PAPERS
Mercerisation and liquid ammonia
treatment of cotton
Peter F Greenwood
fntemational Institute for Cotton, Technical Research Diuision, Kingston Road, Didsbu y,Manchester M20 8RD
‘In considering the published work on mercerising it is often
difficult to correlate the results of one worker with those of
another as the conditions are rarely the same in respect of
the type of cotton, the yam, the concentration of the alkali
and the tension applied during the process.’
J T Marsh Mercerising
INTRODUCTION
In this survey it is intended to review, in the main, technical
research and commercial developments which have been
reported within the past 20 years. This has, in fact, been a
period of fundamental change, in that several techniques
have gained acceptance that would probably not have been
anticipated by many textile technologists of the mid-1960s.
Hot mercerising and ‘dry’ mercerising are concepts that
would have run counter to most finishers’ convictions con-
cerning good mercerising practice. The mercerising of knit-
ted fabrics was in its infancy, widely held to be impracticable
because of the opposing requirements for avoiding distor-
tion, yet applying sufficient tension to produce a lustrous
effect. Liquid ammonia is an unpleasant chemical, which
few people would have predicted to have emerged from the
laboratory into the textile mill.
Much of the mercerising practice then recommended still
remains relevant today, however, and J T Marsh’s classic
book Mercerising [ 11, first published in 1941, must still be
recommended to textile students as the foremost English
language treatise on the subject. The literature concerning
the effects of caustic soda and other swelling agents on the
fine structure of cotton was reviewed in 1966, in an excel-
lent monograph produced by the Shirley Institute [21.
Since then, several shorter review articleson the literature
of mercerising have appeared [3-51. Patel and Var-
ghese 131, in particular, in reviewing the literature up to
1983,have compared the effects, especially in subsequent
dyeing treatments, of caustic soda mercerising and treat-
ment with liquid ammonia.
Two recently published books on fibre chemistry and
technology include extensive reviews of the literature
related to cotton swelling treatments [6,7]. The second of
these includes a comprehensive chapter on the technology
of liquid ammonia treatment of textiles, by Catherine V
Stevens and Luis G Roldan-Gonzales.
FIBRE AND YARN MERCERISING
Although some research and development work has been
carried out on the mercerising of cotton prior to spinning,
and a machine design has been patented [8]for the mer-
342 JSDC Volume 103 October 1987
cerising of fibre in sliver form, using a conveyor system,
there seems to be no record of successful commercial
developments.
Sliver and roving mercerisation techniques have been
employed, however, in several research projects, one
objective being to obtain a more uniform treatment than
was considered possible with either yams or fabrics. Work at
TNO in Holland 191, for example, indicated that fabrics
produced from roving-mercerised fibre responded better to
subsequent resin finishing than conventionally mercerised
fabric, especially when the resin was applied by a low wet
pick-up technique.
At North Carolina State University [lo] mercerised sliver
was spun both into cotton yams and into blends with
polyester. Although the strength of the cotton yams was
lower than that of the untreated controls, that of the blends
was improved because of the increased elongation at break
of the mercerised fibre.
Ramey f 111 experimented with the mercerisation of
locks of seed cotton. Some 22 seed cottons were treated,
ginned in a laboratory roller gin and spun into yam. Ramey
commented that a saw gin might have given better results.
The original objective of the study was to examine the effect
on dust levels in spinning but no conclusion on this point
was reported.
Several workers have compared the behaviour of differ-
ent varieties, either as a result of mercerising alone, or after a
subsequent chemical treatment [ 12-15]. The eventual
objective of such work, still a long way in the future, is to
optimise, by the selection and commercialisation of suitable
varietal traits, the performance of mercerised, crease-
resistant cotton fabrics.
Yarn mercerising has, of course, been commercially
established for many years. A review of progress in the
treatment of sewing threads has recently been pub-
lished 1161.
Machinery developments of interest would include the
cone-to-cone continuous yam mercerising machine
MM-CO from Jaeggli [17], and the improved Meccano-
tessile Titano hank mercerising machine with highly
developed automatic controls [ 181.
Useful summaries of the state of the art of yam merceris-
ing have been produced by Gassmann [ 191, Lombar-
di [201, and Modi and Patel [213.
Various studies have been carried out to examine the
potential formercerised rotor yams 122-251. On the whole,
results have not encouraged commercial developments.
Low-twist yams are said to give most promising results, so
perhaps the generally higher twist levels of commercial
rotor-spun yarns give insufficient space for full fibre swel-
ling.
