What Is The Need of Textile Chemical Processing?

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Textile Chemical Processing

1 WHAT IS THE NEED OF TEXTILE CHEMICAL PROCESSING?


In Textile Chemical Processing the chemical treatments are given to the fabric after
being manufactured. Actually the fabric coming from the loom is not having properties like
absorbency, softness etc and the most important is that the appearance of the fabric is dirty or
pale yellow; we cannot use it directly for making apparels or clothing. So, it is necessary to
go for chemical processing of the material to make it wearable.
The general sequence of processes carried out on gray cloth
Gray Inspection Stitching Mechanical Cleaning Singeing Desizing
Scouring Bleaching Mercerising Dyeing/Printing Finishing

2 GRAY INSPECTION
It is checked whether the grey fabrics are in
conformity with standards, and all weaving faults are
marked out. Fabric inspection involves three possible
steps: perching, burling and mending. Perching is a
visual inspection and the name derives from the
frame, called a perch, of frosted glass with lights
behind and above it. The fabric passes through the
perch and is inspected. Flaws, stains or spots, yam
knots and other imperfections are marked. Burling is
the removal of yam knots or other imperfections from
the fabric. The faults are then mended and any knots
in the material are then pushed to the back. Mending
is obviously, the actual repair of imperfections.
Knotting should be done carefully and thoroughly so
that the repair or holes is not visible.

3 STITCHING
After the goods have been inspected and checked they are classed in the grey room,
according to quality and stamped. Goods of similar weight, width and construction and the
goods which will receive a similar treatment are sewn together, end to end, by sewing
machines especially constructed for this purpose and each batch is given a number called lot
number. The fabrics are usually sewn on circular
machine. Stitching should be done in such a manner
that the creases in fabric at the time of stitching
should be avoided. The use of proper stitching
thread is necessary to avoid stitch marks during
colour padding. For heavy fabrics intended for
mercerizing and continuous operations, the seam
should be wider (15 mm) and stronger.
The pre-cleaning of grey fabrics may be carried
out in a separate unit just before cropping and
shearing operations. The purpose of brushing is to remove the short and loose fibres from the
surface of the cloth. It also removes husk particles clinging to the cloth. Brushing is mainly
done to fabrics of staple fibre content, as filament yams usually do not have loose fibre ends.
Cylinders covered with fine bristles rotate over the fabric, pick up loose fibres, and pull them
away by either gravity or vacuum. The raised fibre ends are cut off during shearing
operation. Brushing before cropping minimizes pilling.
Shearing is an operation consists of cutting the loose strands of fibres from either surface
of a fabric with a sharp edged razor or scissors. By manipulating the shearing it is also
possible to cut designs into pile fabrics. Good cropping is perhaps, the simplest way of
reducing the tendency of blended fabrics to 'pill'. In the case of cotton fabrics, in particular,
care should be taken to see that the shearing blades do not scratch the surface of the fabric,
which otherwise can cause dyeing defects during subsequent dyeing.

4 SINGEING
The objective of singeing is to remove projecting fibres or protruding fibres, which gives
it a fuzzy appearance, from the surface of the fabric so as to give it a smoother, cleaner
appearance. The reason for which singeing is necessary:

I. Singeing improves the end use and wearing properties of textiles.


II. The burning-off of protruding fibres results in a clean surface which allows the
structure of the fabric more clear.
III. Singeing reduces the fogginess caused by differing reflection of light by the projecting
fibre and the dyed fabrics appear brighter.
IV. Singeing is an effective means of reducing pilling in blended fabrics containing
synthetic fibres.
V. Unsinged fabrics soil more easily than singed fabrics.
VI. A closely singed fabric is essential for printing fine intricate patterns.
VII. Singeing process facilitates and speeds up desizing, if the fabric is impregnated with
desizing liquor immediately after singeing.

On the other hand there are singeing faults which are not visible and once occurred can no
longer be repaired. They are:

I. Uneven singeing effect can cause streaks when the fabric is dyed, or bubbles when the
fabric is finished.
II. In the cotton system singeing is done on the grey cloth, but for blended fabrics
containing synthetic fibres grey state singeing is not advisable because small globules
of melted synthetic fibres absorb dye preferentially, giving cloth a speckled
appearance.
III. There is a possibility of thermal damage to temperature sensitive fibres, for instance
polyester.
IV. Stop-offs can cause heat bars on fabrics. Creasing produces streaks which are
magnified when dyed.

Generally, singeing is done on both sides of the fabric. No chemical change occurs in the
fabric during singeing and the reaction is basically one of oxidation. Singeing and desizing
can be frequently combined by passing the singed cloth through the water bath which
includes enzymes. The enzymes digest the various sizing agents, making it easy to remove
them during the scouring operation.

4.1 SINGEING MACHINERY:


Singeing machineries are mainly based on direct and indirect singeing systems. The
direct singeing may be done either on a hot plate, or on a rotary cylinder, or on a gas singeing
machine or on a machine combining plates and gas burners. The special features of indirect
singeing systems are no flame contact, uniform singeing, heat retention zone and singeing by
means of heat radiations. The indirect system produces fabrics which have a softer touch as
compared to other methods. Gas singeing is more convenient, more economical and more
effective than other methods and is well accepted commercially. The plate singeing and
roller singeing machines are now out of date.

4.1.1 PLATE SINGEING MACHINE

Figure - A Plate singeing Machine with alternating arrangement


In plate singeing machine there are two curved Copper plates, 1-2 inches thick. These
Copper plates are set in the fire clay and heated to bright redness by the furnace below or by
suitable heating arrangement. The cloth in open width passes over and in contact with the hot
plates, at a speed of 135 – 225 m/min. Automatic transverse motion is fitted to the machine,
which constantly changes the part of the hot plate in contact with the fibre, to avoid the local
cooling and non-uniform heating of the plates.
The protruding fibres are burnt during the passage of the cloth through the machine.
However the fibres present in the interstices of the warp and weft are not singed. In this case,
as there is actual contact of the fabric with the hard hot surface of the metal, a certain amount
of lustre is impregnated in the cloth due to friction. The drawback of this machine is it may
not be possible to maintain plates at uniform temperature and this causes uneven singeing
which gives rise to faint streaks when the cloth is dyed.
4.1.2 ROLLER SINGEING MACHINE

