Mercerization

Mercerization is a finishing treatment of cotton with a strong caustic alkaline solution in

order to improve the luster, hard and other properties, was names after its discoverer,
John Mercer, and has been in use for sometime. It has been seeing an increase in
application recently.

Effect of Mercerization:
1.

Improve Luster.

2.

Increase ability to absorb dye.

3.

Improve reaction with a verity of chemicals.

4.

Improve stability of form.

5.

Improve strength/elongation.

6.

Improve smoothness.

7.

It has been shown that the increase in the luster occurs because of an effect.

8.

The cotton fiber do convoluted.

9.

The cross-sectional shape changes.

Factors of Mercerizing:
In mercerizing followings are important:
1.

Twaddle

2.

Temperature

3.

Tension

4.

Time

(1) Twaddle (Concentration of NaOH):

If the concentration of NaOH is increased above 56oTw improvement in luster will be
attained but if it is decrease below 48o Tw. The quality of luster will begin to be
adversely
affected.

(2)

Temperature:

High degree of luster is attained at temperature 18-20oC. As the temperature is

increased the quality of luster is adversely affected but on lowering the temperature no
improvement
in
the
luster
is
obtained.

(3) Tension:
For acquiring better luster the material must be stretch to its original dimension (both in
warp and weft direction during mercerization). If the material is allowed to shrink
during mercerizing then quality of luster will be impaired on the other hand if the
material
is
stretched
more
no
improvement
in
luster
is achieved.

(4) Time:
The optimum time for mercerizing is 30-60 seconds by increasing the duration of time
no applicable improvement in the quality of mercerization can be achieved but if the
time limit is less than 30 seconds in the quality of mercerization will be improved.
Read more: http://textilelearner.blogspot.com/2012/04/mercerizing-finishing-process-effect-of.html#ixzz3dOVUurln\

A treatment of cotton yarn or fabric to increase its luster and affinity for dyes. The
material is immersed under tension in a cold sodium hydroxide (caustic soda) solution in
warp or skein form or in the piece, and is later neutralized in acid. The process causes a
permanent swelling of the fiber and thus increases its luster.It is the process of
treatment of cellulosic material with cold or hot caustic conditions under specific
conditions to improve its appearance and physical as well as chemical properties.

Purpose
1.To
2.To
3.

To

What

of
improve

is

improve
improve
the

the

dye

mercerizing
uptake

the
the
and

mercerizing

moisture

lusture
strength
regain.

process

The mercerizing involves these three subsequent steps,

a. Impregnation of the material in 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.

Fig.The material flow chart in yarn

mercerizing

Theory

of

mercerizing

Neales
theory
in
Broad
The hydroxyl groups on long cellulose chains attract the water molecules when cellulose takes up water, the structure
expands transversily as some of the mutual secondary valency linkages are replaced by water hydroxyl linkages.Now
in alkali solution ,some of the hydroxyl hydrogen atoms are replaced by sodium atoms and a system of high ionic
concentration is established.Owing to osmosis ,water tends to enter this system and more secondary linkages are
broken and are replaced by linkages with alkali in water.When the alkali cellulaose is washed the sodium ions and the
hydroxyl ions are diffused away, and the osmotic pressure falls, the cellulose gel contracts by virtue of its elasticity.
During this contraction , hydroxyl hydroxyl linkages are reform but not in such a great number as before and the
orientation of the micells is more random.The greater proportions of free hydroxyl groups accounts for the increase in
the reactivity and absorptive capacity.The decrease in this high absorptive capacity on drying,particularly at high
temperature ,is due to the formation of new secondary linkages on account of greater amplitude of thermal vibrations

of

hydroxyl

groups

Changes

as

during

A.
1.Swelling
2.Cross
sectional
3.Shrinkage

suggested

by

mercerizing

Urqhart.

process

Fiber
morphology
along

changes

from
with

level
beam

shape
longitudinal

to

round

shape.
direction.

B.
Molecular
level
1.Hydrogen
bond
readjustment
2.Orientation (parallelization) of molecular chains in amorphous region along the direction of fiber length.
3.Orientation
of
the
crystallinity
in
the
direction
of
the
fiber
length.
4.Increased
crystallinity
C.
1.Increased
2.Liberation
3.Increase
4.Increase

of

Q.Why
1.Due
Swelling

rate
heat

of
during
in
in

there

the

is

Chemical
reaction
on
hydrolysis
caustic treatment.(heat of sorption
the
alkali
the
absorption

swelling

and

in

and
heat

of

Changes
oxidation
of reaction)
absorption.
iodine.

cellulose?

to
is

due

to

molecular

attraction

with

associated

hydration

in

this

Swelling
instance.

Since the alkali cellulose is more hydrated than native cellulose ,maximum swelling concentration is result of
attraction of alkali cellulose in solution on one hand and free alkali on the other. Hydration of the cellulose increases
with increased fixation of alkali in solution of rinsing concentration upto a certain limit, after which the free alkali exerts
a
dehydrating
effect
on
alkali
cellulose
to
a
greater
extent.
Dissociation of alkali ions from the alkali cellulose compound corresponds to an absorption of OH- ions ,and in this
manner a negative charge results.The cellulose molecules repel each other and absorb water ,this absorption being
greater, the greater is the charge. If however the dissociation of alkali cellulose salt is forced back ,then there is
reduction in the charge. Further if the concentration of the electrolyte is high in swelling liquor ,then charge of
cellulose
particles
is
shielded
by
free
ions
and
force
of
repulsion
is
diminished.
2.Due
to
osmotic
phenomenon.
The fiber is surrounded by a hardened euticle which acts as a dialyzing membrane to induce osmotic action ,which is
better
explained
with
the
help
of
Neales
theory
Q.Why
there
is
a
rise
in
temperature
of
caustic
solution
during
mercerization?
Ans ;-Because when cellulose is treated with a moderately concentrated caustic solution ,the heat is evolved due to
heat
of
sorption
and
heat
of
reaction.
Q.Why
there
is
increase
in
luster
of
yarn
after
mercerization?
Ans:-The cotton hair swells in strong caustic soda solution ,which change its cross section from squashed circular
pipe shape to an oval shaped . if the fibers 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 luster of the
fiber.

Q.What should be caustic concentration for yarn mercerization?

Ans:-Although mercerization can be done with the caustic concentration ranging
between 150Be to 380Be, As for as the economy of the process and optimum
mercerizing effect in yarn , the concentration of the caustic used is 250Be(225 gpl) to 32
0Be(325
gpl)
at
room
temperature.
Q.
What
shall
be
the
ideal
temperature
for
mercerization?
Ans:- The relation between the shrinkage of cotton fiber, the concentration of alkali and
the processing temperature was studied by H. Flecken, and the result is shown in this
Figure.

He treated cotton yarn at 0C to 40C, using 30/38 B caustic soda and measured the
shrinkage by mercerization, and found that the least shrinkage variation is obtained at
10C and 30 B. Therefore, robust conditions insensitive to the concentration of alkali
and temperature must be selected for stable mercerization.

Q.Whether the recovered caustic from mercerizing process is reusable?

Ans:-The caustic soda from the washing process is recoverable and can be reusable
,but it has to be free from the contaminants and must be purified to remove the
undesirable impurities.
Q.What is the mercerizing cycle for yarn mercerizing?

A typical mercerizing cycle in yarn mercerizing is

having
following
steps,
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.

Loading

of

material
Lowering
Caustic

on

the

rollers
of
tray

Pre
Free
Lye
Washing
First

tray
wash
Second
Third
Final

and

in

rest

position.
rollers
movement
tensioning
shrinkage
tensioning
Squeezing
movement
tensioning
wash
wash
wash
Squeezing

14.
15.

Lifting
Unloading

Of
the

Rollers
hanks.

What is the significance of different steps in

mercerizing
cycle?
1.Pre
tensioning
This is the first step in yarn mercerizing cycle ,which runs to uniformly distribute the
greig yarn hanks on the rollers in combination with reversal of direction of motion of
rollers, without any entanglement. The material should become completely wet in this
step.
2.Shrinking
This is the actual caustic treatment step or the mercerizing step in which the yarn is
allowed to shrink freely , the yarn runs for sufficient time in relaxed state to react
completely with the caustic , higher the shrinkage achieved better will be the
mercerizing.
3.
The

lye

tensioning

is

done

Lye
to stretch

the

yarn

back

to

tensioning
original length.

4.Squeezing
To remove the unbound caustic solution from the material, so that the material can be
washed effectively, and quickly to reduce the caustic content . This step also ensure the
to minimize the wastage of excess caustic liquor during washing.
5.
Washing
and
tensioning
The stretch applied to get the maximum luster , material is washed along with stretching
beyond its original length produce better luster. The amount of stretch applied depends
upon the luster required and quality of yarn. The washing temperature is kept near boil
to make washing efficient and short. Time or sequence of washing is so adjusted to
reach a residual caustic content below 10% within a shortest possible time.
6.Final
caustic
content
The final caustic content should be below 10% ,because if it is more it will be sufficient
to carry out further mercerizing effect and the material will shrink back. During the
storage of mercerized material , the water from the exposed areas will evaporate and
got concentrated locally causing mercerizing effect ,which is called local mercerizing
and
will
lead
to
patchy dyeing.
The level of residual caustic in the yarn is achieved less than 3% , if it is on the higher
side ,then the washing is not effective.

Read more: http://textilelearner.blogspot.com/2012/02/mercerizing-object-of-mercerizing.html#ixzz3dOWasbDc

Barium Activity Number:

The ability of mercerized cotton fibre to absorb more iodine, dyes, moisture and alkalis,
and to undergo oxidation or hydrolysis at increased rates compared to unmercerized
cotton, has been used to develop various methods of determining the degree
of mercerization. The most successful method consists of measuring preferential
absorption of barium hydroxide from its dilute solution by mercerized cotton. The extent
of this absorption is more than that by unmercerized cotton under the same conditions.
Thus ratio multiplied by 100, is known as barium activity number, barium number or
baryta
number.
Barium activity number was measured by AATCC test method 89-1998. One gram of
mercerized and unmercerized cotton yarns were each cut into small pieces, dried over
phosphorous pentoxide for 5 hours, then conditioned at 65% relative humidity at
311Cbefore testing and consequently treated with 30 ml of 0.25 N barium hydroxide
solution in 100 ml conical flasks. After2 h, 10 ml of the solution is titrated against 0.1 N
hydrochloric acid. A blank is also run without any yarn sample. For b, s and u being the
titration readings of the blank, mercerized and unmercerized samples, respectively, the
barium
activity
number
may
be
given
as
in
following
equation.

Barium

activity

number

{(b-s)/(b-u)}

100

Appropriately large numbers of conditioned samples are taken, taking into consideration
the moisture regain of the samples. Thus, if the moisture regains 8%, 1.08g of the
conditioned cotton is weighted to get 1g of the bone dry cotton. The barium activity
number of good mercerized cotton may be around 150-160.
Read more: http://textilelearner.blogspot.com/2013/01/barium-activity-number-ban.html#ixzz3dOWqFjDu

1.

Alkaline

Treatments

Mercerization, the treatment of cotton with a strong caustic alkaline solution in order to
improve the luster, hand and other properties, was named after its discoverer, John
Mercer, and has been in use for some time. It has been seeing an increase in
application
recently.
Recently, there has been wide use of so-called alkaline reduction processing, which
treats polyester with a strong caustic alkaline solution to dissolve and remove the
surface
film
in
order
to
improve
the
hand.
The methods and effects involved in the processing of cotton and polyester are
different, but, both involve treatment with a strong alkaline solution before dyeing to
improve the properties of the fiber, and so both can be considered together to be
alkaline
treatments.
Furthermore, in the handling of blended and union weaves of polyester and cotton, both
fibers can be treated effectively with alkalis at the same time, and so it is important that
the two treatments be given equal consideration in such a case.

1.1

Mercerization

Processing

If cotton is dipped into a strong alkaline solution such as lithium hydroxide, caustic soda,
or potassium hydroxide, the fibers will swell and shrink. If the fibers are placed under
tension while in this swollen state and then rinsed with water, the alkali will be removed
and
a
permanent
silk-like
luster
will
result.
Alternatively, after swelling, if the alkali is rinsed off when the fiber is in its shrunk state,
an increase in luster may not be discernable, but the fibers will fix in that shrunk state,
thus
giving
good
elasticity
to
external
stress.
The former is known as tension mercerization and is often simply called mercerization,
while the latter is referred to as slack mercerization. Due to considerations of cost and
efficacy,
only
caustic
soda
is
used
as
the
alkali
in
industry.

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.
In presenting here basic information regarding mercerization, the work of J.I. Marsh
(Mercerising, Chapman and Hall Ltd, 1951) and Matsui (Senshoku kogyo, Vol. 21, No.
11, pp.10-27) were used as references. A few points that are considered important for
dyeing
in
the
future
are
discussed
here.

1.1. a 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 10B, but above 11B, the hair slowly loses its natural twist (this usually
being
in
the
order
of
150-300
times
per
inch).
Above 13B, untwisting and shrinkage in the longitudinal direction now gradually starts
to increase, and as the concentration nears 16B, untwisting and shrinkage advance
rapidly. Between 18 and 22B, 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 24B, swelling and untwisting occur at the same
time, and between 33 and 44B, 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 22B,
and the concentrations for the greatest rate of swelling were distributed from 18 to
26B.
In these very widely distributed results, at concentrations displaying the greatest rate of
contraction, these being in the range from approximately 18-22B to around 33B, 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
33B.
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
22B.
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 17B NaOH 10% mercerized, in 18-19B 40-45%, in 19-20B 70%, in
20-21B 80%, 22B 90-95%, 23-24B 95-100%, and in concentrations above 2425B
100%
mercerized.
According to these results, the concentration of the caustic alkaline solution at normal
temperatures needs to be above approximately 24B 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.

1.1. b Behavior

in changing alkaline solutions

In the previous section, the behavior of cellulose hairs dipped directly into an alkaline
solution of fixed concentration was discussed. Here, the behavior of hair undergoing
treatments involving gradual changes of concentration, being first dipped in strong
alkaline solution and then into progressively weaker alkaline solutions, and conversely,
first dipped in a weak alkaline solution and then into progressively stronger alkaline

solutions, is considered. The first to conduct quantitative measurements of the changes

of a cotton hair undergoing such alkaline treatments were Willows, Barratt and Parker
(J.T.I., 13, p.29, 1922). Their results are shown in Figs. 1 and 2.