FABRIC MERCERISING
Until relatively recently mercerisation of fabrics was limited
largely to the treatment of woven fabric. It was widely
considered impracticable to mercerise knitted fabrics,
because the stretching, believed to be essential for the
development of lustre, had an adverse effect on the elastic
properties of the structure [26,27]. However, in the early
1970sa few finishers did develop techniques for processing
knitgoods on chainless mercerising machines, either by
installing tension controlling devices [28,29],or by proces-
sing between conveyor belts 1261.
The treatment of tubular-knitted fabrics by such methods
has the disadvantage that the edge creases of the flattened
tube are rendered permanent by the process; consequently
it became usual for the fabric to be slit before mercerising,
and processed in open width.
Several developments in fabric guidance and tension
control were reported in the late 1970s, particularly by
Benninger [ 30-321, Kleinewefers [33-381 and Gol-
ler 1391.
However, one serious disadvantage of open-width knit-
goods mercerising was described by Tuncer [401. He
showed that knitted fabric mercerised in open width is
subject to variation in several characteristics from edge to
centre. He found that the wale density was considerably
greater at the edges, the fabric was thicker, and after sub-
sequent dyeing the edges appeared deeper in shade.
Baehr [41] considered that these effects are found in
knitgoods processed by all chainless machines, but
Bechter [421 found that when pre-bleached goods were
processed, the subsequent dyeing was more uniform due
to faster swelling.
It was the Japanese who, taking the bull by the horns, first
produced machines specifically designed for the mercerisa-
tion of knitted fabrics in tubular form. Yokoyama[43]
described two such machines, the Nitsil TI-1 from
Toyobo-Oshima and a Sando Iron Works development. By
1978Sando was reported to have sold no less than 28 such
machines in Japan [44] and three in the United States r451.
To eliminate the edge-creasing problem, Sando introduced
air into the fabric by means of jets, to balloon the tube [&I.
Other machinery manufacturers were rather slow to fol-
low the Japanese lead, but in 1976 the Italian company
Omez showed details of its Mercelux machine at the Green-
vile exhibition. In the early version of this machine the
fabric was held at the correct width using an adjustable
expander frame 147,481. Later machines adopted a
mechanism similar to that of Sando, using air jets to balloon
the tube.
Richardson 1491 included a short summary of knitgoods
mercerising developments in his review of the dyeing and
finishing of knitted cotton in 1978.
By the time of the 1979 ITMA exhibition in Hanover,
several other manufacturers had entered the field L50J,
including MCS and Sperotto in Italy, and Domier and Thies
in Germany. These machines are all fundamentally similar
to the early Omez design, with three main sections: impreg-
nation, stabilisation and washing, this last operation being
carried out with the fabric held at the correct width on an
adjustable frame. In the case of the MCS machine this frame
is flat and horizontal, but the other manufacturers elected to
produce vertical frames of tubular design. Publications deal-
ing with the Thies machine all describe its use for merceris-
ing at high temperature (60°Cand above), claiming that this
produces a softer handle, better absorbency and improved
stability 1511. When a steaming unit is placed between the
impregnation and stabilising sections, the unit becomes a
combined scouring and mercerising range 1521.
Technical data for the MCS 1531,Sperotto [54]and Dor-
nier 155,561machines, on the other hand, include the 'trad-
itional' impregnation conditions of 15-20"C, and Eusch-
er 1551 remarks that no benefits were observed when trials
were carried out on the Dornier machine with hot (60°C)
caustic soda. Dornier claims market leadership in the tubu-
lar knitgoods mercerising sector [56], and this position
appears to be unchallenged. About 55 machines had been
sold worldwide by the middle of 1984 1571, results which
Richardson [58] considered as showing that the technical
problems associated with the process have largely been
overcome. A typical Dornier continuous range for tubular
knits is shown in Figure 1.
A - Caustic soda impregnation section
6 - Reaction section
C - Stabilising and washing section
Figure 1 - Knitgoods merceriser (courtesy Domier GmbH)
Other machinery manufacturers offering equipment for
tubular fabric mercerising include Jaeggli [59], Caber [60]
and Pegg-Whiteley [61,62]. It is interesting to note that
Pegg-Whiteley holds a machinery patent, applied for in
Switzerland, covering the use of a circular stretcher and
spray nozzles for washing-off tubular goods [63].
Omez was taken over by Reggiani in 1983, and the
Mercelux range has been renamed Relux.
