the dye
molecules to the fibre also increases proportionately.
It is therefore certain that if the dyeing is carried out at high temperature right from the beginning,
uneven dyeing will result. In view of these facts, it is important that the dyeing should start at room
temperature, and then the temperature is raised slowly and uniformly to the maximum dyeing
temperature.
All direct dyes show increased absorption with temperature up to a certain maximum. Affinity however
decreases with further increase in temperature. This effect varies from dye to dye. Knowledge of this
aspect is important when mixing different direct dyes to get a particular shade.
Effect of Liquor Ratio

It can be seen that as the initial concentration of

dye in the dye bath increases (or as the material
to liquor ratio decreases), the dye uptake also
increases. Therefore it follows that a deeper
shade is obtained in situations such as the
following.
i)

If a fibre is dyed in a bath containing, e.g., 2%

dye instead of 1% dye.

ii) If the initial dye concentration is say 2%, using

a material-to-liquor ratio of 1:20 would produce
a deeper shade than using a ratio of say 1:30
or 1:40.
This is because the initial concentration of dye
in the bath would be higher for M:L ratio 1:20

Dye uptake (g/kg)

The following figure shows the variation of dye uptake (g/kg of fibre) with changing dye bath
concentration.

Initial concentration of dye in the dye bath (g/l)

16

than in the case of 1:30 or 1:40.

Therefore deeper shades can be obtained by dyeing given shade percentages at low M:L ratios. In
industrial practice, dyeing machines with a low liquor ratio, e.g. jiggers, would give deeper shades than
high-liquor ratio machines like winches, for the same initial dye bath concentration.

17

Schematic representation of the action of electrolyte in exhausting a dye bath

Repulsion due to electrical barrier

Repulsion due to electrical barrier

Attraction

Fibre
surface

Attraction
Dye

Ion

Dye distribution in
dye bath with salt

Dye bath without salt

Distance from fibre surface

Distance from fibre surface

Situation in the absence of salt: It is clear from the figure at the left that in the absence of salt, the anionic (positively charged) dye molecules are
repelled by the negatively charged fibre surface (the zeta-potential). Note the near zero concentration of dye near fibre surface in the graph, in
which the dashed line represents the electrical barrier which no dye molecule will pass.
Situation in the presence of salt: The figure at the right shows how the presence of salt in the dye bath virtually reduces the charge at the fibre
surface to zero (i.e. neutral charge). This happens because the negatively charged fibre surface attracts the Na + cations of the salt while the dye
molecules in the bath repel them. Note that now the fibre surface is neutral and that the dye molecules, having greater attraction for the fibre, are
adsorbed by it. Note the absence of the barrier in the graph. As each layer of adsorbed dye molecules penetrate or diffuse into the fibre, another
layer will be adsorbed, and so on.

18

Application Procedure Direct dyes on cotton

The dyeing process basically involves two steps:
i)

Preparation of the dye bath

ii)

Dyeing

iii)

Dye-fixing treatment

a) Preparation of the dye bath

The dye is dissolved by pasting it with a small amount of water and soda ash (if required). Boiling water
is then added to the paste with constant stirring. If pasting is not done prior to the addition of boiling
water, the dye may form into lumps, and if these persist, will in turn result in speckled (dotted) dyeing.
Stock solutions (i.e. concentrated solutions) are usually prepared and the required volume of these
solutions is taken for dyeing.
b) The dyeing process
(i) The dye bath is set with the required volume of the stock solution of dye, 0.5 to 1% soda ash and
water to make up the desired M:L ratio.
(ii) The well-prepared (i.e. uniformly desized, scoured and bleached) material is immersed into the dye
bath at 40C and dyeing is carried out for 15 20 minutes.
(iii) The prescribed quantity of common salt is added in an even number of instalments at intervals of
10 15 minutes. Common salt is generally preferred to Glaubers salt for reasons of economy.
(Glaubers salt being anhydrous requires the use of larger quantities). The quantities of salt used
are dependent on the shade being dyed and vary between 5 - 20% on the weight of material for
light to heavy shades.
(iv) The temperature of dye bath is slowly raised to the boil (or the recommended maximum dyeing
temperature). The dyeing is continued at this temperature, for a period of 45 - 60 minutes.
(v) The material is then allowed to remain in a cooling bath for 15 - 20 minutes for obtaining better
exhaustion.
(vi) Finally, the goods are removed from the dye solution, squeezed or hydro-extracted and dried.
Typical recipe for Class A (self-levelling) type of direct dye

Direct dyestuff X% (on weight of fibre or owf)

Soda ash

Common salt

5% (owf) for light shades; 10% (owf)-medium shades; 20% (owf) -dark
shades

Temperature

Boil

Dyeing Time

70 to 80 minutes

0.5 to 1% (owf)

For Classes B and C, the procedure is modified according to the dye used.
c) The dye-fixing process
This is also called an after-treatment. An after-treatment is a treatment of the material in a different
bath after the actual dyeing process. The after-treatment is done in a fresh bath containing the required
quantity of a dye-fixing agent. Various kinds of after-treatment are described below.
After-treatment of Direct Dyed Goods
The reasons for the popularity of direct dyes in the dyeing of cellulose fibres are

the low cost of dyeing, and

the simple dyeing procedure.

19

As a matter of fact, these dyes do not possess adequate washing fastness properties and most of
them fade in light. The use of direct dyes therefore becomes undesirable for material that will
subsequently be washed frequently or continuously exposed to light.

20

How does a dye-fixing treatment improve the wash fastness of direct dyes?
A number of methods have been devised to improve the washing fastness properties of direct dyes.
These after-treatments are based on principles like increasing the molecular weight of the dye and
thus decreasing their mobility and solubility in water after dyeing.
Some chemicals applied to the direct dyed material to improve the wash fastness property are usually
very large in size and combine chemically with the dye molecules taken up by the fibre to form still
larger molecules, which have slow mobility. Thus they are less easy to wash out of the fibre.
All the direct dyes, however, are not capable of such after-treatment since, in many cases the colour of
the final product changes i.e. it tends to become duller and sometimes the hue too is altered.
Also, in some cases, the light fastness is improved while in others it is lowered.
Some after-treatments that have been in use are summarised below:
1. Treatment with metallic salts
(a) Treatment with copper salts
Certain dyestuffs are capable of reacting with copper and showing remarkable improvement in light
fastness properties. The dyed material is treated in a bath containing:
Copper sulphate (owf)

0.5 - 2% on weight of the fibre (owf)

Acetic acid (30%) (owf)

0.5 - 2% (owf)

The actual concentrations of the chemicals used depend on the depth of shade of the dyeing. The
treatment is carried out at 80 C for 30-45 minutes. The material is then rinsed and dried.
Commercial products such as Cuperantine, Cuprofix, Cuprophenyl, etc. have also been used
instead of the above chemicals. In some cases, the light fastness is lowered.
(b) Treatment with chromium compounds
Chromium atoms can be introduced in the molecular structure of certain direct dyes, resulting in
more complex structures than those with copper compounds and hence provides a way of
improving the washing fastness properties of the dyes. This treatment however does not alter their
light fastness properties.
The dyed goods are treated in a bath containing:
Potassium dichromate

2 - 3% (owf)

Acetic acid (30%)

2 - 5% (owf)

The treatment is for 30 minutes at the boil. The goods are then rinsed and dried.
(c) Combined copper and chromium treatment
A combination of the treatments with copper and chromium compounds can be employed to get
improvements in washing as well as light fastness properties. The dyed goods are worked in a bath
containing the following:
Potassium dichromate

0.5 - 2% (owf)

Copper sulphate

0.5 - 2% (owf)

Acetic acid (30%)

1 - 5% (owf)

The treatment is for 30 minutes at 80C followed by rinsing and drying.

2. Treatment with formaldehyde
Increasing the relative size of the dye molecules of some direct dyes can also be achieved by
treatment with formaldehyde, thereby yielding improved washing fastness properties. The dyed goods
are treated in a bath containing the following.
Formaldehyde (40%)

2 - 3% (owf)

Acetic acid (30%)

1%

(owf)

The treatment is carried out at 60 - 70C for 30 minutes followed by rinsing and drying.

21

3. Treatment with cationic dye fixing agents

Different types of dye-fixing agents are available for use in the after-treatment of direct dyed goods to
bring about improved washing fastness properties; the light fastness, however, is decreased.
The dye-fixing agents are cationic and capable of
ionising into long cations and small anions.

Long cation

On the other hand, direct dyes are anionic and

ionise into long anions and short cations.

Small anion

Small cation

Long anion

Thus when solutions of these two are mixed, bigger complexes are formed as shown in the following.
R

SO3Na (H2O)
Dye molecule

R4NCl (H2O)
Dye-fixing agent

_
SO3 + R4N+

_
SO3

Na+

Large dye anion

R4 N+

Cl

Large cation

_
SO3 + NR4 (Complex)

The mobility of the complex is much reduced, thus the wet fastness of the dyed material is improved.
The treatment of the dyed goods with 1 - 2% (owf) of cationic dye-fixing agent is carried out at
recommended temperature (varying for different products) for 15-20 min and the fabric is then dried.
4. Topping with basic dyes
Basic dyes do not have any affinity for cellulosic fibres. But special methods have been devised to
apply them to cellulosic material as bright shades are obtained. The process involves the use of certain
mordants, like tannic acid, which act as a bridge between the dye and the fibre as they have affinity for
both cellulose and basic dyes. With direct dyed material the direct dye acts as the mordant and forms a
complex when the material is treated with a solution of a basic dye. Such after-treatment of direct dyed
material with basic dyes is generally referred to as topping with basic dyes.
Theoretically any direct dye can be after-treated with basic dyes, but as topping is carried out in an
acidic medium, direct dyes sensitive to acid (e.g. Congo Red) should not be subjected to this
treatment.
Usually, for topping, a basic dye of similar hue as the direct dye is used. A very small quantity of basic
dye say of the order 0.1 - 0.3% is sufficient to produce brilliant shades on cotton dyed with direct dyes.
Topping with basic dyes is carried out in a cold bath containing a definite portion (half or even quarter)
of the dye solution and the temperature is raised gradually to 60C, and then adding the remaining dye
portions at regular intervals. A small quantity of acetic acid (0.5 to 2%) is added to the dye bath for
obtaining uniform shades.
When all the basic dye has been added the treatment is continued at the same temperature for a
further 45 - 60 minutes. This is followed by rinsing and drying.
For obtaining very fast dyeing, the direct dyed goods are treated with 2 - 4% tannic acid in a hot bath
for 20 - 30 minutes followed by squeezing, and treatment with tartar emetic (1 - 2%) in a cold bath for
20 - 30 minutes. The tannic-acid treated cotton has high affinity for basic dyes. Topping is then carried
out as explained above.
5. Diazotisation and development of direct dyed goods
As discussed earlier, it is possible to enhance the wet resistance of water-soluble dyes by increasing
the size of their dye molecules. Some of the direct dyes contain free amino (NH 2) groups, which can be
diazotised by chemical reaction with nitrous acid (HNO 2). The resulting diazonium salt is then treated
with a coupling component, which results in the formation of an azo (N=N) group.

22

The size of the direct dye molecule is now greatly increased and it will show good resistance to wet
treatments. The chemical reactions are shown below.
Since the azo group itself is a
chromophore, the colour of the
diazotised and developed direct
dyed material will change.
Using
different
coupling
components can thus produce
different colours.
In practice, the direct dyed
material is treated in the cold for
30 minutes in a bath containing

NH2

(Direct dye)

HCl + NaNO 2
(Diazotisation)

(Diazonium chloride)

HO

HO
R

_
N+...Cl

_
N+...Cl

(Coupling)

(Diazonium chloride)

(Coupling component)
(Naphthol)

NaNO2 1 to 3% (owf)
HCl
5 to 10% (owf)

(A large molecule of diazotised

and developed direct dye)

The goods are rinsed and developed with a solution of the coupling component for 15 - 20 minutes.
The material is then washed, soaped and dried.
The Direct Dyeing Process Chart
Grey Cotton Fabric

Grey Preparation Desizing, Scouring and Bleaching

Steam or
other means
of heating

Dye material at 40C for 10-15 min

Direct dye solution

at 40C + 0.5-1%
Na2CO3 as required

While dyeing, raise dye bath to boil @ 2C/min

NaCl (5 to 20%) is
added in two instalments
over 20-30 min
Continue dyeing at the boil for 45-60 min

Drain (drop) the bath

Cationic dyefixing agent
1 to 2 %
Treat in the dye-fixing bath @ 50-60C for 15-20 min

Squeeze the fabric and dry it

Stripping of Direct Dyes

In case of uneven dyeing, patchy dyeing and also when the shade is unacceptably deeper than
desired, the dyes may be stripped (removed from the fibre). Almost all of the direct dyes can be
stripped with a hot, dilute solution of caustic soda and sodium hydrosulphite. However, it may not be
possible to strip all dyes to a complete white, but the treatment may be good enough for the correction
of faulty dyeing.

23

Vat Dyes
Introduction
Vat dyes owe their name to the fact that the foremost member in this series, indigo, was applied to
textiles by means of a fermentation process in wooden vessels commonly known as vats. The dyes
are amongst the oldest natural colouring matter derived from origins like vegetable (plants, stems,
etc.), insects and animals.
Vat dyes provide textile materials with the best colour-fastness of all the dyes in common use. The
fibres most readily coloured by them are the natural and man-made cellulosic fibres, like cotton,
viscose rayon, etc.
Properties of Vat Dyes
1. Vat dyes are insoluble in water.
2. They are generally converted to their soluble leuco-state by means of sodium hydrosulphite
(reducing agent) in the presence of caustic soda.
3. Vat dyes have excellent washing and light fastness.
4. Vat dyes are very expensive compared with the other classes of dye.
5. They are available commercially in different forms such as powder fine, micro-fine, ultra-disperse,
highly concentrated, supra-paste and double-paste.
Classification of Vat Dyes
There are two different ways of classifying vat dyes. One is based on the chemical constitution of the
dyes while the other is based upon their methods of application. The classification of vat dyes by
chemical constitution is discussed in the following.
Classification by chemical constitution
(a) Anthraquinonoid vat dyes
(b) Indigoid vat dyes
(c) Sulphurised vat dyes
O

(a) Anthraquinonoid vat dyes

The anthraquinonoid group covers a large range of shades. The dyes
have good substantivity in water-soluble leuco-form and display superior
washing fastness properties. These dyes require a comparatively high
concentration of alkali than the indigoid dyes and so, are not suitable for
application to protein fibres. The chemical structure of an
anthraquinonoid vat dye is based on anthraquinone, shown alongside.
(b) Indigoid vat dyes

O
Anthraquinone

These dyes are derivatives of the compounds indigotin or thioindigo, as opposed to the
anthraquinonoid vat dyes, which are based on anthraquinone. The indigoid dyes form pale yellow
solutions under weakly alkaline condition.
(c) Sulphurised vat dyes
These dyes are available under brand names like Hydron, Redon, etc. These dyes have good allround colour-fastness properties, which are intermediate to those of sulphur and vat dyes.
The dyeing method is similar to that for vat dyes and the dye has to be chemically reduced using
(caustic soda + sodium hydrosulphite + sodium sulphide) before dyeing. Hydron Blue is a classic
example of this kind of dye.
Classification by method of application
Vat dyes are also classified into four groups on the basis of their methods of application, as shown in
the following table.
There are four classes of vat dyes, IK, IW, IN and IN-Special, stated in the order of increasing
exhaustion and the requirement of chemicals and vatting and dyeing temperature.

24

Group

Vatting
temperature ( C)

Dyeing
temperature ( C)

Caustic
soda (g/l)

Hydros* (g/l)

Common
salt (g/l)

IK

50

25 - 30

1.0 - 3.0

1.0 - 5.0

6.00 - 50

IW

50

40 - 50

1.0 - 5.0

1.0 - 6.5

3.00 - 25

IN

50 - 60

50 - 60

1.5 - 10

1.5 - 10

None

IN Special

These dyes require special conditions

*Hydros or hydro is a commonly used abbreviated form of sodium hydrosulphite

The IK vat dyes (or cold-dyeing dyes; K = kalt or cold in German) are known for their optimum affinity
at very low temperatures i.e. 20 - 30C and require minimum additions of caustic soda and sodium
hydrosulphite. The colour yield is greatly improved in the presence of large amounts of salt.
The IW vat dyes (or warm dyeing vat dyes) are characterised by moderate caustic soda requirements.
These dyes are vatted and exhausted at comparatively low temperatures i.e. 40 - 50 C. The dye
baths are exhausted well in the presence of moderate concentrations of exhausting agent.
The IN vat dyes (or normal dyeing vat dyes) show their maximum affinity for cellulose at 60 C. These
dyes require relatively high concentrations of caustic soda in the dyeing bath. The exhaustion of the
dye bath is achieved even without the addition of common salt. However, these dyes require the use
of retarding agents during dyeing because of their greater affinity for the fibre.
The IN-Special vat dyes or simply IN-Spl dyes (or special dyeing vat dyes), the fourth group of vat
dyes includes specific dyes like blacks, which require relatively higher concentrations of caustic soda,
sodium hydrosulphite and also much higher vatting and dyeing temperatures.
Chemistry and Application of Anthraquinonoid (AQ) Vat Dyes
The anthraquinone class, recognised and made famous first by the ICI trade name Caledon, is the
most important class of vat dye for cotton dyeing. It is easily the largest class and most of its members
possess high all-round fastness. They are characterised by the possession of at least two quinonoid
carbonyl groups. Under alkaline conditions of chemical reaction, anthraquinone, on reduction can give
not one, but several products.
Like the other classes of vat dyes, the AQ vat dyestuffs are insoluble, coloured compounds which can
be easily converted to a soluble form that is substantive to cellulose. These dyestuffs contain two or
more carbonyl groups, which are easily reduced in alkaline solution to the leuco form and then to its
sodium salt, which is water-soluble. The insoluble colour is then regenerated in the fibre by oxidation.
These changes in the carbonyl group of the vat dye are explained by the following representation.
C

Reduce

[H]

Vat dye

OH

+ NaOH

Air

ONa

Sodium salt of
leuco-vat dye

Leuco-vat dye

Regenerated
(oxidised) vat dye

Given below is a representation of the AQ part of the vat dye with the same changes as above.
OH

O
R e du ctio n

O
Anth raq ui none vat dye
(ins o lu ble i n wa te r)

ON a
In p resen ce
o f a lkal i

OH
Le u co -va t dye or vat a cid
(ins o lub le in w ater)

O
Oxida tio n

ON a
"So d ium s a lt of le uco va t d ye
(s olu bl e i n wa te r)

The above steps can be described as follows.

25

O
Anth raq ui none vat
(i ns olub le in w ate r)

1. Vat dye: Insoluble in water

2. Reduction of vat dye
Vat dye + Hydros = Reduced vat dye or leuco-vat dye or vat acid, insoluble in water and having no
affinity for cellulose
3. Solubilising the leuco-vat dye in the presence of alkali
Leuco-vat dye + Caustic soda = Sodium salt of leuco-vat dye, soluble in water and having affinity
for cellulose
4. Oxidising the leuco-vat dye in the fibre
Sodium salt of the leuco-vat dye oxidised in air or chemically = Insoluble vat dye regenerated
Colour change in vat dye solution / bath
When anthraquinone (AQ) vat dyestuffs are reduced and dissolved, a marked change in colour of the
reduced solution usually occurs. Some examples of the colour change are listed below.
Vat Dye

Colour of reduced bath

Vat Dye

Colour of reduced bath

Yellow dye

Blue

Green dye

Blue

Orange dye

Red-violet

Blue dye

Slightly greenish (or yellowish) blue

Most vat dyes are easy to identify when complete reduction has taken place from the distinct colour
change that they show. But some practice and experience is required to clearly identify complete
reduction of the blue dyes.
The solubilised vat dyes (e.g. Hydron Blue, Indocarbon CL, etc show a fairly common change to a pale
yellowish colour upon reduction.
Application of vat dyes
The application of vat dyes to cotton goods involves the following four basic steps.
1. Vatting
This step converts the insoluble commercial vat dye powder into its soluble sodium salt.
2. Dyeing
This step brings about absorption of the reduced and dissolved vat dye by the fibre from an alkaline
reducing bath in the presence of exhausting or retarding agent, as necessary.
3. Oxidation
The soluble sodium salt of leuco-vat dye absorbed by the fibre is converted into its original
insoluble form. This is done either by air or chemical oxidation.
4. After-treatment
The dyed material is subjected to a treatment with boiling detergent solution to get the proper
shade (hue) with brilliance and good fastness properties.
Step1: Vatting
The conversion of insoluble vat dyes into their soluble form involves the following steps:
a) Reduction of the original insoluble vat dye into weakly acidic leuco-vat (or vat-acid) form.
b) Neutralising the leuco-vat dye with sodium hydroxide to give a water-soluble sodium salt of the
leuco-vat dye.
In order to keep the dye in soluble sodium salt form, a sufficient excess of both caustic soda and
hydrosulphite of soda is required to be maintained in the bath. When either alkali or hydros or both are
present in insufficient quantities a complete solution is not obtained.

26

The stability of the vatted dyed solution is greatly affected by improper vattting conditions. It is
therefore very much important to maintain (i) the recommended conditions of temperature and (ii) the
optimum concentrations of hydros and caustic soda during vatting and dyeing.
Methods of vatting
There are different methods of converting vat dyes into their substantive form i.e. sodium salt of leucovat dye. Generally vatting is carried out either by,
(i) Stock vat method or

(ii) Long liquor method (in full volume in the dye bath itself).

