STUDY ON MERCERIZING

EFFECT ON COTTON FABRIC.

Introduction:

Mercerization is one of the most important finishing processes of cotton with a

strong caustic alkaline solution in order to improve the lustre, hand and other
properties. It imports gloss to the fibre, increases its hygroscopicity, strength
and improves its dye affinity. Mercerizing improves the reactions with a variety
of chemicals and elongation of the fibres and also improves the stability of
form. Mercerizing process consists in treatment of cellulosic materials with
concentrated solutions of caustic soda at a temperature of 15 to 18°C.
Mercerised cellulose is hydrated cellulose, i.e., a product which from the
chemical point of view is identical to the original cellulose, but differing from it
in physical properties. This method was patented in 1850 by the English calico
printer John Mercer and hence forth this process has been called as
mercerization.

Cotton Mercerizing Process:

Mercerizing can be done in both yarn state and fabric state. Woven fabrics are
mercerized in full width and mercerizing of knit fabric is possible in both full
width and tubular form. In the past, knitwear was made with mercerized yarn,
but this process was very expensive. Tubular fabric can be mercerized, but this
process offers no control over the technological data of the finished fabric. In
addition, the consumption of caustic soda, water and steam is significantly
higher than with a modern, open width mercerization system. Stages at which
cellulose mercerization is possible are- On greige goods, After desizing, After
desizing and scouring, After bleaching, After dyeing Usually sodium hydroxide
concentration varies from 20% – 30%.

The process, done in a continuous way, involves four subsequent steps:

a. Impregnation of the material in relaxed state, cold caustic solution of required

strength and wettability.

b. Stretching while the material is still impregnated in the caustic solution.

c. Washing off the caustic soda from the material while keeping the material
still in the stretch state.

d. Neutralizing with acids and rinsing.

Physio-chemical changes during mercerization:

Under the action of concentrated alkaline solutions chemical, physio-chemical

and structural modifications of cellulose take place. Native cellulose (Cellulose
I) forms alkali cellulose I with concentrated sodium hydroxide. On washing and
neutralization cellulose II is formed.

As a result of the penetration of the alkali into the lattice, internal hydrogen
bonds are broken and in Cellulose II the number of available hydroxyl groups (-
OH) is increased by around 25%. The treatment with alkali and subsequent
washing may be performed so that the fabric or yarn may either freely contract
or they may be held under tension. In both cases the mercerised cotton has an
increased affinity for both reactive and direct cotton dyes, water and an
increased strength. Cotton yarn or fabric mercerized without tension contracts,
but if held under tension it retains its original dimensions and the luster is
increased. Major changes during Mercerization can be divided into three levels.

At Fibre level, Swelling; Cross sectional morphology changes from beam shape
to round shape and Shrinkage occur along with longitudinal direction. At
Molecular level, It will have Hydrogen bond readjustment, Orientation
(parallelization) of molecular chains in amorphous region along the direction of
fibre length and Orientation of the crystallinity in the direction of the fibre
length. On the other hand it facilitates Chemical Changes like, Increased rate of
reaction on hydrolysis and oxidation; Liberation of heat during the caustic
treatment (heat of sorption and heat of reaction; Increase in the alkali absorption
and Increase in the absorption of iodine.
The effects of mercerization:

 Improved luster
 Increased ability to absorb dye
 Improved reactions with a variety of chemicals
 Improved stability of form
 Improved strength/elongation
 Improved smoothness
 Improved hand

Appearance is improved through increased luster, a deepening of the color and

the production of a transparent look, the feel of the fabric is improved through a
resulting soft hand and improved smoothness, and strength and elongation are
also improved, along with the addition of good stretching ability. The treatment
and handling can be adjusted to fit different requirements, thus allowing for the
best application of the results of different processing.

The Effect of Caustic Alkalis on Cotton:

In the dyeing of cotton, it is well known that if too much caustic soda is used in
vat dyes and other dyes which use caustic soda, the dye's ability to be absorbed
will decline, this tendency being especially strong in weak alkaline vat dyes.

This is thought to be the result of competition for absorption between the dye
and the caustic soda. Caustic soda has an affinity for cellulose fibers, and
through routine dyeing experience, it is well known that the removal of caustic
soda through rinsing is very difficult when compared with the removal of acid.