Manufacturers of open-width machinery have not had
the same success as the tubular specialists in the knitgoods
sector, perhaps because of the difficultiesnoted earlier, but
in certain situations such machines may hold some attrac-
tion. For example, a finisher concerned primarily with
woven fabric may wish to expand into knitgoods proces-
sing. The dual capability of such a machine may then be
convenient. Such machines find a place as well when sub-
sequent coloration is also in open width, in printing or
perhaps pad-batch dyeing.
It was suggested by Bechter [42] that the edge-to-centre
colour and stitch density variations that result from the
mercerisation of knitted fabric in a chainless machine would
not be produced by open-width mercerisers of the chain
type, which, he says, provide means for uniform width-way
JSDC Volume 103 October 1987 343
 stretching. In fact, only one manufacturer, Farmer Nor-
ton 1641, has produced a chain merceriser that is claimed to
be suitable for the treatment of knitgoods. However, such
rnachines may have been rendered unnecessary by a
development to be discussed later - stenter mercerisation.
In contrast to the upsurge of interest in the potential of the
knitgoods sector, the mercerisation of woven fabrics has
seen little change in the period under review. Perhaps the
most interesting developments are taking place in the
impregnation stage. For several years Kleinewefers has
promoted the application of reduced pressure to the fabric
immediately prior to impregnation using its ‘vacuum cap’
unit I65J to facilitate fast, more complete swelling. Among
the advantages claimed is that grey fabric can be impreg-
nated without the need for a wetting agent, so that a caustic
recovery plant can operate without foaming problems.
Removal of trapped air by steam purging using, for
example, the unit developed by Farmer Norton, may
achieve similar effects. In contrast, application from a
foamed liquor has been studied 1661, with the suggestion
that special effects, such as one-sided mercerisation and
differential dyeing, may be produced in this way.
A novel design feature for a chainless merceriser has been
announced by Mather Machinery 1671. This is the Alstonip
system, which consists of a set of buoyant bottom drums in
the saturator and stabilisersections. Maintenance is reduced
as these drums have no bearings. An adjustable squeezing
action is obtained by raising or lowering the liquor level.
HOT MERCERISING
Although according to Marsh I 1I the mercerising effect
diminishes as the temperature increases, in the period
under review there has been a development of interest in
treatments at elevated temperatures. Several patents have
been published, the first probably being that of Rusznak et
al. 1681,who claimed a process for combined scouring and
mercerising in 1965.This was followed by claims on behalf
of Heberlein 1691, and Duckworth and Mather and
P\att 170,711. The interest of the last-named was clearly
aroused by the possibility for extending the versatility of the
Vaporloc pressure scouring unit, and several publications
followed describing cooperation between the British and
Hungarian interests 172-781. In one of these 1771 Duck-
worth and Wrennall describe the basic principles of the
process as follows:
(a) Saturation with caustic soda solution of mercerising
strength, preferably under relaxed conditions, at an
elevated temperature approaching the boiling point of
the caustic soda solution
(b) Controlled hot stretching following saturation
(c) Controlled cooling of the hot-stretched fabric
(d) Traditional, tension-controlled washing (chain or chain-
less)
(e) Traditional final washing (in multiple box washers).
The authors claim that when the process is carried out in
this way the penetration of caustic soda into the textile
structure is extremely rapid, thorough and uniform. This
confirmed a suggestion made earlier by Bechter, Fiebig and
Heap 1791, who reported that mercerising at elevated
temperatures gives a more uniform treatment, but less swel-
ling, and inferred that a second treatment at low tempera-
ture would complete the swelling effect.
Fundamental studies on the influence of temperature on
the mercerising of cotton have been reported in a series of
344 JSDC Volume 103 October 1987
articles by Bechter and other workers at the Institute for
Textile and Fibre Research, Stuttgart 180-841. In one of
these [81I Bechter summarises the practical results of these
experiments with regard to hot mercerising of yarns and
woven fabrics, noting that mercerising at elevated tempera-
tures can lead to improvements in lustre and shrinkage, ha5
no adverse effect on strength and, under certain recom-
mended conditions, can result in a softer handle.
The reported improvements in lustre may be surprising
Most workers have recommended the use of low tempera-
tures, refrigerating the lye to develop full lustre. It may be
that the double treatment produces a different response
compared with that of the standard single-stage process, o n
the other hand, work at ATIRA on grey yarns showed no
substantial improvement in lustre as a result of doublt.
mercerisation [211, and Ahmed and Tahir 1851 reported
that temperatures at least up to 45°C could be used ‘without
any deterioration in lustre’.