Stock vat method: In the stock vat method, the dye powder is pasted with an equal amount of Turkey
Red Oil and hot water at 50 - 60 C is added. This is followed by addition of the required amounts of
caustic soda and hydros; the solution is allowed to stand for the recommended time (10 - 20 minutes)
with occasional stirring. The vatted dye solution is a concentrated solution and is hence called the
stock vat. It is added in two or four portions to the blank bath. A blank bath is a bath that is usually
prepared in the machine vessel; it contains the required quantity of water and the required amounts of
caustic soda and hydros kept at the recommended dyeing temperature; a blank bath contains no dye.
Long liquor vatting: In the long liquor method of vatting, a dispersion of the vat dye is added to the full
volume of the dye bath in the machine vessel itself. (A dispersion is a mixture of dye particles in water.)
The recommended quantity of caustic soda is then added and the solution is mixed well. It is then
brought to the recommended vatting temperature (50-60C), usually by means of steam. The
recommended quantity of hydros is then slowly and uniformly added all around the bath with stirring.
Both the colour and consistency (viscosity) of the bath will change with the addition of hydros. The
colour change will depend upon the dye used and the consistency becomes more viscous. The bath is
allowed to stay, with occasional stirring, until the vatting is complete. Vat Blue RSN is best vatted by
this method.
Quick test for vatting: In order to check whether vatting is complete or not, a drop of the vatting solution
is placed on a filter paper and observed. If the liquor is only incompletely vatted, insoluble particles i.e.
unvatted dye, will be visible at the centre of the place that was spotted. When the dye is perfectly
solublised, the dye solution spreads out uniformly in a radial direction.
The observation of the extent of vatting should be done quickly, when the dye is still in the reduced
state, i.e. before it gets oxidised by air.
Step 2: Dyeing
Actual dyeing takes place in the second step when the sodium salt of the leuco-vat dye is adsorbed on
the surface of the fibre and then diffuses into the interior of the fibre. The adsorption and diffusion are
possible only when the dye is completely dissolved, since the insoluble vat dye has no affinity for the
fibre. It is therefore very much essential to maintain recommended concentrations of caustic soda and
hydros, and the temperature of dyeing.
Precautions in dyeing: Truly speaking, a slight excess of caustic soda and hydros is essential to keep
the dye in soluble and substantive form during dyeing. (Refer to the table on Page___ for the
recommended quantities of these chemicals for the different classes of vat dye.)
Sodium hydrosulphite gets decomposed by atmospheric oxygen and produces acidic products, which
in turn neutralise a part of the alkali. Hence the concentration of sodium hydroxide in the dye bath
decreases. To maintain the dyestuff in soluble form, fresh quantities of caustic soda and hydros are
added.
If these conditions are allowed to worsen even towards the end of the dyeing process, though
exhaustion has taken place, premature oxidation of the leuco-vat dye taken up by the fibre results in
patchy dyeing, showing dark and light areas in the dyed material. It is therefore essential to maintain
fairly alkaline and sufficiently reducing conditions in the dye bath from the beginning to the end of
dyeing.
Test for ideal dyeing conditions: The presence of caustic soda and hydros during dyeing is checked
respectively by means of phenolphthalein paper and vat yellow paper as follows.

27

Hydros: Satisfactory presence of hydros is indicated by the appearance of a blue colour within seconds
of spotting the vat yellow paper with the dye bath solution. If the blue colour does not appear, a fresh
quantity of hydros needs to be added.
Caustic soda: The alkalinity, i.e. presence of caustic soda, is checked with phenolphthalein paper,
which changes from white to intense pink in the presence of alkali.
Dyeing temperature: The dye bath temperature is also checked frequently with an accurate mercury
thermometer and kept at the recommended temperature.
Dyeing procedure
a) The dye bath is set with the required amount of water, caustic soda and hydros and maintained at
the recommended temperature for the particular class of dye being used. The thoroughly prepared
textile material is introduced and worked for 10 minutes in this blank bath. As this treatment
prepares the material with the chemicals that keep the dye in solution, the blank bath is also called
the sharpening bath.
b) The vatted dye solution is divided into two equal portions. One of these is added to the blank bath
and mixed well. The material is run in the dye bath for 10 minutes. The second portion of vatted
dye is then added to the bath and the dyeing is continued at the recommended temperature for 45 60 minutes. The dye is added in portions to control the initial rate of dyeing and bring about level
dyeing, In some cases, the dye is added successively in four portions.
Dye bath assistants or dye bath auxiliaries

These are chemicals or commercial products that are added to the dye bath to facilitate effective and
quality dyeing.
An exhausting agent, e.g. common or Glaubers salt, is added, especially for the IK and IW classes of
dye, in dissolved form during dyeing. Such additions are made in two equal instalments; dyeing after
each addition of salt is usually for at least 15 minutes.
Vat dyes vary in their affinities for the fibre and hence vary in their rates of dyeing. Levelling agents are
used for dyes that tend to rush into the fibre and result in uneven dyeing. These agents retard and
control the rate of dyeing such that level dyeing results are produced.
Retarding the initial rate of dyeing may be achieved by adopting the following methods.
a) Starting the dyeing at lower temperatures and then heating the dye bath slowly to the required
temperature.
b) By adding the dye in two/four instalments, thereby reducing the initial concentration of the dye bath.
c) By incorporating suitable auxiliaries or dyeing assistants called levelling agents or retarders. These
chemicals essentially retard or slow down the dyeing and function via two different mechanisms.
i)

They compete with the dye molecules for the available sites in the fibre and thereby reduce the
effective rate of dyeing.

ii) Alternatively, they form loose complexes by combining with dye molecules; the fibre cannot
absorb these complexes, as they are very large. In the later stages of dyeing, when the
temperature is higher, these complexes are broken down and the dye molecules are set free
for adsorption by the fibre surface.
Some of the commonly used retarders in vat dyeing are,
Dispersol VL (ICI)

Remol OK

Albatex PO

Evasol N (Indokem), etc

Right up to the end of the dyeing step, the dye absorbed by the fibre and the dye in dye bath must be
kept in a completely reduced state, otherwise, the dye is oxidised and this leads to the production of
dull or even uneven shades. Sufficient amounts of sodium hydrosulphite and sodium hydroxide are
thus maintained in the bath even during the completion stage of the dyeing process.
Another very important point to note is that the material is always kept immersed in the dye bath during
dyeing, so as to prevent local oxidation, i.e. oxidation in some portions of the material. This is most
important for open beck dyeing of yarn.

28

Step 3: Oxidation
In this step, the dyed goods are subjected to an oxidation treatment for conversion of the sodium salt of
the leuco-vat dye taken up by the fibre into the original insoluble vat dye. The oxidation process plays
an important role and needs to be carried out under controlled conditions. Improper oxidation leads to
faulty dyeing, especially unevenness, inadequate fastness properties and shade deviations in terms of
hue, tone and depth of shades.
On removal from the dye bath, the material is squeezed or hydro-extracted for complete removal of
excess liquor containing unexhausted dye, sodium hydroxide and sodium hydrosulphite. It is then
subjected to oxidation treatment, which can be done in one of the following ways:
a) Air oxidation, or

b) Chemical oxidation

During airing, the dyed goods are exposed to atmospheric oxygen while in chemical oxidation, use is
made of various chemicals to accelerate the oxidation process.
Some of the important oxidising agents used for the purpose are hydrogen peroxide, sodium
perborate, and sodium hypochlorite. The concentration depends on the agent used, e.g. if 35%
hydrogen peroxide is used, a concentration of 1-2 ml/l may be used.
The oxidation treatment has to be carried out under mild conditions depending upon the chemical
chosen (i.e. low temperature, minimum time and low concentration) to prevent the oxidation of
cellulose.
Step 4: After-treatment
The after-treatment for vat-dyed material consists of soaping it at the boil and then washing it to
remove the soap.
Why is soaping of vat-dyed goods necessary? The leuco-vat dye absorbed by the fibre is converted
into its original insoluble form inside the fibre during oxidation. At the same time dye particles in the
residual liquor (left over after the squeezing of the dyed material) are also oxidised and get loosely
deposited on the fibre surface. These dye particles are not firmly fixed to the fibre, and if not removed,
will contribute to poor rubbing fastness properties of the dyed material.
It is therefore necessary to treat the dyed goods in a hot detergent bath to develop the true shade and
give good fastness properties. During soaping, the loosely held dye particles are removed and held in
suspension to prevent them from depositing back on the material.
Apart from contributing to the fastness properties, the soaping treatment allows the dye molecules to
aggregate and form large crystals. This imparts the true shade to the material. Moreover the resulting
crystals are more resistant to subsequent chemical or physical treatments. The aggregation of dye
particles is accelerated in the presence of detergent at boiling temperature.
The soaping process: A boiling solution of soap or a synthetic detergent is used in this process. It is
advantageous to use soda ash in the soaping bath when soap is used. The treatment is carried out at
the boil in order to achieve the true fastness properties of the dyed material. In a typical soaping
treatment, the goods are treated at the boil in a bath containing 3 g/l soap and 1 g/l soda ash.
The soaping treatment is followed by a washing treatment for 20 - 30 minutes until the material is free
from alkali. The material is finally hydro-extracted and dried.
The phases of vat dyeing
Schematically the dyeing process is divided into two phases.
First phase
The first phase is the exhaustion phase, in which the dye exhausts very rapidly on the substrate (i.e.
the textile material being dyed). Vat dyes in general have a very high rate of exhaustion due to their
extremely high affinity for cotton. About 80% of the colour exhausts in the first five minutes of dyeing.
The tendency of dye to rush to the fibre is called strike. The faster a dye exhausts, the greater are the
chances of uneven deposition of the dye on the fibre. Dye that has deposited on the surface of the fibre

29

has to diffuse into the fibre structure and distribute itself uniformly to be finally visible as level dyeing.
Also, as stated earlier, good dye penetration leads to good fastness and a rich, bright dyeing.
Second phase
The second phase is the diffusion or migration phase. Dyestuff that has a good ability to migrate will
show better levelness in dyeing because it will tend to even out, even though it was initially absorbed
unevenly. On the other hand, dyestuff that displays poor migration will result in uneven dyeing.
Improving levelness in vat dyeing
In order to get an even shade and good fastness properties with dyes that do not possess good
levelling properties, the following methods are helpful.
i) Reducing the rate of dyeing (especially, the initial strike rate) this can be achieved by adding the
dye liquor in two or four instalments or by the use of retarding agents. (See the part on dyeing
assistants under the topic Dyeing Procedure above.)
ii) Use of levelling agents refer to the discussion on dyeing assistants above.)
iii) Use of pigmentation methods this is discussed in the following.
Industrial Methods of Vat Dyeing
Vat dyes may be applied to cellulose textiles by any of the following industrial practices.
a) Leuco-vat dyeing (by exhaust dyeing or padding techniques)
b) Padding (pigmentation) process
c) Vat-acid process
The leuco-vat dyeing technique
In this process, the insoluble vat dye is converted into its soluble and substantive form (leuco-vat form),
prior to application, with the help of sodium hydroxide and sodium hydrosulphite. Vatting is done either
in a small quantity of water (stock-vat method) or in bulk (long-liquor method). The dye is taken up by
the fibre in this leuco-vat form and it is then regenerated to its original insoluble form in the fibre via
oxidation (air or chemical) and soaping.
Since the dye is in soluble form in the dye bath, the particle size is of no consideration except for the
rate of vatting (finer brands vat quickly). It is also important to control the initial rate of dyeing.
Leuco-vat technique using exhaust dyeing
Exhaust dyeing involves dyeing a limited batch of material, over a period of time, from start to finish, in
a single machine that contains the dye liquor, e.g. jigger, package-dyeing machine, etc. Level dyeing in
this case is obtained by one of the following techniques.
i)

In the jigger (fabric dyeing), dye additions are made in equal portions to prevent the tailing
effect and also to control the initial rate of dyeing.

ii) While dyeing yarn (in cheese or beam form) in liquor-circulating machines, the rate of dyeing is
controlled by reversing the flow of liquor through the packages quite often.
iii) Using additional auxiliaries, e.g. retarding agents.
iv) Lowering the temperature of dyeing also reduces the rate of dyeing.
Leuco-vat dyeing using the padding technique: The dyeing of cotton fabric by the leuco-vat process
may also be carried out using the padding technique. Piece goods are padded with a solution of the
vatted dye at as low a temperature as the stability of the vatted dye permits. Additionally, use of
penetrating and defoaming agents is advantageous. After padding, the steps of air oxidation, rinsing
and soaping are carried out. This method is suitable for mass production of standard shades.
For obtaining satisfactory results, a suitable padding mangle should be used so that all air is squeezed
out before entry of the goods in the dye liquor and all the liquor is withdrawn when the goods are
leaving the mangle. Maintaining constant temperature throughout padding calls for the greatest
process control. The padding process is more suitable with dyes having low affinity for the fibre. The
precautions to be taken while padding have been explained earlier.

30

This padding technique for leuco-vat dyeing is difficult to control as a number of variables, like air in the
incoming cloth, proper impregnation, oxidation, etc. For bulk dyeing, the pigmentation process is good.
The pigmentation process
In this process the dyeing is carried out using dyes in the original, non-substantive and insoluble form,
in which they compare very well with pigments; hence the name pigmentation. In fact, the introduction
of vat dyes in the form of very finely divided particles made it possible to achieve uniform deposition of
the dyestuff on yarn and fabric as well. The fine dye particles avoid every chance of filtration through
yarn in package dyeing.
A dispersion of the dyestuff is prepared by sprinkling the required amount of micro-fine (mf), supradisperse (sd) or ultra disperse (ud) brand of dye powder in 10 - 20 times of its weight of luke warm
water (temperature 40C). In no case is pasting done either in boiling water or with any wetting agent,
etc. This leads to aggregation and ultimately lump formation. The fineness of the dye particles ensures
fine dispersions and uniform deposition. The mf, sd and ud brand vat dyes are available commercially.
When the dye is uniformly distributed in the material in pigment form, it is then treated with the alkaline
reducing liquor at the appropriate temperature to convert it to the substantive leuco-vat form, when the
fibre absorbs it. The usual steps of oxidation and soaping follow the dyeing step.
The pad-jig (i.e. padding + jigger) method of dyeing vat dyes is used for this process. The steps in the
pigmentation method are shown schematically below.
Uniform application
of the pigment on to
the fibre (surface
deposition) in a
padding machine

Finely ground vat

dye pigment (mf,
sd or ud brand) is
uniformly
dispersed in
water

Reducing and
solubilising the
pigment on the fibre
surface (to cause dye
diffusion into the
fibre), in a jigger

Oxidation of the
leuco-vat dye
absorbed by the
fibre back to the
original insoluble
vat dye (jigger)

Soaping at the
boil, washing
off the soap
(jigger) and
drying (drying
machine)

The Vat-acid process

This process involves uniform deposition of non-substantive dye particles on the textile material, and
then fixing the dye in the fibre by working the material in a bath containing caustic soda and hydros.
Unlike pigmentation, which is restricted to the mf or sd brands, any form of vat dye can be applied
using the vat-acid process. The basic principle of the vat-acid technique is summarised below.
Principle of the vat-acid process: When a vat dye is reduced as usual with hydros and caustic soda
and then treated with acetic acid in the presence of an acid-stable dispersing agent, it is converted into
leuco-vat acid, which is an extremely fine dispersion. The formation of vat acid can be represented by
the following chemical reactions.
O

ONa
NaOH

OH
CH3COOH

Na2S2O4
O

ONa

OH

( Vat dye )

(Sodium salt of leuco-vat dye)

(Vat acid)

It should be noted that in the presence of insufficient acid, vat acid is not produced and precipitation
may take place in the absence of a suitable dispersing agent. The salient features of the vat-acid
process are as follows.
i) Insoluble vat acid in acidic medium is extremely stable to atmospheric oxidation. The goods to be
treated with vat acid should be free from even traces of alkali.
ii) Vat acid does not have any affinity for cellulose substrates, but it is readily converted into
substantive form by the addition of sodium hydroxide.
iii) Dispersions produced by neutralisation of alkali with acetic acid are much finer than those prepared
by pigmentation, using micro-fine or supra-disperse brands of vat dyes.

31

iv) Development of vat acid is comparatively more rapid and this reduces bleeding of dyestuff in the
developing bath.
v) The process is of special interest for the dyeing of heavy piece goods, twisted yarns, and tightlywoven fine cloth.
Vat dyeing yarn in package form by the pigmentation technique
While dyeing yarn in package form in dye liquor circulating machines such as cone or cheese dyeing
machine, beam dyeing machine, etc the process sequence followed for vat dyeing is the pigmentation
process as suggested below.
i)

The goods in the form of cheeses, cones or beams are thoroughly boiled in a scouring liquor
containing only detergent, but no alkali. Use of alkali, like sodium hydroxide, sodium carbonate, etc.
in boiling condition is avoided because it swells the yarn and results in hardening the packages.
The hard packages ultimately offer considerable resistance to the flow of dispersions of the vat
dyes during circulation.

ii) The detergent boiled yarn is next thoroughly washed with hot water and then cold water and finally
hydro-extracted (centrifuged to remove excess water).
iii) A dispersion of the dyestuff is then circulated through the packages at room temperature (30C) to
uniformly deposit the dye particles on the material.
iv) The required amounts of caustic soda and hydros are added gradually, in two or three portions,
through the expansion tank of the machine, while circulation of the liquor is on.
v) The bath is then heated to the recommended dyeing temperature and liquor circulation is continued
with periodic reversal of the direction of flow, inside-out for a specific period and outside-in for a
specific period.
vi) When the dyeing is over, the necessary steps of oxidation, rinsing, soaping, etc are completed in
the usual manner.

Vat dyeing fabric by the pad-jig process

Padding The fabric may be padded with an aqueous dispersion of the vat dye by means of a suitable
padding mangle. In this respect, the following five important points are considered.
a) The entire surface of the rolls of the mangle should be smooth and clean and also free from any
sort of damage; even a minute scratch on the rubber bowl or a piece of dirt on either of the bowls
will show up on the fabric as a dye stain.
b) The liquor picked up by the fabric should be continuously replaced, i.e. the concentration of the dye
dispersion should be kept constant throughout the process. This is achieved by feeding the stock
dispersion of the dye into the mangle trough at a constant rate from an overhead tank.
c) Depending upon the requirement of shade, the kind of fabric being dyed, etc, the padding may be
done once, twice or even three times, to increase dye pick up.
d) The amount of dye deposited on the fabric depends upon the following factors.
i)

Expression percentage a mangle expression of up to 90% may be used for cotton fabric. In the
case of viscose fabric, the mangle expression should be less, but never below 50%.

ii)

Fabric speed this depends upon the fabric and the machine used.

iii) Temperature of the padding liquor the temperature of the padding liquor should also be maintained
at a constant value.
iv) Quality and goodness of preparation of the cloth being dyed.

e) Care should be taken to see that water drops (e.g. condensed steam falling from the ceiling) do not
fall on the padded fabric. The padded material should not also be touched by hand, especially if it is
dirty or wet.
Jigger dyeing The padded goods are then transferred to a jigger-dyeing machine using calculated
quantities of pad dye liquor in two instalments and the necessary amounts of reducing chemicals. The
Desized,
scoured and
bleached fabric

32

Padding in a
dispersion of mf
or sd, vat dye

Developing the
padded fabric
in a jigger

After-treatment
of the dyed fabric
in the jigger

dyestuff on the fabric is vatted (on the fibre itself) using caustic soda and sodium hydrosulphite. The
time, temperature and other dyeing conditions are maintained in the jigger as required and the fabric is
finally oxidised, rinsed, soaped and washed in the usual manner. The pad-jig steps are shown here
schematically.

Disadvantages of the pad-jig process

a) The process could give lot-to-lot variation if it is not properly standardised.
b) It requires strict process control.
c) Skilled operators are required.
d) Long end-pieces are required at the ends of every roll of fabric, so the cost is high.
e) Only selected dyes, having low affinity for the fibre, and those that can be vatted in long liquors are
suitable.
Machines Used for Vat Dyeing
a) Dyeing of yarn in an open beck
This is the oldest and simplest method for the dyeing of yarn. The process uses an open rectangular
tank and bent rods that are long enough to span the width of the tank. The hanks are hung on the rods,
which usually carry 1 kg of hanks each.
Two operatives standing on opposite sides of the beck do the actual dyeing. The hanks are turned
around manually by means of a straight rod manipulated deftly by the workers. Thus the portions of the
hanks on each of the rods that are exposed to the atmosphere are immersed in turn in the liquor.
Dyeing is carried out by periodically turning around the yarn hanks on each rod. The hanks should be
turned around as frequently as possible.
Bent rod

Why bent rods? The use of bent rods ensures

complete immersion of the material throughout
the dyeing process and hence would result in
even dyeing. A bent rod with hanks suspended
from it and thus completely immersed in the dye
bath is shown in the figure.

Liquor level

Tank
But difficulties are encountered while turning the
material. Moreover, on occasions, if the yarn
has not been properly scoured, the hanks tend
Hanks
to float in the dye bath and make manual
handling a problem.
The tank may be heated by means of firewood, coal or steam. The following precautions are necessary
to achieve uniform dyeing by the open-beck method.

i)

The material should be vigorously moved, especially in the initial stages of dyeing, so that all
parts of the material come in uniform contact with the dye liquor.

ii) While making additions, all the rods of hanks being dyed are removed and piled at one end of the
tank, thereby exposing the material to the atmosphere. This would therefore require frequent
additions of caustic soda and hydros to the bath.
iii) The dyer should have a proper knowledge of the properties of dyes, especially the rates of dyeing
of vat dyes.
iv) Maintaining the liquor ratio and dyeing temperature apart from the presence of caustic soda and
hydros are important checkpoints to ensure level dyeing.
v) While producing mixture shades, the selection of dyes should be made carefully and, as far as
possible, dyes belonging to the same group should be selected. It is always advantageous to vat
each component dye separately.