Figure- A Roller Singeing Machine


The fabric is made to pass over, in contact with rotating cylinders. These cylinders are
made up of cast iron or copper and are heated by internal firing system. In this case, surface
temperature is more uniform than in the case of hot plates. However, the problem of local
cooling of the cylinder by contact with the cloth causes uneven singeing. The rotation of the
cylinder is in the opposite direction to the fabric movement, which erases the neps on fibre
ensuring an efficient singeing.
In this case also, the fibre present in the interstices of warp and weft are not removed
from the surface and the lustre is impregnated to the fabric due to the contact of the hot and
hard metal surface.
4.1.3 GAS SINGEING MACHINE
In this process, the fabric is passed rapidly over a row of gas flames at a high speed
and then immediately into the quench bath to extinguish the sparks. And cool the fabric. The
machine consists of one or more gas burners giving continuous flat or vertical flames. Here
the flame is produced by compressed air and coal gas. The flame is adjusted with respect to
the width of the fabric. The angle of the burners and the height of the flame can also be
adjusted. When the cloth is drawn over flame at a high speed, the protruding fibres burn
without damaging the cloth. The speed of transmission of the cloth through the singeing
machine has to be adjusted to suit the amount of singeing required without the risk of
burning the cloth.
The position of the burner must be taken into consideration according to the fabric to
be singed (Fig. 2-11). There are three different methods of applying flame to the material by
changing the position of the flame to offer:
Figure- Gas Singeing Machine
1. Tangential singeing Fig. 2-11 (a)
2. Singeing onto water cooled rollers Fig. 2-11 (b)
3. Singeing into the fabric Fig. 2-11 (c)
4.2 SINGEING OF DIFFERENT FIBRES MATERIALS:
In singeing the short fibres are burnt off from the surface of the fabric by direct or
indirect heating systems without damage to the cloth by scorching or burning. The thermal
behavior of different kinds of fibres is different and singeing at higher temperature is
naturally associated with greater hazards on excessive contact period and may cause thermal
degradation of the fibre.
In case of vegetable fibres, grey singeing is necessary as it leads to slight yellowing
which needs subsequent bleaching to get high degree of whiteness. Grey singeing is also
economical as singeing at any other stages of processing requires additional washing and
drying. Vegetable and regenerated fibres fabrics can be singed very strongly with maximum
burner intensity to obtain good results. Regenerated fibres normally bum to a little less easily
than natural fibres. Wool has poor combustion properties and are very sensitive to
temperatures and hence woollen materials are not subjected to intense flame like cotton. In
woolen fabric flame is not generally allowed to penetrate the material and this can be
obtained by blowing air through the fabric from the opposite side of the flame so that the
flame will be restricted only on the surface of the fabric. Alternatively, the fabric can be
guided to water cooled guide rollers allowing the flame to heat the cloth. When the flame
strikes the fabric it is reflected by air/steam cushion created within the material.
Amongst the synthetic fibres polyester has the greatest significance. It melts at 280°-
290°C but does not burn till about 500°C. 'Reflector' or 'refractory' singeing machines
produce smears of fused polymer on the surface of the polyester cloth and therefore
unsuitable for polyester material. Thus flame singeing machine with a powerful flame is
needed and also helps in overcoming the problems of oligomers i.e. the small chain polymers
that come to the surface. High temperature singeing process may sometimes change the
glass-transition temperature (Tg) of synthetic fibres that lead to uneven dyeing.
For blended fibre fabrics singeing conditions are to be selected depending on the
sensitiveness of the kinds of fibres to heat, blend composition, weight of fabric and fabric
geometry. For example, singeing should be carefully conducted to avoid heat damage of the
acetate component of the acetate/viscose blended fibre fabrics. Though singeing improves
the resistance to pilling of the polyester/wool blended fabrics, but should not be carried out
on low weight fabrics because of risk of damage. If singeing is carried out after dyeing the
sublimation fastness of disperse dyes used must be adequate to withstand the singeing
conditions.

5 DESIZING
The grey cotton fabric contains natural as well as those added to the fabric such as size
to facilitate weaving.
Size normally contains an adhesive (film former) and a lubricant. For cotton fabrics
the film former is usually starch or a starch derivative. All starches are, by their very nature,
either water-insoluble or only sparingly soluble. For viscose the most important sizing agent
is the cellulose derivative carboxymethylcellulose (CMC), which has good water solubility.
In addition to natural products, such as starch and starch derivatives, synthetic sizes based on
styrenemaleic acid copolymers, polyvinyl alcohol, polyacrylates or polyacrylamides are used
on polyester/cotton or polyester/viscose, as well as mixtures of starch and polyvinyl alcohol.
The synthetic polymer sizes and carboxymethylcellulose are also used on continuous-
filament warps made from acetate, triacetate, nylon or polyester. The lubricant in a size
formulation is usually tallow, but spermaceti, paraffin wax and mineral oils are sometimes
employed. These lubricants impart good smoothness and low frictional properties to the yarn
and are therefore beneficial for weaving, but they are insoluble in water and difficult to
remove from the fibre surface, which can lead to severe problems in desizing. Several
chemical manufacturers offer wax like products that are water-soluble for addition to size
formulations to improve suppleness and smoothness of the yarn; being water-soluble these
are relatively easily removed during desizing.
5.1 CONCEPT OF DESIZING
It is necessary to remove the size from the cloth; otherwise the hydrophobicity of the
wax and the tallow hinder subsequent dyeing and printing. Waxes and tallow are removed in
the later (scouring), while the starch is removed during desizing. Desizing is the term usually
restricted to the removal of starch from the fabric.
Chemically starch is poly-α-glucopyranose in which straight chain (amylase) and
branched chain (amylopectin) polymers are present. These are shown in Fig.

Both of these components of starch are insoluble in water, but they can be solubilised
by hydrolysis of these long chain compounds to shorter ones. The hydrolysis of starch takes
place in following stages.
Starch (Insoluble) Dextrin (Insoluble) Soluble dextrin (soluble)
Maltose (soluble) α-glucose (soluble)

For the desizing purpose the hydrolysis is carried out up to the stage of soluble dextrin
only not to further to α-glucose, because our aim of desizing is to make the size material
soluble.
5.2 CLASSIFICATION OF DESIZING METHODS
The desizing methods can be classified as in
5.2.1 HYDROLYTIC DESIZING

5.2.1.1 Rot steeping


This is the oldest and cheapest
method of desizing. The main feature of this
process is that no special chemicals are
required. The cloth is first impregnated with
warm water (at 40°C) through a padding
mangle and then squeezed to about 100%
expression. One of padding mangle used is
shown in figure. The cloth is then allowed
to stand for days in pits or cemented tanks.
The micro-organisms, naturally present in
water multiply and secrete starch liquefying
(hydrolysing) enzymes which solubilise the starch present in the size on fabric. The cloth is
finally washed with water to remove the starch. The main disadvantage of this process is that
it is a slower process and requires an enormous floor space for storing water impregnating
cloth.