However, within the range of concentrations of caustic soda generally used in

dyeing, the properties and form of cotton does not incur any particular effects,
but if the alkaline concentration is gradually increased, they will be affected.
Due to the different effects on different yarns, which are a collection of single
fibers, or on different knits and wovens (and, in fact, its effect on yarn or knits
and wovens is that which is desired) a variety of factors have complex
cumulative effects, and the basic behavior of cotton exposed to certain alkalis is
difficult to ascertain accurately, but clarification has come through using cotton
hairs (single cotton fibers).

Qualitative observations of the behavior of cotton when exposed to caustic soda

solutions of different concentrations were first conducted by Pop and Hubner
(J.S.C.I. 23, p.404, 1904).

Subsequently, researchers have repeatedly conducted experiments which

included quantitative measurements, but the results have lacked consistency.
While the reasons for this may be related to experimental procedure or certain
errors, essentially, factors involved in the type and the maturation process of
natural macro molecules like those in cotton can result in considerable
differences in the resulting properties, structure and configuration.

In addition to the variations in the responses to alkalis which result from these
factors, a precise experimental procedure is difficult to determine, and this can
also be considered a factor contributing to the difficulties. In the results
observed to date, the behavior of cotton hairs exposed to different
concentrations of caustic alkaline solutions can be summarized as follows.

If a cotton hair is dipped in different alkaline solutions, no change in appearance

will be visible up to 10°Bé, but above 11°Bé, the hair slowly loses its natural
twist (this usually being in the order of 150-300 times per inch).

Above 13°Bé, untwisting and shrinkage in the longitudinal direction now

gradually starts to increase, and as the concentration nears 16°Bé, untwisting
and shrinkage advance rapidly. Between 18 and 22°Bé, shrinkage of the length
reaches its maximium and untwisting for the most part ceases.
However, in the untwisting and shrinkage which have occurred to this point,
while both are related to the swelling of the fiber, the untwisting usually occurs
first, and is followed subsequently by the swelling. Nearing 24°Bé, swelling and
untwisting occur at the same time, and between 33 and 44°Bé, swelling occurs
before untwisting, and the rate of shrinkage that occurs with increases in the
concentration of the alkaline solution decreases.After the point at which the
greatest rate of shrinkage is reached, the rate of increase of untwisting slows
down, but increases more or less linearly with increases in the concentration of
the alkali.

In the data reported by different researchers, the greatest discrepancies exist in

the data related to the rates of shrinkage and swelling of the hairs. The
concentrations which showed the greatest rate of shrinkage straddled the area
between 18 and 22°Bé, and the concentrations for the greatest rate of swelling
were distributed from 18 to 26°Bé.

In these very widely distributed results, at concentrations displaying the greatest

rate of contraction, these being in the range from approximately 18-22°Bé to
around 33°Bé, not only did the actual alkaline concentrations displaying the
greatest rates of shrinkage and swelling differ, but also the rate of shrinkage
itself also varied greatly, sometimes displaying an undulating decline, and
sometimes displaying a smooth and gradual decline. In many cases, however,
the rate of shrinkage started to decrease rapidly above 33°Bé.As can be seen, in
mercerization, the results observed for the behavior of hairs over a range of
alkaline concentrations, while important, show great disparities, and many
points are still awaiting clarification. While many conjectures can be made
regarding these problems, the essence of mercerizing cotton is that in the
swelling of cellulose fibers due to exposure to alkalis, the natural crystalline
structure of the cellulose relaxes and under an appropriate tension, the
dimensions can be set by the conditions, and rinsing with water while these
conditions are maintained removes the alkali and converts the cellulose to a new
crystalline structure, fixing the dimensions. These being the basic principles, the
degree of swelling of the cellulose is the most important factor and it is related
to the alkaline concentration. However, because the swelling of the cellulose
hair in the alkaline solution accompanies a change in the form of the hair itself,
accurate measurements are extremely difficult to attain, and the results to date
for the alkaline concentrations which display the greatest degree of swelling are,
as previously noted, spread over a wide range of between 18 and 22°Bé.

Other methods of measuring the degree of mercerization of cellulose include the

X-ray diffraction method in which the degree of mercerization can be
determined by comparing cellulose I, which has the crystalline structure of
natural cellulose, with cellulose II, which has the crystalline structure of
mercerized cellulose.

