Sie sind auf Seite 1von 48

MERCERIZATION OF COTTON

1. Alkaline Treatments
Mercerization, the treatment of cotton with a strong caustic alkaline solution in order to improve the
lustre, 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
1. Improved luster
2. Increased ability to absorb dye
3. Improved reactions with a variety of chemical
4. Improved stability of form
5. Improved strength/elongation
6. Improved smoothness
7. 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.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 10°Bé,
but above 11°Bé, the hair slowly loses its natural twist (this usually being in the order of 150-300 times per
inch).
Above 13°Bé, untwisting and shrinkage in the longitudinal direction now gradually starts to increase, and
as the concentration nears 16°Bé, untwisting and shrinkage advance rapidly. Between 18 and 22°Bé,
shrinkage of the length reaches its maximium and untwisting for the most part ceases.
However, in the untwisting and shrinkage which have occurred to this point, while both are related to the
swelling of the fiber, the untwisting usually occurs first, and is followed subsequently by the swelling.
Nearing 24°Bé, swelling and untwisting occur at the same time, and between 33 and 44°Bé, swelling occurs
before untwisting, and the rate of shrinkage that occurs with increases in the concentration of the alkaline
solution decreases.
After the point at which the greatest rate of shrinkage is reached, the rate of increase of untwisting slows
down, but increases more or less linearly with increases in the concentration of the alkali.
In the data reported by different researchers, the greatest discrepancies exist in the data related to the
rates of shrinkage and swelling of the hairs. The concentrations which showed the greatest rate of
shrinkage straddled the area between 18 and 22°Bé, and the concentrations for the greatest rate of
swelling were distributed from 18 to 26°Bé.
In these very widely distributed results, at concentrations displaying the greatest rate of contraction, these
being in the range from approximately 18-22°Bé to around 33°Bé, not only did the actual alkaline
concentrations displaying the greatest rates of shrinkage and swelling differ, but also the rate of shrinkage
itself also varied greatly, sometimes displaying an undulating decline, and sometimes displaying a smooth
and gradual decline. In many cases, however, the rate of shrinkage started to decrease rapidly above
33°Bé.
As can be seen, in mercerization, the results observed for the behavior of hairs over a range of alkaline
concentrations, while important, show great disparities, and many points are still awaiting clarification.
While many conjectures can be made regarding these problems, the essence of mercerizing cotton is that
in the swelling of cellulose fibers due to exposure to alkalis, the natural crystalline structure of the cellulose
relaxes and under an appropriate tension, the dimensions can be set by the conditions, and rinsing with
water while these conditions are maintained removes the alkali and converts the cellulose to a new
crystalline structure, fixing the dimensions. These being the basic principles, the degree of swelling of the
cellulose is the most important factor and it is related to the alkaline concentration.
However, because the swelling of the cellulose hair in the alkaline solution accompanies a change in the
form of the hair itself, accurate measurements are extremely difficult to attain, and the results to date for
the alkaline concentrations which display the greatest degree of swelling are, as previously noted, spread
over a wide range of between 18 and 22°Bé.
Other methods of measuring the degree of mercerization of cellulose include the X-ray diffraction method
in which the degree of mercerization can be determined by comparing cellulose I, which has the crystalline
structure of natural cellulose, with cellulose II, which has the crystalline structure of mercerized cellulose.
The results concerning the degree of mercerization of a cellulose hair in different concentrations of caustic
alkaline solutions obtained with the X-ray diffraction method showed that in 17°Bé NaOH 10% mercerized,
in 18-19°Bé 40-45%, in 19-20°Bé 70%, in 20-21°Bé 80%, 22°Bé 90-95%, 23-24°Bé 95-100%, and in
concentrations above 24-25°Bé 100% mercerized.
According to these results, the concentration of the caustic alkaline solution at normal temperatures needs
to be above approximately 24°Bé to ensure the complete mercerization of cellulose fibers (cotton hairs) in
their free state. This gives consistency to the effects of practical mercerization, and, at this concentration,
the swelling and the untwisting of the cotton hair start more or less simultaneously. At alkaline
concentrations in which the swelling occurs subsequently to the untwisting, the crystalline structure of the
cellulose fiber shows signs that it has not undergone complete mercerization.