5.2.1.2 Acid Desizing


The cloth from the singeing machine is impregnated through a solution of dilute
sulphuric acid or dilute hydrochloric acid (0.25% owf), followed by batching for about 8 -12
h. At first sight the use of acid could appear to be dangerous, since conditions, which degrade
starch, are those on which cellulose is also liable to be attacked. Since the hydrolysis of the
starch is exothermic reaction, the temperature of the desizing bath may rise to higher side,
even to 50C, but at this temperature dilute acid solution doesn’t attack or hydrolyze
cellulose. But if the cloth impregnated with dilute mineral acid solution is exposed to the air
during the storage period, localized drying due to evaporation cause increase in the
concentration of acid at that portion and if the concentration is sufficiently high cellulose is
hydrolysed. To avoid this, moistened jute cloth is placed over impregnated fabric. A
subsequent washing after acid treatment completely removes the starch.
Water and aqueous acid extract significant quantities of the impurities. They not only
degrade starch-based product but also offer the advantage of removing Ca and Mg salts from
the cotton fabric. The concentration of the acid can be as high as 2 % for short times and as
low as 0.2 % for overnight stripping.

5.2.1.3 Enzymatic Desizing


The most effective way of removing starch from fabrics is by the use of extracts
containing appropriate enzymes. An outstanding feature of enzyme desizing is the specific
nature of the enzyme action. Enzymes are biocatalysts; they differ from normal chemical
catalysts because they are very specific in their action, are thermo-labile, have relatively low
energies of activation and are usually active only over a narrow range of pH. They are
classified by the names of the substrate they decompose, e.g. amylases degrade amylose,
proteases to proteins, and cellulases to cellulose.
Some properties of enzymes are as follow:
1) Enzymes are complex and high molecular weight protein molecules. Chemically

-amylase is about 100,000.


enzymes are proteins of high molecular weight e.g. molecular weight of the enzyme

2) Enzymes are susceptible to high temperature and pH values outside their optimum
ranges because they can be denatured. Still, most enzymes function best at or near the

is reduced. One exception is -amylase from bacteria, which may under some
neutral point at temperatures between 40-60C; above these temperatures, the activity

circumstances, be used at temperatures in excess of this. The different preparations are


applied under different conditions.
3) Enzymes react at specific parts of the substrate molecule because these are specific to
their action.
Desizing enzymes may be classified based on the source from which they are obtained as
in fig.
Desizing Enzymes

Animal Based Vegetable Based


Examples
Viveral
WASTE PANCREAS Malt Extracted Bacterial
Degomma
Slaughter house Examples Examples
Clotted blood etc Diastofar Biolase.
5.2.2 OXIDATIVE DESIZING

5.2.2.1 Chlorine desizing


The active agent in case of chlorine desizing is gaseous chlorine. For the Cl2 desizing,
open width cloth is impregnated with water and squeezed at required percentage expression.
The squeezed fabric is passed through a chamber, which is provided with a false bottom,
through which Cl2 gas is passed. In this case Cl2 reacts with water present in the cloth
producing nascent oxygen and this nascent oxygen attacks starch, there by solubilizing it.

Cl2 + H2 O  2HCl + [O]


Since cellulose is difficult to oxidize than starch, the oxidation of cellulose is
prevented or minimized by controlling the quantity of Cl2 gas passed and time of contact.
The Cl2 gas may be replaced by dilute hypochlorite solution of 1-2 g/l available Cl2. For this
sodium hypochlorite (NaOCl) or bleaching powder (CaOCl2) is used. For this method the
cloth is impregnated with bleaching solution at 30C (room temperature), squeezed and
allowed to stand for one hour at room temperature. It is then washed and afterwards antichlor
with HCl.

5.2.2.2 Sodium chlorite desizing


In this method Sodium chlorite (NaClO2) is used under acidic condition for oxidizing
the starch present in the grey cloth. Sodium chlorite in the presence of ammonium sulphate
gives good desizing efficiency. Sometimes pH of desizing bath may be adjusted between 4 -
4.5 with the help buffer of Sodium acetate and acetic acid. Cotton fabric is padded at room

and 10 g/l ammonium sulphate and 1g/l of wetting agent. Then fabric is heated to 80-90 C
temperature with an expression of 100% with an aqueous solution of 15g/l Sodium chlorite

for 1 hour. Then it is washed and neutralized.

5.2.2.3 Bromite Desizing


Sodium bromite, is used for the desizing is a salt of bromous acid, HBrO2 (like sodium
chlorite, the salt of chlorous acid, HClO2). This has a powerful oxidising action on the starch.
This is due to the combined effect of bromous acid, HBrO2 and hypobromous acid, HOBr.
This is accompanied by the conversion of bromine dioxide into oxygen and bromine.
Hydrolysis of this bromine produces more hypobromous acid and the nascent oxygen
generated is responsible for the oxidation of starch.
There are different methods of oxidation, but the most likely one is the breaking of
most stable ether linkage of the glucose ring by sodium bromite.
As shown above by the oxidation the ether group converted to aldehyde and then
further to carboxylic acid which lead to reduction in D.P of starch and convert to water
soluble products.
In another mode of oxidation of starch, the opening of the glucose ring by rupture of
C2-C3 link takes place that lead to formation of a dialdehyde. The dialdehyde formed is not
soluble in water, but soluble in hot alkaline solution.

Hence the sodium bromite treatment should be followed by a hot alkaline treatment
with or without an intermediate rinsing operation. On the other hand sodium bromite
treatment also reduces the natural impurities present in the material mainly oxidise the some
of the natural colouring pigments present which lead to the reduction in the chemical
requirement for bleaching.
The general process with sodium bromite involve the padding with liquor contains,
0.3 % sodium bromite, a wetting agent and stabiliser at room temperature. The long padding
time is required for 6-20 min. The pH is the most important factor in this case, the pH should
be around 10, and below pH 9 the decomposition of bromite is rapid. While above pH 11 the
oxidation of starch is very slow. Temperature more than 40°C leads to degradation of
cellulose. Then after storage for desired treatment time fabric is washed and treated with hot
sodium hydroxide solution to remove the converted starch completely.
5.3 TEST FOR DESIZING EFFICIENCY
After the desizing by any of above methods, we now go for checking how far our
purpose is achieved or not. We can check the desizing efficiency both quantitatively as
qualitatively. The quantitative method to check the desizing efficiency is the weight loss.