Fig.1Changes in the length of a cotton hair when dipped in decreasing concentrations of

alkaline solution (NaOH)

Fig.2 Changes in the length of a cotton hair when dipped in increasing concentrations of
alkaline solution (NaOH)
From these results, in comparison with direct treatment with a single concentration,
when the hair is treated with increasing concentrations of alkaline that start from a weak
solution and get progressively stronger, the concentration that displays the highest rate
of shrinkage shifts much higher and the rate of the increase in shrinkage becomes
extremely low. In contrast to this, if the opposite treatment is carried out, the alkaline

concentration that displays the greatest rate of shrinkage shifts conversely lower.
These trends are visible in Fig. 3. This behavior is conjectured to be due to the fact that
the diffusion of the caustic soda inside the cellulose fiber in its swollen state is extremely
slow.

Fig.3 Changes in the length of a cotton hair when treated with a caustic soda solution [Collins
and Williams (J.T.I., 14, p.287, 1923)]
However, there is no data that has actually measured the diffusion of the caustic soda
inside
the
alkali-swollen
cellulose.
The mercerization of cellulose that is exposed to increasing concentrations of alkaline
solution can be considered to display behavior that is similar to that of the wet-on-wet
method,
that
is,
the
wet
mercerization
method.
The cloth not having dried before mercerization, wet mercerization involves application
of a strong uniform squeezing agent and exposure in that state to a strong caustic
alkaline for mercerization. Because the drying of the cloth before mercerization is
omitted, this is very effective as a measure for saving energy, and is used widely in
industry.
Because the water content of the cloth before mercerization (usually around 50%)
steadily dilutes the caustic soda, in order to ensure the practical effectiveness of wet
mercerization, the concentration of the alkaline solution must be preserved through the
steady addition of a correspondingly high-concentration alkaline solution. Furthermore,
to avoid a rise in temperature due to the dilution heat of the alkali and the heat
generation that accompanies the cellulose fiber's absorption of the alkali, the alkaline
solution must be cooled, thus allowing the preservation of a constant temperature.
Measures to preserve the uniformity of treatment have already been implemented and
many factories over many years have made continual efforts to ensure the industrial
success
of
wet
mercerization.

However, many factories have now, for effectiveness, abandoned wet mercerization and
have returned to the previously used dry mercerization. Of course, there are many
reasons for this, including those relating to equipment costs and management, but one
major reason is in regards to quality, because in wet mercerization problems concerning
efficacy
and
uniformity
can
occur
easily.
One possible reason for wet mercerization not being as stable as dry mercerization is
that the behavior of cellulose fibers in alkaline solutions is considered uniform, and the
measures to prevent the diffusion of the caustic alkali inside the swollen cellulose are
insufficient.
In contrast to this, in dry mercerization, the alkaline solution for the first dipping must
have a concentration sufficient for mercerization, and if it sufficiently penetrates the
inside of the fiber with only the usual degrees of temperature and tension control, no
major considerations are required with regard to the change in concentration of the
alkaline solution that acts on the cellulose's structure, and management of the
mercerization
is
extremely
simple.

1.1.

Absorption

of

the

alkali

and

swelling

The cotton hair swells in a strong caustic soda solution, and on viewing the changes in
the cross-section that occur during the mercerization process (see Fig. 4), the cross
section, originally shaped like a squashed circular pipe, clearly becomes oval-shaped,
thus enhancing the luster. The large differences in the swelling that occur due to the
concentration of the alkaline solution are relative to the longitudinal shrinkage of the
hair.

Fig.4 Changes in the cross-section of a cotton hair during mercerization

The effect of the concentration of the alkaline solution on the shrinkage of the length
and the dilation of the diameter, along with the increase in the volume of the hair, are
shown in Fig. 5. The transformation of the cross sectional diameter in relation to
changes in the hair's length are shown in Fig. 6.
Fig.5 Changes in the dimensions of a cotton hair treated with caustic soda

Fig.6 Relationship between the changes in length and cross-sectional diameter of a cotton hair
As can be seen from Fig. 5, the maximum increase in the volume of the cotton hair
occurred for a 16% solution of NaOH, that is, a concentration nearing 22B. However,
after repetitions of the experiment, the concentration of alkaline solution that was
determined to display the greatest rate of swelling and the greatest rate of longitudinal
shrinkage for the hair was different each time, the results being distributed between 18
and 22B. In all cases, however, if this alkaline concentration was exceeded, any
subsequent increases in concentration resulted in a reduction in the degree of swelling.
Many researchers have, in addition, investigated the changes in the amounts of alkaline
and water absorbed by the hair for different concentrations of alkaline solution, and
representative results are shown in Fig. 7. It can be seen that the concentration of
alkaline solution which displayed the greatest rate of swelling for the hair also displayed
the greatest amount of absorbed water, and in solutions above this concentration, while
the rate of absorption of the alkali increased, the rate of absorption of the water
decreased.

Fig.7 Alkaline concentration versus the cotton's absorption of water and NaOH

There are many possible reasons for this, but Neal's explanation using Donnan
Membrane Equilibrium (J.T.I., 20, p. 373, 1929) enjoys much support. However, this
cannot be considered sufficient explanation for all the behavior exhibited by the
cellulose
fiber
in
the
alkaline
solution.
The visible changes in the cotton hair in various concentrations of alkaline solution have
been discussed above, but this is still a weak foundation for a theoretical explanation for
just the externally visible changes. Due to this, examination of the transformations that
occur in the crystalline structure of the molecules of the cellulose is necessary.
Analysis of the transformations of the crystalline structure of the cellulose hair in the
alkaline solution with the X-ray diffraction method has been conducted by Katz and
Mark (Z. Electrochem., 31, 105, 157, 1925), Katz and Viewg (ibid., 157), Suich and
Walff (Z. phys. chem., 8, 221, 1930) and Hers and Trogus (ibid., B12, 381, 1931).
According to these results, the cellulose hair undergoes no visible changes in
concentrations up to around 8% NaOH (approx. 12B), but at 12.5% NaOH (approx.
18B),
the
generation
of
alkali
cellulose
becomes
apparent.
According to the above mentioned observations, above 11B, the untwisting of the hair
starts but is incomplete, and after that, as the concentration increases, the untwisting
and the shrinkage of the hair gradually increase, and as the concentration nears 16B,
these two increase rapidly, and around 18B (while results differ, in the range of 1822B), the rate of shrinkage reaches its maximum and more than half of the untwisting
is
completed.
This point, according to X- ray diffraction method, is also the point at which the
cellulose's structural transformation commences. So, up to 18B, the question is why
does this kind of swelling and shrinkage occur even though no reaction occurs between
the
alkali
and
the
cellulose.
However, at concentrations below 18B, no structural changes in the cellulose are
noticeable with X-ray diffraction. In contrast to the molecules of the cellulose that are
structural units, the alkali cellulose I examined with X-ray diffraction is a compound with
1
mol
of
NaOH
appended,
that
is
C6H10O5NaOH.
For many of those who have examined the amount of alkali absorbed by the cellulose
hair, the point at which there was a change in the degree of absorption was sometimes
at concentrations of 8% (approx. 12B), and sometimes at concentrations nearing
13.0% (approx. 18-19B), and so due to the generation of an inflection point at which
the molecules of cellulose that were structural units were observed to absorb 0.5 mol
NaOH, the generation of a compound of C12H20O10NaOH has been suggested.
Reconciliation of the differing views is problematic, but clarification of the differences
could start from consideration of the fact that the cotton hair has a complex structure,
and
so
is
not
a
simple
singular
thing.
In a cotton hair, which consists of natural cellulose, around 75% of the cellulose has a
crystalline structure, the rest being of an amorphous structure or having constituents of

low molecular weight which, even if reacting with the alkali, would not be noticeable
through X-ray diffraction, and nor would the reactant produced through reactions
between
the
alkali
and
the
outer
skin
of
the
micelle.
The outer skin of the micelle, the non-crystallized cellulose and the constituents of low
molecular weight are considered to constitute over 50% of the total cellulose. Because
the reaction of these constituents of cellulose with alkalis cannot be observed with Xrays, the existence of compounds like C12H20O10NaOH is not verifiable, but due to
the absorption of the alkali, observers believe that over 50% of the constituents of the
cellulose absorb around 0.5 mol in alkaline solutions of low concentrations, thus
generating
the
C12H20O10NaOH
compound.
However, if only amorphous structured cellulose, other cellulose constituents of low
molecular weight and the outer layer of micelles react with the alkalis, when the whole
structure of natural cellulose has not reacted with the alkali, the verification of the
generation of a reactant with 0.5 mol of NaOH attached in the molecules of the cellulose
that are structural units is not possible, and the existence of this type of reactant is
adamantly
denied
by
some.
That is, it is considered that there is simply a phenomenon having such an external
appearance that is produced during the process of the generation of 1 mol of molecules
of cellulose that are structural units and 1 mol of attached NaOH.
According to X-ray observation, the production of alkali cellulose I does not change up
to concentrations of 18% (approx. 24 B), but if the concentration goes above this, the
production of alkali cellulose II can be observed, and at a concentration of 22% (approx.
28-29
B)
alkali
cellulose
I
disappears
completely.
If alkali cellulose I is dried, there is a change in the X-ray interference pattern, and so
the result is called alkali cellulose III. In contrast, if alkali cellulose II is dried, no change
is visible through X-ray observations, meaning no structural changes occur due to
drying.
While alkali cellulose I can take water into its structure, alkali cellulose II appears to be
unable to do so, and due to this difference, in the treatment of cellulose hairs in alkaline
solution, after the maximum rate of swelling is reached in highly concentrated alkaline
solutions, the amount of alkali absorbed increases, but the amount of water absorbed
decreases, and this is consistent with a decrease in the production of alkali cellulose I
and an increase in the production off alkali cellulose II with any increase in the
concentration
of
the
alkaline
solution.
Alkali cellulose I and II become hydrated cellulose, or mercerized cellulose, after rinsing
with water. However, according to results of analysis to determine at what concentration
of alkaline solution the original structure can be preserved if it is treated with gradually
decreasing concentrations of low-concentrate alkaline solution during the rinsing
process, while concentrations above 18B are necessary for the generation of alkali
cellulose I, it can only exist at concentrations of up to 10% (approx. 15B), and alkali
cellulose II is produced at concentrations above 18% (approx. 24B), but at alkaline

concentrations below 6.6% (approx. 10B), the original structure will undergo only very
slight degradation, and thus can be considered extremely stable. This is because alkali
cellulose has little ability to structurally coexist with water, and as mentioned previously
(Figs. 1 and 3), this is evidence of the behavior during mercerization that includes
rinsing accompanied by a gradual decrease in the alkaline concentration.
In conclusion, due to X-ray diffraction observations of the reaction between the cellulose
hair and the alkaline solution, it is believed that in an alkaline solution of low
concentration, the alkali cannot combine with the cellulose molecules inside the micelle,
and so in this state only the outer skin of the micelles and the cellulose that is not a part
of a crystalline structure, that is, the material with low molecular weight, react with the
alkali. As the concentration increases, the crystalline structure of the cellulose swells
and relaxes, and when it reaches it most swollen state, the alkali penetrates the inside
of the micelle, and undergoes a complete reaction with the cellulose.

1.1.d Effects of Constraint of the Hair on Swelling

The results of many researchers determined the alkaline concentrations for which the
swelling of the cellulose was greatest as being in the range 18-22B. This
concentration range does not represent the completion of the production of alkali
cellulose I through the mercerization reaction, but rather the beginning, the end being
nearer the higher alkali concentration of 24B as mentioned previously.
After swelling reaches its greatest point, NaOH thoroughly penetrates the interior of the
micelle, and a reaction between the alkali and the micelle occurs, completing the
generation
of
alkali
cellulose
I.
From 18-22B, the range displaying the greatest degree of swelling, to around 24B,
the cotton hair first contracts momentarily, and then swells again, and at 24B or above
a second swelling peak was observed. These observations cannot be disregarded as
baseless occurrences.
Fig.8 The longitudinal changes of a single scoured cotton hair in a single caustic soda
solution (tensile force: 50mg) (Williams, Barratt and Parker)

Fig. 9 The change in the cotton hair's volume after mercerization

For a natural cellulose like the cotton hair, the structure consists of a complex assembly,
and furthermore it is of course not unlikely that the balance between the generation of
alkali cellulose I and alkali cellulose II is derived from the characteristics of hydration.
In measuring the absorption of alkali and the swelling of a cellulose fiber in an alkaline
solution, measurements and calculations can be based on the changes in the length
and the diameter, or alternatively, the water can be removed from the swollen fiber by
compression or with a centrifuge, after which the composition of the liquid and attached
alkali absorbed by the fiber can be analyzed, thus determining the degree of swelling
and
the
amount
of
water
and
alkali
absorbed.
The degree of alkali absorption can also be determined by measuring the concentration
of the alkali solution before and after the treatment of the cellulose, but getting reliable
results is difficult due to the fine conditions required in the operations and other
considerations, and in the course of an experiment, discrepancies among the
determined values are very significant. However, rigorous measurement with a single
experimental method can provide useful information regarding trends based on relative
changes.
For example, according to the behavior observed for woven fabric and fibers of raw
cotton exposed to alkali, woven fabric only displays around half the degree of swelling
displayed by fibers if both are treated with the same concentration of alkaline solution,
but no such difference exists between their respective degrees of alkali absorption (see
Figs. 10 and 11).
Fig. 10 The absorption of alkali solution by fibers & fabrics

Fig. 11 The amount of NaOH absorbed by raw cotton

Furthermore, in the results of these experiments, there was little visible increase in the
degree of swelling of a fiber accompanying increases in the concentration of the
alkaline, but for the woven fabric there were, and this is in apparent opposition to the
results
for
cotton
hairs.
As another example, aside from the hair, the concentration at which yarn showed the
greatest degree of swelling was determined to be 20% NaOH (26.5B), and this far

surpasses the range of 18-22B as determined for the cotton hair, and so cannot be
dismissed
as
being
simply
due
to
experimental
error.
Inferring from these results, it is believed that when cotton hair under physical restraint,
that is, made into a yarn or a woven fabric that restrains the hair's freedom due to
twisting and to crossing of twisted yarn, is treated with an alkali, it displays different
behavior because the shrinking and swelling displayed originally cannot occur due to
the
constraining
forces.
As an illustration of this, the report by H. Flecken (Textil Praxis, Juni, 365, 1970) shows
that even for the same type of yarn, the behavior of single, double and triple yarns
display differences, as does the shrinkage of woven fabric and hairs (see Fig. 12).