33

vi) Combinations of blue and yellow and yellow and green should be avoided because of differences
in fastness properties and the differential rates of dyeing.
b) Jigger dyeing machine
This machine has already been described and illustrated in a previous section (Unit I). Vat dyes are
applied to cotton fabric or the cotton part of a polyester/cotton fabric by means of a jigger. The steps in
the dyeing process are as follows.
i) The fabric is loaded on the jigger with two 3-metre end-pieces of waste fabric such that it is
batched on one of the draw rollers with the free end-piece threaded through the machine and
wound tightly on the other draw roller.
ii) The required quantity of water is taken in the vessel of the jigger and heated to the vatting
temperature, which will depend upon the class of dye used.
iii) The selected vat dye or mixture of vat dyes is pasted in a separate stainless steel vessel with
TRO and water at the vatting temperature (from the jigger vessel) is added to it so a uniform
dispersion of the pasted dye is formed.
iv) The required amount of caustic soda is then added to the vat dye dispersion and mixed
thoroughly. Then with a check on the temperature of the liquor, to ensure the right vatting
temperature, the required quantity of sodium hydrosulphite is added slowly and steadily to the
liquor while it is being stirred. There will be a noticeable change in the colour of the liquor,
indicating that reduction and dissolution of the dye are taking place. Vatting is then allowed to
take place for another 10-15 minutes, with occasional stirring.
v) The water in the jigger vessel is then brought up to the required volume and dyeing temperature
and the recommended amounts of caustic soda and sodium hydrosulphite are added; the
sharpening bath thus prepared is mixed well.
vi) The fabric is run for two ends in the sharpening bath to ensure that is takes up the dye uniformly
in the next step.
vii) One half of the vatted dyestuff is added to the sharpening bath, mixed well and the fabric is run
one end in the dye solution.
viii) Next the other half of the vatted dye is added to the jigger and the fabric is run another end.
ix) The fabric is then run for four or six more ends in the dye bath depending upon the shade depth;
in between ends, the correct amounts of hydros and caustic soda are ensured by means of tests
with Vat Yellow paper and phenolphthalein paper respectively. Additions of these chemicals are
made if necessary. Depending on the dye class used, if required, salt is added in two portions
over the third and fourth ends.
x) When the dyeing is over, the dye bath is drained and the fabric is oxidised in a fresh bath
containing 1-2 g/l hydrogen peroxide at 40-50C through two ends.
xi) The fabric is then soaped in a fresh bath containing 5 g/l soap and 2 g/l soda ash at the boil for
four ends.
xii) The fabric is finally washed successively in hot and cold water to wash off the soap. It is then
unloaded from the jigger and taken for drying.
c) Standfast molten metal process
The Standfast molten metal dyeing machine comprises of a U-tube made of heavy plates (1.5 m wide,
1.5 m deep and 25 mm thick). The complete dyeing range used for the application of vat dyes can be
diagrammatically represented as in the following figure.

34

Vat-dyed and
w ashed fabric
take up
Feed
rollers

Reduced
vat dye
solution
Salt
bath

U-Tube

Fabric passing through

molten m etal bath

Heating
jacket

Molten metal bath

surrounding fabric

Open soaper w ashing range

The U-tube contains molten metal alloy of composition 26.7% lead, 50% bismuth, 10% cadmium and
13.3% tin. The metal alloy is also called Standfast metal or simply molten metal.
The U-tube is provided with a heating jacket to keep the molten metal at constant temperature and in
the molten state throughout the process. The top of the left arm of the U-tube comprises of a
bottomless stainless dye bath, the molten metal acting as a resting surface for the dye liquor. Similarly,
at the top of the right limb is a salt bath, which performs the washing off function and also acts as a
seal for the melt. The molten metal has the three following functions.
i)

For the fabric impregnated with dye solution, it provides a rapid and even supply of heat in the
absence of air. (No oxidation of the reduced dye takes place.)

ii) The pressure exerted on the fabric is very uniform and just sufficient to leave the required
amount of moisture in the material and thus gives optimum speed of fixation. The effect of the
molten metal bath is equal to padding the fabric at uniform pressure and temperature.
iii) It facilitates the use of an extremely small dye bath (the capacity of which is just about 10 litres).
The outstanding features of the machine
a) Uniform pressure on the fabric in accordance with its thickness helps to cover thick and thin
places.
b) Complete absence of air reduces the consumption of caustic soda and hydros.
c) The machine is suitable for dyeing both small lots of fabric (e.g. 500 m or so) and big lots.
d) The time required for intermediate cleaning of the machine for change over to other shades is
reasonably low.
e) There is no incidence of tailing, i.e. the tendency of the dye-impregnated fabric getting lighter
and lighter with time and length of fabric.
f)

The machine is simple in construction.

Disadvantages of the machine

i)

Elaborate control of temperature is necessary.

ii) Solidification of metal during process can cause fabric damage.

iii) In the event of a fabric tear during running, it becomes very difficult to re-thread the fabric.
iv) The slightest contact of the running fabric with the walls of the tube will tear it. To avoid this
problem, grooves are provided in which the metal melt accumulates.
v) Cloth leaving the machine carries traces of alloy, which cannot be recovered. This results in
loss of small amounts of costly alloy.
Photo-chemical Degradation
Certain vat dyes, especially the yellow and orange ones, suffer from the defect of accelerated oxidation
under the action of light. The changes that result are so severe that they tend to bring about chemical
degradation of the cellulose in the fibre itself. If such photo-sensitive dyes are present in the dyed
material consisting of a combination of grey and coloured yarns, and the goods are bleached with
hypochlorite in the presence of light, the dyed fibre material is very likely to be tendered.

35

The mechanism of photochemical degradation or simply photo-degradation is not well established.

However, the tendering of the cellulose fibres may be due to the formation of hydrogen peroxide, which
is a strong oxidising agent. The photo-degradation of vat dyes depends upon the properties of the
dyes, in particular their chemical structure. Such dyes are not manufactured anymore and alternatives
free from these effects are now available.
Stripping of Vat Dyes
When faulty dyeing results on account of one or more factors like improper vatting, uncontrolled rate of
dyeing, faulty preparation of goods for dyeing, uneven absorption and the factors arising out of
problems in the machine, etc. it becomes necessary to remove (partially or completely) the dyes from
the dyed material.

36

The process of removal of colour from a dyed material for correction of uneven or faulty dyeing or for
any other reason is referred to as stripping. It is very difficult to strip the dye completely from the vat
dyed material because of the great affinity that the leuco-vat dye has for the fibre.
In general, when the unevenness is not considerable, the stripping involves re-vatting of the dye on the
fibre in a bath containing sodium hydroxide and hydrosulphite at relatively high temperature in the
presence of certain levelling agents (e.g. Dispersol VL) which are used as retarding agents while
dyeing.
The degree of levelling achieved depends on the type of dyed material, the type of dye and the
concentration of the levelling agent. This process brings about a partial stripping of the dye on the
fibre, and most of it remains in the dye bath. Hence re-dyeing from a fresh bath containing freshly
vatted dye solution becomes necessary.
When complete stripping is desired, Lissolamine-V may be used in the stripping bath. This auxiliary is
supposed to form stable irreversible products with the sodium salt of the leuco-compound of dyestuff.
The treatment may be carried out in a bath containing,
Caustic soda (70Tw)

10 - 12 ml/l

Sodium hydrosulphite

5 - 6 g/l

Lissolamine V

2 - 3 ml/l

and

The bath is maintained at 90 - 95C for 20 - 30 minutes during the treatment.

Process flow chart for the vat dyeing process
The student is instructed to draw process flow charts for the following vat dyeing processes on the
basis of the information on vat dyeing provided above.
a) (i) Leuco-vat dyeing (exhaust dyeing)
(ii) Leuco-vat dyeing (padding technique)
b) Padding (pigmentation) process
c) Vat-acid process

REACTIVE DYES
Introduction
Stephen and Rattee, two textile chemists, were the first to show that certain dyes can chemically react
with cotton fibre, forming covalent bonds and thus becoming part of the fibre itself. Before the arrival of
these reactive dyes it was not possible to achieve good fastness to hot wet treatments in cellulose
dyed material, except in the vat class of dyes.
Another unique feature of these dyes is the versatility of the application procedures, allowing them to
be applied at temperatures ranging from the room temperatures to steaming methods, similar to those
used for the continuous dyeing of vat and sulphur dyes.
Since their introduction in the 1950s reactive dyes have shown rapid
growth; even today, developments are taking place.
The combination of brightness, fastness and ease of application
associated with reactive dyes enables this class of dyes to be the major
class of dyes used today to colour cellulose fibres.
The first-invented reactive dyes are based on cyanuric chloride, shown
alongside. The structure has the triazine ring structure.

37

Cl
C
N

C
Cl

C
N

Cyanuric Chloride

Cl

Properties of Reactive Dyes

1. The reactive dyes, on account of the sulphonic acid groups in their molecules, are readily soluble in
water.
2. Unlike direct dyes, the reactive dye molecules tend to be much less substantive to cotton and
require much larger quantities of salt for exhaustion.
3. These dyes, unlike any other class of dyestuff, react and combine chemically (forming covalent
bonds) with cellulose. It is this characteristic that gives them the name reactive dyes.
4. The highly reactive dye molecule, called the cold-brand type of reactive dye, has two chlorine
atoms. Its reactivity can be reduced when desirable by blocking one of the reactive chlorine atoms,
giving the hot-brand type of reactive dye.
5. Reactive dye molecules are not as long as direct dye molecules. Short molecules have two
advantages: (a) clarity and brightness of hue and (b) easy penetration and therefore good levelling.
6. Textile materials coloured with reactive dyes have moderate to good light fastness and washing
fastness.
7. Textile materials coloured with reactive dyes have to be thoroughly rinsed and soaped. Reactive
dyes can react with the hydroxyl groups of the water molecule to produce dye molecules with poor
substantivity for the fibre. In fact it is these molecules, which have to be removed by the washingoff process, involving soaping at the boil and rinsing. If these hydrolysed dyes are not removed,
poor rubbing fastness will result.
8. The formation of the covalent bond between the dye and fibre occurs under alkaline conditions.
The presence of acids may reverse this process. Perspiration and atmospheric pollution, which are
both slightly acidic may affect textile materials coloured with reactive dyes and result in some
fading.
9. Reactive dyes can be applied to cellulose fibres by the exhaust dyeing (batch dyeing), semicontinuous dyeing (pad-batch) and continuous dyeing techniques.
Classification of Reactive Dyes
Classification according to reactive system in the dye
The important reactive dye systems can be classified into two major categories depending on the
mechanism of formation of the dye-fibre bond.
1. Tri-azinyl type ring system
These dyes react with cellulose by a process of nucleophilic substitution, i.e. esterification.
Dyes such as Procion (ICI), Drimarene (Clariant), Levafix E (Bayer) and Cibacron (Indo-Swiss), etc.,
fall in this group of reactive dyes.
There are three types of triazine-based reactive dyes:
(i) Cold-dyeing or M-brand dye (ii) Hot-dyeing or H-brand dye and (iii) High-exhaust or HE-brand dye.
2. -Sulphatoethyl sulphone type
These dyes react with cellulose by the mechanism of nucleophilic addition i.e. etherification. The
Remazol dyes (Dye-star), Levafix dyes (Bayer) and Primazin dyes (BASF), etc., come under this
group of reactive dyes.
Chemistry of Reactive Dyes
In general, reactive dyes for cellulose material have certain characteristic structural features.
S

S is the solublishing group

C is the coloured part of molecule

B is the bridging group
X is the reactive group

When applied by the usual techniques in the presence of alkali, the dyes follow the chemical reactions
of nuclophilic substitution or nucleophilic addition as discussed below.

38

Nucleophilic substitution
Triazinyl type reactive dyes (Procion dyes) react with cellulose by a process called nucleophilic
substitution. One of the two chlorine atoms of a dichlorotriazine dye (cold brand) reacts with cellulose
to form a dye-fibre covalent bond by nucleophilic substitution. A portion of the dye reacts with the
hydroxyl groups of water molecules simultaneously, leading to the formation of hydrolysed dye which
now has only one reactive chlorine atom left. Both of these chemical reactions are as follows.
Cl
N
Dye

NH

+
Dye

O Cell

Cl
N

Dye-Fibre
covalent
N bond

Cl

Cl

NH

Triazine reactive dye with two

reactive chlorine atoms
Dye

Hydrolysed
dye
N

HN

OH

Nucleophilic addition
The formation of vinyl sulphone from sulphatoethyl sulphone takes place by addition of alkali, which
reacts with hydroxyl group of cellulosic fibres by a process called nucleophilic addition. Some portion of
vinylsulphone form reacts with water forming unreacted hydrolysed dye. The chemical equations and
the structural features are shown below.
D

SO2

_
CH 2 CH 2 OSO3 Na+

Sulphatoethyl sulphone

NaOH
D

SO2

CH

Cell-OH
D

SO2

CH 2 CH2 O Cell

CH 2
H 2O
D

Bonded to cellulose

SO CH CH2 OSO3H

2 2dye
Sulphato-ethyl-sulphone reactive
as supplied commercially

Vinyl sulphone

SO2

CH 2

CH2 OH

Hydrolysed dye

SO2 CH=CH2 + H2 SO4

VS Reactive dye formed in presence of alkali

Sulphatoethyl
sulphone (cold
reactive dye
as reactive dyes)
VS Reactive dye formed in presence of alkali
Tri-azinyl type
ring system
brand
These dyes are made from cyanuric chloride, in which there are two chlorine atoms.
The first one is reactive even in the cold, the second one at room
temperature and above. The dyeing reaction takes place in the presence
of an alkali even in the cold and hence they are called cold dyeing or cold
brand reactive dyes.
The first reactive dye to be invented was of this type and the ICI Company
of England marketed them as Procion dyes. These cold brand dyes are
now called Procion M dyes. This is also why they are referred to as the Mbrand reactive dye. The chemical structure of a cold brand dye is as
shown. Note the two chlorine atoms, both of which are reactive.

39

Cl
C
N

C
Dye HN

C
N

Cl

Dichlorotriazine type reactive dye

(Cold brand dye or M-brand dye)

Tri-azinyl type ring system (hot brand reactive dyes)

NHR

When two of the three chlorine atoms of the cyanuric chloride are replaced
by a dye and a suitable amino compound, the resulting dye is left with only
one chlorine atom, which is much less reactive than the dichlorotriazine
type dye.
In this case, the reaction with cellulose (also called fixation of the dye on to
cellulose) has to be carried out at higher temperatures and such dyes are
marketed as hot dyeing or hot brand reactive dyes (designated as Procion
H dyes) as shown here. Note that there is only one chlorine atom.
So this dye is less reactive than the above M-brand dye.
Reactions of reactive dye with cellulose and water
R
The reactions of the Mbrand
(dichlorotriazine)
D
reactive dye with cellulose
Cl
_
and water are as discussed
_
OH
Cellulose.O
earlier; the related chemical
R
equations have also been
R
given. In the case of the H D
D
type
dye
(monochloro
OH
O.Cellulose
triazine reactive dye), the
(i)
(ii)
reactions are as shown
here.

C
N

Dye HN

Cl

(Monochlorotriazine
type reactive dye)
Hot brand dye
or H-brand dye

R
N

N
D

Dye

NH

Cl

Cl

(A)

(B)

Note: For writing convenience, the triazine ring (A) is

written in the form of (B) in the equations.

The reaction of the dye with cellulose ions to give compound (i) is desired, but the reaction with water
as shown in (ii), though undesirable, cannot be prevented. However, the reactive dyes combine with
cellulose many hundred times faster than with water.
The main objective in dyeing cellulose fibres with reactive dyes is to obtain the maximum fixation in the
fibre and minimum hydrolysis with water. The greater the exhaustion of the dye bath, the better is the
fixation of dye to fibre and the lower is the amount of hydrolysed dye. The smaller the amount of
hydrolysed dye, the easier will it be in the final washing operation.
Methods of Dyeing Cotton with Various Reactive Dye Brands

1. Cold-brand reactive dyes (Procion-M, etc)

Application - The application of reactive dyes involves the following three steps:
i) Exhaustion step: Dyeing in the presence of sodium chloride (NaCl) to effect as much exhaustion of
the bath as possible.
ii) Fixation step: Causing the dye to chemically react with the fibre in the presence of an alkali e.g.
sodium carbonate (Na2CO3), trisodium phosphate (Na3PO4), caustic soda (NaOH), etc.
iii) Washing-off and Soaping step: After-treatment of the reactive dyed cotton material, i.e. washing,
soaping at the boil, washing, etc).
Chemical reactions in reactive dyeing
In the two reactions shown
alongside, the first one, namely the
reaction between dye and fibre is
strongly preferred.

1. Reactive dye + cellulose

The second reaction between dye

and water is not preferred as the
dye becomes unreactive and
useless as far as the fibre is
concerned.

2. Reactive dye + water

Cl

+ HO

Reactive dye

Cl

Cell

in presence of alkali

Cellulose

+ HO

Reactive dye

Water

Cell + HCl

Dye fibre bond

OH + HCl

Hydrolysed dye

Note: D is the dye and R is the reactive (functional) group

40

Dyeing procedure
a) Preparation of cotton for dyeing
Bleached material prepared for dyeing must be free from alkali. Where necessary, treat it in a liquor
containing 0.5 - 1.0 part of acetic acid (30%) per 1000 parts of water prior to adding dye solution.
This treatment prevents premature localised fixation and improves levelling of the dyes.
b) Preparation of dye solution
The M-brand dye powder is pasted with cold water and dissolved by adding water at 50C. The
required quantity of water is then added with stirring to dissolve the dyestuff.
c) Dyeing Process
The M-brand dyes are cold-dyeing dyes and are therefore dyed at room temperature.
(i) Exhaustion step: The bath is set with the required quantity of water made up to the M:L ratio
suitable to the machine being used. The bath pH is then adjusted to 6.5 to 7.0 with acetic acid.
The material is run in this bath for 10 minutes at room temperature. The function of acetic acid is
to ensure that there is absolutely no alkalinity in the bath during the exhaustion step. Any
alkalinity in the incoming fabric will be neutralised by the acetic acid. Alkalinity is avoided here to
prevent hydrolysis of the dye in the bath.
After the run in the acidic-pH bath, add pre-dissolved dye in two portions, giving 15 minutes after
each addition. Then add pre-dissolved common salt or Glaubers salt to the bath in two portions
and run the material for 15 minutes after each addition.
(ii) Alkali-fixation step: When as much exhaustion of dye into the material has taken place, add the
required quantity of pre-dissolved alkali (soda ash) in two portions and dye for 15 minutes after
each addition. Then drain the dye bath. The quantities of salt and soda ash for different liquor
ratios are given in the following table.
Note:
a) As the depth of shade
increases, the salt and soda
content increases.

b) As the liquor ratio increases,

the
soda
decreases.

ash

content

Depth of Shade

Salt

Up to 0.5%
0.5 to 2.0%
2.0 to 4.0%
Above 4%

30 g/l
40 g/l
50 g/l
50 g/l

Soda Ash at Different M:L Ratios

1:5
1:10
1:20
1:30
5 g/l
5 g/l
3 g/l
2 g/l
10 g/l
5 g/l
4 g/l
2 g/l
15 g/l
10 g/l
8 g/l
4 g/l
20 g/l
15 g/l
10 g/l
5 g/l

(iii) Washing-off and Soaping (After-treatment)

Washing: For maximum fastness, wash the material efficiently after dyeing. The material is washed
in cold running water for 10 minutes.
Soaping: Treat the washed material with 1 - 2 g/l of neutral soap at the boil for 15 minutes and
wash it free of soap, first with hot water, then with cold water. Ordinary soaps mostly contain alkali
and such soaps tend to strip (remove) the dye from the fibre, hence neutral soap is used.
The dyeing cycle chart and the process flow chart for M-brand reactive dyeing are shown below.
Dyeing Cycle for M-brand reactive dye
Enter goods at
Add predissolved dye
pH 6-7

10 m in

15 min

Add salt
(1st half)

Add salt Add soda ash Add soda ash

(2nd half)
(1st half)
(2nd half)

15 m in

15 m in

15 m in

15 m in

Dyeing
continued

20 - 30 m inutes

Room temperature
Drop bath, w ash-off
and soap

41

Process Flow Chart M-brand reactive dye

S c o u r e d /B le a c h e d y a r n
E n te r g o o d s in b la n k b a th

B la n k b a th
pH
- 6 .0 to 7 .0
T e m p - R o o m T e m p e ra tu re
M :L
- 1 :2 0
T im e - 1 0 m in u te s

A d d p r e -d is s o lv e d d y e a n d d y e fo r 1 5 m in u te s
A d d p r e -d is s o lv e d c o m m o n s a lt in 2 p o r tio n s to d y e b a th a n d d y e fo r 1 0 m in u te s e a c h

A d d p r e -d is s o lv e d s o d a a s h in 2 p o r tio n s to d y e b a th a n d d y e fo r 1 5 m in u te s e a c h

D y e in g c o n tin u e s fo r 2 0 - 3 0 m in u te s

S queeze and w ash

S o a p in g b a th
S o a p a t th e b o il a n d w a s h

N e u tra l s o a p - 1 to 2 g /l
T im e
- 1 5 m in u te s
D y e -fix in g a g e n t (o p tio n a l)

S o fte n in g /D y e -fix in g tr e a tm e n t (if r e q u ir e d )

S q u e e z e a n d d ry

D y e -fix in g a g e n t - 2 -3 g /l
T im e - 3 0 m in u te s
T e m p e ra tu r e - 4 0 o C
p H - 6 to 6 .5 (A c e tic a c id )

2. Hot-brand reactive dyes (Procion-H, Indocron-H, Chemictive-H, Amective-X, etc)

Application The application of H-brand reactive dyes to cotton materials involves the same steps as
those for M-brand dyeing.
i) Exhaustion step: To exhaust or transfer as much of the dye on to the fibre as possible.
Exhausting agent: 1. Common salt or

2. Glaubers salt (anhydrous sodium sulphate)

ii) Fixation step

In this step the dye reacts with the fibre forming a covalent bond in the presence of an alkaline fixing
agent, like soda ash or trisodium phosphate or a mixture of soda ash and caustic soda.
iii) Washing-off and Soaping step
In this step, the dyed material is washed, soaped and again washed to remove unfixed and
hydrolysed dye from the fibre and thereby result in good colour fastness properties.
Chemical reactions these are the same as those shown for the M-brand dyes above.
Dyeing procedure
a) Preparation of the goods for dyeing
The procedure is the same as for the cold brand reactive dyes.
b) Preparation of dye solution
Paste the dye powder with cold water and dissolve it by adding water at a temperature of 80C.
c) Dyeing process
i)
ii)
iii)
iv)
v)

Set the dye bath at 50C.