6 SCOURING
The desizing process is actually a destarching process because in this the starch present
on warp yarns is liquefied by either hydrolytic or oxidative reaction and removed in
subsequent washing step. But after desizing the fabric still contains fats and waxes (both
natural as well as added), which adversely affect the absorbency of the fabric. These
impurities are removed from the fabric by the process of “Scouring”.
Thus the main purpose of scouring cotton fabric is to remove the natural as well as added
impurities of essentially of hydrophobic nature as completely as possible and leave the fabric
in highly absorptive state without undergoing a significant chemical or physical damage.
The scouring process is done by boiling the fabric in an alkali solution. The main
processes occur during scouring are:
I. Saponification of oils present in the fibre.
II. Waxes and unsaponifiable material is removed by emulsification of the same.
III. Pectins are changed into their soluble salts of pectic acid.
IV. Mineral matters are dissolved.
V. Proteins are hydrolysed into degradation soluble products.
VI. Dirt or dust is removed and held in a stable suspension by the detergents present in the
scouring bath.

1. Vegetables oils, animal fats and mineral oils are not soluble in water. Thus when grey
cotton fabric immersed into water, the oil present in cotton will not allow the water to
spread on the fibres. These vegetable oils are glycerides of fatty acids like stearic acid,
palmitic acid, and oleic acid. When such oils are heated with NaOH the oil splits into its
constituents fatty acids and glycerine, out of which glycerine is water soluble. The fatty
acid again react with NaOH to form its sodium salt i.e. soap which is also soluble in
water. That’s why this reaction is called saponification. Thus the saponification reaction
converts the insoluble and water immiscible oil is converted to water-soluble products.

CH2 – OOC - C17H35 CH2 – OH


CH – OOC - C17H35 CH – OH + 3C17H35 - COOH
CH2 – OOC - C17H35 CH2 – OH
Tristearin (Glyceride of stearic acid) Glycerine stearic acid
2. The waxes present in the cotton as well as in size formulations cannot be removed by
saponification. Waxes are esters of high molecular weight fatty acids and alcohols. The
waxes and lubricating oils are not converted into their soluble products. They are
therefore removed by emulsification.
3. The Pectin substances are present in the cotton in the form of insoluble salts of Calcium,
Magnesium and Iron. These bivalent metal salts are solubilized in alkaline solution.
Pectic acid is a compound of high molecular weight containing carboxylic group for
every 6 Carbon atom. It is insoluble in water but soluble in alkaline solution.
4. The quantity of inorganic matters is in the range of 0.7- 0.6% by the weight of anhydrous
cotton. The main constituents are Na2C03, K2O, Na2O, K2CO3, CaO, and CaCO3. 85% of
these materials can be removed by simply boiling with water. Phosphorous present in the
form of organic and inorganic compounds which are mostly soluble in hot water and
which can become insoluble in the presence of alkali earth metals. Therefore use of hard
water during scouring can precipitate alkali earth metal phosphate, which can get
deposited on the surface of the fibre instead of getting eliminating from it.
5. The scouring process requires use of soft water because the use of hard water would
cause precipitation or insolubalizaion of soap. It must be considered that cotton fibre
contains Ca and Mg salts (pectin salts) which are freed during alkali treatment and can
also contribute to the insolubility of soaps and at the same time remains attached to the
fabric in the form of hydroxides. Thus they might disturb subsequent operations such as
bleaching, dyeing and printing. It is therefore necessary to add sequestering agents
(chelating agents or metal complexing agents e.g. Nitrilo Triacetic Acid (NTA), EDTA,
gluconic acid. Sequestering agents also help in the elimination of iron, which can give
problems during subsequent bleaching with hydrogen peroxide.
6. Cotton proteins consist of protoplasmic residues. Proteins are mainly concentrated in the
primary wall. The known colour, which appears during scouring, could be due to the
reaction between proteins and carbohydrates in the alkaline medium.
7. During scouring some dust, dirt and solid particles are loosened from the fabric. These
particles leave the fabric and enter into the scouring bath but again get deposited on other
parts of fabric/fibres. So to remove these particles and to keep this in suspension or
dispersion form, detergents are added in scouring bath.

A detergent is a good wetting agent. If the detergent is used in scouring bath another wetting
agent need not be added to the scouring bath.
Therefore, there are three components in a cotton scouring bath: caustic, to swell and
dissolve the motes and to saponify oils and waxes, surfactant, to lower the bath's surface
tension so it can wet-out the fabric faster and to emulsify oils and waxes and chelating agent,
to form water dispersible complexes with heavy metals.
6.1 GENERAL RECIPE FOR SCOURING:

7 BLEACHING
After the removal of the waxes and other hydrophobic type of impurities from grey
fabric by the desizing and scouring the fabric is now in a more absorbent state. But still have
the pale appearance due to the presence of natural colouring materials like pigments etc.
these pigments can not be removed the only way to tackle these pigments is to decolourise
them using suitable oxidising agents. This will make the fabric in a super white form. This
process of decolouration of natural pigments is called the bleaching. The process of
bleaching gives a sparkling whiteness to the fabric and hence makes it suitable for further
processing.
7.1 METHODS OF BLEACHING
The various chemicals employed to carry out bleaching process are:
1. Dilute hypochlorite solution preferably Sodium Hypochlorite (NaOCl)
2. Hydrogen Peroxide (H2O2) solution
3. Sodium Chlorite (NaClO3) solution
4. Certain peroxy compounds like peracetic acid
5. Potassium Permanganate (KMnO4) solution

Now we discuss the effect of different bleaching agents under various conditions of
concentration, pH, temperature, time and activators. So that we can choose optimum
conditions of bleaching with a particular bleaching agent.
7.1.1 SODIUM HYPOCHLORITE BLEACHING:
It is done by using sodium hypochlorite (NaOCl) as a bleaching agent. This process is
also known as chemicking. NaOCl is a highly unstable compound at normal conditions of
temperature and pH. It doesn’t exist as solid form. As it is highly unstable so it undergoes
self decomposition by the following reactions:
2NaOCl NaCl + NaClO2
3NaOCl 2NaCl + NaClO3
2NaOCl 2NaCl + O2
The bleaching mechanism of sodium hypochlorite consists of the following reaction:
NaOCl NaCl + (O)