Fig. 12 The concentration of NaOH versus the shrinkage of cotton hairs and cotton fabrics
Due to the degree of constraint on the swelling and shrinkage of single fibers, ie. hairs,
changes will of course occur in the numerical values related to the swelling of cellulose
fibers, but in general, increases in the degree of constraint moves the peaks of these
values towards higher alkaline concentrations. While the diffusion and penetration of the
alkali solution from the exterior to the interior of the hair occurs freely for hairs under no
constraint, for hairs under constraint, not only will the swelling of the exterior of the hair
narrow the gaps in the micelles, thus delaying the interior diffusion and penetration of
the alkaline solution, but also the concentration gradient, which is the driving force for
the internal diffusion of the alkali, will be raised, thus lowering the swelling rate itself.
Thus, the result is that when a single fiber is under great constraining force, the
concentration displaying the greatest rate of swelling will increasingly move towards
alkalis of higher concentration.

1.1.e Heat generation during mercerization and the

effect of temperature
In mercerization, aside from the heat production due only to the behavior of the
cellulose fiber and the alkaline solution, as in the reaction between the cellulose and the
alkali, the swelling, and the hydration, there is also dilution heat which is generated
through the dilution of a strong alkali either with the water content of the cellulose which
has been absorbed from the air, or the water present during mercerization in a wet
state,
as
in
wet
mercerization.

1.1.e.1 The reaction heat of the cellulose fiber and the

alkali
Heat is generated by the cellulose, which acts as a very weak acid, bonding with the
alkali. Heat is also believed to be produced by the deformation of the molecular
structure caused by the hydration and swelling of the alkali cellulose.
This kind of heat generation, due to the reaction of the cellulose fiber with the alkaline
solution, has been measured for some time, but the values relating to it determined by
different
researchers
vary
significantly.
However, all the results show that heat generation due to the reaction between the
cellulose and the alkali, like heat generation in other typical chemical reactions, is not
simple, and varies according to the concentration of the alkali and other factors.
The results of Neal (J.T.I. 20, 1929, p.373), which can be considered to be relatively
reliable, are displayed in Fig. 13. According to these results, from a concentration of
around 120g/L NaOH, or about 15-16B, the reaction heat increases sharply, and from
around 240g/L, or 26B, the reaction heat increases in more or less constant
proportion with increases in concentration.

Fig. 13 The reaction heat of cellulose and NaOH

These results accord well with the results for the untwisting and swelling of the cotton
hair and those measured for the relationship between the formation of alkali cellulose I
and the concentration of the alkali as observed with X-rays. There is even a very slight
generation of heat when cellulose fibers swell in water. While different researchers
recorded different results for this heat generation, it is in the range of 2.6-4 Cal/g of
cotton.
In contrast to this, with an increase in the concentration of the alkali solution of 1M in the
range from 15-16B to 19-20B for which the swelling was greatest, the heat
generation was 8.93 Cal/g, and from a concentration of around 22B, at which the
production of alkali cellulose I was more or less complete, the rate of increase of
generated heat was 3.40 Cal/g cotton/M NaOH. Above 42B, this became 3.0 Cal/g
cotton/M
NaOH.
While the time required for the completion of this heat generation for concentrations
below about 34-35B was less than five minutes, above 42B it was ten minutes, and
above 22M NaOH, 100 minutes was required, the reaction needing a very long period of
time
to
complete.
For concentrations that are used in practical mercerization, heat generation per
kilogram of cotton is 20Kcal for 22B, 22 Kcal for 24B, 24Kcal for 26B, 27 Kcal for
28B, and 29Kcal for 30B. Increases in the temperature of the alkali solution or of
the yarn or the fabric will influence the effectiveness of the mercerization, so
mercerization
is
normally
carried
out
under
a
cooling
process.
At concentrations below 22B, significant differences in behavior with regards to heat
generation are displayed between fibers that have been mercerized once before and

fibers that have not been mercerized at all. Items that have been mercerized once
before display the absorption of alkali and generation of heat even in alkali solutions of
low concentration. (See Fig. 14)

Fig.14 The heat generated by mercerization (Okamura, Naturwiss, 21, 393, 1933)

1.1.e.2 Heat generation through dilution of the alkali

solution
It is well known that if a strong caustic soda solution is diluted with water, a large
amount of heat will be generated, but in the mercerization of cellulose fibers, heat
generation also occurs due to the dilution of the alkali solution by water that has been
absorbed
by
the
cellulose
from
the
air.
With regards to this effect, Tschilikin (Textilber, 14, 1933, p.404) reported that the
addition of 15cc of water to a 491g/L solution of NaOH to produce 500cc of solution
yields 788 Cal/g water, and similarly, in a 604g/L solution of NaOH yields 1312 Cal/g
water.
Thus in practical mercerization under these conditions, the mercerization of 300g of
cotton yarn having an absorbed water content of 5% with 485cc of alkaline solution will
result in an increase in the temperature of the solution of approximately 23C in the
former case and by approximately 40C in the latter due to only the dilution heat of the
absorbed
water.
This would appear to be excessive, but calculation of the dilution heat of the alkali
solution gives 1.99Kcal/mol for the former and 2.69Kcal/mol for the latter, neither of
which are excessive values. However, if the concentration of the alkali solution is
significantly greater than that used in practical mercerization, at around 40B or 45B,
then
this
cannot
necessarily
be
used
as
practical
data.
Because there is no accurately measured data available to determine the extent to

which the dilution heat influences the mercerizing process, the following results were
determined through calculations with the aid of a chemistry handbook. The infinite
dilution of approximately 36B NaOH and 23B NaOH (data for concentrations
between these two values is unavailable) yields 0.9 Kcal/mol and 0.06 Kcal/mol
respectively, and so in mercerization under the above conditions, even with the factors
mentioned above, the increase in temperature of a 36B solution would only be 913C, and only 0.3-0.9C for a 23B solution. So in practical mercerization at a
concentration of around 30B, the increase in temperature of the solution due to the
water absorbed in the yarn can be estimated to correspond to only around 1-2C under
the
above
conditions.
However, in wet mercerization, the alkaline solution used for feeding must be a highly
concentrated solution of 49-50B, and the yarn or the fabric has a high water content,
so the resulting amount of dilution heat is large, and the resulting temperature increase
cannot
be
ignored.
While the concentration of the alkaline solution used for feeding in wet mercerization is
presently 49-50B, if the concentration of the caustic soda solution is reduced to 2829B the dilution heat becomes 2.13 Kcal/mol, and 2.89Kcal/mol at 24-25B, and 3.1
Kcal/mol
at
22B,
thus
allowing
the
problem
to
be
ignored.

1.1.e.3 The effect of temperature during mercerization

The reaction between the cellulose fiber and the alkaline solution is an exothermic
reaction, and any increase in the treatment temperature reduces the absorption of the
alkali, thus reducing the effectiveness of the mercerization. Furthermore, increasing the
concentration of the alkaline solution to counteract the reduced absorption in order to
achieve the same effects from the mercerization will not necessarily be successful.
Sisson analyzed a cotton yarn treated with a wide range of alkaline concentrations and
processing temperatures with X-ray diffraction, divided the results into the three
divisions of complete mercerization, partial mercerization and un-mercerized and
created a chart showing the relationship between the alkaline concentration and the
temperature. The result is shown in Fig. 15.

Fig. 15 The temperature and concentration for the mercerization of cotton

According to these results, regardless of the increase in the concentration of the alkali,
above about 60C, complete mercerization does not take place. The concentration of
around 30B in mercerization at room temperature, that is, around 20C, is in the
middle of the chart for complete mercerization, and this, interestingly, is fairly consistent
with stable conditions determined by experience in practical mercerization and with the
results
of
all
researchers.
For example, these results are consistent with the results of Beltzer (R.G.M.C., 1902, 6,
25, 34; see Fig. 16) who investigated the relationship between shrinkage and the effects
of temperature and alkaline concentration in the mercerization of cotton yarn, and the
results show that the concentration of 20B represents a line beyond which behavior
during mercerization changes.

Fig. 16 The shrinkage of yarn in caustic soda solutions of different temperatures and
concentrations
Similarly, the results of Birtwell, Chblenens et al (J.T.I., 21, 1930, p.85; see Fig. 17)
show that temperature has its greatest influence on the shrinkage of cotton yarn at
concentrations of 3N NaOH, (approx. 16B), and above 4N (approx. 20B), that
influence diminishes.

Fig. 17 The shrinkage of cotton yarn in NaOH

H. Flecken (Tex. Praxis., Juni, 365, 1970; see Fig. 18) measured the shrinkage of cotton
yarn at concentrations of 30B and 38B for temperatures from 0C to 40C, and
reported very small variations for temperatures in the range of 10-30C at a
concentration of 30B, and this result can also be found in the center of Sisson's
mercerization chart.

Fig. 18 Temperature versus shrinkage rate in the mercerization of cotton yarn

From the above, it can be seen that in order to conduct stable mercerization,
appropriate conditions are those at which the influence of the alkali concentration and
the temperature are minimal, that is, those conditions as displayed in the center of
Sisson's
mercerization
chart.
While luster, hand, and dimensional stability are the three results most commonly
demanded of mercerization, the extents to which these three are achieved are not only
determined by a combination of the changes relating to the absorption of alkali, the
shrinkage and the swelling, and neither are these three characteristics all affected by
different
conditions
in
the
same
way.

In any case, in industrial processing, economy and operability are also major concerns.
Due to this, processing is not necessarily best implemented by treating the relationship
between alkaline concentration and processing temperature as a function according to
the aims of mercerization, and sometimes all the factors involved should be treated
independently. In regards to this, the effect of temperature on the hand of the fabric is
especially large, as is that of the tension exerted during the processing.
A typical method, called cold mercerizing, involves processing with an alkaline solution
at temperatures below 5C, commonly in the range of minus 10-15C. In this
processing, which gives the yarn or fabric a feeling of transparency and a harshness
like that of linen, due to which this processing is also called imitation linen finishing, the
alkaline
solution
is
in
the
range
of
15-30B.
However, when the concentration is below 15B and the temperature is as low as
minus 10C, the degree of shrinkage decreases and the swelling and the relaxing of the
cellulose structure due to the absorption of alkali is insufficient to gain these results.
While one reason why alkali processing at low temperatures such as these produces a
harder hand is that it is not able to produce the same degree of swelling as processing
at room temperature or higher, another important factor is considered to relate to the
fact that by lowering the temperature, the freedom of the cellulose's molecular structure
is
fixed
in
a
restrained
state.
In contrast to cold mercerization, processing at high temperatures is good for producing
a soft hand, but at temperatures above 60C, processing produces partial
mercerization, complete mercerization not taking place. Thus, in mercerization to
produce a soft hand in addition to a good luster and stability of form, adjustments
cannot be limited to the temperature conditions of the alkali dip. Consideration of the
entire process involved in the completion of mercerization is necessary. The same can
also
be
said
of
cold
mercerization.

1.1.f

Tension

During

Mercerization

In mercerization there are two types of tension, one produced by the constraining force
in opposition to the swelling caused by the twisting of the hair or the structural density of
the fabric when the single fibers which constitute the yarn or the fabric, ie the hairs,
absorb alkaline solution and swell, the other being intentionally exerted on the yarn or
fabric during mercerization. The former type of tension occurs due to the relationship
between the force of the swelling and the constraining force in opposition to it, and
although not certain, as it is due to the force of the swelling, it can be expected to
increase with increases in the concentration of the alkaline solution or decreases in the
processing
temperature.
The resulting negative tension can be derived by measuring the load required to keep
the yarn or the fabric at the same length as that before processing, but because this
tension cannot be adjusted during mercerization itself, if any adjustments are required,
measures must be taken during the design stage of the yarn or the fabric.

The latter tension, being a tension intentionally exerted during mercerization, can be
considered in three stages, these being during the penetration of the alkaline solution
and the swelling, during the fixing of the dimensions and the enhancing of the luster,
and during the removal of the alkali. Along with the concentration of the alkaline solution
and the temperature during the treatment, control of the tension during the different
stages is important in the supervision of the mercerizing process.