Check the pH of the dye bath to ensure that it is just below 7.
Adjust pH with acetic acid if necessary.
Enter the material and run it in the bath for 10 minutes.
Add pre-dissolved dyes and continue dyeing for 15 minutes.

42

vi)

vii)

Add the salt in three portions (10%,

30% and 60%) during the period of
raising the temperature from RT to 80
- 85C in 30 minutes. (See the
adjacent table for quantity of salt)

Salt and Soda Ash Requirements

H-brand reactive dyes
Depth of Shade
Salt
Soda Ash (g/l)
(g/l)
(% on weight of goods)
Up to 0.5
0.5 to 1.0
1.0 to 2.0
2.0 to 4.0

Dye for 20 minutes at 85C after the

last salt addition.

30
45
60
70

10
15
15
20

viii) Add the alkali. If soda ash alone is

used, it should be added over 10
Above 4.0
90
20
minutes.
If a mixture of soda ash and caustic soda is used, the pre-mixture should be added over 15
minutes. (See the above table for the amount of alkali to be taken.)
ix) Dye for a further 30 - 60 minutes at 85C depending upon the depth of shade. (30 min for light
shades, 45 min for medium shades and 60 min for dark shades)
x) Finally drop the bath.
d) Washing-off and soaping
Wash-off the dyed goods, using the following process, to get maximum fastness.
Minutes

Operation

10

Cold wash

10

Cold wash

15 - 30
10

Soap at the boil. For heavy shades two 15-minute soaps are preferred. Neutral
soap is used for the soaping.
Warm (50C) wash
Cold wash until the wash liquor is clear
Drop the bath and squeeze and dry the dyed material.

The Dyeing Cycle for H-brand Reactive Dyes

Add salt
(in 3 portions)

Add soda ash

(in 2 portions)

80 - 85 C 20 m in
Enter
Add pregoods at
pH 6-7 dissolved dye

50 C 10 min

10 - 15 min

Dyeing
continued

30 - 60 m in
Drop bath,
wash-off,
soap and
wash

30 min

15 min

3) High-exhaust brand reactive dyes (Procion-HE, Indocron-HE, Amective-HE-X, etc)

The main features of HE brand reactive dyes are listed below.
1. These dyes have exceptionally high build up (dye absorption).
2. Wide variation in material to liquor ratio does not affect the exhaustion and fixation efficiency of the
dyes.
3. Due to high fixation of the dye, subsequent washing and soaping treatment is much easier and
hence economical.

43

Application The application of HE-brand reactive dyes to cotton material involves the same three
steps as those given for H-brand dyes.
Chemical reactions in dyeing These are the same as those given for the M-brand dyes.
Fundamental Chemical Structural Difference between M and H-Brand dyes and HE-Brand Dyes
a) The M and H-brand dyes are monofunctional reactive dyes. They contain only one triazinyl group,
with two and one chlorine atoms respectively.
b) The HE-brand reactive dyes, on the other hand, are bifunctional dyes. They are different from the
above dyes because they are made up of two triazine groups.
These dyes are further classified as homo-bifunctional reactive dyes as both the functional groups
are based on the same type of compound, namely monochlorotriazine. (See Appendix for more
information on the chemical classification of reactive dyes.)
Dyeing procedure
a) Preparation of goods for dyeing
This is the same as stated previously for M brand dyes.
b) Preparation of dye solution
The procedure is the same as that for the H-brand dye. Paste the dye powder with cold water and
dissolve the dye by adding water at 80C.
c) Dyeing process
i)

Set the dye bath at 25C with acetic acid.

ii)

Ensure that its pH is just below 7.

iii)

Adjust the pH with acetic acid if necessary.

iv)

Enter the material and run it for 10 minutes.

v)

Add pre-dissolved dyes and continue dyeing for 15 minutes.

vi)

Add the salt in three portions (10%, 30% and 60%) during the period of raising the
temperature to 80C in 30 minutes. (See the table below for the amount of salt.)

vii)

Dye for 20 minutes at 80C after the last salt addition.

viii) Add the alkali; if soda ash alone is used this should be added over 10 minutes. If a mixture of
soda ash and caustic soda is used, the pre-mixture should be added over 15 minutes. (See
the table below for the amount of alkali to be used.)
ix)

Dye for a further 30 - 60 minutes at 80C depending upon the depth of shade.

x)

Drop the bath.

Salt and Soda Ash Requirements HE-brand reactive dyes
Glaubers salt or NaCl

Depth of
Shade (%)

0.5 to 1.0
1.0 to 2.0
2.0 to 4.0
Above 4.0

Alkali
Soda Ash and

Unmercerised
Cotton

Mercerised
Cotton or
Viscose
rayon

Soda
ash
only

Na2CO3

NaOH
(solid)

45
60
70
90

30
40
55
65

15
15
20
20

5
5
5
5

0.2
0.5
0.5
0.5

44

Caustic Soda

Fixation
Time
(minutes)
45
45
60
60

d) Washing-off and soaping

For maximum fastness, wash the dyed goods efficiently. The wash-off cycle is as follows.
Minutes

Operation

10

Hot wash (70C)

10

Hot wash (70C)

15 - 30
10

Soap at the boil. For heavy shades two 15-minute soaps are preferred.
Hot wash (70C)
Wash cold until the wash liquor is clear.
Drop the bath and squeeze and dry the dyed material.

The Dyeing Cycle for HE-brand Reactive Dyes

Add salt (in 3 portions)

80 C
Enter
Add pregoods at dissolved
pH 6-7
dye

Add alkali
(in 2 portions)

20 min

10 - 15 min

Continue
dyeing

30 - 60 min
Drop bath,
wash,
soap,
wash

30 min

25 C 10 min 15 min

4) ME-brand reactive dyes (Sumifix Supra dyes, Benzafix-ME dyes, etc)

Properties of ME-brand reactive dyes
1. Reactive ME dyes are low temperature, high-exhaust dyes having the advantages of both monochloro triazine dyes as well as vinyl sulphone dyes. Like the HE-brand dyes these are called
bifunctional dyes, but as the two functional groups are of different kinds, they are classified as
hetero-bifunctional reactive dyes.
2. The dyes offer a high grade of all-round fastness properties including light, perspiration, chlorine
and peroxide washing.
3. They also have the advantages of high degrees of exhaustion and fixation, better alkali stability,
excellent levelling properties and high reproducibility.
4. Reactive ME dyes react with the cellulose fibres at low temperatures and can be applied by the
cold-pad-batch method.
Dyeing procedure
a) Preparation of goods for dyeing
This is similar to that described for the other reactive dyes.
b) Preparation of dye solution
Paste the dye powder with cold water and dissolve by adding water at a temperature not higher
than 50C. This process is the same as that for the M-brand reactive dye.
c) Dyeing cycle
i)

Set the dye bath at 25C with acetic acid.

ii)

Ensure that its pH is just below 7.

iii)

Adjust the pH with acetic acid if necessary.

iv)

Enter the material and run it for 10 minutes.

v)

Add pre-dissolved dyes and continue dyeing for 15 minutes.

vi)

Add the salt in three portions (10%, 30% and 60%) during the period of raising the
temperature to 60C in 30 minutes. (See the following table for the amount of salt.)

45

vii)

Dye for 15 minutes at 60C after the last salt

addition.

viii) Add the alkali. If soda ash is used as alkali

this should be added over 10 minutes. If a
mixture of soda ash and caustic soda is used,
the premixture should be added over 15
minutes. (See the table for the amount of
alkali for different shade depths.)

Salt and Soda Ash Requirements

Reactive ME dye
X%
Glaubers or common salt

50 g/l

Soda Ash

20 g/l

Dyeing time

60 minutes

Dyeing temperature

60C

ix)

Dye for a further 30 - 45 minutes at 60C depending upon the depth of shade.

x)

Drop the bath.

d) Washing-off and soaping

This after-treatment is done efficiently after dyeing for maximum fastness. The wash-off cycle is given
below:
Minutes

Operation

10

Wash cold

10

Wash cold

15 - 30

Soap at the boil using neutral soap. For heavy shades two 15-minute soaps are
preferred.

10

Wash warm (50C)

Wash cold until the wash liquor is clear.
Drop the bath and squeeze and dry the dyed material.

Dyeing Cycle for ME-brand Reactive Dyes

Add salt
(in 3 portions)

60C
Enter
goods at
pH 6-7

Add predissolved
dye

25C 10 min

20 min

Add alkali
(in 2 portions)

Continue dyeing

10 - 15 min

30 - 60 min
Drop
bath,
wash,
soap,
wash

30 min

15 min

5) Vinyl Sulphone (VS) based reactive dyes (Remazol dyes) )

Introduction
These dyes are based on the chemical group called vinyl sulphone, which is the reactive group in the
dyes. The VS dyes are mainly used in the dyeing and printing of cotton textiles.
Principle of dyeing cotton with VS dyes
VS dyes are reactive dyes containing a sulphato-ethyl sulphone group in their molecules. In the
presence of alkali, the dyes are converted into their reactive form i.e. vinyl sulphone, which reacts
chemically with the hydroxyl group of cellulose to form an ether linkage. As explained earlier, the
reaction is one of nucleophilic addition.

46

Chemical reactions in dyeing

As seen in the following reaction, the reactive dye as supplied is a -sulphato-ethyl sulphone. This
group changes to the vinyl sulphone group in the presence of alkali. It is the vinyl sulphone dye that
can react with cellulose and not the suplhato-ethyl sulphone dye.

D SO2 CH2 CH2 O SO3 Na+ Alkali

Reactive dye as supplied

(-suphatoethyl sulphone)

SO2 CH

CH2 + Na2 SO4 +H2O

Vinyl sulphone
reactive dye

The VS dye reacts with cellulose (e.g. cotton fibre) as follows:

SO2

CH

CH2 + OH

VS dye

Cell

Cotton fibre

SO2

CH2

CH2

Cell

Dye-fibre (ether) bond

Properties of VS reactive dyes

1. The VS dyes have extremely good solubility.
2. They have excellent brightness of shade.
3. They are versatile, being applicable both by dyeing and printing.
4. It is easy to wash the unfixed dyestuff because of the moderate substantivity of the dyes.
5. The dyes posses good all round fastness.
Dyeing procedure
a) Preparation of the goods for dyeing
In order to obtain satisfactory results, the preparation of the cotton material, prior to dyeing, is most
important. The goods should be scoured and bleached in order to make it highly absorbent and
free from any alkalinity or acidity.
b) Preparation of dye solution
Soft or softened water should be employed, avoiding alkalinity especially when dissolving the dyes.
The dyestuff is made to a smooth paste with cold water and dissolved by adding hot water at a
temperature of 80C.
c) Dyeing Process
i)

Set the dye bath at room temperature.

ii)

Ensure that its pH is just below 7.

iii)

Adjust pH with acetic acid if necessary.

iv)

Enter the material and run it for 10 minutes.

v)

Add pre-dissolved dyes and continue dyeing for 15 minutes.

vi)

Raise the temperature

and add the salt in two
portions, the first portion
after
5
minutes
of
temperature rise and the
second portion after 10
minutes dyeing. Continue
dyeing for another 5
minutes till temperature
reaches 60C. (See table
for the quantities of salt.)
vii) Dye for 10 minutes at 60C.

Liquor ratio
Dyeing temperature

60C

40C

Glaubers salt

50 g/l

50 g/l

Trisodium phosphate
OR
Soda ash plus

5 to 10 g/l

10 to 15 g/l

5 g/l

5 g/l

Caustic soda (72Tw)

1 cc/l

2 to 3 cc/l

60 to 90 min

90 min

Alkali:

Dyeing period after final alkali

addition

1:20 to 1:30

viii) Add pre-dissolved alkali in two portions in 10 minutes. (See the table above.)

47

ix)

Dye for a further 60 to 90 minutes after final alkali addition.

x)

Drop the bath.

[ Note
a) In the case of the VS dyes the dyeing can also be carried out at 40C. As the temperature is
lowered, the quantity of alkali used and the final stretch of dyeing are both increased compared
to the dyeing at 60C.
b) It must be noted that in the case of VS dyes, the exhaustion step has the dye is in the sulphato-ethyl sulphone form, which has moderate substantivity for cellulose. Also, in this form
no reaction takes place with the OH group of the cellulose or the water in the bath.
It is only in the fixation step, in the presence of alkali, that the dye is converted to the reactive
vinyl sulphone form. If the exhaustion is good, most of the dye is inside the fibre. There will thus
be a tendency for the much of the absorbed dye molecules to react with the cellulose in the
fibre rather than the water molecules.]
d) Washing-off and soaping
To achieve optimum fastness properties, the unfixed dyestuff must be thoroughly washed off after
completion of the dyeing. This step is achieved as follows.
i)

The material is rinsed in cold water and then neutralised with water containing 2 cc/l acetic acid.

ii) This is followed by a rinse in hot water. The material is then soaped at the boil in a bath
containing neutral detergent. Alkaline soaping of vinyl sulphone dyed material is not advisable
as it undergoes hydrolysis as shown below.
iii) The material is finally rinsed in hot and then cold water.
The Dyeing Cycle for VS-brand Reactive Dyes
S a lt ( in 2 p o r tio n s )
A lk a li (in 2 p o r tio n s )
1 0 m in
5 m in

1 0 m in

3 0 - 6 0 m in

6 0 oC o r 4 0 oC
W a s h -o ff

E n te r
goods

1 0 m in

P r e d is s o lv e d
dyes pH 6 - 7
5 m in

1 0 m in
5 m in

R o o m te m p e ra tu re

Recent developments in reactive dyes

Ciba Dyes Company has come out with a Cibacron range of reactive dyes that are improved versions
of the existing reactive dyes.
1. The development of a mixed functional dye containing a new aliphatic vinyl sulphone system and a
mono-fluoro-triazine-bridging group was designed for application by the padding technique.
The unique feature is the introduction of a fluorine
atom in the triazine ring instead of the regular chlorine
atom. A diagrammatic representation of this dye is
shown in the figure for a Cibacron C dye. These dyes
have medium to low affinity, good build up, easy
wash-off, high fixation and good dye-fibre bond
displaying good resistance to acids and alkali.

48

Cibacron C Dye

Dye

NH(CH2)n X(CH2)m SO2CH=CH2

where n, m are integers and X is a hetero atom

2. The Cibacron FN dye has a structure similar to the above and has been developed for warm
exhaust applications to cellulose and blends and also for pad-batch applications.
i)

These dyes show excellent washing-off, and have good wash and light fastness.

ii) They show high fixation.

iii) The dye-fibre bond is highly resistant to oxidants (detergents) under acid and alkaline
conditions.
iv) The chromophore is highly sulphonated.
3. The Cibacron LS dyes are low-salt-dyes and these are based on bis-monofluorotriazine.
These dyes require less than a quarter of the salt required for normal dyeing and this allows for
efficient operation of waste water treatment plants.
It is clear from the above that bifunctional reactive dyes have higher fixation than monofunctional
reactive dyes and hence are more economical. In case of bifunctional dyes the number of reaction
possibilities is greater than that for the monofunctional dye.
Industrial Applications of Reactive Dyes
1. Exhaust dyeing this has been explained above for the five brands of reactive dye, namely
M, H, HE, ME and VS brands.
2. Pad-batch dyeing
3. Continuous dyeing
Pad-batch Dyeing
In this process, dye and alkali are padded on to the material which is then rolled up (batched) on a
perforated or non-perforated beam, then covered with water-proof material to prevent evaporation, and
stored by slowly rotating the rolls to avoid local seepage of dye liquor.
After batching for the requisite time, loose dye is removed by rinsing and soaping at boil in an openwidth soaper range. Depending on storage temperature any of the following two sequences are
employed.
(i)

Cold batching

(ii)

Hot batching

Cold batching: This offers the advantage of simplicity in equipment, high production, and high efficiency
of fixation and excellent quality of dyeing. It is suitable for all depths of shade and can be used for any
length of run. It is also a highly productive alternative to pad-jig method. A typical cold-batch sequence
is shown in the figure below.
THE COLD PAD-BATCH TECHNIQUE

Batch

Pad
(dye + alkali)

Batch is now washed and soaped in

the open soaper machine

Padded batch is covered

and kept rolling slowly

Hot batching: In this method the fabric is padded with the dye and alkali, passed between infra-red
heaters to preheat the fabric to 50 to 95C and then batched on a large roller in a hot chamber.
Batching is done under controlled conditions of temperature and humidity to ensure diffusion and
fixation of the dye on fibre. Addition of common salt or Glaubers salt is necessary in order to obtain
adequate fixation and to minimise migration during hot batching.

49

Due to their high substantivity

and the danger of tailing (the
dyed
fabric
getting
progressively lighter and lighter)
especially in the presence of
salt, padding methods are not
often applied to the reactive HE
dyes. A hot-batch sequence is
shown in the figure.

IR heaters

Pad (dye + alkali)

THE HOT PAD-BATCH

TECHNIQUE

Hot batching chamber

Continuous Dyeing
Continuous dyeing is based on the principle that the reaction between cellulose and reactive dye takes
place in the presence of water and alkali in a short time at high temperature and higher pH values.
Depending on the reactivity of the dye, two processes are available:
1. Single padding process
2. Double padding process
1. Single padding process
The pad liquor contains the dye and alkali and fixation is done at higher temperature. Urea and sodium
alginate (migration inhibitor) are also added to the dye bath.
The following sequences are possible.
i) Pad (dye, soda ash, urea) - dry - bake

In this process reactive dye along with the wetting agent, soda ash (10 - 20 g/l) and urea (200 g/l) is
padded on to the cloth. After padding the material is dried at 110C followed by a baking (dry-heat)
treatment, for 3 minutes at 160C or 30 seconds at 200C.
The main function of the urea is
to facilitate the dissolution of the
dye
and
its
hygroscopic
properties are useful during the
baking when no water is present.
This is most suited for heavy
shades with good fixation. In
order to avoid migration and
uneven dyeing, a good hot-flue
drier giving slow and even drying
is necessary. This sequence is
shown in the figure.

Bake or
Thermo-fix

Pad
(dye + urea + alkali)

To open
soaper
machine for
rinsing and
soaping

Dry in a hot-flue
drying machine

ii) Pad (dye, urea, bicarbonate) - dry process

To open
soaper
machine for
rinsing and
soaping

Pad
(dye + urea + bicarbonate)

Dry in a hot-flue drying machine

50

This is a valuable process for cheap

and easy production of pale and
medium depths of shade.
By modifying the process with an
inclusion of a high concentration of
urea in the padding liquor for heavy
shades, satisfactory dyeing can be
done. Care must be taken to avoid
migration and uneven dyeing effects
by giving slow even drying in the hotflue drier.

iii) Pad (dye, bicarbonate) - steam process

This process requires minimum dyeing

equipment. It is very suitable for the
production of high quality pale shades
particularly on viscose rayon and it gives
a high rate of productivity. A highexpression padding mangle and a good
quality steamer are necessary for good
results.

Rinsing and
Soaping

It is during the steaming that the sodium

bicarbonate forms sodium carbonate for
the dye fixation. The process sequence
is as shown above.

Pad
(dye + bicarbonate)

Steam

2. Double padding process

In this process the fabric is padded with the dye solution and padded again, (with or without
intermediate drying) with an alkali solution containing a high concentration of salt, to minimise bleeding,
and then steamed. Two double padding processes are given below.
i) Pad (dye)drypad (alkali)steam process: This process enables the use of all the Procion brands

whether cold dyeing or H brands thus making it possible to mix both the brands and offering the
widest range of shades.

To
washing
range

Pad (dye)

Dry
(Hot-flue drier)

Pad
(alkali + salt)

Steaming
unit

After padding through dye solution

and hot-flue drying, the cloth is
padded
through
a
solution
containing caustic soda and salt. It
is then passed immediately into
the steam chamber. The salt in the
padding
bath
reduces
any
bleeding of dyestuff from the
padded material into the alkaline
bath. See the following figure.

ii) Pad (dye)pad (alkali) process (Molten-metal method): This is also a double padding process. The

fabric is first padded with the dye solution and then passed through the alkali bath at the top of the first
arm of the U - tube containing molten metal. The second padding takes place when the fabric passes
through the molten metal bath. At the right-hand side of the U-tube the fabric emerges after passing
through a salt bath to be finally washed and soaped in an open soaper, as illustrated in following figure.
Reactive-dyed
and washed
fabric take up

Alkali

Pad (dye)

Salt
bath

U-Tube

Fabric passing through

molten metal bath
(second padding)

Heating
jacket

Open soaper washing range

Molten metal bath

surrounding fabric

The Standfast molten metal process is particularly suitable for the production of very high quality pale
to medium depth dyeings on all classes of piece goods.