The bleaching action of sodium hypochlorite depends on several factors the most
important of which is the pH. The pH of solution highly influences the action of bleaching
agent. Because the hypochlorite ionize differently under different pH conditions and active
component can be affective in these different stages are:
1. At pH greater than 8.5 the hypochlorite is present as NaOCl.
2. Between pH 5 and 8.5 the solution consists of predominantly the hypochlorus acid
(HOCl).
NaOCl + H+ HOCl + Na+
3. As the pH falls below 5 the liberation of chlorine takes place and when the pH falls
below 3 the whole HOCl converted into chlorine.
In the region of pH -7 hypochlorous acid
and hypochlorite are present in
approximate same concentrations the rate
of attack on cellulose is greatly enhanced.
As the pH falls below 5 the liberation of
chlorine takes place which pollutes the
environment and corrode the container. In
the pH region above 8.5 (in between 9 to
11) very little changes occur in cellulose
i.e it is the normal working range for
hypochloride solution. Thus the suitable
pH range for sodium hypochloride
bleaching is the 10-11. Now the other
factor which affects the efficient
bleaching after pH is the concentration.

Generally the concentration of NaOCl which give 2-3 g/l available chlorine is
enough. The variation of rate of oxidation with change in concentration of NaOCl shows that
there is a continuous steep increase in the bleaching action until the concentration is 5 g/l
available chlorine. The concentration giving more than 5 g/l available chlorine has negligible
change in the rate of oxidation. Commercially the concentration should be such that the
available chlorine should be 2-3 g/l.
The other important factor considered for efficient bleaching is the temperature. The
NaOCl bleaching should always be carried out at room temperature. The elevated
temperature causes a rapid oxidation which may cause even tendering of the fabric. Also the
variation of rate of oxidation with temperature is more prominent at higher concentration of
NaOCl.
Longer the treatment time larger is the oxidation of material and our aim to achieve
good whiteness with minimum damage to material. Generally a solution containing 2g/l
available chlorine requires 2 hours for good whiteness; the same effect can be obtained in 80-
90 mins by using solution of 4g/l available chlorine.
General Recipe:
Concentration - 2-3 g/l available chlorine
pH - 10-11
Temperature - Room temperature
Treatment time - 2 hours

7.2 HYDROGEN PEROXIDE (H2O2) BLEACHING:


The bleaching process carried out by NaOCl is known as Half bleach because the
whiteness obtained is temporary not permanent. So, the hypochlorite bleaching should
followed by another bleaching treatment. Now instead of NaOCl, strong oxidising agent
H2O2 is used to carryout bleaching. This bleaching with H2O2 called as full bleach because
the whiteness obtained is permanent. Properties of H2O2


It is a colourless syrupy liquid


It is absolutely stable under acidic conditions


It is sensitive to sunlight.


It decompose if allow to react with heavy metals.
It is highly unstable to alkali like NaOH, Na2CO3, rapidly decomposition takes place.
2 H2 O2 2 H2O + O2
Concentration of H2O2 the concentration of H2O2 is expressed in terms pf Volumes.
This volume means the volume of O2 gas in ml liberated by complete decomposition of 1 ml
of H2O2 solution at NTP.
2 H2 O 2 2 H2 O + O2
2×34 gm 32 gm at NTP
2×34 gm 22.4 ltr at NTP
34 gm 11.2 ltr at NTP
34% H2O2 solution 100ml 11.2 ltr
34% H2O2 solution 1ml 112 ml of O2 at NTP

7.2.1 MECHANISM OF PEROXIDE BLEACHING


Though hydrogen peroxide is stable in acidic medium, but bleaching occurs by the
addition of alkali or by increased temperature. Hydrogen peroxide liberates perhydroxyl ion
(HO2-) in aqueous medium and chemically behaves like a weak dibasic acid. The
perhydroxyl is highly unstable and in the presence of oxidisable substance (coloured
impurities in cotton), it is decomposed and thus bleaching action takes place. Sodium
hydroxide activates hydrogen peroxide because H+ ion is neutralized by alkali which is
favorable for liberation of HO2-.
H2O2 + NaOH H2O + HO2-
However, at higher pH (above 10.8) the liberation of HO2- ion is so rapid that it
becomes unstable with the formation of oxygen gas which has no bleaching property. If the
rate of decomposition is very high, the unutilized HO2- may damage the fibre. A safe and
optimum pH for cotton bleaching lies between 10.5 to 10.8 where the rate of evolution of
perhydroxyl ion is equal to the rate of consumption (for bleaching). At higher pH, hydrogen
peroxide is not stable and hence a stabiliser is frequently added in the bleaching bath.

The process of regulation or control of perhydroxyl ion to prevent rapid


decomposition of bleach and to minimize fibre degradation is described as stabilisation.
Stabilisers for peroxide normally function by controlling the formation of free radicals. These
are complex blends of a selection of materials serving a number of functions. They could

 Alkali, e.g. caustic soda/carbonate/silicate.


include any of the following:

 Dispersant, e.g. acrylates/phosphonates.


 Sequestrants, e.g. EDTA/TPA/gluconates.
 Inorganics, e.g. magnesium salts.
 Colloid stabilisers, e.g. acrylic polymers.

The selection of alkali to be used in peroxide bleaching is dependent on the fibres or


blends being bleached. Sodium silicate is the most conventional, easily available and widely

 Act as a stabilizer
used stabiliser. This sodium silicate act as a multifunctional agent:

 Keeps the metal ions away i.e. act as sequestering agent


 It also acts as a buffer and maintains the alkaline pH.
Actually sodium silicate itself not acts as a stabilizer instead it reacts with MgCl2 present
in water thereby giving MgSiO2 which act as a stabilizer.
Though sodium silicate works as multifunctional agent but now days avoided to use as
a stabilizer. This is due to the following disadvantages associated with the use of silicate:
 The removal of silicate after bleaching is difficult.
 There are several compounds are formed by action of sodium silicate which are also

 During dyeing some light spots are formed on fabric containing traces of sodium
difficult to remove.

silicate. This is due to the presence of sodium silicate.