1.1.f.1

Tension

and

penetration

of

the

alkali

In the initial penetration of the alkaline solution and swelling of the fibers, the surface
tension of caustic soda solution increases with increases in concentration, and for
temperatures of around 18C, at a concentration of 24B, a concentration commonly
used in mercerization, it is approximately 84dyncm-1, and at 30B it is 89dyncm-1.
The surface tension of water at the same temperature is 73.05dyncm-1, and for acids,
and especially organic acids, the surface tension decreases with increases in
concentration, becoming significantly lower than that of water, although for inorganic
acids in the range of practical application, there is very little difference from water.
From this, it is clear that the wetting of the yarn or the fabric with the alkaline solution
during mercerization is not easy to achieve, and after the cellulose fibers come into
contact with the alkaline solution, the surface of the yarn or the fabric will swell, and
because the spaces between individual fibers contract, the air inside the yarn or the
fabric will be less likely to escape to the outside, thus making the penetration of the
alkaline solution more difficult, easily producing a state called wetted surface. The wet
ability of a material or a yarn can be substantially reduced by insufficient preprocessing
or excessive drying, so sufficient pretreatment along with treatment when the amount of
residual water is close to that naturally absorbed by cotton, is desirable because these
factors raise the degree of wetting and the internal penetration of the alkali.
In practical mercerization, the dipping time for yarn and material that has been
processed adequately is commonly set at around 40-50 seconds, and results of
investigations into the effects of tension during this time show that when there is no
tension the shrinkage nears equilibrium after 60 seconds, but under high tension the
same processing time will only produce about half the amount of shrinkage, and around
120 seconds, or twice as much time, is necessary to produce the same amount of
shrinkage
as
when
there
is
no
tension.
These results were determined by the point at which the degree of shrinkage more or
less reaches a value of equilibrium, but from the original results concerning sufficient
penetration of the alkali into the inside of the cellulose fibers micelle and the
subsequent reaction with the cellulose, the time required was determined to be two
minutes for hairs and around five minutes for yarn or fabric. Thus in industrial
mercerization, an alkaline dip of less than one minute will result in partial mercerization
of
only
around
70%
for
yarn
and
40-60%
for
fabric.
In order to conduct adequate mercerization, in addition to sufficient pre-processing of
the yarn or fabric to enhance its wettability, measures must be taken to ensure that no

tension is in force during dipping in alkali despite any occurrence of shrinkage, while a
sufficient amount of time is also allowed. This kind of tension control is easy in the case
of yarn done as a batch, but in the continuous treatment of fabric it is difficult to achieve,
there
being
many
cases
of
large
deficiencies.
Penetration agents for use in mercerization enhance the wettabilty during the alkali
processing by accelerating the penetration of the alkaline solution into the structure of
the yarn or fabric, but the excessive time required for the diffusion of the alkaline inside
the
hair
remains
a
problem.
High temperature mercerization is a method for allowing the rapid penetration and
diffusion of the alkaline inside the hair to allow complete mercerization as far as the
inner layer of the micelle. In addition to lowering the surface tension of the alkaline
solution by raising its temperature, the internal diffusion of the alkali itself is greatly
accelerated because the swelling decreases due to a drop in the celluloses absorption
of alkali.Thereafter, the temperature is lowered in order to increase the absorption of
alkali and thus increase the rate of the mercerization reaction. Due to considerations of
cost,
however,
this
method
is
little
used.

1.1.f.2 Tension after the swelling due to the alkali

The tension introduced after the swelling of the yarn or the fabric is a mechanical
tension exerted to resist the force of the shrinkage of the shrunk yarn or fabric and, by
stretching, it fixes the dimensions as required. At this time, the problem in the
processing is not the degree of tension required but the amount of stretching. For the
generation of a good luster, stretching to the original length before the processing is
usually the norm, but stretching beyond the original length will enhance the luster even
more. However, stretching is not often beyond the original length of the yarn or the
fabric due to the mechanical difficulties and the negative effects on hand and strength.
In so-called tensionless mercerization, which is totally without stretching, the
improvement
to
luster
is
extremely
slight.
The results of investigations into the relationship between the degree of stretching and
the luster of a cotton hair (J.T. Marsh) are shown in Table 1.
Table 1 The relationship between the degree of stretching of a cotton hair during
mercerization and the resulting luster.(J.T. Marsh)

The increase in luster is due to the cellulose hair, swollen with the alkali, becoming more
circular (it becomes, in fact, elliptical), which stretching enhances, and the surface of the
hair becoming smoother. The luster of cotton fibers is decided by the ratio between the
long and short axes of the cross section of the cellulose air, and it improves as the cross
section becomes more circular. (See Fig. 19)

Fig. 19 The axial ratio of the cross-section of single cotton fibers and their luster
While mercerization can greatly improve luster, it cannot make up for deficiencies in the
luster of the raw cotton itself, and in order to produce products of superior luster,
primary considerations relate to the choice of raw cotton, the twisting and manufacture
of the cotton yarn and the structure of the fabric. While changes in the mercerization
process do influence the improvement of luster to a certain extent, any effect that
surpasses
the
more
basic
variations
cannot
be
expected.
As mentioned previously, after fibers have swollen sufficiently in mercerization under
conditions free from externally-applied tension, applying tension to yarn in batches is
easy, but in the continuous treatment of fabric, because control is difficult to exert,
supervision of the tension and the dimensions of the fabric are incapable of allowing
conditions ideal for free shrinkage during the penetration of the alkali and the swelling.
The result is close to that of mercerization at fixed length (a method which involves
treatment while preserving a certain length, not allowing the shrinkage of the fabric
which arises from the swelling and shrinkage accompanying the penetration of the
alkali), the penetration of the alkali being less than ideal, and the effects of
mercerization
being
reduced.
Thus, this is one reason why the mercerization of yarn is valued in the production of
high-grade products. In addition, the fixing of the dimensions by tension during the
process, along with the removal of the alkali through the washing which follows, plays
an important role in enhancing the shrink-resistance of a product.
Cellulose with relaxed bonding due to swelling is fixed in the new dimensions at this

time, and the tension is maintained as the alkali is removed, because crystallization due
to the bonding of cellulose molecules in their new positions must be allowed to occur.
The fiber in its swollen state, in addition to having swelling sufficient to cause distortion
to the celluloses molecular chains or structure due to the stretching, must also hold
enough alkaline solution or water to prevent the intermolecular bonding of the cellulose.
In processing for which the conditions are similar to those of mercerization at fixed
length, the alkaline solution required for swelling does not enter the yarn or fabric in
sufficient quantities before the time allotted for swelling is up due to the tension or the
wringing of the liquid. During that time, free alkaline solution will be absorbed by the
fibers, and a certain degree of swelling will occur, but the fibers are stretched when
there is still an insufficient amount of alkali or water between the molecules in the
celluloses
structure,
or
in
the
air
gaps
in
the
micelle.
The result is that the yarn or fabric will break because it cannot withstand the tension.
When alkali cellulose fibers in a relaxed state are distorted, as can occur easily in weak
fine count yarn or fabric, if the water which fills the spaces between the molecules is
insufficient, the hydrogen bonds will break and the fiber will snap, but if the amount of
water is sufficient, the alkali cellulose is considered to be able to respond to the
distortion
by
deforming.
The amount of water content required at this point is decided by the amount of
absorbed alkali, and in cotton fabric it will be at least above 100%, while in the case of
yarn, more is necessary. In tensionless mercerization in which no tension is exerted
after the swelling which follows the absorption of the alkali, if total mercerization does
not take place in the inside of the cellulose structure, the desired degree of stretching
will
of
course
not
be
attained.
If the alkali-swollen fiber is stretched and the dimensions set as required, rinsing with
water in that state will remove the alkali, but if the tension is relaxed when the alkali has
still not been sufficiently removed, the fiber will swell and shrink again, and the
effectiveness of the setting of the dimensions will be reduced due to the remaining alkali
cellulose.
Any Alkali cellulose I and II generated can exist for a short time at around 15B or
below 10B respectively, as has been shown through X-ray observations. In
measurements of the shrinkage of the cellulose, when hair that is treated with high
concentrations of alkali is treated with alkali solutions of decreasing concentration (see
Fig. 3), even at concentrations of 10Tw, if the degree of shrinkage is still close to its
maximum, treatment under a fixed tension until the alkali is more or less totally removed
was
found
to
be
ideal.
In industry, practical mercerization involving the hydrolytic cleavage of the alkali
cellulose inside the cellulose and the preservation of the tension until the absorbed
alkali is completely removed is nearly impossible, and so in practical production, the
tension is released when the alkaline concentration of the cleaning liquid reaches an
appropriate
point,
and
the
rinsing
continues
until
neutralization.

When the alkaline concentration of the cleaning liquid goes below 5Tw, or 3.5B, the
setting of the dimensions is considered to be sufficient, but the concentration cannot be
adequately supervised and is basically decided not by the alkaline concentration of the
cleaning liquid but by the amount of alkali that remains in the fiber.
One of the most effective methods for removing alkali solution is the use of hot water,
but in this too the sufficient preservation of the tension of the swollen fiber is very
important, and in order to prevent the fibers from becoming brittle, the temperature must
be kept below 80C. Additionally, vacuum dehydration allows the deformation of the
swollen fiber due to mangle nip to be avoided while effective cleaning is still carried out.

1.1.g

Drying

After

Mercerization

Fibers in their wet state at the conclusion of mercerization have a very high degree of
swelling, and have large internal air gaps. But if the fibers are dried, these gaps will
contract as the water evaporates. The final fixed sizes of the gaps inside the fibers are
altered by different temperature and tension conditions during the drying.
An idea of these changes can be determined by considering the changes in dye
absorption rates and in moisture absorption rates. H. Flecker (see above), using
Benzopurpurin B4, investigated the changes in the degree of absorption as relating to
the alkaline concentration (Fig. 20), the degree of tension (Fig. 21), and the type of
drying after mercerization.
Fig. 20 Alkaline concentration versus the absorption of dyestuff

Fig. 21 Tension during mercerization versus the absorption of dyestuff

Fig. 22 Drying conditions after mercerization versus the absorption of dyestuff

According to his investigations, a relationship does of course exist between variations in
the cellulose micelle's degree of swelling and the amount of dyestuff absorbed as
determined by alkaline concentration, and the air gaps in the fiber can vary in size up to
20% according to the level of tension that is applied. That is, in comparison to untreated
fiber, absorption of dyestuff is twice as high after mercerization, and 2.4 times as high
after tensionless mercerization. Furthermore, the absorption of dyestuff is reduced by
one third after natural drying in air, and by nearly one half after drying at 110C in
comparison with non-dried fiber, which suggests the contraction of the air gaps inside
the
fiber.
The repeated hydration and dehydration of the cellulose fibers results in the contraction
of the micelles' air gaps, and while the reduction of the hygroscopicity and the amount of
dyestuff absorbed are well known, the influence on cellulose fiber and cellophane is
especially severe immediately after mercerization when the internal structure has a low
level
of
crystallization.
According to L.E. Hessler (Tex. Res. J., 24, p.822, 1954), the level of crystallization of
cotton before mercerization was 89%, while after mercerization it was 64%, and that of
viscose rayon was 45%. The results were particularly severe in cellulose having a low
level of crystallization such as cellophane (see Fig. 23).

Fig. 23 The effect of preprocessing on cellophane's moisture absorption

In addition, the results of Coward and Spencer (J.T.I., 14. p.32, 1923), who measured
changes in the amount of absorbed water using a centrifuge, are shown in Table 2.
Table 2: Changes in the amount of water absorbed due to conditions of washing
and drying following mercerization

From the above, it can be seen that the size of the air gaps in the cellulose's micelles,
that is, the fiber's internal volumetric capacity, is altered by the tension and temperature
conditions during the rinsing and drying at the conclusion of the mercerization process
which, in addition to altering the hygroscopic characteristics and producing variations in
the absorption and reactivity of the dye, also significantly influence the hand of the
fabric.
Despite these factors, items lacking mercerization are of course inferior to mercerized
items, and the drying which follows mercerization is best done at a low temperature
under tensionless conditions, drying methods involving an ironing effect as with a
cylinder drying machine being best avoided. These points in particular should be kept in

mind

during

the

1.1.h

dyeing

and

finishing

Types

of

of

mercerized

products.

Mercerization

Mercerization is widely used, and in the mercerization of different kinds of cellulose

products, including blended products, the machine used and the treatment conditions
must be selected in accordance with the type of fiber, the form that it is in and its
properties, and also in accordance with the aims and the timing of the mercerization.
The wide range of treatment methods can approximately be broken down into the
following
divisions.
Parentheses
denote
established
terminology.
1.

Classification

according

to

the

form

of

a) Yarn

the

product

mercerization

Batch :

Hank mercerization

Cheese mercerization

Continuous :

Single end mercerization

Tow mercerization

Warp mercerization

b) Knit Mercerization

Open mercerization

Closed mercerization (Round mercerization, tubular knit mercerization)

c) Cloth mercerization

2.

Chainless mercerization (Roller mercerization)

Chain mercerization (Stenter mercerization)

Batch-up mercerization
Classification

a) Water content

according

to

the

marcerizing

conditions

Dry mercerization

Wet mercerization

b) Tension

Fixed-length mercerization

Tension mercerization

Tensionless mercerization

c) Alkaline concentration

Low-concentration alkaline mercerization

High-concentration alkaline mercerization

Two-step mercerization

d) Temperature

Ambient-temperature mercerization

High-temperature mercerization

Low-temperature mercerization

3. Classification according to timing

Gray mercerization

Pre-dyeing mercerization

Post-dyeing mercerization

4. Classification according to the number of treatments

Single mercerization

Double mercerization

5. Classification according to the type of alkali used

Caustic soda mercerization

Ammonia mercerization

6. Other

Alkali pad-dry method

Alkali pad-steam method

While other variations are also used, mercerization in industry is generally implemented
according to a combination of the basic factors as listed above.

1.

Hank

mercerization

This is currently the most commonly used method of mercerization, and generally
entails rolling a 54-inch long (the length of one loop) hank weighing about 500g a
number of times between two adjustable rollers. The yarn is moved by the turning of the
rollers, with penetration of the alkali, application of tension and rinsing occurring
automatically.
In this, one cycle takes about three to five minutes, and four to eight kilograms can be
treated at one time. In the latest machines, all operations are automated, including
control of the alkaline solution's concentration and temperature and the addition and
recovery of the alkali, along with application of tension on the yarn and rinsing. The only
manual operation is the paying in and out of the yarn, meaning that the procedure can
be
implemented
with
a
high
degree
of
effectiveness.
If, in order to increase the level of efficiency, the length of the hank is increased,
handling becomes difficult and if the weight of the hank is increased, the changes in
length during the shrinkage and extension of the internal and external sections of the
hank can differ, and variations in the length of the yarn in each loop can increase due to
disarrangement of the yarn, which can all result in uneven mercerization.
An advantage of hank mercerization is that during the yarn's absorption of the alkali,
treatment can be carried out without tension, and so the alkali solution is able to
penetrate the inside of the yarn sufficiently, and after the fibers have swelled sufficiently,
any level of tension can be applied and the yarn rinsed for removal of the alkali. This
allows the production of goods with satisfactory mercerization effects.
However, if the winding or the handling of the hank is inappropriate, disarrangement of
the lengths of yarn in one loop can result in different tensions, leading to uneven
mercerization,
which
can
often
result
in
patchy
dyeing.
Uneven mercerizing due to uneven tension is an unavoidable problem in current
methods of mercerization. While in theory reduction of the amount of yarn in one hank
increases the evenness of the mercerization, this not only reduces productivity, but also
results in many yarn-piecing defects during production of the weave or knit due to
inadequate
yarn
length.
For these reasons, using yarn that has been hank mercerized and then dyed for

finishing into solid-color fabrics can result in a barre effect, preventing the fabric's use in
a product, and so hank mercerization of pre-dyed yarn is mainly used for products with
narrow stripes or a checkered design when barre is not noticeable.
Another problem in hank mercerization is that conventional rinsing after mercerization is
insufficient, and without neutralization through separate rinsing with hot water, the
remaining alkali can cause problems. While in theory there are no reasons preventing
sufficient neutralization through removal of the alkali in this method, complete treatment
of batches in hank form has a low efficiency, and so is not used due to the cost and the
level
of
productivity.
Thus, if treatments must be conducted separately, the effectiveness of simple
conventional rinsing during the alkali treatment is negated. Furthermore, handling in
hank form is necessary in the scouring and bleaching which follow, as well as in the
dyeing, and there is a tendency for the quality of the yarn to deteriorate due to
disarrangement
of
the
yarn.
Finally, after drying, winding from the hank to a cone or cheese is necessary, and the
effort and labor hours needed for this are a major disadvantage.