51

After-treatment of Reactive Dyes

In the dyeing of certain deep shades or when inefficient washing equipment is used, difficulties may
arise in removing unfixed colour. In such cases, in addition to the usual soaping treatment under boiling
conditions, an after-treatment with a cationic dye-fixing agent of the type used for direct dyeing. These
agents react chemically with the sulphonic acid groups in the dye molecule and form an insoluble dyeagent complex. This is retained by the fibre during wet treatments at temperatures up to 60C so that
staining is greatly reduced.
When the best possible washing-off treatment has been given, the dye-fixing after-treatment is carried
out in a fresh bath of cold water and the temperature is then raised to the optimum level for the specific
agent selected (50-60C). A final rinse is not essential. However, treatment with dye-fixing agent
should never be regarded as a substitute for the most efficient washing-off process.
Stripping of Reactive Dyes
Partial stripping of dyed goods for rectification of any dyeing faults may be carried out by treatment of
the goods with 5 - 10 ml/l of glacial acetic acid at 80 - 90C. Formic acid (10 ml/l) is preferred for
stripping of reactive dyes from viscose goods. Stripping is continued until the shade is reduced to the
desired extent. Thorough soaping and washing is necessary to ensure removal of stripped dyes.
Complete stripping of reactive dyes to a white is very difficult but they can be stripped to an extent
suitable for re-dyeing either in same shades or to dark shades. The goods are treated at the boil in a
solution of 5 g/l soda ash for 20 - 30 minutes. The washed-off goods are bleached with sodium
hypochlorite (1Tw) followed by washing-off and soaping at the boil for 10 - 15 minutes.
Fastness Properties of Reactive Dyes
Fastness properties of reactive-dyed cellulose fibres
Light fastness
Exposure to light under low humidity does not affect light fastness, but under high humidity there is a
reduction in light-fastness, particularly in pale shades.
Wash fastness
Reactive dyes have very good wash fastness, because of its strong covalent bond. However, if chlorine
is present in the wash water there is an effect on the covalent bond and fading will occur.
Catalytic fading
Some reactive dye mixtures have a tendency to undergo catalytic fading.
Phototropism
Certain reactive dyes when treated with cation-active dye-fixing agents such as Fixanol PN and certain
crease-resisting finishes increase the phototropic tendency of these dyes. The shades usually change
to violet or reddish blue when the dyed material is subjected to severe irradiation such as ultra-violet
light or when exposed to intense sunlight. The shade gradually returns to the original shade when
normal light is restored.
Sensitivity to metals
Reactive dyes are sensitive to metallic ions, especially to copper. In the presence of such metals,
suitable metal-sequestering agents should be used, but with care, as any excess results in a loss of
colour.
Storage of dyed materials
It has been found that medium and heavy shades of Procion Brilliant Red 2B on cotton when not resin
finished, show migration marks or stains the adjacent white material when stored in humid acidic
condition. This effect is much less with viscose rayon. Certain amines, such as ethylene diamine, when
added to the soap bath in the washing operation, cause marked reduction in bleeding. This treatment
however alters the shade to some extent.

52

Classification of reactive dyes on the basis of the reactive system

R e a c tiv e d y e s

B ifu n c tio n a l

M o n o fu n c tio n a l

H o m o -b ifu n c tio n a l

M u ltifu n c tio n a l

H e te r o -b ifu n c tio n a l

(a)

Monofunctional reactive dyes

(b)

Bifunctional reactive dyes - these are further classified as,

(c)

i)

homo-bifunctional and

ii)

hetero-bifunctional dyes, as shown in the chart below.

Multifunctional reactive dyes

(a) Monofunctional reactive dyes

These dyes are characterised by the presence of reactive groups (one or two reactive species) at
individual locations in the dye molecule. All the reactive dyes developed during the early stages of
development were monofunctional reactive dyes.
Typical examples of this kind are dyes having mono-chloro or di-chloro triazine or vinyl sulphone
reactive groups. Although di-chloro triazine dyes contain two reactive chlorine atoms, located on the
same triazine ring, they are considered as monofunctional reactive dyes.
(b) Bifunctional reactive dyes
These dyes have been introduced recently to the reactive dye range. They are characterised by the
presence of two reactive groups of same type (mono or di-chloro-triazine) or two different types (monochloro-triazine and vinyl sulphone) at two different locations in the dye molecule. The bifunctional dyes
are divided into two types.
i) Homo-bifunctional dyes having two reactive systems of the same type (triazine or vinyl sulphone)
ii) Hetero-bifunctional having two reactive systems of the mixed type (triazine-vinyl sulphone)
The various bifunctional combinations that can be formed are listed below.
MCT/MCT

MonoChloroTriazine/MonoChloroTriazine

(homo-bifunctional)

VS/VS

VinylSulphone/VinylSulphone

(homo-bifunctional)

MCT/VS

MonoChloroTriazine/VinylSulphone

(hetero-bifunctional)

FT/VS

FluoroTriazine/VinylSulphone

(hetero-bifunctional)

FCP/VS

FluoroChloroPyrimidine/VinylSulphone

(hetero-bifunctional)

These dyes have very high exhaustion leading to high fixation and better colour yield. Due to the high
exhaustion and fixation, the quantity of dye in the dye bath as well as that removed from fabric during
washing and soaping is small. The extent of pollution due to effluent discharge is thus also low. This
category of reactive dye has become very popular for exhaust dyeing applications. The high
exhaustion of these dyes is because of the high molecular weight of the dyes, similar in range to that of
direct dyes. The high fixation is due to presence of two reactive groups which can react independently
with cellulose with the formation of a cross-link.

53

General Factors Affecting the Results of Reactive Dyeing

The following factors are important for getting satisfactory exhaustion, fixation and good fastness
properties.
1. Affinity of the dye
The affinity of a dye for a textile fibre is determined by its molecular structure and therefore is not under
the control of the dyer except that he can select dyes from among the available dyes, those most
suited to his/her particular process of dyeing.
If a reactive dye has a high affinity for cellulose, its exhaustion is also high and its fixation is efficient.
But because of the difficulties associated with washing-off of hydrolysed dye, reactive dyes usually
possess comparatively low affinity except the H-E dyes, which by virtue of their having two reactive
centres give a high degree of fixation and hence less hydrolysed dye to be washed-off. In fact a
disadvantage with all other commercial reactive dyes presently marketed is that the proportion of
dyestuff entering into chemical reaction during fixation rarely exceeds 70% and thus the dyed material
requires vigorous soaping and washing treatments.
In exhaust dyeing, dyes of rather higher affinity give better colour yield; especially when dyed at long
liquor ratios and when the washing-off process is less critical. In dyeing by continuous processes,
however, dyes of lower affinity have an advantage, as they are less liable to tailing but are still
efficiently fixed at the short liquor ratios involved in padding processes. Clearly then, knowledge of the
affinity of dyes is advantageous in selecting those most suited to a particular application process.
2. Material to Liquor ratio (M:L ratio)
The liquor ratio has a powerful effect in determining exhaustion, and this is particularly significant with
low-affinity reactive dyes. The use of low liquor ratios makes it possible to apply a wider range of
reactive dyes economically and in all cases leads to more efficient fixation by reducing wasteful
hydrolysis in the dye-bath.
However, the machinery available determines the liquor ratio, but the most efficient method of applying
reactive dyes to yarn will be to use package dyeing machines rather than the open-beck. In the case of
piece dyeing, jig application will be more efficient than winch dyeing and the most efficient of all batchdyeing processes will be the pad-roll or pad-batch technique. These advantages are more obvious with
dyes that have low exhaustion in a long liquor ratio but with those of higher affinity like the reactive H-E
dyes the liquor ratio will not have a significant effect on the exhaustion of the dye bath.
3. Concentration of electrolyte
In the first phase of dyeing, the reactive dyes behave like direct dyes and therefore electrolytes are
used for improving the exhaustion percentages. It has been stated earlier that cellulose fibres acquire
a negative charge when immersed in water, i.e. their surface is anionic. Reactive dyes too are anionic.
So the fibre repels the dye molecules when immersed in a reactive dye bath. When a salt such as
sodium
chloride or Glaubers salt is now added to the bath, it first ionises to form positive sodium
ions and negative chloride or sulphate ions. The sodium ions move towards the fibre and neutralise the
negative surface charge. The chloride/sulphate anions repel the dye anions in the dye bath and cause
them to move towards the fibre surface, where they get adsorbed.
Further, since the sodium cations are attracted to the fibre surface during the initial stages of dyeing,
they too have a tendency to rush to the fibre and get adsorbed unevenly. If this happens, it is difficult
to remobilise them and bring about evenness. It is for this reason that the salt is added slowly and in
portions.
Sodium sulphate is milder in action compared with sodium chloride as it liberates only half the amount
of sodium ions liberated by sodium chloride, considering equal quantities of the two salts. Therefore,
for reactive dyes like Turquoise Brilliant Blue, which do not easily give level shades, the use of sodium
sulphate (i.e. Glaubers salt) is highly recommended.
4. pH of dye bath

54

The pH of fixation of reactive dyes on cotton and viscose actually depends on individual dyes, and the
temperature and time of dyeing. The pH requirements decrease with increasing temperature and time
of dyeing for most of the dyes. The optimum pH for cotton lies between 10.8 to 11 at 20 - 25C and
10.3 at 20 - 25C for viscose. Soda ash, trisodium phosphate (TSP), sodium bicarbonate and sodium
hydroxide are the alkalis useful in reactive dyeing; of these, soda ash is the best for cold brands. For
the hot brands TSP or a mixture of sodium bicarbonate and soda ash (50:50) is preferred. The
removal of caustic soda after dyeing is a tedious process so its use in the dyeing of cotton with reactive
dyes is somewhat restricted. However a mixture of soda ash and caustic soda is also used for the
fixation of reactive dyes on cellulosic fibres.
The amount of alkali required for fixation depends on the reactive dye brand used, the depth of shade
and the liquor ratio of dyeing. This is indicated for each brand of reactive dye in Section 3.2.5. The
alkalies most commonly used are,
Soda ash

A combination of soda ash and caustic soda, or

Trisodium phosphate.

It is preferable for heavy materials and viscose rayon, to use sodium bicarbonate instead of soda ash,
as it ensures maximum colour yield and better levelness because of less swelling.
5. Dyeing temperature and reactivity
The decreased substantivity caused by raising the dyeing temperature aids both the levelling before
the addition of alkali and the washing-off of unfixed dye at the end of the process. The reactivity of the
dye, also plays an important part in this.
As stated earlier, the highly reactive dyes, i.e. the cold brand dyes, can be applied efficiently at
temperatures as low as room temperature. The hot brand dyes, on the other hand, are approximately
1000 times less reactive and require temperatures of 80 - 100C for fixation.
The reactivity of a particular dye can be increased further by (a) increasing the alkalinity of the dye bath
(i.e. increasing the pH value), and (b) raising the temperature. A raised dye bath temperature is usually
needed to aid penetration and hence to obtain level dyeing. However higher temperature increases the
reactivity of the dye, so there is a danger of getting unlevel dyeing especially with the cold brand dyes;
this in turn requires further control of reactivity through a reduction in the pH of the dye bath.
Substantivity and reactivity are therefore manipulated together to control the quality of dyeing.

6. Time of dyeing
The dye is generally added to the bath in two portions. The salt may also be added in two lots.
Exhaustion normally takes place in 20 to 30 minutes. There is no specific
advantage in extending
the exhaustion phase beyond 30 minutes. The alkali is then added also in two lots, and the dyeing
continued for 30 to 90 minutes. The depth of shade and the reactivity of the dye decide the time of
dyeing. For deeper shades, longer times are required.
7. Nature of the fibre
There are marked differences in the degree of exhaustion obtained with reactive dyes on different
cellulosic fibres. Viscose rayon gives the highest exhaustion and cotton the lowest, with mercerised
cotton occupying an intermediate position.
Bifunctional Systems
Bifunctional reactive dyes and low salt reactive dyes were developed more recently for producing
better fixation of dye and to reduce environmental problems.
Homo-bifunctional reactive dyes
The concept of dyes with two reactive systems of the same type were developed for exhaust dyeing
having higher substantivity and better exhaustion and fixation values compared to the monofunctional

55

dyes. The dye-to-fibre bond is stable to mild acids and alkalis and to oxidising agents and the
chromophores are generally stable to combinations of light and moisture or residual peroxy detergent.
The structural representation of a homo-bifunctional reactive dye is shown in Figure 3.16, for Procion
HE and Procion H-EXL dyes.
Hetero-bifunctional reactive dyes
Bifunctional dyes with mixed reactive system in the dye molecule uses the advantages of both the
triazine and vinyl sulphone system i.e. higher affinity of triazinyl and lower affinity due to the vinyl
sulphone. The triazinyl group (higher reactivity) reacts with the fibre faster and this is followed by the
reaction of vinyl sulphone (medium reactivity) which is slower in forming a stable dye-fibre bond.
The reactive-ME range of dyes also belongs to the above type of system having medium substantivity
and excellent migration. The presence of two reactive groups in the molecule gives improved fixation.
They produce level dyeings at temperatures of about 60C.

DISPERSE DYES
Introduction
A disperse dye is a dye with extremely low solubility in water but in which it is in a finely dispersed
state. The size of a disperse dye particle is in the region of approximately 0.5 - 1 mm. Disperse dyes
are applied in the form of a fine aqueous dispersion. The fibres most readily coloured by disperse dyes
are cellulose acetate, polyester, acrylic and nylon. Chemically, the disperse dyes belong to various
classes such as azo, anthraquinone, methylene, and diphenylamine. They are non-ionic dyes and do
not have any polar groups.
Properties of Disperse Dyes
1. Generally, these dyes are insoluble in cold water. However, they are soluble in hot water to some
extent, the solubility increasing with temperature.
2. A feature of disperse dye molecules is their lack of polar groups. This is why they are not readily
soluble in water.
3. Textile materials coloured with disperse dyes have fair to good light fastness. The average light
fastness rating is 4 - 5.
4. Disperse dyed textile materials have moderate to good wash fastness, being 3 - 4 on the average.
This is due partly to the insolubility of the dye and partly to the hydrophobic nature of the fibres to
which they are usually applied.
5. Some of the disperse dyes are, however, sensitive to nitrogenous fumes present in the
atmosphere, especially that polluted with exhaust fumes from automobiles.
6. Disperse dyes have the ability to undergo sublimation, that is, they can be vaporised without
significant change in their colour. Their ability to sublime is the result of a stable electron
arrangement. This property is used to advantage in transfer printing.
7. Excessive hot pressing or ironing of disperse dyed or printed textiles may result in colour loss.
8. The dyes are generally small in molecular size have low molecular weight.
9. They are available in the form of powder, liquid and micro-dispersed granules.
Classification of Disperse Dyes
The disperse dyes can be classified into groups according to their sublimation fastness and covering
power as follows.
Group 1: Dyes possessing excellent covering power but poor sublimation fastness.
Group 2: Dyes possessing good covering power and moderate sublimation fastness.
Group 3: Dyes possessing moderate covering power and good sublimation fastness.
Group 4: Dyes possessing little ability to cover irregularities but having excellent sublimation fastness.

56

Theory of Dyeing
The first step: One of the first obvious requirements of a dye is solubility.
dyes, which are generally regarded as insoluble, their dissolution in the
dispersability and solubility. Dispersibility is aided by the presence of
solubility by the rise in temperature. Neither of these characteristics
characteristics.

With regard to the disperse

dye bath depends on their
dispersing agents and the
is influenced by the fibre

The second step: As has been described earlier, the second step relates to the adsorption of the dye
molecules on to the fibre surface. Dyestuff adsorption by the fibre surface is influenced by two
characteristics, (i) the solubility of the dye in the dye bath and (ii) its solubility in the fibre.
The third step: After adsorption, the next step in a dyeing process is penetration of the dyestuff
molecules into the fibre structure. The overall rate of dyeing is governed by such penetration or
diffusion of the dye from the fibre surface into the fibre.
Under the normal dyeing conditions of time and temperature the rate of adsorption is always higher
than the rate of diffusion and it is therefore the third step that governs the overall rate of dyeing.
In any dye bath, when the amount of dye absorbed by the fibre equals the amount of dye desorbed by
it (coming out of it), the dye bath is said to be in equilibrium. When equilibrium dyeing is reached, the
following subsidiary equilibria are established.

If the amount of dye present in the dye bath is not sufficient to saturate the fibre in the dyeing process,
only the first two equilibria are established. If the fibre is saturated, the third equilibrium is attained and
the dyeing is completed. Thus the aqueous solubility of the dye and the diffusion of the dye in the fibre
are the two factors governing the dyeing process that are more important. If these factors are affected,
the rate of dyeing, the percentage exhaustion of the dye bath and the level dyeing characteristics of the
disperse dye are also affected.
Auxiliaries Used in Polyester Dyeing
i) Dispersing agent
a. A dispersing agent assists the process of reducing the particle size of the dye.
b. It increases the solubility of the disperse dye in water.
c. It helps to avoid agglomeration of dyes during dyeing.
d. It influences the rate of exhaustion.
ii) Levelling agent
a. Non-ionic levelling agents retard the rate of dyeing.
b. Carrier type levelling agents are used in high temperature dyeing to get uniform dyeing.
c. They also help to avoid the deposition of oligomers on the fibre surface.
iii) Antifoaming agent
Antifoaming agents are used in a disperse dye bath to control the foam as excess foaming gives
specky dyeings.
iv) Wetting agent
A small quantity of wetting agent in the dye bath facilitates the dye liquor to be absorbed uniformly
and quickly.
v) pH and redox buffers
These agents protect the dyes from degradation in a high temperature bath.

57

Mechanism of Disperse Dyeing on Polyester

(a) The disperse dye dissolves in the aqueous dye bath, (b) the resulting dye in solution is adsorbed by
the fibre surface and (c) the adsorbed dye diffuses into the fibre through the liquid phase.
The boundary layer on the fibre surface remains a stationary liquid layer through which the dye has to
diffuse in order to reach the fibre surface. In principle, the dye is adsorbed on the fibre surface from the
diffusional boundary layer, which, in turn, receives the dye from the bulk of the agitated liquor. The
thickness of the diffusional boundary layer under circulation conditions in different machines may vary,
which, in turn, may vary the rate of dyeing from machine to machine. The rate of dye transfer through
the boundary layer depends on the diffusion coefficient, fibre surface and the change in chemical
potential in the process.
In the polymer/water/disperse dye system there must be sufficiently large free volume. Carriers are
often added which acts as plasticisers and increase the free volume of the system so that the diffusion
rate is increased.
The free volume model of dyeing has already been explained in an earlier section. (See Intro to Unit 1.)
Methods of Dyeing Polyester with Disperse Dyes
Polyester is difficult to dye because of a high degree of orientation and high cohesive forces and
compact structure. Hence for the dye to diffuse into the fibre, certain dyeing conditions which will
loosen the fibre structure must be selected. The dyeing methods are divided into exhaust methods and
continuous methods.
i) Exhaust method
This method involves dye transfer from aqueous baths into the fibre. Exhaust dyeing is carried out at
boil using carriers and high temperature conditions. Woven, knitted and texturised polyester fabrics
are dyed by these method.
ii) Continuous method
The dye is mechanically fixed on to the fibre and then made to diffuse into the fibre by thermal
treatment called thermosoling, in which the dye is applied to the fibre mechanically and then
thermo-fixed at 200-220C, when the fibre become thermoplastic and the dye diffuses into the fibre.
In thermo-fixation dyeing, the water in the pad liquor is completely removed by drying before the dye
is fixed in the fibre.
Polyester fibre may be dyed by the following methods.
CARRIER METHOD
Principle of dyeing
Certain chemicals called carriers are added to the dye bath to act as swelling agents for polyester
fibres. They swell the fibres in an aqueous dye bath held at the boil and thus enable the chain
molecules in the fibre to move about more easily. The increased ease of movement of the fibre
molecules increases the inter-molecular distances so that there is more space to accommodate the
dyestuff molecules. The swollen fibres permit large dye molecules to diffuse more rapidly into the fibre.
Thus the carriers increase the solubility of the dye and the rate of dyeing and generally make it easier
for the dye molecules to be absorbed by the fibre.
Some chemicals that have been used as carriers are, o-phenylphenol; p-phenylphenol;
dichlorobenzene, trichlorobenzene; dimethyl terephthalate, etc. Carriers enable dyeing to be carried
out at boiling temperature under normal atmospheric pressure, without the need for special equipment
such as high-pressure machines, which are expensive.
The influence of Tg (the glass-transition temperature) on the dyeing temperature of compact fibres like
polyester that is also devoid of polar groups capable of attracting dye molecules is well known. If the
Tg is high the dyeing temperature must also be high and vice versa. With regard to polyester, the
dyeing temperature must be at least 40C higher than its Tg, which is close to 90C. The dyeing
temperature must thus be about 130C for satisfactory dye penetration to occur.

58

How then does a carrier enable the dyeing of polyester at 100C? Carriers are swelling agents and
open up the fibre structure. This lowers the Tg such that dyeing can be done at 100C.
The carrier is usually added first to the dye bath or it is added slowly during the dyeing process. This is
so because, if it is added all at once, the dyestuff may rush on to the material.
Factors to be considered while selecting a carrier for polyester dyeing
i)

Efficiency of the carrier

ii)

Availability at low cost

iii)

Any adverse effect on the fastness properties of the dyes

iv)

Absence of unpleasant odour

v)

Non-toxicity

vi)

No degradation or discoloration of the fibre

vii)

Ease of removal after dyeing

viii)
ix)

High stability under the dyeing conditions

Compatibility with the dyestuff

x)

Ease of dispersion in the dye bath

xi)

Non-volatility in steam

xii)

Uniform absorption by the fibre.

Obviously, no single carrier possesses all of the desirable characteristics and in selecting the most
suitable carrier some compromise will be unavoidable.
Method of dyeing polyester with carriers
A typical method involves the use of a closed automatic jigger with a direct or indirect heating system,
which is a must in order to get satisfactory dyeing. The bath is set with an anionic wetting agent, a
dispersing agent, a carrier and acetic acid to adjust the pH at 5.5 - 6.5.
The fabric is run in the blank bath with carrier for 30 minutes at 60C and then previously-dispersed
dye is added to the bath after filtration. The dispersion is added in two lots at 60C. The temperature is
then slowly raised to the boil and dyeing continued for 90 minutes.
Removal of carrier: After the dyeing is complete, the bath is run off and the fabric is treated with boiling

water or scoured with 1 g/l non-ionic detergent to remove loosely-held carrier.