So, instead of sodium silicate we prefer to use newly developed organic stabilizers known as

 Amino-polycarbonic acid
(Stabilizer-NS) Non silicate stabilizer. Commonly used organic stabilizers are:

 Aliphatic acids
 Aldoamines etc.
7.2.2 GENERAL RECIPE OF H2O2 BLEACHING:
H2O2 Concentration - 2-4%
Sodium silicate - 0.5-1%
NaOH/Na2CO3 - 0.5-1%
Sequestering agent - 0.1-0.3%
pH - 9.5-10.5
Temperature - 80-85°C
Time - 90 mins

7.3 COMPARISON OF HYPOCHLORITE AND PEROXIDE BLEACHING:


H2O2 Bleaching Sodium Hypochlorite Bleaching

Peroxide is universal bleaching agent can be It is mainly used for cellulosic fibres not for
employed to wool, silk as well as cotton. protein fibres like wool, silk.

Peroxide is milder agent so degrading affect Hypochlorite is having degrading affect on


on cellulose is less. cellulose.

Peroxide also gives mild scouring action so It doesn’t give any scouring action.
simultaneous scouring and bleaching is
possible in continuous process.

It doesn’t affect the coloured material so it It can’t be used over coloured material.
can be used for coloured materials.

With H2O2 there is no need of danger of There is a problem of corrosion and


equipment corrosion and no unpleasant unpleasant odours.
odours.

Only rinsing after bleaching is sufficient Hypochlorite bleaching needs an antichlor


treatment.

Bleaching with peroxide is a costlier than Relatively it is less costly.


hypochlorite.

Hydrogen peroxide bleaching requires No such need of stabilizers in hypochlorite


stabilization usually with silicates which bleaching.
have problem of stains on subsequent dyeing.

7.4 SODIUM CHLORITE (NACLO2) BLEACHING:


Besides NaOCl and H2O2 we may se sodium chlorite (NaClO2) as a bleaching agent.
NaClO2 is a stable compound under alkaline or neutral conditions but it rapidly decomposes
under acidic conditions giving the chlorine dioxide ClO2 which act as oxidising agent.
ThisClO2 act as a bleaching agent. But we often avoid using sodium chlorite bleaching
because: NaClO2 have a corrosive action on the equipment and the ClO2 liberated have a
obnoxious smell.
5 NaClO2 + 4HCl 4 ClO2 + 5 NaCl + 2 H2O
In the past time the NaClO2 was used for bleaching only synthetic materials like
polyester, nylon etc. due to which this bleaching process also known as Synthobleach.
Treatment conditions for sodium chlorite bleaching are:
Temperature - 95°-100° C
pH - 10-11
Treatment time - 1-2 hours

7.5 BLEACHING OF WOOL AND SILK:


Scoured Wool varies in shade from the light cream of wools considered to have good
color to discolored The main problem is that the whiteness of wool attained during bleaching
is not permanent. Wool tends to yellow over a period of atmospheric exposure of
approximately six months. Amongst the oxidising agents hydrogen peroxide is most
commonly used because sodium hypochlorite gives a deep rust color and sodium chlorite
develops pink coloration on wool. Traditionally wool is bleached by oxidative processes
either in the presence of alkaline stabiliser or under acidic condition of hydrogen peroxide

In the alkaline condition, wool is treated at pH 8-10 with a 1.5-3 volume solution of
hydrogen peroxide containing 2-3 g/1 stabilizer, which may be sodium silicate or sodium
pyrophosphate. Bleaching may be carried out at 50°C for 3 to 5 h and then rinsed, treated
with dilute acetic acid and rinsed again. The level of whiteness can be controlled by
concentration of hydrogen peroxide, length of treatment time, pH and temperature of
treatment bath.

7.6 BLEACHING OF VISCOSE:

Filament viscose rayon may not require bleaching since this is normally carried out
during manufacture. However, viscose in staple form requires bleaching as it may not
necessarily include a bleaching treatment during its manufacture. The same reagents as those
used for bleaching linen and cotton fabrics are useful for these fibres. For very good
whiteness, rayon may be bleached on a jigger with alkaline hypochlorite or combined scour
and bleach using hydrogen peroxide (up to 1 vol. strength) containing sodium silicate and
alkaline detergents-at a temperature of about 70°C.

7.7 BLEACHING OF BLENDED FIBRE FABRICS:


7.7.1 POLYESTER/CELLULOSIC BLENDS:
Polyester fibre in blends with cellulosic fibres in the ratios of 65/35 and 50/50 are
common construction. When cellulose portion is rayon, the blends rarely require bleaching,
but when cotton is present bleaching is usually necessary. Bleaching treatments of such
blends are normally required to remove the natural colours of cotton, sighting colours and if
the polyester portion is turned yellow at the time of heat-setting operation. Chlorine
bleaching, peroxide bleaching and chlorite bleaching are employed widely. If the polyester
portion requires bleaching, then chlorite bleaching is used, as this bleaching agent bleaches
both polyester and cellulose. If the polyester portion does not need bleaching, then peroxide
bleaching is more convenient. Alkaline hydrogen peroxide bleaching is the most preferred
system for polyester/cotton blends.

7.7.2 POLYESTER/WOOL BLENDS:


In general, blends containing wool and polyester fibres can be bleached with hydrogen
peorxide either in acid or alkaline medium without risks of damage. In acid medium, the
fabric is treated with a solution containing 30-40 ml/l H2O2 (35%), 2-4 g/1 organic stabilizer,
0.25 g/1 wetting agent and 0.25 g/1 detergent at pH 5.5-6 (acetic acid) for 40-60 min at 80°C
or 2-2.5 h at 65°C. The treated fabrics are then given warm and cold rinse. In alkaline
medium, the bath comprises of (35%), 30-40 ml/l H2O2; sodium pyrophosphate, 2-4 g/l;
ammonia to maintain the pH 8.5-9. The bath is set at 40°C and the goods are treated for 2-4
h, and rinsed well in warm and cold water.