2.

Cheese

mercerization

Carrying out mercerization, scouring, bleaching, and, in some cases, dyeing, along with
oiling or sizing, with the yarn in cheese form results in a major rationalization, which can
raise
productivity
and
reduce
costs.
However, mercerization in cheese form can only be expected to achieve halfmercerization, and not the same degree of evenness as hank mercerization or other
types of mercerization. This prevents the method from being used beyond a limited
number of possible applications. However, this method is considered very valuable in
those applications in which it provides a satisfactory degree of quality.
One problem is how to limit the difference in shrinkage between the inside and the
outside of the cheese. Important factors in this are the adjustment of the twisting and
the density of the winding of the yarn, the size of the take-up tube, the thickness of the
layers during the winding, and the alkali concentration and temperature during the
treatment.

3.

Single-end

mercerization

This method, also called, cone-to-cone, or cheese-to-cheese, involves taking up yarn

into a cheese or cone shape, and, with one machine per cone, conducting alkali
penetration, rinsing (with hot and cold water), neutralization, rinsing again, and drying in
consecutive order with the correct scheduling, and then taking up into a cheese or cone
form.
The yarn speed in this being approximately 450m/min, the productivity per machine is
low, and the equipment costs are high, but because the sequence is automated, it only
requires
a
very
small
number
of
staff.

The mechanism for conducting mercerization with these machines involves three
revolving rollers: two squeezing rollers which are pressed tightly together and a third
roller placed, at a certain distance, more or less parallel to these two. Yarn is lined up in
parallel from one end to the other of the third roller, which is removed from the nip space
of the two squeezing rollers, and moved in a spiral perpendicular to the roller, during
which time the alkali penetrates, tension is applied and rinsing (both with hot and cold
water)
and
neutralization
occur.
This is basically a form of fixed-length mercerization, and while the tension is not freely
adjustable, in addition to adding finely engraved grooves to the surface of the third,
slightly separated, roller, the diameter of the center and the two ends of the rollers can
be adjusted in response to the shrinkage of the yarn due to the absorption of alkali and
can
apply
tension
after
the
absorption
and
swelling.
However, these factors are also determined by the rollers, and the conditions cannot be
changed according to the yarn and the desired effects as in hank-mercerizing, so the
quality of the yarn after treatment is limited to a certain range.
A problem in this form of mercerization is the relative difficulty of controlling the tension
on the yarn as it is introduced, and differences in the level of tension between machines
and between cheeses or cones can occur easily and lead to patchy dyeing. Due to this,
in addition to giving special attention to tension control, it is important to adopt
centralized supervision in order to ensure the same conditions for each machine,
including
those
of
alkali
concentration
and
temperature.
Other problems relate to yarn breakage, yarn overlap, and yarn skewing. While
mechanical supervision is important, the yarn count and quality of the yarn undergoing
treatment also has a large influence, and so choice of chop number and supervision of
quality
are
very
important.
In general, this method of treatment requires two-fold yarn with a yarn count less than
60, and it is unsuitable for the treatment of yarn with fine yarn counts higher than this.

4.

Tow

mercerization

Normally, 400 or so yarns are wrapped around a beam or a ball with a warper and 8 to
10 of these beams or balls are set in a stand. Yarn is unreeled from the balls or the
beams at the same time and lined up in ropes made with light twisting, which are
mercerized continuously in a manner similar to that of roller mercerization of fabric.
A large number of threads are gathered together and lightly twisted into a rope-like form
in order to prevent the problems that arise as threads break and become entwined on
the rollers. However, if too many threads are twisted together, the mercerization may be
uneven, but if there are too few, problems can occur when threads break, and so it is
important
that
the
number
twisted
together
be
appropriate.
The equipment used in this method looks like a row of soapers, and each treatment
bath is driven separately, tension on the yarn is controlled, and the shrinkage due to

swelling during absorption of the alkali and the level of strain after this can be adjusted
freely.
This type of equipment can produce a large amount of yarn of consistent quality and so
this method is suitable for the production of mercerized yarn for use in knits, and the
treatment of fine yarn that is two-fold yarn with a yarn count of around 100-110 is also
possible.
However, when treating several thousand threads of yarn at once at a rate of around
20m/min, it is difficult to ensure that each yarn is sufficiently mercerized in comparison
to the single-end method, and the resulting swelling of the yarn can easily be somewhat
greater than that of the single-end method. However, in addition to producing a soft
hand in the final product, this type of mercerization is very even, and so it is the best
method
for
attaining
level
dyeing.
One problem concerning the type of equipment used is the separation of the yarns in
the rope after it is dried at the conclusion of the mercerization process, and the way in
which the yarns are unwound is very important for ensuring the smoothness of the
operation.

5.

Warp

mercerization

While tow mercerization involves the treatment of a lot of yarn lined up in rope-form, in
warp mercerization yarn is wound onto a beam and fed into a machine with the same
system as in a slasher-sizing machine. Mercerization takes place with sheets of
separate threads, and the machinery used can be exactly the same as that in tow
mercerization.
Thus, in the warp-beam method and the tow method, only the handling is different, and
aside from measures for achieving penetration, there are no major differences between
the
two
methods.
Machines for these methods have been produced for quite some time, and, due to
considerations concerning yarn breakage, these machines have been used with the tow
method
with
dozens
of
yarns
at
a
time.
If mercerization can be carried out with the warp-beam method, it can be more rational
than the tow method because yarn that has been mercerized from beam to beam can
be
extracted
in
beam-form.
A problem, however, is that during treatment the breakage of a single thread can lead to
major difficulties, and so if the yarn is not of very good even quality, industrial
implementation of this method is difficult. A representative example of continuous
treatment with a number of gathered threads is the continuous dyeing of indigo denim,
but the important factors in this can be learned from treatment in rope-form used in
order to avoid problems associated with yarn breakage even when the yarn to be dyed
has
a
thick
yarn
count
of
around
10.

1.1.h.2

Knit

Mercerization

1).

Open

Mercerization

This type of mercerization involves treatment of circular knits after they have been
opened, and fabric that has had its selvage gummed as required is treated like a weave.
This method is used in the mercerization of products with strict shrinkage restrictions in
both the vertical and horizontal directions and fabric with motifs in which skewing often
occurs.
Recently, demand for this kind of mercerization has been increasing, especially in reply
to improvements in knitted products. Originally, horizontal stitches in single knits
became spiral shaped, and because of this fabrics would naturally have a tendency to
twist, the selvage curling when open-cut, thus making fabric difficult to handle.
Thus, to prevent these problems from occurring and to conduct treatment continuously
in an open state, all types of mechanical means are necessary, and while preventing
excessive shrinkage in the horizontal direction and curling of the selvage, immersion in
alkali
and
swelling
of
the
yarn
must
be
carried
out.
Machine manufacturers have tried various measures to achieve this, including adhesive
transfer from one roller to another, use of a roller with a large diameter, meshed
engagement with an irregular roller, grooves on the surface of the roll and the use of a
screw roll, but mainstream methods involve, in the last phase, attaining the required
vertical and horizontal dimensions on a pin stenter, and, while preventing distortion due
to
sagging,
removing
the
alkali
and
setting
the
dimensions.
Dimension setting for cotton knits is precise, and important factors in the quality of the
product include a residual shrinkage kept below 2-3%, a satisfactory level of elongation
and tensile recovery strength, no deformation of the stitches, three dimensional
swelling, a soft hand and good luster. Because skewing and uneven stitch density must
be avoided, a high degree of technique and supervision are required in mercerization,
and even now this technology is not perfect, and different companies continue to
conduct
committed
research.

2).

Closed

Mercerization

(Tubular

Mercerization)

This method involves not opening round knits but mercerizing them in their tubular
state. Knits are usually treated as two flat pieces of material which have been laid
together. For this, strong tension or pressure applied longitudinally to the folds of the
two edges of the long sides of the fabric causes differences in yarn density on both
faces of one of the knits, which results in a line of broken stitches on the outside of the
fabric and the formation of a concave broken line called an edge mark on the inside of
the
fabric.
To prevent the production of this edge mark, between the swelling of the yarn with alkali
and the rinsing to remove the alkali, the control of the tension and adjustment of the nip
are of course important, but other methods that prevent the formation of edge marks
include introducing air to the inside of the tube at strategic spots due to which the knit
expands to a cylindrical shape, setting several round plastic blades or rings with

alterable circumferences at intervals inside the tubular knit, or inserting a bar-shaped

frame inside, thus preventing the fixing of the edges during the treatment, and also
expanding
the
width
of
the
fabric.
However, when solid material is inserted into the tube in order to increase the width of
the fabric, the frictional resistance increases with increases in the width of the fabric,
and because a great deal of force is required to move the fabric, there is a limit to the
degree to which a fabric can be expanded in the horizontal direction, and even when air
is introduced inside, preservation of air pressure above the level of resistance to the
expansion of the fabric is limited because of the escape of the air.
For these reasons, in closed mercerization, setting the dimensions of the fabric in its
entirety is basically very difficult, and there are of course certain constraints in regards
to
this.
However, the result obtained is very good in comparison with products which have not
been mercerized in terms of appearance and quality, and with regards to the setting of
the dimensions, and so aside from products of especially high quality, if the design of
the yarn or of the knitting and the settings of the mercerizing machine are appropriate,
the production of goods which satisfactorily meet the requirements of the market is
possible
even
with
round
mercerization.
Among the machines for this type of treatment, machinery which blows air into the knit
is considered superior because tension control is simple, and so machinery of this sort
has been constructed. Furthermore, even when air is not blown in, air contained in the
structure of circular knits themselves collects inside the tube during the moisture
extraction process, resulting in a cylindrical shape forming naturally, and so some
machines make use of this quality in conducting effective treatment.

1.1.h.3
1)

Cloth

Mercerization

Chainless

mercerization

This method of mercerization running fabric through a number of rollers without the use
of a clip stenter is also called roller mercerization. The machine used has a number of
stainless rollers, or stainless and rubber rollers, of a relatively-large diameter tiered
zigzag in close contact to each other inside a long trough, with the lower tier designed to
submerge
in
alkaline
solution
for
mercerization.
The absorption of alkaline solution and fabric swelling take place as fabric sequentially
glides through the surface of these rollers, and, although this movement from roller to
roller in close contact with them reduces the widthwise contraction to a minimum, the
resulting fabric expansion remains within a limited range, thus displaying the
mechanism
of
mercerization
at
fixed
length.
A similar device is used for the removal of most alkali following this initial stage of alkali
penetration and fabric swelling, and an open-width soaping machine for further removal
and
neutralization.

Therefore, the machinery required is extremely concise and the cost is low, in
comparison with the chain mercerization method described in the following chapter.
However, this method is subject to a considerable number of constraints due to
inflexible widthwise control over fabric depending on the kind and use.
With all cotton and its blends with polyester, in machines of this type there is trouble in
the dimension settings of 100% cotton and blends with low polyester content, while
blends with high ratios of polyester, even those of a plain structure, there will be no
problem since control by heat setting is possible, with only a limited widthwise shrinkage
being
expected
from
mercerization.
Roller mercerization is not at all suitable, particularly for these sheer plain weaves. This
type of machine is widely in use in Europe, in contrast to its scarce usage in Japan.

2)

Chain

mercerization

In order to make up for the shortcomings of the roller mercerizing machine, a clip
stenter is used for post-mercerization treatment, in which a widthwise tension is applied
then most alkali is showered off the fabric kept on the stenter, followed by thorough
alkali removal and neutralization using an open-width washing machine.
As for practical machinery, a heavy padding mangle is used for the application of
alkaline solution in the 2 dip/2 nip method, with sufficient time allowed for penetration
and swelling of the fabric in a timing cylinder, instead of undergoing an operation using
so many rollers and so much solution as in roller mercerization, to ensure reduced use
of
the
alkali.
Since the chain mercerizing machine operates at an extremely high speed of 120200m/min, a clip stenter is commonly used after two consecutive treatments of alkali
application/penetration. It is a device of considerable size, capable of holding, while
maintaining a widthwise tension, 70-90m fabric at a speed of 120m/min., or 117-150m
at 200/m, so that sufficient time is allowed, approximately 35 seconds for
polyester/cotton blends, and 45 seconds for 100% cotton, between the initial application
of alkali solution and the subsequent start of showering the alkali of the fabric.
Furthermore, thorough removal of the alkali is ensured in this stenter stage, through
repeated
showering
and
vacuum
treatment.
The efficiency of the vacuum treatment will be most influential in the removal of alkali,
especially in cases of using heavy cotton weaves, deficiencies in alkali removal makes
the showering, even in an increased amount, an ineffective flow over the fabric surface
and allows the fabric to be released from the stenter while still immature, resulting not
only in incomplete setting of the widthwise dimension but also in fluctuations in the
dyeing
stages
that
follow.
Moreover, in the case of sheer cotton weaves, sufficient application of alkali solution will
be important, since the relationship between controls over tensile strength for the
obviation of crease production during the timing cylinder stage, controls over the fabric
width on the stenter and the amount of alkaline solution required is extremely delicate.

Considering the points mentioned above, the performance of chain mercerizing

machines developed to date seems hardly satisfactory. The removal of the remaining
alkali after the stenter stage barely comes into question in terms of the resulting
mercerization effect, however, a crucial watershed will be whether the remaining alkali
can be reduced to less than 3B before the fabric leaves the stenter.

