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Degumming of silk

Article  in  Review of Progress in Coloration and Related Topics · October 2008

DOI: 10.1111/j.1478-4408.1992.tb00091.x

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Degumming of silk
M L Gulrajani
Dept of Textile Techiiology, fiidiaii liistitufe of Technology, New Delhi 110 016, fiidia
Degumming of silk involves the cleavage of peptide bonds of sericin, either by hydrolytic or
enzymaticmethods, and the subsequent removal of sericin from the silk fibroin.Hydrolysis of sericin
can be carried out under neutral, alkaline or acidic conditions to give four fractions, each having
different properties. Boiling-off in alkaline soap solution is the most popular degumming method.
There are many qualitative methods of assessing the extent of degumming; however, quantitative
methods have yet to be developed. Degumming can be carried out on yarn or fabric, in manually or
mechanically operated machines. Mechanisms of degumming remain to be investigated.

INTRODUCTION The processes used for degumming can be classified

The terms 'degumming' and 'boiling-off' have been used into five main groups:
interchangeably in literature. It has been stated that the (a) Extraction with water
purpose of boiling-off silk is three-fold: to remove the (b) Boiling-off in soap
sericin, the reagents added by the throwster in soaking (c) Degumming with alkalis
raw silk and any incidental dirt picked up in any of the (d) Enzymatic degumming
operations of reeling, throwing or knitting [l]. Removal (e) Degumming in acidic solutions.
of natural wax, some colouring components and mineral
The processes developed for degumming, though ad-
matter is also achieved during boiling-off.
equate for local requirements, have not been systemati-
Since all the natural and acquired impurities except
cally investigated. Hence the literature on this subject is
sericin constitute only a very small fraction and are
replete with references on processing details, but lacks
comparatively easily removed, the degumming process
any serious scientific analysis of this important process.
may be considered primarily as one of cleavage of peptide
The purpose of this review is to summarise and comment
bonds of sericin, either by hydrolytic or enzymatic meth-
on the work carried out on degumming since 1920. A
ods, and its subsequent removal from fibroin by
previous review by Howitt covered a period up to the
solubilisation or dispersiori in water. Removal of sericin
early 1940s (41.
results in a silk yarn or fabric with soft handle and
enhanced lustre.
The amount of sericin in raw silk measured in terms of
SERICIN
weight loss varies between 17and 38%.Some of the good Sericin forms an outer covering of silk fibre and is classi-
Chinese and Japanese varieties show about 17 to 17.5% fied as a kind of scleroprotein. Many investigators have
while yellow Italian silk has about 23% sericin and some reported that it is not a homogeneous protein but is
Thai varieties have as high as 38% [2,3]. Silk is produced composed of two [5], three [6,7] or even four (81 distinct
in several countries, as shown in Table 1, and the fibres components. The fractionation of sericin into various
from different regions contain sericin of diverse chemical componentsis carried out by dissolving it in hot water for
and physical properties. different time periods, during the course of which the
sericin undergoes hydrolytic cleavage. Hence these dis-
tinct fractions may not be true forms of components
Table 1 World raw mulberry silk production (tonnes) present in sericin. On the other hand, photomicrographs
of stained cross-sections of a silk gland show a triple layer
Country 1970 1975 1980 1985 1988 of material lying on top of the fibroin core [9]. Although
such differential staining is not necessarily good evi-
China 11124 15000 23485 32000 34 400 dence for the presence of chemically different forms of
India 2258 2376 4593 7029 9 000 sericin, it does indicate some measure of heterogeneity of
Japan 20515 20168 16155 9592 6 900 the sericin within the gland itself. More recent studies
USSR(est.) 3000 3300 4254 4000 4 000
S Korea 2845 5545 3279 1850 1 000 have shown that liquid sericin of the internal thread
N Korea 700 2 100 3500 3 500 glands is composed of a large number of proteins of
Brazil 259 930 920 1558 1 700 differing qualities [lo].
Thailand 479 637 612 930 930 Komatsu has separated sericin into four fractions,
Others 2300 1150 1114 1400 1 500
namely sericin I, 11, I11 and IV, on the basis of the differ-
Total 42780 49806 56512 61859 62950 ence of their solubilities in hot water (81. The four frac-
tions differ in their acid composition as well as in physical
Source Texf. Prog., 21 (4) properties (Tables 2 and 3).