1.1B- 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. C- 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 22°Bé. 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 22°bé. 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. 12°Bé), but at 12.5% NaOH (approx. 18°Bé), the generation of alkali cellulose becomes
apparent.
According to the above mentioned observations, above 11°Bé, 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 16°Bé, these two increase rapidly, and around 18°Bé
(while results differ, in the range of 18-22°Bé), 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 18°Bé, 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 18°Bé, 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 C6H10O5•NaOH.
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.
12°Bé), and sometimes at concentrations nearing 13.0% (approx. 18-19°Bé), 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 C12H20O10•NaOH 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 X-rays, the existence of compounds like C12H20O10•NaOH
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
C12H20O10•NaOH 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 °Bé), 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 °Bé) 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 18°Bé are necessary
for the generation of alkali cellulose I, it can only exist at concentrations of up to 10% (approx. 15°Bé), and
alkali cellulose II is produced at concentrations above 18% (approx. 24°Bé), but at alkaline concentrations
below 6.6% (approx. 10°Bé), 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.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 18-22°Bé. 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 24°Bé 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 18-22°Bé, the range displaying the greatest degree of swelling, to around 24°Bé, the cotton hair first
contracts momentarily, and then swells again, and at 24°Bé 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 (26.5°Bé), and this far surpasses the range of 18-22°Bé 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.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.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 15-16°Bé, the
reaction heat increases sharply, and from around 240g/L, or 26°Bé, 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-
16°Bé to 19-20°Bé for which the swelling was greatest, the heat generation was 8.93 Cal/g, and from a
concentration of around 22°Bé, 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 42°Bé, 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-
35°Bé was less than five minutes, above 42°Bé 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 22°Bé, 22 Kcal for 24°Bé, 24Kcal for 26°Bé, 27 Kcal for 28°Bé, and 29Kcal for 30°Bé. 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 22°Bé, 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.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 23°C in the former case and by approximately 40°C 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 40°Bé or 45°Bé, 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 36°Bé NaOH and 23°Bé 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 36°Bé solution would only be 9-13°C, and only 0.3-0.9°C for a 23°Bé
solution. So in practical mercerization at a concentration of around 30°Bé, the increase in temperature of
the solution due to the water absorbed in the yarn can be estimated to correspond to only around 1-2°C
under the above conditions.
However, in wet mercerization, the alkaline solution used for feeding must be a highly concentrated
solution of 49-50°Bé, 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-
50°Bé, if the concentration of the caustic soda solution is reduced to 28-29°Bé the dilution heat becomes
2.13 Kcal/mol, and 2.89Kcal/mol at 24-25°Bé, and 3.1 Kcal/mol at 22°Bé, thus allowing the problem to be
ignored.
1E.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 60°C,
complete mercerization does not take place. The concentration of around 30°Bé in mercerization at room
temperature, that is, around 20°C, 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 20°Bé
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. 16°Bé),
and above 4N (approx. 20°Bé), 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 30°Bé and 38°Bé for temperatures from 0°C to 40°C, and reported very small variations
for temperatures in the range of 10-30°C at a concentration of 30°Bé, 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 5°C, commonly in the range of minus 10-15°C. 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 15-30°Bé.
However, when the concentration is below 15°Bé and the temperature is as low as minus 10°C, 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 60°C, 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.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.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 18°C, at a
concentration of 24°Bé, a concentration commonly used in mercerization, it is approximately 84dyncm-1,
and at 30°Bé 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 cellulose’s
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. 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 cellulose’s
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
cellulose’s 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 15°Bé or below 10°Bé
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 10°Tw, 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 5°Tw, or 3.5°Bé, 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 80°C. 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. 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 110°C 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 dyeing and finishing of mercerized products.