3)

Batch-up

mercerisation

In this method, an alkaline solution is padded onto fabric which is then rolled up, and
when padding is completed the alkali is removed through continuous cold rinsing.
Although the use of the method is not common in Japan, a certain degree of application,
including
in
knits,
can
be
found
in
Western
Europe.
Despite costs for facilities being remarkably low, it is not an interesting method except
for some special cases, as quality management and productivity remain problematic.
Still, for the growing cases of carrying out alkali reduction for the polyester side of
cotton/polyester blends to achieve both the mercerization of cotton and the alkali
reduction of polyester in a single treatment, the application of this cold batch method is
particularly interesting as a device that can combine the two separate stages which
would
otherwise
raise
facility
problems.

Classification
Conditions

According

to

the

Mercerizing

a) Classification according to the water content of

substrate during treatment
There is dry mercerization and wet mercerization, the dry and wet denoting the state
of the substrate, i.e. yarns, knits and weaves, during treatment.
Dry mercerization is the method commonly implemented for its stable mercerizing
effects and easy management, except for when the wet method is used in order to omit
the drying stage required for the dry method after scouring and bleaching of a yarn or
weave.
This wet mercerization requires, as mentioned previously, not only a sizable cooling
device as a measure against the generation of a considerable amount of heat due to the
water content of the fabric and yarn used, an alkaline solution of a higher concentration
than the dry method and a longer processing time to ensure thorough alkali penetration
within the cellulose fiber as well as sufficient swelling of the fiber, but also a thorough
control over the alkaline solution to achieve success, especially when dealing with a
weave, as there are quite a few flaws in the methods of maintaining a constant
concentration and even dispersion of alkali in the treatment bath.
Despite the fact that carrying out complete scouring and bleaching primarily proves
much better for cellulose fiber in terms of ease of mercerization and the resultant effect,

the norm has been that, because no sizing agent is present in a yarn or knit from which
little trouble is expected, gray mercerization is carried out with the addition of an alkali
penetrating
agent,
then
scouring
and
bleaching
follow.
If the wet method were implemented as frequently as the dry method, scouring and
bleaching would naturally be carried out before mercerization for a greater mercerizing
effect,
improved
product
quality
and
reduced
cost.
As for weaves, because their weaving stage generally includes warp sizing and waxing,
carrying out gray mercerization will not produce a good result even with the use of a
penetrating agent no matter how powerful it might be, which is why desizing, scouring
and bleaching are carried out before mercerization. Even in this case, the fact that many
manufacturers carry out mercerization after going through a drying stage indicates how
difficult the management of product quality is with the wet method.
However, only a limited effect of mercerization can be expected especially in gray yarns
and knits, and in order to apply mercerization in producing quality goods or to produce
superior mercerization results, smooth operation should be made possible in all cases
with the wet method, holding a true, full command over the process.

b)

Classification

according

to

tension

The chief objective of mercerization is the improved luster, which, as described earlier,
can be attained by applying tension to fiber while in a swollen and shrunken state, and
there are two ways of attaining this state of tension; one is by letting the fiber swell and
shrink with the use of alkali while preserving its original length, and the other by letting
the fiber contract freely then applying tension before bringing it back to the original
length.
The former is classified for convenience as fixed-length mercerization and the latter
tension mercerization, however, conditions somewhere between the two are most often
the case in practical mercerization. Mechanical or operational reasons are usually
responsible for this, and it is rare that conscious efforts are made with regard to the
resultant
effect.
Equally, the configuration for the length of time required for maintaining tension is dealt
with from the standpoint of meeting the standards of finished products as part of
customary commercial requirements, and the industrial case of configurations being set
genuinely with regard to the mercerization effect is hardly seen.
Because neither configurations for tension application nor dimensions are set in order to
maximize the resultant effect, inadequacy is commonly found not only in the quality of
the finished product but also in the fabrics shrinkage and hand. As has been seen so
far, tensionless mercerization is a process in which the fiber is freely allowed to swell
and shrink due to alkali absorption without any tension being applied, and after the alkali
is washed off, dimensions are set, and is a process from which a stretch cotton with
around 20% elasticity can be attained, using a fiber which is designed to produce a
minimal resistance to contraction in alkali in its yarn and woven/knit state.

Among cotton knits and weaves commercially available nowadays, many have semistretch,
if
not
full-stretch,
properties.

c) Classification according to alkaline concentration

As mentioned earlier, an alkali concentration higher than 24-26B is required in the
treatment liquor under ambient temperature conditions in order to achieve the expected
mercerization effect with a concentration around 30B resulting in a higher stability,
however, supposing that the amount of alkali absorption by the cellulose fiber is a
criterion for the effect of mercerization, any discussion based only on alkaline
concentration will be meaningless because the amount of alkali absorbed by the fiber is
determined by both the alkaline concentration and the processing temperature.
The concentration used in practical industrial mercerization is therefore the same as
that of preliminary mercerization, i.e. in the range between 20B and 30B. Though it
is natural, in the industrial context, that an alkaline concentration as low as possible is
preferred out of concern for production costs, by lowering the processing temperature,
an effect which is equivalent to that which results from a high-temp/high-concentration
treatment can be attained even with a low alkaline concentration.
While the lower limit of concentration has conventionally been 22-24B, a lower
concentration of around 20B may be used depending on the kind of weave. All
alkaline concentrations within this range can be regarded as the same in terms of the
resultant practical mercerization effect and it is the standard range used in
mercerization. Equally, mercerization using an alkali solution of an even lower
concentration between 14B and 18B is called low-concentration mercerization, in
which
the
usual
mercerizing
effect
cannot
be
attained.
This mercerization process with a low alkaline concentration mainly aims to improve
dyestuff absorption in cotton and to produce a supplementary effect of scouring, and
with little alteration in the fabric dimensions and improvement in luster being expected, it
only requires a simple device, effective in the production of casual wear that takes
advantage of cottons natural feel and pile superior in softness, and has traditionally
been used in post-treatment for the improved hand and dimension-setting of
preliminarily
mercerized
knits.
Meanwhile, an alkali solution of a high concentration of 31-32B is often used in
mercerization which is carried out at a high temperature ranging from 50-60C up to
80C. There is a method of mercerization that takes place in two steps using two
solutions of a high and low alkaline concentration, being referred to as BP116553 in
Textils
Manufactullr;
June
P-24,
1971.
(sic)
This two-step mercerization uses initially an alkaline solution of 30-32%, i.e. 36-38B,
followed by that of 10%, i.e. 15B, aiming at the creation of a product superior in luster
and strength by inducing a higher degree of swelling in the fiber than the standard (onestep) mercerization method, for which the fiber, while being free of tension, is
completely transformed into alkali cellulose II in the first step, then stretched to the
original length with tension being applied, and sustaining the same state, is allowed to

transform

d)

into

alkali

cellulose

Classification

in

low-concentration

according

to

alkali

solution.

timing

There are usually three options as to when mercerization can be implemented during
the course of dyeing and finishing. There are three different stages at which the process
is carried out. Gray mercerization is carried out in the very first stage of the whole
process, i.e. normally after singeing while the substrate is still in the loom state, or in
other words, a method that deals with gray goods, then there is pre-dyeing
mercerization, which occurs before dyeing and after the pretreatment stages of
desizing, scouring and bleaching, and lastly post-dyeing mercerization takes place after
dyeing,
during
the
finishing
of
the
yarn,
weave
or
knit.
As has been stated earlier, gray mercerization is more frequently implemented with
yarns and knits, while pre-dyeing mercerization is generally applied in solid-dyed
weaves, and post-dyeing mercerization in yarn-dyed products, such as gingham, certain
top-end knits and some special high-quality weaves. Post-dyeing mercerization is used
for gingham not because it is counted as one of the quality goods that the method deals
with, but rather because the use of pre-dyeing mercerization would raise problems in
terms of productivity and costs as it is often seen with quality yarn-dyed weaves, which
are made of yarns that are mercerized before being dyed and finished.
In contrast to this, when post-dyeing mercerization is used for top-end knit products or a
certain kind of weave, some particular effects of mercerization are expected from this.
Among various reasons that support this application, the first thing that can be pointed
out is that the dyeing and finishing process causes deterioration in luster, which is
observed when a yarn or weave is mercerized prior to dyeing and finishing.
Deterioration in luster due to dyeing and finishing can be attributed to distortion of the
yarn, roughening and depredation of the fiber surface caused by dyestuff adhesion and
the
influence
of
chemicals
used
in
the
dyeing
process.
Post-dyeing mercerization is therefore the one which can produce a significant
difference in the quality of the finished product, such as the luster, the depth and
integrity of shade as well as the shape. However, carrying out complete post-dyeing
mercerization requires the use of dyestuff with a high fastness to high-concentration
alkaline treatments, or otherwise the treatment has to be kept within an extent which
does not adversely affect the dyeing result. Naturally, the result of such incomplete
mercerization will not be the same as that which is usually expected from post-dyeing
mercerization and will be inferior to that of thorough pre-dyeing mercerization, and most
gingham products fall into this category. Moreover, whether mercerization is carried out
while in the form of a yarn, weave or knit will considerably affect the quality of the final
product.
That is to say, in the case of yarn mercerization, each single yarn as it is not woven or
knit is free of physical restraints and can be mercerized without any change in the
shape of its circular cross section as opposed to weave or knit mercerization, in which a
yarn can easily become flattened and loose shape, thereby resulting in a product of

inferior quality, because of its state of being tied together and due to mechanical
handling. Therefore, in the choice, carrying out yarn dyeing and mercerization prior to
weaving or knitting is preferred for achieving a superior quality in the finished product.

e) Classification according to the frequency of

treatments
As mentioned in the previous chapter, the effect of mercerization on the finished product
quality differs considerably according to when the process is carried out, however, a
satisfactory quality cannot always be attained simply by timing the process well.
There are cases when the fastness of the dyestuff used is inadequate for the process
depending on the hue regardless of the fact that carrying out post-dyeing yarn
mercerization naturally involves problems in the handling itself and in productivity, and
for which nothing but pre-dyeing mercerization is available as an option.
Furthermore, as thorough pre-dyeing mercerization inevitably results in the hardening of
hand, it is not always the best method in terms of the resultant product quality and hand.
In addition, there is another problem in that a product quality as good as that of postdyeing mercerization cannot be attained because, as mentioned earlier, the effect of
mercerization
deteriorates
in
the
subsequent
dyeing
process.
A method that can cover such shortcomings is double mercerization, in which thorough
yarn mercerization is carried out first, followed by dyeing of the yarn then knitting or
weaving before going through mercerization again, with the dyeing process sometimes
being shifted after the second mercerization. In order to maximize benefits from the
effect of the first mercerization and to eliminate the disadvantages involved in it, a lower
alkali concentration should be used in the second mercerization under milder conditions
than
that
of
the
first
round.
Top-end knit products should require such a handling much more than weaves because
of
their
structural
characteristics.

f) Classification according to the type of alkali used

Among the kinds of alkali with which the same kind of effect as mercerization is
observed through bonding itself with cellulose fiber and making it swell, apart from
caustic
soda,
lithium
hydroxide
and
caustic
potash
are
known.
What is notable is that, with lithium hydroxide, an extremely high level of swelling can be
observed at a concentration one half that of caustic soda and, as for caustic potash, that
the effect of mercerization can be attained without causing damage in rayon fiber, its
action being more moderate than caustic soda. However, with the cost of both
chemicals being particularly high compared to caustic soda, cases of their application
are scarce in contrast to the almost exclusive use of caustic soda. Moreover, this
tendency is expected to remain unchanged for a long time to come.

Other than inorganic alkalis, there are also organic amines, quaternary ammonium
bases and ammonia with which the same effect of mercerization can be observed,
resulting from their action that induces swelling in cellulosic fiber. Of these substances,
the industrial application of liquid ammonia has begun, which is generally referred to as
ammonia
mercerization.
Although no effect of mercerization is observed when ammonia is used in a solution or
in its gas state, when it is allowed to act on cellulosic fiber while in a liquid form the
swelling can be completed within an extremely short time span. Mercerization effects
will result through applying tension to the swollen fiber and removing alkali from it.
Because the surface tension of liquid ammonia at the ambient temperature is 25.95dyn
cm-1, which is smaller than one third of around 90dyn cm-1 in caustic soda
mercerization, its wetting and penetrating properties are so extremely good that
complete penetration is possible with a half to two thirds of a second of soaking, and the
swelling
of
the
cellulose
within
a
few
to
15
seconds.
This is again one third of the time required in caustic soda mercerization, showing the
advantage of being a quick process. However, the boiling point of liquid ammonia being
around -33C, the swelling induced in the cellulosic fiber is quite unstable and the fiber
soon returns to its original state due to the vaporization of ammonia even when the
temperature
is
maintained
below
the
boiling
point.
Here, as in caustic soda mercerization, tension should be applied while in the swollen
state, and maintaining the same state, the ammonia has to be removed in order to
attain
the
effect
of
mercerization.
With regard to the environment in which tension is applied, Peabodys patented method
uses a 90% ammonia gas with a 80% ammonia content being maintained during the
process and removes the ammonia at first in a saturated ammonia solution at a
temperature between -7C and -10C, secondly after squeezing and during drying at
28C
and
finally
during
drying
at
100C.
Including the use of hot water (88C) in the Prograde method, these conditions used for
the removal of ammonia can considerably affect not only the cost of ammonia recovery
but also the result of mercerization, however, details concerning the use of such
conditions
are
not
known.
When ammonia-mercerized products are compared to their alkali-mercerized
counterparts, the former is said to be considerably inferior to the latter in the degree of
improvement in dyestuff absorption and insufficient in luster, but superior in the degree
of improvement in strength and the durability of dimension stability, as well as in
maintaining
cottons
soft
hand

Others
In addition to the conventional method of mercerization, which consists of soaking in a
caustic soda solution, leaving the fabric to swell while tension is applied and rinsing off
the alkali, various other methods have been released with modifications made in order

to

enhance

the

resultant

effect.