A team of Russian workers has produced several publica-
tions describing the development of a combined merceris-
ing and scouring process [86-88]. A unit designed for the
treatment is described in a British patent application of
1980 1891.In the process grey fabric is boiled in caustic soda
of a concentration between 18and 27%, containing a small
amount of sodium bisulphite and a wetting agent. Fabric
width is not controlled throughout the machine, but the
fabric is pulled out at intervals by a series of spiralled and
angled rollers. The patent also describes a second stage in
which the fabric is simultaneously bleached and dyed, so
that the complete preparation and dyeing sequence can be
carried out as a fully continuous process.
STENTER MERCERISING
In 1980the German machinery builder Artos announced a
development that surprised those finishers experienced in
conventional mercerising [901. In the process, called the
Mercevic technique, the fabric is first padded with a liquor of
mercerising strength, and after a delay period, is dried o n a
pin stenter. It is claimed that the fabric suffers no adverse
effects, even if stored in this condition for several months
The process was developed initially for knitgoods, to
improve dye uptake, but experiments as yet unreported
were being conducted on woven fabrics.
Details of a similar technique developed at about the
same time by the chemical manufacturer Sandoz were
revealed at a Textile Institute conference in Leicester 191I
The Sandoz technique (called the S M process) was said to
be in use by ten West German processors for open-width
treatment of single jersey and interlock fabrics. After pad-
ding with caustic soda at 3 7 T w and skying for 40-60 s, the
fabric is stentered at a temperature not exceeding 140°C. A
US patent covering the process has been published I92 1
Schuierer [931 has emphasised the importance of good
after-washing following the dying stage, and suggested the
use of a perforated beam.
From trials carried out with the S M process atthe Interna-
tional Institute for Cotton (IIC),it can be recorded here that,
although results may compare well with other methods, in
particular for colour yield and lustre, nevertheless certain
precautions are necessay. The machinery must be com-
pletely resistant to strong alkali, and must be thoroughly
cleaned after each run. The dry fabric can emit an unpleas-
ant and hazardous alkaline dust, from which operatives
must be protected. Nevertheless such a process may be of
some interest to a finisher with spare stenter capacity.
CAUSTIC RECOVERY
When large quantities of caustic soda are used for mercer-
isation the installation of equipment for the recovery and
recycling of the sodium hydroxide is often essential, for
economic and environmental reasons. Often it is possible to
use the dilute liquor in other processes, such as scouring or
dyeing, provided it is sufficiently clean. Usually, however,
the mercerising department produces far more dilute liquor
than can be utilised in other ways, and increasing effluent
disposal charges are making recovery an attractive proposi-
tion.
The usual caustic recovery plant is based on an evapora-
tive process. Gassmann [94] has described a two-stage
evaporator system that will accept dilute (6"Bg) liquor at a
rate of 1 180 kg/h and produce 180 kg/h at 3VB6. The
equipment, costing SFr 200,000 (in 1978),was said to pay
for itself in 20 months. Much the same conclusion appeared
in a more recent publication describing a similar instal-
lation 1951, which is shown in Figure 2.
Kuhn 1961 reported even more impressive results from a
two-stage evaporator system installed in a yarn mercerising
works. For the added capital cost of Fr 350,000 (in 1977)
required for the inclusion of the recovery system in the
overall installation, it was calculated that savings in the
second half of 1984 were about Fr 750,000.
Chiasson 1971 has presented some useful notes for
microcomputer simulation of the operation of an
evaporator-based caustic soda recovery plant.
When mercerisation is carried out on woven fabrics in the
grey state, recovery of caustic soda has been impracticable
due to the presence of significant amounts of size in the
waste liquor /951. However, studies at the University of
Innsbruck 198,991have indicated methods, such as treat-
ment with peroxide, that can be used to purify contami-
nated lye.
TREATMENT OF COTTON WITH LIQUID
AMMONIA
Liquid ammonia treatment of cotton first attracted commer-
cial interest in the mid-1960s when two processes were
announced almost simultaneously. These later became
known as the Prograde process (for yarns) and the Sanfor-
Set process (for fabrics). The first was developed primarily
for the treatment of sewing thread by J & P Coats [loo];
later it was offered as a process for yarns for knitting [ 1011.
The fabric treatment was developed by the Norwegian
Textile Institute, which assigned the patent to an industrial
consortium, Tedeco (Textile Development Com-
pany) [1021. Tedeco came to an arrangement with the
Sanforized Company, part of the US Cluett, Peabody
group, to commercialise the process under the trade name
Sanfor-Set.