1. H- Types of 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 the product
a) Yarn mercerization
Batch :
1. Hank mercerization
2. Cheese mercerization
Continuous:
1. Single end mercerization
2. Tow mercerization
3. Warp mercerization
b) Knit Mercerization
1. Open mercerization
2. Closed mercerization (Round mercerization, tubular knit mercerization)
c) Cloth mercerization
1. Chainless mercerization (Roller mercerization)
2. Chain mercerization (Stenter mercerization)
3. Batch-up mercerization
2. Classification according to the marcerizing conditions
a) Water content
1. Dry mercerization
2. Wet mercerization
b) Tension
1. Fixed-length mercerization
2. Tension mercerization
3. Tensionless mercerization
c) Alkaline concentration
1. Low-concentration alkaline mercerization
2. High-concentration alkaline mercerization
3. Two-step mercerization
d) Temperature
1. Ambient-temperature mercerization
2. High-temperature mercerization
3. Low-temperature mercerization
3. Classification according to timing
1. Gray mercerization
2. Pre-dyeing mercerization
3. Post-dyeing mercerization
4. Classification according to the number of treatments
1. Single mercerization
2. Double mercerization
5. Classification according to the type of alkali used
1. Caustic soda mercerization
2. Ammonia mercerization
6. Other
1. Alkali pad-dry method
2. 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 half-mercerization, 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 atonce 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.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. H. 3- Cloth Mercerization
1) 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 mosta 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 120-200m/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 3°Bé 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 According to the Mercerizing Conditions
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 fabric’s 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 semi-stretch, if not full-
stretch, properties.
c) Classification according to alkaline concentration
As mentioned earlier, an alkali concentration higher than 24-26°Bé is required in the treatment liquor
under ambient temperature conditions in order to achieve the expected mercerization effect with a
concentration around 30°Bé 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 20°Bé and 30°Bé. 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 22-24°Bé, a lower concentration of around
20°Bé 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 14°Bé and 18°Bé 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 cotton’s 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 31-32°Bé is often used in mercerization which is
carried out at a high temperature ranging from 50-60°C up to 80°C. 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. 36-38°Bé, followed by that of
10%, i.e. 15°Bé, 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 (one-step) 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
into alkali cellulose I in a low-concentration alkali solution.
d) Classification according to 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 post-dyeing 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 -33°C, 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, Peabody’s 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 -7°C and -10°C, secondly after
squeezing and during drying at 28°C and finally during drying at 100°C.
Including the use of hot water (88°C) 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 cotton’s soft hand
g) 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 Babcock’s Mercevic (sic) method and Sandoz’s 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.
Mercerizing | Object of Mercerizing | Mercerizing Treatment on Cellulosic Materials
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 of mercerizing
1.To improve the lusture
2.To improve the strength
3. To improve the dye uptake and moisture regain.
What is the mercerizing 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 as suggested by Urqhart.
Changes during mercerizing process
A. Fiber level
1.Swelling
2.Cross sectional morphology changes from beam shape to round shape.
3.Shrinkage along with longitudinal 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. Chemical Changes
1.Increased rate of reaction on hydrolysis and oxidation
2.Liberation of heat during the caustic treatment.(heat of sorption and heat of reaction)
3.Increase in the alkali absorption.
4. Increase in the absorption of iodine.
Q. Why there is a swelling in cellulose?
1. Due to Swelling
Swelling is due to molecular attraction with associated hydration in this 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 0°C to 40°C, using 30°/38° Bé caustic soda and measured the shrinkage by
mercerization, and found that the least shrinkage variation is obtained at 10°C and 30° Bé. 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. Loading of material on the rollers in rest position.
2. Lowering of rollers
3. Caustic tray movement
4. Pre tensioning
5. Free shrinkage
6. Lye tensioning
7. Squeezing
8. Washing tray movement
9. First wash and tensioning
10. Second wash
11. Third wash
12. Final wash
13. Squeezing
14. Lifting Of Rollers
15. Unloading the 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. Lye tensioning
The lye tensioning is done to stretch the yarn back to 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 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.