Typical among those are Babcocks Mercevic (sic) method and Sandozs SM method
(Spannrahmen Mercerisation; stenter mercerization), the latter being said to be suitable
for the mercerization of knits. Though, as stated earlier, the use of stenters has begun in
the mercerization of knits in order to properly align knit stitches, what is different about
the SM method, consisting of the same process from soaking in alkali for free
contraction to pinning on a stenter for stitch alignment as the conventional method, is
that, after those stages, the alkali-soaked knit fabric is dried whilst still on the stenter.
In contrast to conventional methods in which the alkali is removed through showering
after those stages, in the SM method, the fabric is removed from the stenter after being
dried on it, then the removal of alkali and neutralization takes place in the usual way
before the fabric is dried again while its width is adjusted on the stenter.
Although details are not known as to what this interim drying process after the addition
of alkali signifies in the SM method, it can be assumed that the operation from soaking
in alkali to pinning would become easier through the application of a relatively high
pickup rate and a weak alkaline solution, as well as the aligning of knit stitches on the
stenter, and since the alkaline solution is concentrated during the drying process, it
would
result
in
high-concentration
mercerization.
It is conceivable that interesting results can be obtained from this, given that appropriate
conditions
are
set
to
minimize
deterioration
in
cellulose.
Meanwhile, there is another method that can be called the pad-steam method, in which
the fabric is fed into a normal or high-pressure steamer after the padding of the alkaline
solution, thereby simultaneously carrying out mercerization and scouring, or thereby
preventing
the
hardening
of
fabric
hand
due
to
mercerization.
This pad-steam method is the opposite of high-temperature mercerization so to speak.
Whereas high-temp mercerization takes an approach of cooling the fabric after allowing
some time for high-temp/high-concentration alkali soaking to improve the resultant
effect, in this pad-steam method, quick steaming is carried out in saturated, normal or
high-pressure steam of around 5kg/cm2 after the adding of a relatively strong alkaline
solution of about the concentration of that used in high-temp mercerization under
ambient temperatures. In this, high-pressure steaming is said to be particularly
effective.
Generally speaking, the higher the temperature of the alkaline treatment, the poorer and
the less sufficient the effect of mercerization results, however, it is assumed that, from
carrying out high-pressure steaming, no degradation is expected in luster because
water itself induces swelling in cotton, as well as that products with a soft hand can be
obtained.
Of course, there is no question that scouring effects can also be obtained by going
through this process. Unlike the conventional methods that simply control the fabric
tension under a single set of conditions with the alkaline concentration and process

temperature maintained at a fixed level, these new processes are a manifestation of

efforts towards attaining more rational, multi-purpose effects through breaking down the
mechanism of every action in the process of mercerization and deliberately altering the
alkaline concentration, temperature or the moisture content (which automatically leads
to alteration in the alkali concentration) during processing, in order to realize optimum
conditions
and
to
produce
optimum
effects.
At present, these methods cannot be said to have been perfected sufficiently, nor are
they widespread generally. One reason for this is that such changes during processing
would cost considerably in terms of facilities and energy use, moreover, another
considerable factor is that no technology has yet been established to make possible
these
conditions,
or
for
them
to
take
effect.
However, the use of different methods to those existing at present is expected to spread
if more emphasis is given to mercerization, with more attention paid to it not as
something from the past but as a technology for the future.
Read more: http://textilelearner.blogspot.com/2013/06/mercerization-process-of-cotton-fabric.html#ixzz3dOXPKPk3

5. Mercerization

1844 - John mercer observed the effect.

1850 Filed a patent for treatment of cotton with concen. NaOH solution with improvement in strength &
dyeability.
1890 Horace Lowe; found if shrinkage is controlled, the fabric becomes lustrous.
Tension Mercerization (Lowe) & Slack Mercerization (Mercer)

Mercerization is carried out for the following purpose.

1.

Improving lustre (silky look, in tension mercerization only).

2.

Improving tensile strength.

3.

Improved dimensional stability.

4.

Increasing uniformity of dyeing & improving color yield (savings in dyestuff).

5.

Improving Elasticity or Stretch material (in slack mercerization only).

Mercerization is a process of impregnating the textile material with a concentrated solution of

cold NaOH, keeping it in contact with this cold solution for a given time with or without
tension, and subsequently rinsing it.

MECHANISMMercerization causes swelling in fibre

Swelling causes Cross-section to become rounder, loss of convolutions & detwisting leading to more
lustrous surface
Opening of fibre structure
Increase in amorphous content due to decrystallization
Although mercerization is accompanied by swelling, it is more closely related to internal modification of
fiber.
Effect is observed at 18-24 % w/w NaOH solutions.
Higher no of OH groups available as compared to un-mercerized cotton
Higher moisture regain, dye-uptake and reactivity
The effect of mercerization is related to the size of the sodium hydroxide hydrates (NaOH.
xH O). The concentration of NaOH solution determines the value of x or the size of the hydrate.
A dilute solution has larger sized hydrates, which can cause swelling in cotton fibre by entering
2

the amorphous phase of the fibre. At higher concentrations, the hydrate volume is smaller.
Such hydrates cause lower swelling but have the ability to penetrate the crystalline phase and
change the crystal structure. Such changes are capable of inducing important structural
modifications in fibre structure.

In the table given below, the composition of NaOH hydrate, corresponding NaOH concentration
and the type of hydrate formation are shown:

Sodium Hydroxide Hydrates: Composition, Type and Concentration of Maximum Frequency

Composition of
hydrate

NaOH Conc. (% by
Wt.)

Type of hydrate

NaOH.20H O

6-9

Hydrated ion pair

NaOH.12H O

13.5-15

Hydrated ion pair

NaOH.10H O

18

Solvated dipole hydrate

NaOH.H O

69

Dipole hydrate

NaOH.7H O

22.8-24.1

Solvated Dipole hydrate + D.H.

(7.4 A)

NaOH.5H O

30.2-30.9

Dipole hydrate

NaOH.4H O

34.8-35

Dipole hydrate

NaOH.3.5H O

38-38.8

Dipole hydrate

NaOH.3.1H O

41.8-42.6

Dipole hydrate (Dia 6 A)

NaOH.2H O

52.6

Dipole hydrate

In the table given below, the variation in the hydrodynamic volume with changing hydrate type
is given.
Composition of hydrate

Hydrodynamic volume (dia )

Dipole Hydrate

5-8

Solvated dipole hydrate

8-10

Hydrated ion pair

10-15

Separated Hydrated ion pair 15-20

When a sodium hydroxide solution of a given concentration is used for treatment of a cellulosic
fabric (cotton), it forms a ternary complex, the composition of which is governed by the
concentration of NaOH solution. This complex is known as soda cellulose. These soda
celluloses have well defined crystalline character which is verified from their x-ray diffraction

patterns.

Given below is the phase diagram of soda celluloses.

Phase diagram of soda celluloses

In the figure given above, it can be seen that soda celluloses of defined x-ray diffraction
pattern are formed on treatment with NaOH solutions of different concentrations at different
temperatures. Although it seems that there are well defined boundaries for formation of
various soda celluloses, in reality it is not the case.

Na-Cell I forms when cotton or ramie is treated with 12-19% (w/w) NaOH solutions at 20C.
Decomposition of Na-Cell I leads to cellulose II formation. At higher concentrations, Na-Cell II
is formed. Drying of Na-Cell I results in formation of Na-Cell III.

Washing of Na-Cell I and II results in formation of Na-Cell IV. In fact, Na-Cell IV is only a
cellulose hydrate as washing removes the alkali and decomposes the ternary complex. In a
way it is a swollen form of cellulose.

At low temperatures, Na-Cell V is formed. During washing of Na-Cell V, Na-Cell IV is formed

first and then Cellulose II is formed.

In the table given below, composition of Na-Celluloses and corresponding hydrates is given.

Soda Celluloses: Composition and corresponding sodium Hydroxide hydrates

Soda celulose type

Comoposition

Corresponding hydrate

C H O , NaOH, 3H O
6

10

NaOH. 5H O
2

NaOH. 7H O
2

Na-Cell I
NaOH. 10H O
2

(C H O ) , NaOH. 2H O
6

10

NaOH. 12H O
2

(C H O ) , NaOH. 1.5H O
6

Na-Cell II

10

C H O , NaOH. H O
6

10

NaOH. 3-3.5H O

NaOH. 2H O
2

Na-Cell III

C H O , NaOH. 2H O
6

10

NaOH. 4H O

CH O , HO
6

10

C H O , 0-0.3NaOH. H O
6

10

Na-Cell IV (Q)

NaOH. 20H O
2

NaOH. 12H O
2

C H O , 1.3 or 1.5NaOH. 2H O
6

10

Na-Cell V
C H O , NaOH. 4-5H O
6

10

NaOH. 5H O
2

NaOH. 7H O
2

What are Cellulose I and Cellulose II?

The native form of cellulose which occurs in cotton and other natural cellulosic fibres, is known as
cellulose I. It has it unique crystal diffraction pattern (monoclinic). It is a thermodynamically less stable
form of cellulose. When cellulose in converted to regenerated cellulosic fibres like viscose, dissolution of
cellulose is an intermediate step. During regeneration, it gets converted to a different crystalline form,
known as Cellulose II.

During mercerization also, some native cellulose gets converted to cellulose II. The extent of this
conversion depends on process conditions like temperature, tension, NaOH concentration etc.

In the table given below, the dimensions of unit cell of cellulose I and II are given:

Crystal form

Dimension a ()

Dimension b ( )

Dimension c ( )

(degrees)

Cellulose I

8.35

10.30

7.9

84

Cellulose II

8.14

10.3

9.14

62

The figure below arrangement of cellulosic chains in crystalline register in cellulose I and II respectively. It
is easy to see that the formation of intra and inter chain hydrogen bond formation in the two crystalline
forms.

Swelling of cellulose fibres in Alkali solutions

It must be clear that mercerization involves disruption of crystalline part of cellulose. For this to happen,
alkali solutions of sufficiently high concentrations which can form alkali hydrates of such sizes which can
enter the crystalline phase must be employed. Swelling occurs during mercerization but it is not the
sufficient condition for mercerization to take place.

This will be clear from the figure shown below which shows swelling of cotton fibres with different alkali
concentrations at different temperatures.

Cellulose--model films and the fundamental approach. Eero Kontturi, Tekla Tammelin, Monika Osterberg
Chemical Society Reviews , 35(12):1287-304: 2007;

Swelling of cotton fibres at different alkali

concentration and temperature

In the figure, the first sharp peak due to swelling appears at around 10% NaOH concentration. This could
be very high at low temperatures. In fact, if viscose was to be treated with 10% NaOH solution at 0 C, it
will dissolve!

The swelling occurring at this concentration is solely due to amorphous swelling and does not result in any
of the effects associated with mercerization. It is temporary in nature, but can cause large shrinkage due
to high degree of swelling involved.

At higher concentrations, the swelling goes down and increases again at around 30% concentration. This
swelling is caused by disruption of crystalline phase of cellulose. Generally the mercerization is carried out
at 18-24% NaOH concentration and the swelling caused is much less than that occurring at 9-10% NaOH
concentration. Hence it can be concluded that swelling is necessary but not the sufficient condition for
mercerization to occur.

The effect of mercerization on various physical and other properties of cotton is discussed in following
sections.

Structural Modification

Effect of NaOH Concentration

It has been discussed that mercerization leads to conversion of cellulose I to cellulose II. Native cellulose
is Cellulose I and regenerated cellulose (example viscose) is cellulose II. However, during mercerization,
conversion of cellulose I to cellulose II is only partial. Hence mercerized cotton is a combination of both
crystalline forms. The extent of conversion is dependent on various process parameters like concentration
of NaOH, time of treatment, temperature and tension employed in the process.

In the figure given below, the effect of NaOH concentration on crystallinity of cotton is given (time 60 sec,
temp 20 C, tension- to maintain length change=0%)

Effect of alkali concentration of crystallinity of cotton

From the figure it can be inferred that the formation of cellulose II is favoured at higher alkali
concentrations. The overall crystallinity of cotton also goes down slightly on mercerization.

Effect of temperature

Temperature seems to have a similar effect on conversion of cellulose I to cellulose II. Overall crystallinity
also goes down. This is shown in the figure below:

Effect of temperature on crystallinity of cotton (time 60

sec, temp 20 C, tension- to maintain length change=0%)

Enhancement in lustre

Cotton owes its non lustrous appearance to its non uniform twisted, convoluted, bean shaped fire cross
section. As there is continuous change in the fibre cross section along its length, it has poor specular
reflection which is responsible for high lustre. On mercerization, the fibre swells gradually and the false
twist and the convolutions gradually disappear. The cross section becomes almost circular and the fibre
acquires the shape of a regular uniform cylinder. This process of gradual change in the fibre cross section

is depicted in figure below:

Gradual change in cross section of cotton fibre on

mercerization

In the above figure, stage 1-5 show swelling of cross section of fibre. It is easy to see conversion of a
bean shaped flat cross section to almost round shape and gradual disappearance of lumen. Stage 6 and 7
are associated with removal of NaOH from fibre on washing and drying. It is important to note that on
loss of sodium hydroxide during washing and subsequent drying, the fibre shrinks in cross sectional area,
but maintains its rounder shape. Overall, there is very little gain in fibre volume due to mercerization, and
hence the density of the fibre remains unaffected.

The rounder, more uniform (convolution-less) and regular cross section results in more specular reflection
which results in higher lustre. However, it must be noted that the process of removal of convolutions and
other surface irregularities (wrinkles and creases) is greatly aided by tension. Hence tension mercerization
always results in more lustrous product as compared to a slack mercerized one.

The presence of protruding fibre ends on the yarn surface suppresses lustre. Hence cotton yarns meant to
provide high lustre must also be singed in order to maximize lustre.

Mechanical properties

Mercerization has been found to increase the tensile strength of cotton fibres even though a drop in
overall crystallinity is recorded. The main reason for this phenomenon to occur is swelling of fibres. The
presence of many convolutions and false twists in the fibres cause weak spots to be present. These weak
spots act as zones of stress concentrations due to lower cross sectional area on application of a tensile
stress. Swelling, which is an integral part of mercerization process, removes convolutions and false twists
and the fibres acquire a more uniform cross section along its length. With weak spots gone, the fibres
exhibit enhanced tensile strength as compared to a non-mercerized fibre.