7.7.3 NYLON/CELLULOSIC BLENDS:


Blends of nylon and cellulosic fibres may be bleached with either H2O2 or NaClO2
H2O2 does not bleach nylon and normal methods of bleaching degrade nylon. Blends
containing 30% or less of nylon may be bleached by the continuous H2O2 method, and in
such cases cotton will absorb the peroxide preferentially and so protect the nylon from
damage. The goods are entered into a bath containing 2-3 volume H2O2, 1 g/1 sodium
hydroxide flake, 0.2 g/1 peroxide stabilizer, 0.25 g/1 sequestering agent at 40°C the
temperature is raised to 85°C and then the treatment continued for 1 h. The treated goods are
then cooled and rinsed thoroughly. Hypochlorite does not damage nylon but it has got no
bleaching action on it. Sodium chlorite causes no degradation of either cellulosic or
polyamide and is a better bleaching agent the fabric is treated with a solution containing
sodium chlorite (2-5 g/l) at pH 3 to 4 at 90°C for 11/2 to 2 h. This is followed by a treatment
in a 2 g/1 solution of sodium carbonate at 40-50°C and finally hot and cold rinses are given
in water.

7.7.4 NYLON/WOOL BLENDS:


It is difficult to bleach this blends since the method normally used for nylon degrade
wool. Alkaline H2O2 bleaching always damages the polyamide fibres to some extent. Normal
alkaline H2O2 bleaching process may be used with safety on blends containing up to 25%
polyamide, but acid bleach must be used when proportion exceeds this figure. The fabric can
be bleached with a solution containing 12-15 ml/1 H2O2 (35%); 2 g/1 tetrasodium
pyrophosphate, 1 g/1 EDTA (30%) at 60-65°C for 45-60 min and then rinsed well in water.

7.8 DETERMINE THE BLEACHING EFFICIENCY:


7.8.1 ABSORBENCY TEST:
The simple test of measuring the absorbency of sample consists of allowing a drop of
water to fall from a fixed height (2.5 cm) on to the conditioned fabric sample, which is
mounted on an embroidery frame of about 6 inches diameter. A stop watch is started as soon
as the drop falls on the fabric and stopped as the water drop is completely absorbed by the
fabric. This complete absorption of drop is ensure by appearance of a dull spot on fabric i.e.
the reflected light disappear from the edge of drop. This time is termed as the absorbency
time.
Yet another method for absorbency test is the measurement of the time required for
the sample of about 1 inch size to sink in water, termed as sinking time. A drop absorbency
or sinking time of about 5 sec is generally considered satisfactory for well prepared fabric.
In case of synthetic fabrics or their blends the above test methods are not applicable
and for such materials strip test is used. In this we measure the height of water raised by
capillary action in the fabric. In his test method a 5cm wide strip is cut across the filling
direction. Then numbers of these strips are immersed 1mm deep in 1% aqueous solution of
C.I. Direct Blue 86 for 2 sec and then immediately placed on wire screen. After drying, the
capillary rise of dye solution is measured.
7.8.2 WHITENESS:
Whiteness is related to the luminosity as well freedom from yellowness. It is measured
by measuring the reflectance of the specimen against a standard white (magnesium oxide/
ceramic) tile which represents a whiteness value of 100.
7.8.3 CUPRAMMONIUM FLUIDITY:
This test indirectly measures the chemical degradation of cotton cellulose during pre-
treatment process. The principal of this method is based on the fact that the damaged
cellulose has lower M.W due to less DP. So the solution of damaged cellulose will be less
viscose and have more fluidity as compare to undamaged one. In this test, the conditioned
cotton sample is exactly weighted and dissolved in cuprammonium hydroxide solution. The
flow time of this solution between two fixed mars on a calibrated viscometer (fluidity tube) is
measured at a specific temperature. The fluidity value, F is calculated from F= C/t, where
“C” is viscometer constant and “t” is flow time. The results are expressed as Rhes (poise-1),
which is reciprocal of unit of viscosity. Fluidity value of 5-8 is considered satisfactory for
normal bleached cotton fabric.

8 SILK
8.1 DEGUMMING OF RAW SILK
Degumming is at the heart of wet processing of raw silk. The main purpose of the
degumming process are to remove the Sericin from the fibre, to remove some impurities (e.g.
waxes, fats, mineral salts) affecting both the dyeing and printing processes, to make the fibre
highly absorbent for dyes and chemicals and to reveal the lustre of fibroin and to improve the
appearance of the fibre. The fact that the raw silk contains two components fibroin and
Sericin, which covers the filaments. Sericin contains some impurities, for example, waxes,
fats, mineral salts and pigments. Sericin has the same amino acid residues, as fibroin but the
proportions contained in both components are quite different. As a result of this, the
degumming process must be carefully carried out on silk in the appropriate conditions
otherwise the fibroin may be damaged. The pH range from 4 to 8 is normally safe for fibroin
and it has been found that alkaline conditions are less harmful to fibroin than acid conditions.
In contrast to fibroin, the solubility of Sericin is very high at pH values between 1.5 and 2
and between 9.5 and 10.5. The Sericin is removed from the fibre but the fibroin must not be
damaged
Table - Composition of raw silk
Fibroin 70-80%
Sericin 20-30%
Carbohydrates 0.7%
Wax materials 0.4-0.8%
Inorganic matter 0.6%
Natural pigments 0.2%
There are 5 ways of Degumming silk
8.1.1 DEGUMMING WITH WATER UNDER PRESSURE AT 115C
Water at room temperature does not dissolve silk but silk is highly susceptible to dissolution
in boiling water. For complete removal of Sericin, in case of cultivated varieties of silk, it is
necessary to extract the silk yarn with water at 120C for 4 hours. For this reason, this
process gives a risk of fibroin being damaged when the time of treatment is prolonged. This
process needs large autoclaves to treat the fibre in silk industry. A further disadvantage is
that this process gives incomplete degumming and sometimes soap or synthetic detergent
must be added to improve the degumming effect. Therefore this process is very difficult to
control and now it is not used in silk industry in order to remove Sericin from silk.
8.1.2 DEGUMMING WITH SOAP (AT 98C)
Different soaps like olive oil, palm oil can be used for degumming. Marseilles soap, an olive
oil soap, is an outstanding soap for degumming because of its high degree of hydrolysis
which gives better lustre. For example, this process may be carried out using 10 – 20 g/l soap
at 92 – 98 C for 2- 4 hours adjusted pH to 10.2 – 10.5 in order to react effectively upon the
sericin.
The degumming action of the soap is due to alkali formed, which forms a chemical bond
with Sericin and produce soda salt, on the hydrolysis of the soap. The Sericin, in the form of
soda salt, is separated by soap and dissolved in water due to the emulsification action of
soap. The quantity and type of soap required degumming generally depends upon the nature
and type of silk.
Disadvantage of soap degumming are
The process requires soft water. The metallic ions such as Ca and Mg combine with soap and
produce insoluble metallic soap, which deposits on fibre and reduces the lustre of fabric.
Combination of soap and alkali accelerate the process.
As a result of the high temperature, this process tends to attack both sericin and fibroin
because of the sensitive nature of fibroin itself and chemical similarity of fibroin and sericin.
8.1.3 ALKALI DEGUMMING
Alkalis hydrolyse protein by attacking the peptide bonds and are said to have severe
damaging effect on proteins. Hence, this process has to be carried out under controlled
condition, so as not to result in over degumming. For this process, pH should be maintained
between 9.5-10.5. Below pH 9.5, rate of degumming is too slow causing prolonged exposure
and hence mechanical damage. Above pH 10.5 there is a danger of fibroin being attacked.
Alkalis used for degumming are caustic (NaOH), caustic soda (Na2CO3), sodium bicarbonate
(NaHCO3), K2CO3, Na2SiO3, trisodium phosphate, sodium phosphate, borax and ammonia.
Among these caustic soda is the most preferred alkali. Alkali is rarely used alone, since it
leaves the silk rather harsh in handle and it is recommended to use buffer system. Hence
caustic soda and sodium bicarbonate is the widely used buffer.
The optimum concentrations are: Na 2CO3 – 1.06%
NaHCO3 – 0.84%
Non-ionic surfactant – 0.3%