Reduction clearing treatment: The dyed material is then given a reduction-clearing treatment with 2 g/l

caustic soda and 2 g/l sodium hydrosulphite at 60C for 30 minutes to remove the unfixed colour from
the fabric. The fabric is now washed thoroughly with hot and cold water.
To remove the carrier completely from the fibre, a heat treatment is given at 150 - 180C for 30 - 60
seconds, depending upon the type of carrier used.
Carrier dyeing recipe

Disperse dye

X%

Anionic wetting agent -

0.1 to 0.5%

Dispersing agent

0.1 to 0.5%

Carrier

Y%

Acetic acid

0.1 to 0.5% (pH = 5.5 - 6.5)

Precautions to be taken during carrier dyeing

1. Care must be taken to ensure that no creaming up of the carrier takes place during the dyeing
process and that the temperature of the dye bath does not fall below the melting point of the
carrier; otherwise the later will crystallise out, resulting in specky dyeing.
2. While running the cloth initially in the blank bath (i.e. in a bath containing all the required chemicals
but no dye), the temperature of the bath should be maintained uniformly to avoid uneven pick up of
the carrier.

59

3. The pH of the bath should be maintained on the acidic side, i.e. 5.5 to 6.5.
4. Complete removal of the carrier after dyeing is very important as any residual carrier will not only
impair the fastness to light and washing of the dyed textile but also cause irritation and impart an
unpleasant odour to the fabric.
Advantages of carrier dyeing
a) Dyeing can be carried out more rapidly at atmospheric pressure.
b) The dye penetration is good.
c) No special equipment such as high pressure (HP) and high temperature (HT) dyeing machine is
required. The process is therefore suitable for the handloom and khadi industry.
d) The carriers also act as levelling agents.
Disadvantages of carrier dyeing
a) It adds considerably to the dyeing cost.
b) It involves a relatively lengthy dyeing process.
c) Complete removal of carrier is difficult and any residue affects the fastness properties of the dyed
material.
d) Some carriers tend to result in dyeing with decreased light fastness.
e) Some carriers are toxic.
f)

Residual traces of carrier can cause the fabric to develop an unpleasant odour.

g) Some carriers have low emulsion stability and can cause carrier spots, which are impossible to
remove.
h) Some are dye specific i.e. they possess different efficiencies with different dyes; others have poor
compatibility with certain dyes.
i)

Certain carriers have an adverse effect on some fibres blended with polyester.

The carrier method is to be preferred less than the HTHP method for staple fibre or for yarn, but the
carrier method has the outstanding advantage that it can be used for dyeing fabric in an open-width
form. As of today, carrier dyeing of polyester is banned and is no longer used.
High Temperature High Pressure (HTHP) Dyeing Method
Principle of HTHP dyeing
In this method the polyester fibre is dyed at high temperature (above 100C) and high pressure (using
pressurised equipment) in an aqueous bath. The HTHP conditions help to bring the fibre to a
temperature well above the Tg of the fibre, so excellent diffusion can take place and good dyeing
results are obtained.
Types of HTHP dyeing machines
1. Pressure jigger
2. Pressure winch
3. Package dyeing machine
4. Beam dyeing machine
5. Jet dyeing machine
Precautions to be taken during high temperature dyeing
Some precautions are necessary in high temperature dyeing. For example, the dye bath should not be
alkaline as it affects the polyester fibre, especially at elevated temperature and loss of strength of the
fibre may result. Alkalinity also decreases the exhaustion of some disperse dyes and decomposes
others. The safe pH region is 4.5 to 6, and this can be maintained by adding acetic acid or sodium or
potassium dihydrogen phosphate to the dye bath.

60

Only microfine disperse dyes with good dispersion stability under drastic HT dyeing conditions are
used for HT dyeing. The dye crystals and aggregates, resulting from the use of non-microfine dye, filter
off on the fabric, giving poor fastness properties. Rubbing fastness of heavy shades is very poor at
times. There is a danger of oligomer deposition on the fibre and the inner surface of the HT dye vessel.
The residual dye in the bath crystallises out and deposits on the fibre surface during cooling. To avoid
these problems, the exhaust bath is dropped at as high a temperature as possible. A reduction-clear
treatment also improves the rubbing fastness.
Dyeing of polyester fabric using high temperature dyeing method (Beam dyeing machine)
The beam dyeing machine
The beam-dyeing machine is a HTHP machine for the dyeing of fabric. Essentially, it is a package
dyeing machine in which the fabric, wound uniformly over a perforated beam, is loaded into a main dye
vessel and the dye liquor is circulated through the layers of fabric in a systematic manner, inside-out
for a definite period and then outside-in for a definite period, until the dyeing is over.
The following figure shows the main parts of a beam-dyeing machine. This machine is also used for
dyeing a beam of warp yarn, especially for the production of denim.
BATCHING OF CLOTH ON THE BEAM
In beam dyeing, a length of the fabric to be dyed is wound carefully on to a perforated beam and
placed inside the dyeing machine. Dye liquor is circulated through the fabric at high temperature and
pressure in a systematic manner until the dyeing is complete.
It is important in high temperature beam
dyeing that the fabric is wound on the beam
correctly and under constant tension, so that
a uniform shade is obtained in the entire
length of the dyed fabric.

It is advisable to use accurately constructed

batching devices that ensure uniform
batching of the fabric with moderate but
even tension throughout the batching.

C
A

Batching should be neither too tight nor too

loose. The beam is first lapped with loosely
woven lapping cloth.

A - Main dye vessel

B - Heat Exchanger
C - Pressure Lid
D - Beam with fabric
E - Main Pump

Eight to ten layers of such cloth are sufficient to prevent slipping of the roll of fabric and to avoid
perforation marks. Another important factor to be considered during batching is the length by which the
material extends beyond the perforated area on the beam and this is generally learnt through
experience. This idea is to get uniform dyeing.
Dyeing
The batch of fabric is entered into the autoclave and the vessel is filled with water. Complete removal
of air should be ensured before starting the actual dyeing process. The dye bath is set at 50C with 1
g/l dispersing agent and 0.5 g/l wetting agent; 0.5 - 1.0 g/l levelling agent is also included, if required.
The pH of the bath is adjusted to 5 - 6 with acetic acid. The liquor is circulated through the beam for 15
minutes at 50C.
The dyestuff is pasted and then dispersed in 10 to 20 times its weight of water at 40 - 50C for 5
minutes to ensure uniform and thorough wetting. The dye dispersion is added to the dye bath and the
temperature of the bath raised to 90 - 95C within 10 minutes. Further increase in temperature from 95
to 110C should be very slow and uniform as this is the critical zone for the dyeing of polyester fibre
and the dye uptake and levelness of dyeing depend very much on it. A rate of temperature rise of half a

61

degree per minute from 90 - 95C to 110C would be suitable and take about 30 - 40 minutes. The
temperature increase is kept at this rate while the dyeing is continued for another 30 minutes when the
dye bath temperature reaches 125 - 130C. The heating is then adjusted to maintain this temperature
and the dyeing continued for 30 - 45 minutes at this temperature.
The direction of liquor circulation is mostly kept inside out during the whole dyeing cycle so that the
position of the fabric roll on the beam is not disturbed. But with tightly woven fabric the direction of
liquor circulation is changed periodically to give a 7-minute circulation inside-out and a 3-minute
circulation outside-in. The latter process, involving periodic interchanges of the liquor flow directions,
has been found to give more uniform results. At the same time, it must be stated that there are
greater chances of the position of the fabric roll being disturbed. It is up to the dyer to standardise, by
trial and error, the dyeing conditions to get the best results while conforming to given requirements.
After dyeing at 125 - 130C for the required time a sample is taken out for shade matching and if any
addition of dyestuff is necessary, it is done after cooling the dye bath to 80 - 90C so as to avoid
uneven dyeing. After every addition, the dyeing should be done for at least 15 minutes at the dyeing
temperature.
Upon completion of the dyeing, the bath should be dropped without cooling as large crystals of dye are
formed below 90 - 95C and if these are allowed to settle on the fabric it would result in poor rubbing
fastness of the dyeing. If necessary, the high pressure can be used to eject the dye liquor rapidly.
Dropping the bath in this way gives cleaner dyeing with good rubbing fastness particularly in medium
and heavy shades. The material is then rinsed in water and given the reduction clearing treatment that
is explained below.
Reduction clearing
This treatment is given after the dyeing step to remove any unfixed dye from the fabric. It is carried out
with caustic soda (1 g/l) and sodium hydrosulphite (1 g/l) at 60C for 20 - 30 minutes. The batch is then
washed and unloaded.
Recipe for HTHP beam dyeing

Disperse dye

Dispersing agent

Wetting agent

Levelling agent

Acetic acid

X%
-

0.5 g/l
-

1 g/l
0.5 to 1 g/l (optional)

enough to get pH = 5 - 6

Advantages of the beam dyeing machine

a) Since the fabric is wound flat on the beam, no rope creases develop as they do in winch dyeing
because the fabric is maintained at full width during dyeing.
b) Loading and unloading of the fabric is easy and the time of dyeing is short.
c) Due to the low M:L ratio normally used in beam dyeing, much less than the usual quantities of the
dyeing assistants and sometimes the dyes are required for a given weight of fabric and the
consumption of steam, water and electric power is also low.
d) Both cloth and yarn can be dyed on this machine. If yarn is to be dyed, it is obviously in the form of
a warp beam.
Disadvantages of the beam dyeing machine
a) Woven texturised or knitted fabrics or crimped fabrics cannot be dyed successfully on the machine
as they get flattened or compressed and become harsh and boardy.
b) Fabrics of different widths cannot be dyed together on a single beam.
c) The dyed fabric may display moir effect if it is pressed tightly due to shrinkage.
d) Uneven dyeing may occur if the beam is fully loaded, as the dye liquor has to penetrate several
layers of fabric.

62

e) If the fabric is not wound carefully and uniformly and if creases are allowed to form, faulty dyeing
results. The creases become permanent after dyeing. Faulty batching can also result in patchy
dyeing, centre to selvedge shade variation, tailing effect, etc.
High pressure high temperature JET-Dyeing Machine
The jet-dyeing machine is an extension of the HPHT winch-dyeing machine. It is looked upon as a
welcome improvement over the winch machine, which has many disadvantages. The HPHT beamdyeing machine was found unsuitable for dyeing knitted goods and texturised fabrics.
In order to preserve the delicate structure of such fabric and to avoid fibre damage, the jet-dyeing
machine was developed by Burlington Industries and Gaston County Machine Co. of USA introduced
the first machine in 1963.
Four forms of energy are involved in jet dyeing machines. These are,
1. Chemical this is used in the actual dyeing
2. Thermal to heat up the dye liquor
3. Mechanical to bring about fabric transport
4. Fluid to cause movement of the dye liquor
Types of jet dyeing machine
Jet dyeing machines with different shapes and sizes of dyeing vessels are available today. The
machines are vertical, horizontal or inclined. They are also classified as partially flooded, fully flooded
and soft overflow type machines. In the fully flooded and overflow machines, the material is transported
partly by a small drive winch and partly by jets.
Only at the winch does the
fabric move through air
space, otherwise the fabric
is totally submerged in the
dye liquor.

D
C
B

A
G

A - Main dyeing vessel

D - Sight window

F - Circulation pump

B - Jet

E - Heat exchanger

G - Dye liquor

C - Reel

Major Parts of a Typical Regular Jet Dyeing Machine

63

The jet dyeing machines

can usually be operated up
to 140C under high
pressure
and
have
capacities
capable
of
dyeing 100 to 150 kg of
fabric at a time.
A line drawing of a typical
jet-dyeing machine is given
here. Jet dyeing has
introduced a new concept
in the dyeing of cloth in
rope
form,
particularly
knitted cloth and texturised
polyester fabric.

In the conventional winch, the dye bath is virtually stagnant and the fabric moves. In a jet-dyeing
machine, both the dye liquor and the fabric move; hence the relative contact between the dye
liquor and the fabric is much greater than that in the other machines; this helps to give better
dyeing results. Further, the fabric is wholly immersed in the liquor and is therefore not
subjected to stretch; it is, therefore, in a relaxed state, which gives it a good, soft and full
handle. The fabric in rope form is opened and transported by the jet of dye liquor and is
moved forward.
Soft-Overflow Jet Dyeing Machine
In order to overcome the problem of a conventional jet dyeing machine, new horizontal jet dyeing machines
based on soft overflow systems have been designed to minimise undue tension on the fabric and in which the
fabric follows the path similar to that in a conventional winch. A soft-overflow jet-dyeing machine is shown below.

B
A

D
C

A Jet
B Reel

C - Main dye vessel

D Fabric in dye vessel

64

E - Circulating pump
F Heat exchanger

Rapid jet dyeing machines

Jet dyeing machines are also classified as (i) Conventional jets (ii) Rapid jets and (iii) Super rapid jets,
depending upon the following factors.

1. Rate of circulation of dye 2. Rapid heating rate and cooling rate

liquor
3. Liquor to goods ratio
4. Reduced dyeing time
5. High capacity pump
6. Powerful heat exchanger
The rapid jet dyeing machine can dye 18 - 22 batches of texurised polyester fabric in 24 hours.
Method of dyeing on jet dyeing machine
a) The dye bath is prepared to include 0.5 g/l Lissapol D, 3 ml/l Dispersol AC (25%) and 0.5 ml/l
sodium hydrogen phosphate to bring the pH between 5 and 6; the dyestuff dispersed in 10 times its
weight with warm water is then added to the bath.
b) The pre-set polyester fabric free from size and lubricant is entered at 60C and the dye bath
temperature is raised quickly to 130C and the dyeing continued at this temperature for 1 hour.
c) The fabric is then rinsed, reduction cleared, washed, and soaped with 2 g/l Lissapol D and rinsed
again. It is then given an anti-static treatment with 0.25% Cirrasol TCS.
Advantages of jet dyeing machine
a) Fabrics of two different widths can be dyed at a time so that two lots can be combined together for
dyeing.
b) No special batching device is required for winding the fabric as in beam dyeing.
c) There is no flattening effect on the fabric as in beam dyeing.
d) Besides dyeing polyester, jet dyeing machines can be used for dyeing acetate, nylon or acrylic
fabrics at atmospheric pressure for obtaining a fuller and softer handle. Scouring can also be
carried out at atmospheric pressure for improving fabric quality, as there is no machine that can
scour cloth with texturised or crimp yarn in a relaxed state.
Disadvantages of jet dyeing machine
a) There is possibility of entanglement of light-weight fabrics during dyeing.
b) Loose fibres removed from the fabric may get redeposited on the fabric surface as well as on the
interior of the jet dyeing vessel; this problem does not arise in beam dyeing.
c) Yarn cannot be dyed in a jet dyeing machine whereas it can be dyed in a beam dyeing machine.
Problems in jet dyeing
In a jet dyeing machine, control of the following mechanical parameters is required to obtain uniform
dyeing:
1. Addition of chemicals and dyestuff at particular stages and temperatures
2. Rate of rise in temperature
3. Fabric speed and turnover
4. Rate of cooling
The problems that can normally arise in jet dyeing are briefly discussed below.

65

Foaming problem
Due to the highly turbulent conditions in a jet-dyeing machine, pronounced foam is produced in the
machine. Development of foam causes slippage of fabrics on metering rolls or winch reels and
interferes with the operation of the pump and jet system, ultimately resulting in entanglement of fabric
and stoppage of the machine.
Specific defoamers based on silicone emulsions, which are stable to high temperature of dyeing, may
be successfully used to overcome this problem.
Oligomer problem
Another problem in dyeing textured polyester fabric is oligomer formation. These are compounds of low
molecular weight structures formed during the polymerisation of polyethylene terephthalate. Cyclic
trimers create the most problems in processing.
The degree to which the trimers exude to the surface of the fibre is generally determined by various
steps of the fibre making process. Processes such as drawing, texturing, heat setting, etc. influence
the severity of the trimer problem in wet processing.
The hot drop of exhausted dye liquor helps to eliminate most of the trimer as it is suspended in the
liquor at high temperature.
Rope marks
The design of the jet dyeing machines and the jet should be such that during dyeing of the fabric the
rope opens at the jet. Rope marks which are formed get continuously shifted so that the major rope
marks do not stay on the fabric and whatever minute creases are left on the fabric can be removed by
drying the fabric at elevated temperature e.g. 190C with little wet tension. Alternatively, the rope marks
can be removed by re-dyeing the fabric in open width.
If the speed of the fabric on the reel of the jet-dyeing machine is kept high in the region of 250 - 350
metres/minute the crease formation is minimum. With a high speed of the fabric, the chances of
creases opening out and shifting continuously are more and fewer creases and rope marks develop in
the fabric.
Some special auxiliaries like Palatex-S (BASF) can be used in jet dyeing machine to minimise crease
formation. This auxiliary primarily acts as a lubricant helping the creases to open at the jet spray,
towards the selvedges, during the circulation.
Difference between the regular jet-dyeing principle and the soft overflow principle
The standard jet-dyeing machine is very useful for dyeing fairly
strong woven fabric as it can withstand the tensions that
transport it through the dye liquor without showing any dyeing
Part of the
dye liquor
faults, creases or fabric distortion.
overflowing
Regular jet: In this case the jet is so designed that all the dye
out of the jet
liquor entering it is involved in pushing the fabric. The jet is
Dye liquor
entering jet
narrow so the dye liquor passes through it with very great force,
Dye
pushing the fabric too with great force.
liquor
entering
Soft-overflow jet: On the other hand, the soft overflow type of
jet
machine uses a jet system in which a part of the dye liquor
entering the jet comes out of it. Thus only the remaining part of
the dye liquor is involved in pushing the fabric.
Conventional jet flow
Soft overflow jet flow
Further, the overflow jet is wider compared to the conventional jet, and the velocity of the dye liquor
passing through it would therefore be much less. The fabric is thus transported with gentle force that
keeps the shape and construction of a delicate fabric from being distorted or damaged.
The Thermosol Dyeing Process

66

Principle The Du Pont thermosol process is a continuous process in

which dry heat is utilised effectively in the disperse dyeing of synthetic
textiles.Considering polyester dyeing, the thermosol process involves three
steps, namely padding the fabric through a dispersion of the dye, next
drying it and then heating it for about one minute at 200C.
At this temperature many disperse dyes are molten whilst the fibre is in a
plastic state with its chain molecules vibrating vigorously. Thus, the dyeing
consists essentially of a liquid dye dissolving in a fibre, which itself is like a
viscous liquid; hence the name thermo-sol process.
Basically, the mechanism of thermosol fixation of the dye is the same as
that for exhaust dyeing. The dye is dissolved directly in the fibre when
exposed to temperatures of the order of 200C.

10 seconds

20 seconds

30 seconds

60 seconds

Dyeing by this method is a relatively simple process and consists in general of the following four steps:
i) Padding the material with disperse dye or a combination of dyes used for polyester/cellulose blends.
ii) Drying the padded fabric.
iii) Fixation of the dyestuff within the material by means of dry heat at 180-210C for 90 - 60 seconds
(i.e. 90 seconds at 180C or 60 seconds at 210C).
iv) After treatment of the material for synthetic fibres and dyeing and development of the other
component fibre in the case of a blended textile.
The basic operations such as preparation of the fabric, padding, drying, thermosoling, etc., must be
carried out under carefully controlled conditions to obtain optimum results.
Continuous dyeing of polyester
The thermosol process of Du Pont is used extensively for continuous dyeing of textile material made of
polyester alone or when mixed with other fibres. The process is based upon padding with a disperse
dye. This is followed by drying, which causes a film containing the dye to adhere to the surface of the
fibres. The next stage consists of heating to 180 - 220C for periods of 60 to 30 seconds. The stages
are depicted in the following figure.
a) Padding
The padding liquor normally
contains the following ingredients;
i) Disperse dyestuff
ii) Thickener or migration inhibitor

Dryer - 120C

iii) Wetting agent

Dye is fixed in the fabric

at this stage

iv) Urea (if necessary)

v) Acetic acid to adjust pH at 5.5
to 6.0.

Thermosol unit 180-220C

Padding in dye
dispersion

Using a thickener in the padding liquor The pick up of dye on the cloth can be improved by the use of
suitable thickeners in the dyeing liquor. In addition to improved pick up, the thickener also prevents
migration of dyes from the inner parts of the fabric to the exterior fabric zones thereby avoiding the
danger of uneven results. Sodium alginate is the most satisfactory thickener for polyester dyeing.
b) Drying
After padding, the material passes through a drying unit, which may be a hot-flue chamber, heated
cans, or an infrared pre-dryer before entry into the drying unit proper. Care should be taken to ensure
that the temperature is uniform in the dryer.
c) Thermosol unit

67

The dried material containing a film of the padding mixture is then heated to the desired temperature,
which is somewhere between 180 and 220C in a hot-flue oven or on cans heated by gas. This heat
treatment helps to fix the dye in the fibre and is thus called thermo-fixation.
At the high temperature at which thermo-fixation is carried out, thermal agitation of both the polyester
and the dye molecule is substantially increased. This permits much more rapid diffusion of the dye into
the fibre. The actual mechanism of fixation is probably mainly one of solution of the dye in the polymer
i.e. a solid solution phenomenon, but the possibility of hydrogen bonding between the carbonyl groups
in the polymer and the amino or hydroxyl groups in the dye cannot be excluded. In any case, the
predominant force of attraction between dye and fibre consists of van der Waals forces.
After-treatment of the dyed fabric: After the dyeing is complete, the material is well rinsed and
soaped. If a heavy shade has been dyed, the fabric is given a reduction-clear treatment with 1 - 2 g/l
hydrosulphite and 2 - 3 g/l caustic soda for 20 minutes at 70C.