Increase in tensile strength can be summarized as:

Removal of convolutions results in removal of weak spots at the point of reversal

Fibres have more uniform, circular and smoother cross section after mercerization

The fibrills are arranged parallel along the fibre axis

Fibre alignment along fibre axis is better in case of tension mercerization as compared to slack
mercerization

Effect of tension

Mercerization has a significant effect on mechanical properties of cotton. In the figure given below,
tenacity, breaking elongation and Youngs modulus of cotton mercerized with 300 gpl NaOH solution at 20
C for 60 sec are plotted. The tension is varied to allow 10% shrinkage to 4% stretch. The elongation and
modulus are indicated on secondary vertical axis. It is clear that the enhancement in both tenacity and
modulus is higher at higher tension. It is easy to visualize this since it results in better alignment of
molecular chains in fibre axis direction (higher orientation). However, in case of elongation, it is reverse.
With increasing tension, the elongation at break decreases monotonically. It is to be expected as
increasing orientation would lead to lower elongation. At negative tension though (shrinkage occurring)
the breaking elongation is higher than that of unmercerized cotton.

Hence it can be concluded that if improving the tenacity of cotton yarn is the main objective,
mercerization should be carried out under tension.

Effect of Alkali concentration

The effect of alkali concentration on tenacity, breaking elongation and Youngs modulus of cotton
mercerized with NaOH solution of variable concentration at 20 C for 60 sec at constant length are plotted
in the figure given below. The alkali concentration is varied from 100 to 300 gpl. Again, the elongation
and modulus are indicated on secondary vertical axis.

Effect of Tension on Mechanical Properties of Cotton

Yarn during Mercerization

Effect of NaOH conc. on Mechanical Properties of

Cotton Yarn Mercerized at Constant Length

Dyeing Properties

Since mercerization results in change in physical structure of cotton, as manifest in change in crystal
structure, crystallinity and lustre, it affects the dyeing behavior of cotton. The important changes that
cause this are:

Mercerization decreases the crystallinity (increases amorphous content)

Modifies the texture
Overall effect greater moisture absorption, greater reactivity towards chemical reagents and dye
molecules

Mercerized cotton has higher

Dye absorption ( dye pickup)

Rate of dyeing
Visual colour yield as compared to unmercerized cotton
Improvement is more marked in slack mercerization (lower tension)

Increase in colour yield can allow for a saving of 15-50% in dyestuffs. Indeed many times, this is the
reason for subjecting cotton goods to mercerization.

Interesting - mercerized cotton appears darker than unmercerized cotton even when the dye absorption
is same.

The effect of mercerization on dye absorption and apparent color yield is shown in the figure below. The
concentration of sodium hydroxide is varied from 150 to 350 gpl.

Effect of Mercerization on Dyeing Properties of Cotton

Yarn at constant length (dye- CI Direct blue 1)

The increased Visual color yield (darker shade) of mercerized cotton is due to increased dye absorption as
well as the optical effect.

Kubelka Munk Equation

Defines the colour yield in terms of reflectance of dyed material

K Light absorption factor, S light scattering factor, C is concentration and a is a constant

R - reflectance

K changes linearly with concentration (within some limits)

Upon mercerization

1.

S decreases (less internal scattering from a rounder x-section)

2.

Non uniformity of the operation causes increase in colour yield (apparent)

Non-uniformity of the mercerization results in peripheral fibres absorbing most of the dye. This may cause
the cotton goods to appear darker in shade.

If improving the dyeability is the only aim then 150-190 gpl NaOH treatment is ideal.

In general, the increased dye absorption and the optical effect may contribute roughly equally towards
increased Visual colour yield after mercerization.

Wetting agents for mercerization:

Mercerisation liquor of concentrated NaOH solutions is generally applied at low temperatures (15-20 C).
Under these conditions, liquors possess high viscosity and swelling of fibers is high and rapid. This results
in poor and non uniform penetration of cotton textiles by NaOH solutions.

Sometimes goods are mercerized in greige or non-scoured state. The presence of sizes or cotton waxes

further hinders penetration of NaOH in the cotton yarns/fabric. Therefore the use of wetting agents to
increase the wetting of goods by mercerizing liquor is resorted to, which results in faster and more
uniform treatment of cotton goods.

Since the liquor is highly alkaline, the prospective wetting agent must be:

Soluble and stable in alkali solutions of mercerizing strength

Should be efficient (effective at low concentration)

Should have low affinity to fiber

Should be low foaming

Normal wetting agents are not sufficiently soluble in moderately concentrated caustic soda solution.
Products based on cresylic acid (a mixture of o-, m- and p-cresols) were used sometime back. However
these are toxic and non-biodegradable in nature and its use in mercerization in on wane. Addition of
solvent additives such as alcohols (e.g. cyclohexanol), ethers, ketones, lower fatty acid amides increases
wetting power of mercerizing liquor.

The biodegradable wetting agents

Certain alkylarylsulphonates
some organophosphonates (e.g. sodium methyloctylphosphonate)
alkylated diphenyloxide sulphates (e.g. dodecyldiphenyloxide sulphate)
especially sulphated aliphatic alcohols (e.g. 2-ethylhexyl sulphate). most effective have chains with
4-8 carbons
Example: sulphated 2-ethylhexanol, activated with about 10% butanol and unsulphated 2ethylhexanol.
Hot mercerization

Although mercerization is an exothermic process and is more efficient at lower temperatures (typically a
temperature range of 15 to 20 C is used), it has following drawbacks:

At lower temperatures, NaOH solution of mercerizing strength has high viscosity and surface
tension

When a yarn/fabric is mercerized, swelling of fibres at yarn surface due to mercerization causes
compaction of yarn structure

This results in poor penetration of NaOH solution in the core of yarn

The treatment becomes non-uniform

The basic problem of poor penetration leading to non uniform mercerization can be tackled by carrying out
mercerization with hot (60 to 100 C) NaOH solution of mercerizing strength. This is known as hot
mercerization.

However, since mercerization wont take place at high temperature, the temperature of the treated fabric
has to be brought down.

Therefore, hot mercerization becomes a two stage process, in which the first stage is treatment of cotton
fabric with hot NaOH solution of mercerization strength and the second stage is the reduction in
temperature of the treated fabric to bring about the mercerization.

As the temperature of the fabric is brought down, swelling may start and the fabric may shrink and hence
the dimensions may need to be maintained during cooling stage by desired applied tension.

Advantages:

Hot NaOH solution has low viscosity and higher penetration power
Swelling of cotton fibres in hot NaOH solution is low, hence more uniform treatment
Faster process, leading to: higher productivity and compact unit
Period of contact between material and NaOH can be reduced by upto 50%
The fabric can be stretched to greater degree as the fabric becomes more plastic
More uniform coloration
Better dye uptake (less colour yield)
Can permit elimination of scouring process
However, under conditions prevailing in hot mercerization, degradation of cellulose at high temperatures in

presence of air can take place.

The sequence

Saturation of cotton with NaOH under relaxed conditions (50 oC to boiling point) for 4-20 seconds
Controlled hot stretching
Cooling the stretched material to less than 25 C temperature
Tension controlled washing (till NaOH concentration in fabric falls below 60 gpl level)
Final washing under relaxed conditions
Since NaOH is also an agent for carrying out scouring of cotton fibre, yarn/fabrics at high temperatures,
hot mercerization can also be suitably modified to carry out both mercerization and scouring in one
operation.

Sequence for combined mercerization and scouring

Hot saturation of fabric with alkali solution

Steaming of relaxed or stretched material for
10 min at atmospheric pressure
5 sec under pressure (130-140 C)
Cooling and mercerization
Washing
There is another variation of hot mercerization. The sequence is as follows:

Washing of fabric at 95 C
Hot squeezing (high speed steam injection)
Impregnation in NaOH at 20 C
Impregnation in NaOH at 30 C
Stabilization under tension
Washing
The advantages of this variant are:

More uniform treatment faster process, hence process time can be reduced

More productivity or more compact unit

Higher stretching is possible; this will result in higher mechanical strength/lustre
Higher stretch is possible if stretching proceeds while cooling
Uniform dyeability
Dyeuptake is better but colour yield is lower

Mercerization of blends

Sometimes blends of cotton and viscose need to be mercerized to bring dyeuptake and lustre of cotton at
par with that of viscose

Problems faced in mercerization of cotton/viscose blends

Solubility of viscose in alkaline solutions causes weight and strength loss

Dissolution occurs at 80-130 gpl concentration of NaOH

(Viscose becomes highly swollen)

This problem can be solved by using a modifying sequence of mercerization as described below:

Hot impregnation (saturation with hot mercerization liquor to minimize swelling of viscose)
Addition of electrolyte in the mercerizing liquor
Use of KOH or admixture of NaOH and KOH (KOH induces less swelling)
HOT water rinse (at 90 C); viscose solubility is less at higher temperature
Addition of electrolyte (NaCl) in rinsing bath (electrolyte suppresses swelling of viscose)
Machines for Mercerization:

Fabric Mercerization with Tension

1. Stenter type or chain mercerizing machine

2. Chainless mercerizing machine

3. Chainless and pad less mercerizing machine

Hank Mercerizing Machine

Yarn mercerization

Yarns are mostly mercerized in hank form. Yarn mercerizing machines generally consist of two rollers, on
which the hank can be mounted. A device can be used to apply tension (to stretch) on the hanks. After the
hanks are mounted, the rollers can be lowered into a tray which consists of caustic soda solutions of
mercerizing strength. The hanks are allowed to saturate with alkali, the tension is generally applied later.
After sufficient time is allowed for mercerization (1-2 min) the hanks are squeezed and rinsed. The tension
is released once the residual alkali concentration drops below 60 gpl. For optimum gain in tensile strength
and lusture, a tension causing stretch of 0.5-3% is applied, higher tension results in lower tensile strength.

Fabric mercerizing machines:

Fabric mercerizing machines are generally continuous operation machines with the ability to apply
controlled lengthwise tension. There are mainly two types of machines:

1.

Those equipped with a chain to apply a controlled width wise tension (Pad chain mercerizing
machine)

2.

Chainless machines, which apply the width wise tension by means of expander bars or bowed
roller (Chainless mercerizing machine)

Pad chain mercerizing machine

In these machines fabric is saturated with alkali solution and padded. The saturated fabric passes over a
set of rollers (airing rollers) which allows the swelling or mercerisation to take place. Fabric is again
saturated and squeezed and passed into a stenter where length and width wise tension is applied. Width
wise tension is applied using stenter clips on chain.

This is followed by sprinkling of fabric with water to remove alkali. The tension is maintained till the alkali
concentration drops below 60 gpl. After this, fabric can be rinsed and neutralized in open width washing
machine (Tension may be relaxed).

The tension applied by means of clips in weft direction can be higher which can impart higher lusture to
the fabric. However the tension in width wise direction can cause the fabric to expand in a non uniform
way, as shown in the figure below. Also there is a risk of fabric getting torn near the edges where it is held
by clips.

Chainless mercerizing machine tackle above problem by using bowed rollers (figure below) to apply width
wise tension. The clips of chain mercerization machine are replaced by an expander unit consisting of
bowed rollers. The stretch or tension applied in weft direction is determined by warp wise tension in the
fabric which in turn is controlled by oscillating rollers. Other features are more or less similar to chain
mercerization units.

Determination of degree of mercerization:

Although there are many methods to do this, one quantitative test based on the ability of mercerized
cotton to absorb barium hydroxide is widely used. Mercerized cotton can absorb more Barium hydroxide
than un-mercerized cotton and this is the basis for this test. The test method is described below:

Mercerized and un-mercerized cotton samples (2 gm each) are treated with 30 ml of N/4 Barium hydroxide
for two hours in conical flasks at room temperature. Preferential absorption of barium hydroxide by cotton
samples reduces the strength of Barium Hydroxide solutions. The amount of Ba(OH) absorbed can be
determined by taking 10 ml of Ba(OH) solution from each of the flasks and titrating it with N/10 HCl,
2

phenolphthalein being used as an indicator. Fresh Ba(OH) is also titrated (blank titration) to accurately
assess the actual Ba(OH) in solution.
2

The Barium Activity Number is given as:

BAN = (B-M) / (B-C)*100

Where B = Volume of HCl (ml) required for blank titration

M = Volume of HCl (ml) required with mercerized cotton

C= Volume of HCl (ml) required with un-mercerized cotton

For completely mercerized cotton the value of BAN is around 155 and for semi mercerized cotton it varies
in between 115 and 130.

Causticizing
Quite similar to the mercerization process as introduced by Mercer, that is, without tension, does not
cause appreciable causticizing collection of material fact in some states there is even a slight
lengthening due to absorption of caustic bath .

The causticizing is a treatment of textile finishing slightly higher intensity for the purge yarns and fabrics, it is
useful to clean the cotton fiber, and give a slight improvement in dimensional stability, is used to particular to
improve the dyeing affinity.
Normally using concentrations of 8 to 9 B where you get the higher elongation of the fiber. Up to a
concentration of 9.5 B causticizing considering the caustic treatment carried out, as it does not change the
physical state and the convolution of the fiber.

Causticization also known as semi-mercerization is the process of treatment of cotton with caustic soda concentration
varying from 11%-16%. The causticization differs from mercerization in two aspects viz concentration of caustic soda
used is lower than that of mercerization and no tension applied during causticization. The process is usually carried
out after scouring or after bleaching for the limited purpose to improve the dye uptake of fabric. The conventional
operation of causticization is a separate treatment of dried fabric after scouring or bleaching involving the additional
operations like drying before causticization, washing for the removal of akali followed by drying before dyeing. This
adds to cost and extended process time resulting in loss of productivity. In the present investigation, a process of

causticization of cotton in grey stage by padding or treatment on jigger with 14% (W/V) caustic soda followed by two
stage combined desizing, scouring, and bleaching and dyeing without drying on jigger is suggested for reduction in
cost and higher productivity. The results showed complete removal of starch, instantaneous water drop absorption
and good whiteness. The causticization of grey fabric showed improvement in dye uptake of selected direct, reactive
and vat dyes to an extent of 24% and 55% compared to uncausticized cotton fabric. There was no loss of tensile
strength after the causticization and combined pre- treatment, however causticization gave increase in % extension.
The work reported is of technical nature of industrial importance.