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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.
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.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)
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.
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.
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
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).
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.
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
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.