A similar, although not identical, technique was
developed in France by the research company
OPI [ 103,1041. Some of these early developments, particu-
larly relating to knitgoods processing, have been summar-
ised by Richardson [491.
Heap [lo51 has examined the nature of the improve-
ments in properties resulting from treatment of cotton with
liquid ammonia, and was able to classify the various proces-
ses in terms of the method used for removing the ammonia
from the fibre. Aqueous removal, such as was employed in
the Prograde process, was designated as the 'water system',
while evaporation under substantially non-aqueous condi-
tions, as employed in the Sanfor-Set treatment, was termed
the 'dry-steam system'. He suggested that the water system
produces yams or fabrics that are like mercerised cotton,
'only not quite', whilst the dry-steam system produces fab-
rics which are like unmercerised cotton, 'only better'.
The ammonia-water system, according to Heap, gives
an improvement in colour yield (in subsequent dyeing),
which is often only slightly less than that obtained by mer-
cerisation. However, the fact that the colour yield is inferior
to that obtained with caustic soda has probably been the
main reason for the lack of commercial success of this
technique. The machinery builder Platt Sac0 Lowell (then
Platt International) made several units for the Prograde
technique, which were marketed for manufacturers of knit-
ting yarns, with claims for improvements in lustre and dye
uptake. There was also an added advantage that, being a
continuous process, it resulted in reducing the incidence of
knots [ 1011. However, production of the machine ceased in
1977 and little has been heard of the process in recent
years.
The ammonia-dry-steam process, on the other hand,
has made steady progress. Several Sanfor-Set installations
Figure 3 - Caustic soda recovery plant (courtesy Kasag
Export)
JSDC Volume 103 October 1987 345
are operating in the US, Europe and China. The European
machines have been built by Monforts of West Ger-
many I1061and the others by Morrison in the US. Figure 3
shows a typical plant layout. Early commercialisation of the
process in the United States concentrated on denim 11071,
for which it was claimed that the treatment eliminates pro-
gressive shrinkage after the first wash, and reduces seam
puckering and leg twisting. Better retention of colour in
repeated laundering, due to reduced fibrillation, and
improvements in handle and smooth drying were also
noted.
Two techniques have been patented for the treatment of
pile fabrics by the Sanfor-Set process. The problem is to
obtain stabilisation of the base structure without incurring
excessive shrinkage in the pile. Burlington I1081 proposed
the use of an engraved roller to apply the ammonia prefer-
entially to the back of the fabric. Cluett, Peabody 11091
suggested a pretreatment of the pile with resin to prevent
the occurrence of shrinkage in a subsequent ammonia
treatment. Troope 11101 described the application of this
technique in the finishing of corduroy, and in the same
paper mentioned the commercial success of ammonia-
treated cotton shirtings in the US market and the introduc-
tion of treated cotton sheeting.
An essential component of the equipment developed by
OPI in France was a modification of one of its earlier
developments, the so-called lame d’air (airknife). Originally
this used compressed air to blow excess liquor from fabrics
impregnated with aqueous solutions; in this modification
ammonia gas is used 11031. Roos I 1111 has summarised
the commercial developments that were anticipated for the
process, and listed the benefits as better dimensional stabil-
ity, attractive appearance and soft handle, good colour
retention after repeated laundering, easy-care by virtue of
good crease resistance and quick drying (20% faster).
Although, as Richardson I491 has already reported, OPI
ceased operations in 1976 due to financial difficulties, the
process has recently been revived by Franco-Belgian inter-
ests, and production has begun at a works near Brussels.
The machine is situated within a chemical plant manu-
facturing ammonia-based fertilisers, eliminating the need
for an ammonia recovery plant. (The recovery of the liquid
ammonia represents a significant proportion of both capital
and operating costs for most installations.) The OPI patents
described a process of the ammonia-dry-steam type, but at
least one publication has mentioned a technique for knit-
goods treatment involving removal by aqueous
means 112I
Mercerisation followed by liquid ammonia treatment can
be used commercially to improve easy-care characteristics
and this will be described later, but it is of interest to note
here that an American company, Joshua L Baily, has
patented a combination of slack mercerisation and liquid
ammonia treatment for the production of cotton stretch
fabrics 1113).
RESEARCH STUDIES
Major research programmes on the behaviour of cotton
after treatment with caustic soda or liquid ammonia have
been carried out in several parts of the world, including
Germany (Universityof Stuttgart), South Africa (SAWTRI),
the United States (USDA, New Orleans) and the USSR
(IvNITI).