The results concerning the degree of mercerization of a cellulose hair in

different concentrations of caustic alkaline solutions obtained with the X-ray
diffraction method showed that in 17°Bé NaOH 10% mercerized, in 18-19°Bé
40-45%, in 19-20°Bé 70%, in 20-21°Bé 80%, 22°Bé 90-95%, 23-24°Bé 95-
100%, and in concentrations above 24-25°Bé 100% mercerized.

According to these results, the concentration of the caustic alkaline solution at

normal temperatures needs to be above approximately 24°Bé to ensure the
complete mercerization of cellulose fibers (cotton hairs) in their free state. This
gives consistency to the effects of practical mercerization, and, at this
concentration, the swelling and the untwisting of the cotton hair start more or
less simultaneously. At alkaline concentrations in which the swelling occurs
subsequently to the untwisting, the crystalline structure of the cellulose fiber
shows signs that it has not undergone complete mercerization.
Different mercerizing machinery/technology:

The fabrics undergo value addition by special mercerizing process. At present

different types of mercerizing machines are installed in different manufacturing
unit. Different types of machine is available depending on the fabrics required
to be processed (Knit, Woven), expected quality level, energy efficiency,
addition of caustic recovery unit, form of fabric (open width, tubular) etc. Some
categories of mercerizing machines are-

 Knitted fabric mercerizing m/c.

 Woven fabric mercerizing m/c.
 Automatic hank yarn mercerizing m/c.
 Chainlesss-padless mercerizing range.
 Clip mercerizing m/c.
 Open width fabric mercerizing m/c with caustic recovery unit.

Dornier (Germany) and Goller (China) are the prominent brand or manufacturer
of mercerizing machines. Goller introduced their latest mercerizing range
consists the features of counter current flow, dipping washing, low energy
consumption and power spray.

Mercerization increases fibre lustre:

Concentrated solutions of caustic soda cause considerable swelling of cotton

fibre. The changes in cellulose physical properties are being irreversible. When
the fibre swells, its volume undergoes considerable changes; at maximum water
absorption, the cross section of cotton fibre is increased by 40 to 50% with
inconsiderable increase in length (about 1 to 2%). Swelling of fibre changes its
cross section from squashed circular pipe shape to an oval shaped.

Lustre of a fibre is due to the regular reflection of light incident on the fibre
surface, which depends on the cross-section of the fibre. If the fibres are placed
under a tension or stretched position in the swollen state and then washed to
reduce the caustic concentration below a particular limit, then there is an
increase in the lustre of the fibre.

1. Before mercerizing

2-5. Swelling stage with 18% sodium hydroxide

6. Washing stage after mercerization

7. Final stage

The main factors influencing the factors of selling are temperature of treatment,
the concentration of the alkali in the solution and additions made to the solution.

Mercerization increases tensile strength:

When cotton fibre, yarn or cloth is mercerized, its strength increased by 10-
50%. The tensile strength increase depends on various factors, such as
temperature of impregnation, concentration of alkali in impregnating bath,
construction of yarn etc. Lower the temperature of mercerization, greater is the
tensile strength (breaking load of the yarn). Increase of alkali concentration up
to 520 Tw, tensile strength increased gradually and further increase of alkali
concentration decrease the tensile strength. For long staple fibre yarn, greater
the twist, greater is the tensile strength of mercerized material.

Ecological impact and recovery of Sodium hydroxide:

The main ecological impact in mercerizing is the high concentrated residual lye.
Treating cotton materials with strong sodium hydroxide and washing it off gives
a large volume of dilute NaOH solution, which cannot be discharged into the
drain for economy and pollution points of view. By suitable means it is possible
to recover/reuse 90-95% of NaOH used in mercerizing. The alkaline load of
waste water is reduced drastically and acid required for waste water
neutralisation is minimised. Wash liquor may be used for the preparation of
sodium hypochlorite solution (for use in bleaching). NaOH from the
impregnated fabric may be recovered by washing using counter-current
principle and by using steam in a recuperator.

Conclusion:

Looking at the information presented so far, we can conclude that mercerized

cotton absorbs more water and dye than unmercerized cotton, and that the twist
in yarn will affect the water handling properties of that yarn proportionate to the
amount of twist. Mercerized cotton gains more lustrous surface than
unmercerized cotton. Tensile strength and hygroscopicity also increased by
mercerizing cellulose materials.