Degumming can be carried out at 100C for 2 hours with MLR 1:40.
8.1.4 ACID DEGUMMING
It is comparatively safe method, as the action of organic acids was reported to be much less
pronounced on silk than that of mineral acids. Different acids used for degumming are Lactic
acid, Tartaric acid, Oxalic acid, Succinic acid, Citric acid. Degumming is carried out with
0.05 moles/L acid and 3g/l non-ionic surfactant at 100C for 60 min. considering the weight
loss and tenacity the best result are obtained with succinic acid and monochloro acetic acid.
8.1.5 ENZYMATIC DEGUMMING
Enzymes are proteins, catalysing a specific chemical reaction, which are known as ‘bio-
catalysts’. They work at atmospheric pressure and in mild conditions (e.g. at 40C, pH 8.0).
Trypsin, papain and bacterial enzymes are the main types of enzymes for silk degumming.
These enzymes are called ‘proteases’ because they degrade and their degradation products
are polypeptides, peptides and other substances by hydrolysis of the –CO-NH- linkage.

Proteolytic enzyme action on protein


Enzymatic degumming has the following advantage over the conventional degumming with
alkaline soap.

 It has a specific reaction thereby it may give a minimum damage to fibroin.


 It has a lesser risk of over degumming than alkaline soap degumming,
 Weight loss can be easily modified by adjusting the concentration of enzyme, the

 With the enzyme method, silk is treated at low temperature (e.g. at 40C) not only
reaction time and the use of optimum pH and temperature.

 Enzyme treatment is an environmentally friendly process because enzymes are readily


reducing energy costs but also preventing fibre weakness.

biodegrade in nature.
 There is no soap required in enzyme degumming process. Therefore, uneven dyeing
problem caused by metallic soap can be avoided.
Enzymatic degumming also has some economic disadvantages as:

 It needs some pre-treatment processes, since the gum must be swollen before the

 It is very slow reaction compared to alkaline soap degumming.


enzyme bath.

Degumming of the silk is carried out in form of hanks as well as fabric.


8.2 WEIGHTING OF SILK
The process of increasing the weight of silk material is known as “Silk Weighting”.
Silk approximately losses 25% weight after degumming. This loss in weight leads to greater
loss of money because silk is a very expensive material. To compensate this loss some
weighting material is artificially added to the silk material by chemical means.
Major objectives of weighting:


To increase the weight


To reduce the lmpiness


To impart bulky effect.


To control the scroopy feel.
To give body to the silk material.
Weighting methods:
Generally the metallic Tin salts are used for weighting the silk. There are 3 methods of
weighting of silk.
1. Silk material is soaked/dipped in the Stannic chloride (SnCl4) solution, followed by
fixation with Sodium carbonate (Na2CO3) and then washed the material. By this
process there is a slight increase in weight. But it also reduces the strength of the silk.
2. The material is soaked in Stannic chloride (SnCl4) solution followed by fixation with
sodium phosphate.

Stannic Chloride + Sodium Phosphate Stannic Phosphate

It is then washed and acidified with small quantity of H2SO4 & again washed the
material. Increase in weight is sufficient/ considerable in this method but it also
reduces the strength.

3. Material is soaked in Stannic chloride (SnCl4) solution followed by fixation with


Sodium silicate. It will give sufficient weight & not reduce the strength of silk.

Stannic Chloride + Sodium Silicate Tri silicate of Tin


A better process is the combination of these 3 processes:
1. Picking/Soaking with Stannic chloride (SnCl4) solution.
2. Phosphating: Followed by the fixation with Sodium phosphate.
3. Washing
4. Acidifying: Treatment with small quantity of H2SO4.
5. Washing
6. This process is repeated several times until we get required weight after this the
material treated with sodium silicate.
8.3 SCROOPY FEEL OF SILK
A typical type of sound in the silk material is called the scroopy feel i.e a crisp sound of silk
called the scroopy feel. This feel is largely accepted & appreciated by the market. This feel is
given by the treatment with 2 – 3% of acetic acid or tartaric acid or citric acid in cold
conditions i.e at room temperature and dried. This process is given at the end of wet
processing. This feel is also obtained by the treatment of very dilute mineral acid.
8.4 ANTICREASE TREATMENT
Silk is by nature crease resistant but to give body to the silk material treatment of some gum
material like gum Arabic, gum tragacanth or dextrin (a type of gum having viscosity) is
given. Kandari is a special vegetable product which has no smell and it appears like onion.
The thin solution of this kandari is applied for finishing of silk sarees. The solution is
prepared by boiling this vegetable product with water for several hours & then filters it with
muslin cloth. This solution is used for finishing of silk sarees. This solution is applied by
brush or by spray.
Silk sarees tightly & fully stretched on a hexagonal roller and then this chemical solution is
applied by brush or sprayed over the saree. This hexagonl roller provides tension to fabric
and no crease is there on the fabric.
After dyeing the fabric is wound over the rollers.

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