In a series of publications under the general heading
340 JSDC Volume 103 October 1987
‘Treatment of cotton with swelling agents’, Bredereck and
others at the University of Stuttgart have described various
aspects of research into the behaviour of cotton treated with
caustic soda and liquid ammonia 1114-121 1 In the first of
these 11141, the rate of swelling of cotton fabric in liquid
ammonia is shown to be much faster than the rate in caustic
soda, but the final equilibrium level of swelling is greater for
caustic soda (20% concentration). In the same paper it is
shown that the forces generated when fabric strips are held
at constant length are much greater in liquid ammonia than
in caustic soda, and in liquid ammonia, unlike caustic sodd,
the forces are almost unaffected by pre-tensioning the
fabric.
Work at the Southern Regional Research Center, New
Orleans, I122 I showed that if yarn is treated in a slack form,
much greater force is required to restretch ammonia-treated
yarns than mercerised yarns. It is suggested that this may be
due to the formation of bonds between nitrogen atoms and
hydroxyl groups, and that these are much stronger than
those between oxygen atoms and hydroxyl groups. In
further work at SRRC, Andrews et al. 11231 found that
when yarns were treated under tension, four times as much
force was required with liquid ammonia than with caustic
soda to maintain the original length.
Other work on fabric 11241 indicated that the load
required to restretch to the original length in liquid ammonia
was 1.5 and 2.2 times that required in caustic soda at 20 and
100°C respectively.
X-ray crystallography has been widely used in studies on
the effects of swelling treatments on cotton fibres. Rousselle
et al. 11251 found that both liquid ammonia and caustic
soda caused decrystallisation of cotton cellulose. Variation
in applied tension had little effect on the degree of crystalli-
sation. Studies undertaken in the USSR 1126,1271 con-
firmed the decrystallisation does indeed take place, but
concluded that tension reduces the decrystallisation effect
to some extent. The work in Russia continued 1128-1301
with further X-ray analysis of ammonia-treated and mercer-
ised cotton, from which a classification scheme was pro-
posed; in this the most desirable effects were produced by
the ammonia (evaporation) method, followed equally b y
ammonia (aqueous scour) and hot mercerising, with con-
ventional mercerising the least effective. Bredereck I 119I
obtained a similar ranking in studies of shear angle effects
Bredereck and Saafan I1211 and Saafan et al. I131I
found that evaporative removal of ammonia resulted in a
highly disordered cellulose, with the degree of crystallinity
being reduced from 78% for untreated cotton to 38% after
treatment. They also reported the formation of a significant
amount (35%)of cellulose 111. This was found to revert to a
highly ordered cellulose I after treatment with water and
heat (such as might be applied in a dyeing process) from
which cellulose 111 could not be re-formed by subsequent
ammonia treatment. A similar study at SAWTRI has also
been reported 11321.
The well known Goldthwait red-green test has been
proposed as an indicator to characterise swelling treatments
on cotton. In the test a mixture of red and green direct dyes
is used to compare the maturity of cotton fibre samples.
Immature fibres dye red, mature fibres green. Von-
hone [133] observed that caustic soda mercerisation
increased the fibre’s affinity for the green component, and
suggested a ‘causticisation number’, related to the strength
of the green hue. Vonhone further noted that fabric treated
with liquid ammonia 'under industrial mill conditions' dyes
red, a phenomenon which he did not attempt to explain.
Bredereck and Saafan [ 1341, however, showed that with
certain dyes liquid ammonia (dy-steam system) could
cause a reduction in subsequent colour yield. This was
attributed to a change in pore size, and in particular to a
reduction in the number of pores large enough to admit the
dye molecules.
Rowland, Wade and BertoniBre at the USDA New
Orleans laboratories used a gel filtration technique to meas-
ure changes in pore size resulting from swelling treat-
ments 11351. Various sugars and glycol derivatives were
used as eluents. The pore structure of untreated cotton was
compared with those of mercerised and ammonia-treated
(evaporation-water-wash) fibres. The results showed an
increase in accessibility after both swelling treatments, but
for higher molecular weight eluents the increase was much
less for the ammonia-treated fibre than that shown by the
mercerised material.
Results such as these indicate reasons for the fact that the
ammonia (dy-steam) process is carried out commercially
almost exclusively after dyeing. Mercerisation, however, is
normally carried out prior to dyeing, to take advantage of
the significant improvement in colour yield.