68

Advantages of the thermosol process

a) Being a continuous process, the process can economically dye large yardages of fabric.
b) No carrier is required and hence problems associated with carriers do not arise.
c) Excellent dye utilisation (75 to 90%) is achieved.
d) This is an open-width treatment and hence wrinkles and rope marks are not formed.
e) Simultaneous heat setting and dyeing can be carried out.
f)

The dyeing is unaffected by pre-heat-setting.

g) High uniformity of shade can be obtained throughout the fabric.

h) The fabric is dyed in open-width form. This avoids the danger of abrasion of any cellulose fibres in
a blend with polyester.

Dyeing of Polyester/Cotton Blends

Introduction
The dyeing of polyester/cotton blends needs special attention on account of the fact that the
component fibres possess dissimilar characteristics. Processes have been developed that involve
dyeing of both the components either separately in two different dye baths or simultaneously, in the
same dye bath. For dyeing of the cotton component various classes of dyestuff e.g. direct, vat,
reactive, etc. are available whereas for polyester the only choice is disperse dyes.
Different coloured effects can be produced while dyeing these blends:
a) Solid shade dyeing: Both the components of the blend are dyed to the same tone and depth of
shade.
b) Contrast dyeing: Two components of the blend are dyed in different colours.
c) Reserve dyeing: Only one component of the blend is dyed whereas the second
left undyed.

component is

d) Two-tone dyeing: The same dyeing effect and tone is produced in different depths of shade
percentage in the two fibres.
Pre-treatment of Polyester/Cotton blended fabrics
In the modern and highly competitive area of textile dyeing the key to uniformity, reproducibility and
high quality fabric lies in the correct pre-treatment of the fabric prior to dyeing. It is common experience
that almost 70% of the faults in the finished fabric may be traced back to some faulty pre-treatment. It
is therefore necessary that precise process control is necessary to produce fabrics of uniform
absorbency and whiteness.
Pre-treatment procedure
Polyester/cotton blends are subjected to a variety of pre-treatments to ensure good results in dyeing.
Two typical routes are stated in the following.
(a)

Singeing
Desizing
Heat-setting

Washing

Bleaching

(b)

Desizing
Causticising

Drying

Heat-setting

Washing
Drying

Mercerising/Causticising

Singeing

Drying

Mercerising/

The pre-treatment procedure that starts with desizing produces pre-treated goods which give the best
results in dyeing.
Polyester/viscose blended fabric is preferably pre-treated as follows as it cannot withstand the alkali
treatments of mercerisation/causticising.
(a)

Singeing

Desizing

Washing

Heat-setting

(b)

Desizing

Washing

Singeing

Heat-setting

69

Drying

Fabric dyed by the exhaust method is normally singed after dyeing to avoid the dyeing defect referred
to in industry as sooty appearance or dye specks, which are caused by melted beads of polyester,
which tend to dye to a darker shade than the fibres themselves.
However, this does not generally occur in Thermosol dyeing which gives better coverage of such faults.
If the singeing operation is not performed efficiently the uneven surface fuzz will lead to shading
problems and the resistance to pilling too will be uneven and poor.
Heat-setting
What it is and why it is necessary: Heat setting is primarily carried out to improve the dimensional

stability of the fabric to hot wet processing, particularly for minimising creasing problems and for the
prevention of fabric shrinkage during dyeing.
Heat setting is usually carried out on a stenter machine, the fabric being maintained at the required
final dimensions and shape at 190 - 210C for 20 - 40 seconds. The heat-setting temperature should
be higher than subsequent processing temperature.
In normal use, the heat-set fabric will permanently retain the dimensions and shape given to it during
the heat setting process.
Heat setting precautions: The slightest variations in the treating conditions i.e. temperature, time and

tension will influence the setting effect. Uniform conditions of the heat setting are therefore essential.
The goods must be dry before they are heat set and remain under constant tension as they pass
through the setting system. This is particularly important because the degree of setting is reflected in
the dye uptake subsequently.
When is the best time for heat setting?

a) If the goods are to be pre-treated in rope form or to be dyed later on by the exhaust process, it is
advisable to heat set the material first.
b) If the fabric is to be dyed in rope form or open-width form on a winch, pre-setting is absolutely
necessary to avoid crease marks and the formation of permanent running creases. Textured
polyester should be heat-set at about 170 - 175C to preserve the bulkiness.
c) Heat setting prior to dyeing has the advantage that the dye selection is not restricted by
considerations of fastness to dry heat treatments. Heat treatment is also liable to change the dyeing
properties of the material; polyester fibres that are set at 160 - 180C are dyed by many disperse
dyes to weaker shades than those that have not been heat-set or have been set at higher
temperatures. For this reason heat setting prior to dyeing should be carried out at temperatures of at
least 190C.
Dyeing of P/C blended fabric
Polyester/cotton blends can be dyed by the batch-wise (exhaust dyeing) technique or the continuous
methods. The selection of a suitable dyeing method depends on the type of fabric, the batch size and
the requirements of the dyed and finished fabric.
For dyeing by the batch-wise exhaust process the following equipment may be used.
a) Beam dyeing machine
b) Jet dyeing machine
c) High temperature winch or jigger
For continuous dyeing, the thermosol process is the most important.
Many classes of dyes and dyeing processes are suitable for polyester/cotton blends. Polyester fibre is
always dyed with disperse dyes, whereas the cotton part of the blend can be dyed practically with all
classes of dyes suitable for dyeing 100% cotton. Almost always, the polyester part is dyed first.
Cross dyeing: In the selection of disperse dyes, care must be given to their fastness to cross dyeing,
which is the resistance of the dye on the first (or dyed) fibre to the chemicals used in dyeing the second
fibre. In the case of P/C blend dyeing it is the resistance of the disperse dye on the polyester part of the
blend to the dyeing chemicals and conditions used for the cotton component.

70

Cross staining: In the selection of dye classes and dyes for the cotton part, care must be taken to avoid
the possibility of cross staining. Cross staining means the staining by a dye meant for one of the
components of a blend on the other component. Reactive dyes give negligible cross staining of
polyester whereas vat, solubilised vat, sulphur and azoic colours show moderate to severe cross
staining (i.e. staining on the polyester component). However, cross staining can generally be removed
by reduction clearing.

The Dyeing Processes The most common processes and dyes used for dyeing P/C blends
1. Exhaust dyeing methods
a)

Two-bath dyeing processes: Dyeing the polyester part first with disperse dyes and then
dyeing the cotton part with vat, direct, reactive, sulphur, azoic dyes, etc.

b)

One-bath dyeing processes: In these processes, the dyes for both of the fibres are
included in the same dye bath and the dyes are applied simultaneously. Some dye
combinations are as follows.

c)

i)

Disperse dyes and vat dyes

ii)

Disperse dyes and reactive dyes

iii)

Disperse dyes and direct dyes

Inverse dyeing processes: These are rarely used and involve dyeing the cotton part first,
followed by dyeing the polyester component.

2. Continuous processes
The following processes are used for the continuous dyeing of P/C blends.
i)

Continuous dyeing with disperse and vat dyes

ii)

Thermosol/thermo-fixation process with disperse and reactive dyes

iii)

Continuous dyeing with pigment colours

The selection of a suitable dyeing process and the right classes of dye depends on many factors, such
as economy, the equipment available, batch size, and depth of shade and its brilliance, and the fibre
blend ratio.
Process Details Exhaust dyeing methods Two-bath dyeing methods
Two-bath dyeing methods involve additional labour and time but they often produce shades of good
fastness properties.
The polyester component of the blend is dyed with disperse dyes by any suitable method. After
this, the surface dye is removed by the reduction clearing treatment and then the cellulose
component is dyed with suitable dyes.

When vat dyes are used, an intermediate reduction clearing treatment soon after the dyeing of the
polyester component is not necessary as the vat dye bath would contain the caustic soda and
hydros that is normally used for reduction clearing of the polyester dyed component. Very often the
polyester component is dyed in a high-temperature dyeing machine and the cellulose component is
dyed in a fresh bath in some other machine, e.g. a jigger.

In carrier dyeing, the two-bath method is preferable because the stability of the carrier emulsion is
limited in the presence of a large amount of salt and other chemicals that are necessary for dyeing
the cellulose component of the blend. In subsequently dyeing with vat dyes, the retarding effect that
some carrier emulsions exert on the vat dyes must also be considered.

While dyeing the cellulose component of the blend, preference is usually given to those dyes which
produce shades with fastness properties that are as good as those of the disperse dyes used for
the polyester component. This principle is illustrated in the following figure for disperse-dye and

71

reactive-dye combination. The figure has five parts starting from the undyed fibres to both fibres
being fully dyed.
1

PET
Disperse

Reduction

Reactive

Soaping and

clear

Dye

Washing

(HTHP/
Carrier)
Cotton
(COT)

PET dyed
COT cleared

PET dyed +
COT stained

COT dyed

PET and COT

both dyed

The steps in the dyeing of the (disperse + reactive) combination are listed below.

The polyester (PET) part is dyed first using the HTHP method or the carrier method of dyeing.
These processes have been described earlier. Note in Part 2 of the figure that the PET fibre is fully
dyed and that surface dye is also present. See also that the cotton part, which has little affinity for
disperse dye is also slightly stained on the surface.

The PET-dyed material is then given the reduction-clearing treatment to remove surface dye. In
Part 3 of the figure note that the surface dye has disappeared in both of the fibres.

The blended material is now dyed with a reactive dye, according to the procedure described earlier.
In the figure note that the cotton part is fully dyed and that surface dye is also present.

Finally, the material is soaped and washed to remove the surface dye on the cotton part, as seen in
Part 5 of the figure.

Process Details Exhaust dyeing One-bath dyeing process

Disperse and vat dye combination: The principle of applying this combination is illustrated below.
PET

Cotton
(COT)

Disperse

Caustic

Vat

Hydros

PET dyed
COT + Vat pigment
+ Disperse stained

Soaping and

Oxidation

Washing

COT + Reduced
vat dye and
disperse cleared

COT dyed

PET and COT

both dyed

The steps in the (disperse + vat) dyeing are as follows.

The polyester (PET) part is dyed first using the HTHP method or the carrier method of dyeing.
These processes have been described earlier. Note in Part 2 of the figure that the PET fibre is fully
dyed and that surface dye is also present. See also that the cotton part, apart from the slight
staining by the disperse dye, is fully covered on the surface by vat dye particles.

The next treatment is in a bath of caustic soda and hydros. Two events take place in this bath.
o

It acts as a reduction-clearing bath and removes the surface dye on the PET-dyed part. Note
the absence of disperse dye on the PET surface.

It also acts as a reducing bath for the vat dye on the surface of the cellulose part. The vat dye
pigment is reduced to the leuco state here and is taken up by the fibre.

72

In the third step, the material is treated in an oxidising bath to convert the vat dye back to its
insoluble state. Note the continued presence of vat dye on the cellulose fibre surface.

Finally, the material is soaped and washed to remove the surface dye on the cotton part, as seen in
Part 5 of the figure.

Dyeing Recipe and Conditions of Dyeing

All vat dyes may be used for the one-bath high-temperature dyeing process provided that the dyes are
finely divided enough. The IK vat dyes are not preferred because the dye liquor requires to be cooled
to about 30C in order to obtain full colour yield. Therefore when IK dyes are to be used it is preferable
to dye by the two-bath process.
A typical dyeing recipe for single-bath dyeing consists of the following ingredients.
Disperse dye

X%
Vat dye

Y%
Dispersing agent

0.5 to 1%
Wetting agent

0.5 to 1%
pH

4 to 5 (attained with 1 - 2 ml/1 of 30% acetic acid)

Treat the material for a few minutes at 60 - 70C in a blank bath of acetic acid, dispersing and wetting
agent. Then add dispersions of the disperse and vat dyes and proceed as described below.
a) Dyeing the polyester part When the dyes have been dispersed uniformly in the dye bath, raise
the temperature to 120 - 135C. Dye at this temperature for 60 - 90 minutes. The heating rate
depends primarily on the depth of shade and the liquor circulation. It is advisable to reduce the rate
of heating in the case of pale to medium shades because 70 - 80% of the amount of disperse dye
used goes on to the polyester fibre during the heating phase. In contrast, the bath may be heated
relatively rapidly when dyeing dark shades because the major part of disperse dye does not go on to
the fibre until the bath has reached about 120C.
b) Dyeing the cellulose part When the desired shade is obtained on the polyester component, cool
the dye bath to 80C and dye the cellulose fibre by adding the required quantities of caustic soda
and sodium hydrosulphite. This will of course depend on the class of vat dye used. (The
manufacturers recommendations must be followed.)
In the case of IW dyes, 10 - 15 g/1 Glaubers salt is added to the dye bath for better exhaustion after
it has been cooled to 50C.
Vat dyes level out perfectly at 80C. For this reason, dye first at this temperature for 15 minutes and
subsequently cool the bath to 60 or even 50C, if required, and continue dyeing for a further 15
minutes.
When dark shades are to be produced on polyester/cotton and polyester/viscose blends it is
advisable to cool the bath to 60 or 50C to obtain the full colour yield. Vat dyes display the greatest
affinity for cotton or viscose in this temperature range.
When dyeing polyester / polynosic blends it is not necessary to cool the bath to 60C because vat
dyes show the highest affinity for polynosic fibre at temperatures around 80C.
c) Intermediate rinse: The material is rinsed after the cellulosic fibre has been dyed. In the case of
package dyeing, it is advisable to circulate the water from inside to outside of the packages, rinsing
with overflow of water.
d) Oxidation and soaping: Both of these can be achieved simultaneously using the following recipe.
Hydrogen peroxide (35%)
1 - 2 ml/l
Anionic detergent
0.5 - 1 g/1
pH
9 - 10
First treat the material for 10 - 15 minutes at 50C with hydrogen peroxide. Then add the anionic
detergent and raise the temperature to 95C. Soap for 10 - 15 minutes.

73

Continuous dyeing processes

Disperse/Vat Combination
The sequence of operations involved in this method is given below.
(a) Padding the fabric with disperse and vat dyes

(b) Intermediate drying (including pre-drying)

(c) Thermosol treatment

(d) Chemical padding, steaming and fixing the vat dyes

The combination of thermosol and pad-steam process has proved to be one of the most reliable and
economical methods of dyeing polyester/cotton blends. A schematic diagram of this continuous dyeing
process is shown in the following figure.

Pad
(Disperse + vat dyes)

Chemical pad
(Caustic + hydros)

Infrared pre-drier

Drier

Thermosol unit

Cooling zone

Step 1: Disperse dyeing of PET

Steamer

Open soaper with 7-10 compartments

Step 2: Vat dyeing of cotton

Disperse and vat dyes selected for this process should be in an extremely fine state of dispersion.
Liquid brand disperse and vat dyes are normally preferred. The sublimation fastness of disperse dyes
should be high.
The process can be described briefly as follows.
Dyeing the polyester component: the Thermosol Process
i) The blended fabric is padded uniformly with an aqueous dispersion of disperse and vat dyes. The
padding liquor also contains a suitable migration inhibitor to ensure that the dyes do not migrate
during the drying step and give rise to uneven dyeing.
ii) Next, the fabric is dried on a hot-flue or float-dryer at 100 - 110C.
iii) The dried fabric is then subjected to thermo-fixation in a thermosol unit for 90 - 60 seconds at 200 220C (i.e. 90 seconds at 200C or 60 seconds at 220C) and then cooled. The disperse dye is now
fixed in the polyester fibre.
Dyeing the cotton component: the Pad-Steam Process
i) The next step is to bring about the dissolution of the vat dye to allow it to be taken up by the
cellulose component of the blended fabric. The material coming out of the thermosol unit is

74

therefore passed through a chemical pad containing an alkaline reducing bath of caustic soda and
sodium hydrosulphite at the right temperature to convert the vat dye into its soluble leuco-vat form.
The composition of the chemical pad bath depends on the vat dyes used. An excess of reducing
agent should be used in order to complete the reduction of vat and unfixed disperse dyes. The
addition of common salt to the pad bath minimises the bleeding of dyestuffs into the reducing liquor.
ii) To facilitate the adsorption, diffusion and fixation of the vat dye, the fabric is steamed for 25 - 40
seconds at 100C in a steaming unit.
It is advisable to reduce very deep shades on a jigger rather than on a pad-steam unit, as the
reduction and fixation of vat dyes in high concentration is difficult in the short steaming time. The
reduction clearing of unfixed disperse dyes takes place simultaneously with the reduction of the vat
dyes. The process is described in the next section.
iii) The fabric emerging from the steamer is passed through the washing and soaping compartments of
an open-width soaper, squeezed and dried.
Other methods of fixation of vat dyes
Although the pad-steam process is economical for the continuous fixation of vat dyes on the cotton
component of a P/C blend, other efficient batch-wise and semi-continuous processes are also available
for small batches.
Pad-jig development
In this method, the vat dye is reduced and fixed in the cellulose component of the P/C blend by means
of a jigger machine. This method of vat dye fixation is widely used particularly for dark shades. It offers
the advantage of better penetration of the dye into the fibre than the pad-steam technique, especially
when the fabric is densely woven.
The amount of caustic soda, hydrosulphite and Glaubers salt to be used in the jigger depends on the
depth of shade and the liquor ratio used. In general, the caustic soda concentration varies from 20 to
40 ml/l (70Tw NaOH), hydrosulphite concentration 10 to 20 g/l and Glaubers salt concentration 20 to
40 g/l.
The amount of hydrosulphite suggested is only approximate because the amount of air brought into the
development bath depends on the type of fabric. It must be ensured that the temperature of the liquor
remains constant while dry fabric is introduced into it. Vatting commences at 70 - 75C and the dyeing
is completed in a cooling bath (60C). Generally speaking, batches of 300 to 400 kg size (15 to 20
minutes per end) are dyed by giving four ends and small batches 6 to 8 ends.
Disperse/Reactive dyes
Continuous one-bath one-step thermosol dyeing process
As mentioned earlier, the thermosol process is economical for the dyeing of polyester. Reactive dyes
too can be fixed into the cellulose fibre by dry heat treatment, such as that used in the thermosol
process. Therefore, the fixation of disperse and reactive dyes can be carried out simultaneously during
the thermosol treatment.
As alkali is required for the fixation of the reactive dye, not all disperse dyes are suitable for this
process. Some of them undergo a change in shade and their colour yield is affected considerably
during the thermosol treatment in alkaline medium. Therefore disperse dyes that are resistant to alkali
should only be used. The alkali used in this process is 10 g/1 of sodium bicarbonate or soda ash.
Padding Recipe The general pad-bath recipe is as follows:

Disperse dye (alkali resistant)

X g/l

Reactive dye (preferably H-brand)

Y g/1

Sodium bicarbonate or soda ash

5 - 20 g/1

Urea

100 - 200 g/l

Migration inhibitor

10 - 20 g/1

75

 Wetting agent
1 - 2 g/1
The first step is to pad the fabric at room temperature taking the usual precautions as mentioned for
disperse/vat dye application.
The next is to dry the fabric at 100 - 110C followed by thermo-fixation at 190 - 200C for 90 - 60
seconds during which disperse and reactive dyes are fixed simultaneously on the polyester and cotton
components respectively.
Finally, the dyed fabric is washed and soaped as usual in an open-width soaper machine.
The disperse dyes used in this process should have minimum staining on the cellulose fibre, no
interaction with the reactive dyes and good stability in alkaline conditions. Liquid disperse dyes are not
suitable because the reactive dyes are liable to react with the hydroxyl group of the glycol present in
them.
The use of urea as a dye bath additive has the following advantages:
a) It increases the degree of fixation of the reactive dyes during the thermosol treatment.
b) It increases the rate of fixation of disperse dyes.
c) It reduces the risk of discolouration of cellulose during the high-temperature fixation treatment.
d) It aids the dissolution of reactive dyes in the padding liquor.
Although the use of urea is strongly recommended in the thermosol dyeing of disperse-reactive dyes, it
has certain drawbacks. It is highly volatile and results in the formation of objectionable odour during
fixation in the thermosol unit.
Pad-steam/pad-batch processes for the reactive dyeing part instead of thermosol
In the thermosol method where the simultaneous fixation of reactive and disperse dyes is carried out it
is necessary to incorporate a suitable alkali in the pad liquor for fixation of the reactive dye.
This necessity limits the choice of disperse dyes to only those dyes which are not sensitive to alkali. In
order to overcome this problem, especially when the choice of disperse dyes is limited, the pad-steam
process is used. The general sequence is as follows.
a) Padding with disperse and reactive dyes without alkali
b) Drying and thermosol treatment
c) Padding with alkali
d) Batch or steam
e) Rinsing and soaping
Padding liquor Recipe The fabric is padded in liquor conforming to the following recipe.

Disperse dye

X g/l

Reactive dye

Y g/l

Migration inhibitor

10 g/l

Wetting agent

1 - 2 g/l

Dyeing the polyester part The padding is done at room temperature using an expression of 60 70%. Drying and the thermosol treatment follow this. Note that the reactive dye is also taken up in this
step.
Fixing the reactive part To fix the reactive dye the fabric is subsequently padded with,

30 ml/l caustic soda (70Tw)

250 g/l Glaubers salt (anhydrous)

Temperature room temperature

Steaming: It is then either steamed without drying in saturated steam at about 102C for 30 - 60
seconds
Batching: Alternatively, it is batched and wrapped with a plastic film for 2 - 8 hours at room
temperature. The batch should be rotated continuously at slow speed to facilitate even fixation.

76

Soaping and Washing: Whether the reactive dye is fixed by steaming or by batching. the rinsing
and soaping is carried out in an open soaper when the unfixed disperse and reactive dyes are
removed.

77

Colour Fastness of Dyes

Introduction
Textiles meant for export have to meet the requirements of quality if they are to be accepted by the
buyer. Besides the requirements of specified fabric construction parameters those minimum specified
during the domestic laundering and colour fastness to indicated are paramount importance.
Standard methods of test
There are national and international standards for methods of testing dyed textiles (as there are for
most material in general). Some of the important organisations that are concerned in the development
of standard test methods are given below.
Name of the Standards Organisation
American Association of Textile Chemists and
Colorists
American Society for Testing and Materials
British Standards Institution
Bureau of Indian Standards
Deutsche Standards
International Organisation for Standardisation
Japanese International Standards

Common
Abbreviation
AATCC
ASTM
BSI
BIS
DIN
ISO
JIS

National or International
National - USA
National - USA
National - UK
National India
National - Germany
International / Based in
Geneva, Switzerland
National - Japan

It can be seen that all the above except the ISO are national-level organisations. The ISO test methods
have come about with a view to bring in international unity in testing and the expression of results.
Buyers may specify an ISO or an AATCC or a BSI or other test standard for the product they are
buying. The appropriate test method can be found in the manuals for testing brought out by the
respective organisations. Thus a test-method for say colour fastness to washing, recommended by any
of the organisations noted above will contain specific details of the washing test and the conditions
under which it should be performed and the information that the test-report should contain and so on.
Though there is some variation in procedural details or conditions of test between the tests
recommended by these organisations for a given property there is no appreciable difference in the
principles of the test methods. It is important for the student to know the principles of tests for colourfastness of dyed textiles. Also with regard to procedural details the BIS test methods for colour
fastness to washing and rubbing will be with as not very different from the respective ISO of BS test
methods and also as these are the properties commonly tested.
Colour Fastness of Dyed Textiles
This is probably the most important property of coloured textile material, since any shortcoming in this
property may adversely affect the useability of the end products.
Colour fastness is the property of a dye that enables it to retain its colour in its original depth and tone
throughout the wear life of the product to which it has been applied.
There are several agencies or factors to which colour fastness testing is prescribed. An agency or
factor in this context is a deteriorating influence. Some agencies are of consumer significance, i.e. of
importance to the end user of textile products; others are producer significant, i.e. those related to the
manufacturer of textile products. Some agencies are listed below:
Consumer (end-user) significant
1.
Washin
2.
Rubbing
g
3.
Daylight 4.
Artificial
light
5.
Perspir
6.
Dry
ation
cleaning

Producer (manufacturer) significant

1. Scouring
2. Bleaching
3. Merecerisation

4. Cross-dyeing

5. Heat-setting

6. Carbonisation

78

A number of tests may therefore have to be done to determine the resistance of a given dye to all of
the above agencies.
Basic principle of a colour fastness test
a) A test-specimen of specified dimensions is taken from the sample to be tested, e.g. 10 cm 4 cm,
for a washing fastness test.
b) Undyed fabric conforming to standard specifications and dimensions is taken e.g. 2 pieces each of
10 cm 4 cm dimensions for a washing-fastness test.
c) The test-specimen is placed in between the two pieces of undyed fabric and stitched around at the
four edges, as shown in the figure below.
First single-fibre undyed
adjacent fabric
Test Specimen
Second single-fibre undyed
adjacent fabric

Composite Specimen (sewn

along all four sides)

This results in a composite specimen. For some tests only one stitch along one common edge is
recommended.
d) The composite specimen is subjected to the deteriorating influence (agency) against which the
resistance is being determined. The conditions are as per the specifications of the standard testmethod used.
e) The test-specimen is evaluated for change in colour and the adjacent undyed fabric pieces are
evaluated for extent of staining and appropriate ratings are given for the colour fastness of the test
sample.
Assessment of colour fastness
The assessment of colour fastness is carried out by assigning ratings for two aspects.
i)

Change in colour (of the test-specimen)

ii)

Staining (of adjacent fabric)

Grey scale for change in colour

This scale consists of nine pairs (or five pairs in the old scale) of standard grey chips, each pair
representing a difference in colour of contrast (shade and strength) corresponding to a numerical
fastness rating, the differences in colour between the chips of each pair are given a numerical value
ranging from 5 to 1. The two sides of a nine-step grey scale for change in colour are shown below.

5-4

4-3

Front side of a 9-Step Geometric Grey Scale for

evaluating change in colour

(4-3) or (3-4)

2-1

Reverse side of the scale

Front Side of Scale

Numerical Rating/Grade
Qualitative Grade
5
Excellent

(5-4) or (4-5)

3-2

Reverse Side of Scale

Numerical Rating/Grade
Qualitative Grade
3
Good (Average)

Very good-excellent
Very good
Goodvery good

(3-2) or (2-3)
2

(2-1) or (1-2)

79

Fair-good
Fair
Poor-fair

Good (Average)

80

Poor

Grey scale for staining

This scale consists of pairs of normally white and grey colour chips, each representing a difference in
colour or contrast (shade and strength) corresponding to a numerical rating for staining. Here too the
ratings are from 5 to 1, the qualitative descriptions and the difference between the adjacent chips for
the ratings being as shown in the table above. The two sides of a nine-step grey scale for assessing
staining is shown below.

5-4

4-3

Front side of a Geometric Grey Scale for evaluating

staining

3-2

2-1

Reverse side of the scale

Conditions for assessing colour fastness

a) Part of the original fabric and the treated specimen are placed side by side in the same plane and
oriented in the same direction.
b) The grey scale is placed nearby in the same plane.
c) The surrounding field should be a natural grey colour approximately midway between that
illustrating class 5 and that illustrating class 4 of the grey scale for assessing change in colour.
d) The effect of the backing in the appearance of the textiles may be avoided by using two or more
layers of the original and tested specimens ( folding the original and tested specimens twice will
give four layers).
e) Illuminate the surface with north skylight in the northern hemisphere, south skylight in the southern
hemisphere or an equivalent source with an illumination of 600 lx or more.
f) The light should be incident upon the surface approximately perpendicular to the plane of the
surfaces.
g) The difference between the original and the tested specimen and the differences represented by
the grey scale are compared visually).
Assignment of rating
The fastness rating of the specimen is that rating of the scale which has a perceived colour difference
equal or nearest in magnitude to the perceived colour difference between the original and the treated
test specimen. In a 5-step scale intermediate ratings such as 4-5 or 3-4 may be given if the contrast
does not correspond to the whole number chips on either side of the intermediate rating.

Determination of colour fastness of textile materials to washing

1) Principle of the test
A specimen of textile in the form of fibre yarn or fabric, in contact with pieces of specified adjacent
fabrics in mechanically agitated in a soap or soap- soda solution, rinsed and dried. The change in
colour of the specimen and the staining of the adjacent fabrics are assessed with the grey scale.
2) Sampling: the sample should be a representative sample or one agreed to between the buyer and
the seller
3) Apparatus: A suitable mechanical washing device conforming to the following requirements to be
used.
a)

A water bath containing a roller by means of which containers usually stainless steel,
sometimes glass) of 500ml capacity are rotated at a speed of 40+2 rev/min

b)

Means of thermostatically controlling the temperature of the water bath so as to maintain the
temperature in the containers at that specified for the washing test performed, to an accuracy of
40+2C.

81

A schematic figure of a
typical mechanical washing
device, sometimes called a
`Launder-o-meter is shown
here.

3
1 Temperature setting
arrangement

Essentially
the
device
2 Temperature display
consists of an outer vessel
in which water or other
3 Timer, for setting the time of
treatment
heating medium can be
filled up to the desired level.
4 Outer vessel containing water
A rotating arrangement is
5
5
5 SS Containers holding test
fitted in the vessel, as
specimen
shown in the figure. The test
and treating liquor.
specimens and the soap or
S Main switch of the machine
soap-soda solution, as the
5
5
4
test demands, can be
placed in a set of four, six or
Water heated to the required temperature
eight
stainless
steel
containers, depending upon
the size of the launder-ometer.
The containers are closed with lids such that they fit tightly to the containers. The containers are
mounted on to the rotating device, the outer vessel is covered and the device is switched on.
4) The five washing tests: The washing fastness of dyed textiles may be performed under five
different standard test conditions as shown in the table below. It can be easily seen that the severity
of the test increases as we go from Test 1 to Test 5.
(Test specimen = 10 4 cm, made of 100% cotton; first adjacent fabric = cotton)
Washing
Fastnes
s Test
No.
1

Second Adjacent
Fabric

Sodium
carbonate
solution, g/l

Temperature,
C.

Time of
treatment,
min

No. of
Steel balls
used

M : L Ratio

(10 x 4 cm)

Soap
solution,
g/l

Wool

Nil

40 2

30

Nil

1 : 50

Wool

Nil

50 2

45

Nil

1 : 50

Wool

60 2

30

Nil

1 : 50

Viscose

95 2

30

10

1 : 50

Viscose

95 2

240

10

1 : 50

5) General Test Procedure

a) Place one composite specimen, with or without steel balls as specified, in the container. Add the
necessary amount of soap or soap-soda solution previously heated to the temperature specified in
the test to give the liquor ratio of 1:50 Treat specimen for the specified time at the specified
temperature.
b) Remove the composite specimen; rinse it twice in cold water and then in cold running tap water for
10 minutes. Squeeze it.
c) Remove the stitches along the two long sides and one short side. Open out the composite
specimen and dry in air at 60C at room temperature.
d) Evaluate the change of the treated test specimen and the degree of staining of the pieces of
adjacent fabric with the help of grey scales and assign the ratings, bearing in mind the conditions
stated earlier.

82

83

Determination of colour fastness to Rubbing (Crocking) (IS766L1988)

This test is designed to determine the degree of colour that may transfer from the surface of coloured
textiles to other surfaces by rubbing. It is applicable to textiles made from all fibres in the form of yarn
or fabric whether dyed, printed or otherwise coloured.
1. Principle of the test
Specimens of the textile are rubbed with dry rubbing cloth and with wet rubbing cloth, by means of
a rubbing finger of specified dimensions. The staining of rubbing cloth is assesses with the grey
scale for staining and ratings are assigned for dry-rubbing fastness and wet-rubbing fastness of the
specimen.
2. Sampling
The sample shall be representative of the original lot of fabric to be tested or as agreed to between
the buyer and the seller.
3. Apparatus
A suitable testing device called crockmeter should be used. It consists of the following features, as
shown in the figure below.
a) A flat base to which the test specimen is fixed so as to be free from slack, that may cause folds
and wrinkles during rubbing.
b) A rubbing finger comprising a cylinder of 1.6 cm track on the specimen with a downwards force
of 9 newtons.
c) Rubbing cotton cloth - this should be desized, bleached and without finish and cut into a 5 cm
5 cm square.
Schematic figure of a crockmeter
7
1 Base of the instrument
2 Specimen fixed on to the base
3 Clips to hold the specimen flat on the base 4 Rubbing finger
5 Rubbing cotton cloth fixed at the lower end of (4)
6 Distance showing the 10-cm track 7 - Weight on the rubbing finger

3
6

3
1

4. Test Specimen
This should not be less than 14 cm 5 cm. Two pieces are to be used for dry rubbing, one warp-way
and the other weft-way. Similarly two pieces are required for wet rubbing.
5. Test procedure
Fix the test specimen to the rubbing device by means of clamps such that the long direction of the
specimen follows the track of the device.
When testing multi-coloured textile, care should be taken to position the specimen in such a way that
all coloured of the design are rubbed in the test. If the areas of colour are sufficiently large, more test
specimens may be taken and individual colours assessed separately.
a) Dry Rubbing: The dry rubbing cloth is fixed flat in place over the end of the finger of the testing
device. Operate the apparatus and rub the test specimen to and fro in a straight line along a track
10 cm long, 10 times to and fro in 10 seconds, ensuring that there is a downward force of 9 N on
the rubbing finger.
b) Repeat the test described above with a fresh dry test specimen and with a wet rubbing cloth that
has been wetted to ensure a take up about 100 percent of its mass of water. Dry the rubbing cloth
at room temperature.
c) Assign ratings for the staining of the cotton cloths with the grey scale for staining. Assign one rating
each in the warp-way and weft-way directions of the fabric for the dry rubbing fastness and similarly
one in each of these directions for the wet rubbing fastness of the test fabric.
General Colour Fastness Properties of Dyes
The colour properties of dyes in general to the frequently met agencies in everyday life are included in
the following table. The staining properties of the dyes and their general uses are also included.

84

General Colour Fastness Properties of Dyes

COMMON AGENCIES IN EVERYDAY LIFE OF TEXTILES
Dye class

Light

Washing

Hot
pressing

Dry
cleaning

Staining
(Bleeding)

Perspiration

Crocking

Poor
resistance;
stains
adjacent
cotton visibly

Uses
Primarily for cellulose fabrics; some
dyes are good for cotton/wool
blends; some for cheaper quality
fabrics. Much used for printing on
dischargeable dyed backgrounds
Primarily for acetate; also
triacetate, nylon, polyester acrylic,
modacrylic, olefin as well as
cellulose fibres. Wide use in
apparel, decorative fabrics. Used
for dyeing and printing

Substantive
direct

Poor to
moderately
good

Poor

Good

Good

Good

Good in most
shades on cotton
and rayon

Disperse

Fair to
excellent,
depending
on fibre

Fair to good;
better on
polyester than
on acetate or
nylon

Some colour
change
possible

Good

Good

Good

Stains wool
badly

Good

Good

Fair to good
depending on
dye, depth of
shade

Good
resistance

Used for cotton and wool and

military uniforms.

Good

Good

Good
resistance

Applicable to all fibres for obtaining

bright colours.

Good

Good for light to

medium shades;
very poor for dark
shades

Good

Vat

Generally
excellent

Good

Generally
good; some
colour change
with certain
dyes

Reactive

Good to
very good
on most
fibres; poor
to moderate
on nylon

Good;
generally
sensitive to
chlorine
bleach

Not affected

Good

Pigment

Very good
to excellent

Good

Good, if
properly
bound

Good

85

Used for all fibres;

especially in printing.

Dyeing Machinery
Textile materials are dyed in various forms such as the following.

Loose stock (Loose fibre) Cotton, viscose staple fibre (sf), etc are commonly dyed as loose
fibre for the production of mlange yarn. This is yarn produced by spinning a mixture of raw
cotton and dyed cotton. A randomised coloured effect will be seen in the resulting yarn and this
is called the mlange effect.
Yarn (in the form of hank, cop, cheese, cone, warp, etc.) Different machines would be
required for dyeing these kinds of yarn.
Cloth (woven and knitted) Here also different machines are required for woven and knitted
fabric.
Garments These are dyed is special garment-dyeing machines.
The dyeing of different forms of textiles requires different kinds of machinery, since the method of
handling the material to be dyed varies from one form of textile to another. By adopting different
techniques of dyeing and different kinds of machinery, textile material can be processed by

Batch

Semi-continuous and

Continuous methods of dyeing

Fibre processing: Fibre processing is practised only rarely, for special

requirements, like the production of mlange yarn. The yarn package
dyeing machines of today have the required accessories like perforated
baskets, to accommodate fibre processing.
In such a machine, instead of the usual carrier for yarn packages, a
perforated basket is used to contain the fibre to be dyed. The basket has a
central tube which is also perforated, as shown in the figure.
The fibre is packed to uniform density in the annular space in the basket
and the process liquor is circulated alternately inside-out and outside-in in
the package dyeing machine until the treatment is complete. (Refer to
description of package dyeing machine below.)
Yarn Processing: Yarn has necessarily to be processed in batches, in the form of hanks or packages.
Warp sheets can be dyed in batch and continuous form.
For processing hanks, the following machines are used.
Open-beck dyeing machines - this has been described earlier (under vat dyeing).

Closed-beck dyeing machine e.g. the Hussong type this is not used much these days.

The cabinet dyeing machine these are of more recent origin.

For processing yarn in cone or cheese form, the cone or cheese dyeing dyeing machine is used and
for yarn in the form of a warp sheet, a beam dyeing machine or continuous dyeing range is used.
The Hussong dyeing machine
One of the oldest automated hank yarn
machines is the Hussong machine,
illustrated in the following figure. It
consists essentially of a frame carrying
poles on which the hanks are hung and
which can, when loaded, be lowered into
a rectangular vessel containing the dye
liquor. The liquor is circulated by means of
an impellor, which is kept away from the
yarn by a partition. When the impellor
rotates, it pushes the dye liquor down and
into the main yarn compartment through a
perforated false bottom located below the
suspended hanks of yarn.

A Impellor;
B Hank Rods; C Hanks
D False Bottom; E Steam Pipe
B

86

The impellor can be rotated in opposite directions alternatively so that the circulation is either from
below the false bottom upwards, and back into the impellor compartment over the top, or in the reverse
direction.
There is a steam pipe located at the bottom of the main dye vessel to heat up the process liquor when
required. The false bottom also serves to separate the steam pipe from the yarn.
As the operating principle here is one where dye liquor passes through a mass of yarn, the density of
yarn packing should be uniform. This is achieved by ensuring uniform packing of the yarn on the poles.
The skill and experience of the operator who loads the machine will also contribute to uniform dyeing.
During dyeing the direction of the flow must be alternated in a definite sequence. When the flow is in
the downward direction the liquor does not come into sufficiently intimate contact with the portions of
the hank upon the pole, and this would lead to poorly-dyed portions unless the yarn is lifted whilst the
flow is upwards. In practice the upward direction is used for the greater period of the dyeing cycle
because it lifts off the hanks from the perforated top of the poles, and enables the liquor to come into
uniform contact with every part of the yarn.
This type of machine has been used extensively for the scouring, bleaching and dyeing of cotton
hanks.
Cabinet dyeing machine
Cabinet dyeing machines are used for dyeing yarn in hank form. This machine is also used for all preand after-treatments such as scouring, bleaching, acidifying (neutralisation), washing, soaping, etc.
The machine is suitable for the application of most of the dye classes. It is generally used for dyeing
cotton, wool and high bulk acrylic yarns.
In the cabinet dyeing machine, the hanks hang on oval sticks in two or four compartments (the number
of compartments depends upon the capacity of the machine) and the liquor is circulated through them
by means of a special reversible propeller, which is located at the lower part of the main chamber of
the machine, as shown in the figure below. The speed of the impellor is adjustable to suit gentle
handling of fine or delicate yarn.
Reversal of the flow of liquor can be
effected automatically by means of a
special cyclic device with pre-selection
of times. An automatic temperature
controller or a completely computerised
programme with all pneumatically
activated valves for fully automatic
operation is available. Devices for
heating and distribution of the liquor are
also fitted in the lower part of the
cabinet.
A sampling device enables sampling to
be performed very easily and safely.
Sampling is done in all machines to dye
the bulk material to the right shade.

A Heat
Exchanger
B Dye Liquor
Cooler

C Impellor

D Expansion
Tank

E Static Pump

F Main Dye
Vessel with
two sets of
hanks

Provision is available in this machine for different spacing of the hank rods, making them suitable for
different reeling lengths and types of yarn.
Hydrostatic pressure and static pressure models are available for working temperatures up to 100C
and 108C respectively.
The M : L ratio is normally 1:15 or 1:20 depending upon the hank size. Cabinet hank dyeing machines
are available for dyeing hanks in three sizes of 54, 72 and 90.
Cabinet dyeing machines are available as single-tier and double-tier models
Single-tier machines are available for dyeing in capacities of 50 kg and 75 kg for cotton yarn. Doubletier machines are available for dyeing in capacities of 100 kg, 200 kg and 500 kg of cotton yarn.

87

Package dyeing machine

A package-dyeing machine can be used for the scouring, bleaching or dyeing of different kinds of yarn
packages, such as cops, cones, cheeses, etc. The machine used for a specific kind of package will
depend upon the shape of the package itself, e.g. a cop-dyeing machine can process only yarn cops.
However, in the modern package dyeing machines available today, cones or cheeses of yarn and even
hank yarn and loose fibre can be conveniently processed.
Principle of working
In a package dyeing machine, cones or cheeses can be loaded on a yarn package carrier that has a
base plate on which are mounted a number of perforated tubes around which yarn packages can be
pressed down. All the perforated tubes are connected through the base plate to a main tube through
which the dye or other treatment liquor can flow through under pressure. Dyeing is effected by forcing
the liquor through the packages, either in an inside-out direction or in the outside-in direction as shown
in the left-hand side of the figure that follows.
Major parts of a package-dyeing machine
The main parts of the machine are shown at the right-hand side of the figure.
a) There is a main dye vessel or metal kier into which a yarn package carrier can be loaded. The
treatment liquor containing chemicals or dyes or just water, can be pumped into the vessel via the
stock tank and the transfer pump. The turbo pump forces the liquor through the packages.
b) The liquor from the main kier passes into a heat exchanger via the top and then into an expansion
tank, from where it is circulated back into the main vessel via an injection pump. As explained
above, the circulation of the liquor can be adjusted to be inside-out or outside-in and this is done in
a systematic manner, for pre-set periods of time, so as to get even dyeing or processing results.
HTHP conditions are used in the machine, so temperatures of up to around 140C and pressures
well above the atmospheric pressure are possible.
K
L

E
D

I
G
H

Inside-out liquor flow in cheese dyeing

J
B

C
A - Dyeing vessel;
B - Turbo Pump
C Transfer Pump;
D Stock Tank
E Expansion Tank; F Injection Pump
G Water; H Hot Water

I Steam
J Steam Condensate
K Compressed Air
L Heat Exchanger

Outside-in liquor flow in cheese dyeing

The package-dyeing machine can be used for dyeing cotton or polyester/cotton or 100% synthetic
material like textured polyester or nylon yarn.
Fabric processing: This is achieved by batch methods and continuous methods. The machines used
for the batch methods are winch, jigger, padding mangle, beam dyeing machine, jet dyeing machine,
etc. All of these machines have been discussed in earlier sections. The continuous methods use the Jbox bleaching range, molten-metal dyeing range, the pad-steam-wash range, the thermosol range, etc.
These too have been described in the preceding sections.s

88