IMPROVED DYEING CHARACTERISTICS
Although Mercer himself remarked on the apparent
increase in affinity as a result of swelling with caustic soda,
few quantitative studies of the effect were reported until
relatively recently. Goldthwait [ 1361 noted this point, and
after describing a study involving one dye, C.I. Direct Blue
78, concluded that 'the darker dyeing or greater colour yield
of mercerised cotton as compared with the same cotton
unmercerised, as far as attributable to optical effects, takes
place to different degrees at different depths of colour,
rather than in a fixed ratio as may have been thought'.
In fact, this point had already been made, with reference
to dye savings in knitgoods mercerising, a few months
earlier. In work camed out by IIC I1371 in which four reac-
tive dyes were examined, two depths of shade were
matched on unmercerised and mercerised fabric. Savings at
2% depth averaged 40%, while at 6%with the same dyes
the average saving was 60%. Curves were later published
showing the effects more fully 11381, and these are repro-
duced as Figure 4. Goldfinger [139]felt able to attribute the
major part of the colour increase to a reduction in light
scattering within the fibre.
801 I- -'--T --' ' ' ' ' 1 '
2 4 6 8 10
Amount of dye on unmercerised fabric, % 0.w.f.
A - C.I. Reactive Yellow 84
B - C.I. Reactive Blue 187
C - C.I. Reactive Violet 23
D - C.I. Reactive Black 5
Figure 4 -- Mercerisation and dye saving
Work at the Technical University in Budapest [140,1411
indicated that about half the total dye savings could be
attributed to optical effects, It was suggested that the internal
light scattering of the cotton was influenced by changes in
pore volume. With decreasing pore volume resulting from
swelling, the K / S ratio was said to increase.
Bredereck and Wolf [ 1421 measured the change in the
size of the lumen resulting from treatments with both caustic
soda and liquid ammonia, and also examined dyeing
characteristics of the fabrics using both direct and reactive
dyes. They concluded that a reduction in lumen diameter
was the primay cause of reduced scattering and the con-
sequent improvement in colour yield, and incidentally pro-
vided an explanation for the fact that immature cotton
(which has a large lumen) responds particularly well to both
treatments.
A comparison of colour yield on mercerised and
ammonia-treated (water removal) cotton fabrics, for a
range of reactive dyes, has been reported [143]. Although
both treatments increased colour yield, mercerisation pro-
duced the greater improvement. This conclusion was sup-
ported by work at SAWTRI [144] that had the added
dimension of including both ring-spun and rotor yarns. In
each case the rotor yam dyed more deeply than the corres-
ponding ring-spun yarn.
The need for information relating to the greater affinity for
dyestuffs of mercerised fabrics has been recognised by at
least two dye manufacturers. Hoechst [1451 and ICI L1461
have both published leaflets giving recommendations for
the batchwise dyeing of mercerised cotton knitgoods.
IMPROVED EASY-CARE FINISHING
The improvement in smooth drying characteristics confer-
red on cotton fabrics by the ammonia-dry-steam process
was noted at a n early stage of its commercial development.
Troope [1471 commented that an increase of one full
number of the Monsanto scale could be expected, with the
greatest effect on heavier, more loosely constructed
materials.
Heap [lo51 and Bredereck [1191 suggested that the
ammonia-dry-steam process should be a very suitable pre-
treatment for cross-linking (resin finishing). Because of the
improvements in stability, crease recovery, flexibility and
softness of handle conferred by the treatment, it was con-
sidered that the amount of cross-linking agent could be
substantially reduced, with consequent gains in strength
and resistance to abrasion. This had been demonstrated
already, in fact, in some work at SAWTRI [ 1481 published
' 1
in 1976, describing some results from a pilot-scale liquid
ammonia treatment range, based on an earlier design
patented by the USDA New Orleans laboratory. Treated
cotton woven fabrics were compared with commercially
mercerised samples of the same fabrics [149,150]. The
ammonia (evaporation) treated fabrics showed significant
improvements in crease recovery, tear strength and flex
abrasion. After durable-press finishing, average strength
losses for a range of fabric weights were:
12 (a) Resin finished only, 47%
(b) Mercerised and resinated, 39%
(c) Ammonia-treated and resinated, 34%.
Later work by Cotton Inc. confirmed these fin-
dings [1511. The combination of a liquid ammonia pre-
treatment, followed by cross-linking has in fact been the
subject of a patent taken out by BASF [152].
JSDC Volume 103 October 1987 347
 The inclusion of both mercerisation and ammonia treat-
ment in a single finishing line may have important advan-
tages. For example, mercerisation may be included to give
improved dye yields, while liquid ammonia treatment prior
to resin application will improve the relationship between
strength and crease recovery.
Work at IIC [153,1541 has indicated that some of the
adverse effects of mercerising, particularly in relation to low
wet pick-up finishing (such as non-uniformity of liquid dis-
tribution in the fabric), can be reversed and further
improved by a pretreatment with liquid ammonia. These
effects are due, it is suggested, to changes in the fibre
swelling characteristics.
Raheel, in a series of papers, has explored the potential of
a two-stage pretreatment sequence 1155-1581 and found
that the combined treatment gave some improvements
over liquid ammonia alone, notably in abrasion resistance,
tensile strength and wrinkle recovery after repeated laun-
dering. Liquid ammonia was found to reduce fibrillation in
the laundering of resin-finished goods.
Considerable interest has been shown in the response to
liquid ammonia treatment of fabrics woven from open-end
yarns, especially in combination with a cross-linking finish.
The harshness and low tensile strength of open-end yarns in
comparison to ring-spun yarns have limited their accep-
tance in certain end uses. Cluett, Peabody has taken out a
patent I1591 for liquid ammonia treatment of open-end
yarns to improve softness of handle. A study at
SAWTRI [160] reported that single thread strength of
open-end and ring yarns was affected equally by ammonia
treatment, but Russian work indicated that at high twist
levels the open-end yarn responded better.
The Northern Piedmont section won the AATCC inter-
sectional competition in 1977 with a study on the relative
behaviour of ammonia-treated fabrics woven from ring-
spun and open-end yarns, particularly as a pretreatment for
durable-press finishing I1611. The following is an extract
from the conclusions of the study.
'By the proper selection of pretreatments, the filling ten-
sile strength, filling tear strength and abrasion resistance of
fabrics from open-end spun yam can be made better than
fabrics from ring-spun yarns having no special pretreat-
ment. The relative cost of special treated fabrics from
open-end spun yarn as compared to fabrics from ring-spun
yarn would depend on the yarn size and yardage of fabrics
finished.
'The best compromise pretreatment for good abrasion
resistance, filling tensile strength and filling tear strength was
liquid ammonia treatment plus Microstretching.' (Micros-
tretch is a mechanical treatment for fabrics, details of which
are available from the Sanforized Company. )
In 1983 IIC briefly reported a study 11621 in which a
sheeting construction had been produced from both ring-
spun and rotor yams, and compared after cross-linkingwith
and without a pretreatment with liquid ammonia. It was
concluded that the weaker open-end yams can be
improved to perform equally with ring yarns in easy-care
fabrics, if they are given a liquid ammonia pretreatment.
CONCLUSION
The improvements that are conferred to cotton textiles by
mercerisation or liquid ammonia treatment are widely
documented. Mercerisation increases colour yield, confers
lustre and improves appearance. Liquid ammonia treat-
348 JSDC Volume 103 October 1987
ment can give significant improvements in many properties,
notably in dimensional stability and appearance after laun-
dering. These characteristics can all add considerable value
to the treated fabric, and broaden the range of effects that
can be offered by the enterprising finisher.
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100 YEARS AGO
From abstract of paper entitled ‘Spidersilk ’, by P L Simmonds
(J. SOC. Arts, Oct 1887),Journal, October 1887
Monsieur Camboni, a French missionary at Madagascar,
has sent home specimens of some large spiders, their
cocoons and silky fibre, which, he asserts, can be utilised
for spinning tabrics.
If this spider silk is as strong as asserted, it differs
materially from some brought to Europe in the 17th
century from the tropics, which was greatly admired for its
fineness and brilliancy of colour, and made into gloves.
Louis XIV. wishing to encourage this new industry,
ordered some garments to be made of it, but was
disgusted with them the first day he wore them, as they
tore in all directions.
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Twenty years ago the possibility of utilising the silky
fibre of these large spiders was pointed out by M
Blanchard, in a conference on silk at Sorbonne. It suffices,
he tells us, to take between the fingers the voluminous,
ovoid, elongated abdomen of this spider, which always
has a thread hanging from one of its glands, and to wind
this on a reel or bobbin, for the source seems in-
exhaustible.
Whether people will be thankful for the introduction of
this huge spider remains to be proved, although it may be
useful in keeping down the plague of flies and mosquitoes
in certain localities.
JSDC Volume 103 October 1987 349