REV.PROC.COLORATION
VOLUME
22 1992 79
 Table 2 Amino acid composition of sericin fractions, whole being a resinous polymer present on the surface, is com-
sericin and fibroln paratively easily accessible to degumming chemicals.
The typical chemical composition of the fibroin and
Sericin fraction (mot Yo) sericin given in Table 2shows that the three major amino
acids in fibroin are glycine, alanine and serine; while
Amino Whole
acid I II Ill IV seric in Fibroin those of sericin are serine, aspartic acid and glycine, with
threonine also present in significant amounts.
Theoretically the method of degumming should be
Gly 13.21 12.81 15.69 11.89 13.49 43.7
Ala 4.68 6.69 6.68 9.30 5.97 28.8 based on the attack of the degumming agent on the
Val 2.97 2.21 3.21 4.16 2.75 2.2 specific peptide bonds formed by the major amino acids
Leu 0.86 0.96 1.27 6.26 1.14 0.51 of sericin. However, the various methods of degumming
Ile 0.59 0.57 0.85 3.50 0.72 0.71
0.68 0.31
have been developed through empirical observations
Pro 0.58 0.63 0.66 2.75
Phe 0.45 0.44 0.50 2.83 0.53 0.61 and their mechanisms have not been established.
Trv 0.19 0.20 0.25 0.23 0.21
0.17 0.15 0.12 0 0.1 5 Extraction with water
0.04 0.04 0.04 0.12 0.04
34.03 36.64 28.15 12.40 33.43 11.9 Extraction with water under pressure at 115°C has been
10.34 8.48 11.36 7.25 9.74 0.9 used by various investigators to isolate sericin from fibroin
2.53 2.43 3.15 2.45 2.61 5.1 and classify it into different fractions [5,6,13]. However,
16.94 16.95 16.13 12.64 16.71 1.3
4.73 3.64 4.09 11.32 4.42 1.0 this process has not been seriously considered commer-
3.20 2.65 3.68 3.93 3.10 0.46 cially. Some workers believe that sericin is soluble in hot
1.25 1.22 1.49 1.87 1.30 0.16 water while others feel it is hydrolysed.
3.28 3.29 2.64 7.11 3.30 0.31
The initial dissolution characteristics of sericin also
depend on the quality of ripening of cocoons [14]. The
sericin in unripe cocoons develops a crystalline structure
Table 3 Properties of sericin fractionated with hot water
(p structure) at high temperatures and high humidities,
and has inferior dissolution characteristics [15,16].
During the reeling process silk cocoons are kept in a
Sericin hot water bath at 50-60°C, with the result about 1-3%
Whole sericin is solubilised in water [17]. Subsequent heating of
I II Ill IV sericin raw silk yarn in water at high temperatures for varying
time periods results in gradual removal of sericin [18].By
Content (“10) 41.0 38.6 17.6 3.1 100
autoclaving in water at 115°C for 180 min about 96%
Dissolution rate sericin can be solubilised. It is suggested that for complete
coefficient 5.33 1.76 0.70 0.22 removal of sericin it is necessary to extract the silk yarn
Moisture regain (Yo) 16.7 16.2 15.7 14.7 16.3
Specific gravity 1.400 1.403 1.408 1.412 1.407
withwaterat120aCforfourperiodsof2h[19].Autoclaving
Crystallinity (7’) 3.0 18.2 32.5 37.6 15.06 of silk in water at high temperature causes a considerable
lowering of viscosity and increase in amino group con-
tent of the fibre [20].

The molecular conformation of sericin is observed to Boiling-off in soap solution

be a mixture of randomly coiled and p structures. The
randomly coiled structure changes easily into the p struc-
ture by heating in a moist state. The molecular mass of
sericin is reported to be between 1.6 x lo4 and 3.09 x lo5
[ll).A more recent study by the same investigator has
determined it as 1.0 to 1.2 x lo5 from both intrinsic
viscosity and electrophoretic patterns [a].
The sericin content of cocoon filaments varies accord-
ing to the position in the layer of the cocoon. The greatest
proportion of sericin is present in the outer layer, while
the least is in the innermost layer. Moreover, a difference
between maximum and minimum amounts of as much
as 50% has been found by Tsumokaye [12].
METHODS OF DEGUMMING
Although sericin and fibroin, the two components of raw
silk, are both proteins, they differ considerably in their
chemical composition as well as accessibility. Sericin,
Boiling-off of silk in soap solutions has been practised for
more than 200 years [21].This process continues to be the
most favoured, albeit with some modifications. Olive oil
soap, sold commercially as Marseilles soap, forms the
basis of this degumming process [21-27). According to
Howitt (41,’It would appear that the superiority of olive
oil soap is merely a traditional fallacy ‘. Many other soaps
have also been tried with some degree of success. These
include red oil [22], palm oil [25], lard oil [25] and oleic
acid [28] soaps, the last of which has shown promise.
Grove-Palmel has stated that no soap that has a hard
fat for a base can safely be used, and no soap whose 1%
solution will gel when cool is suitable [29]. He has further
stated that three kinds of soap have proven excellent for
boiling-off silk:
(a) A pure oil soap containing 65% fatty anhydrides, 8%
combined alkali,25% water and less than 0.3%of free
sodium hydroxide

80 REV.PROG.
COLORATION
VOLUME22 1992
@) Monopol soap, made from sulphonated castor or
linseed oil, containing 6 5 7 5 %fatty anhydrides, 3%
combined alkali, 1 2 1 5 % water and no free alkali
(c) Marseilles soap, made from olive oil containing 60-
63% fatty anhydrides, 7% combined alkali, 2 6 3 0 %
water and up to 2.3%free sodium hydroxide.
Besides these requirements the soap used fordegumming
should be neutral, readily soluble in water and free from
colouring matter.
The quantity of soap required for complete degumming
depends a great deal upon the nature and type of silk.
Generally 20-30% soap on the weight of material is used
[21,23,30],which works out at 6-7 gfl for a liquor ratio of
3040:l. A degumming time of 90 to 120 min a t the boil is
considered sufficient. Hougen has given a general rela-
tionship (31) (Eqn 1):
log K = 2.236 - 8.21N"
whereKis thedegurnmingcoefficientandN"istheinitial
normality of the soap solution. According to this investi-
gator the most rapid rate of degumming occurs at a
normality of 0.053 N. The rate of degumming was found
to be three times faster at 93°C than at 82°C.
The commonly practised single-bath boiling-off
method works out to be very expensive. Methods of
recovery of soap from spent baths have not been com-
mercially successful. The use of standing baths is recom-
mended to offset the high cost of soap. Standing baths
have their own drawbacks of accumulated sericin, oily
scum, colouring matter and fatty acid portions of soap,
affecting the quality and efficiency of the process.
In order to eliminate these drawbacks, processes have
been developed whereby silk is boiled-off first in a par-
tially exhausted soap liquor, and finished in a bath of
fresh soap. In operation this system approximates a
countercurrent flow of silk and soap liquor. Raw silk is
about 75%degummed in the'used' or partially exhausted
soap liquor. Soap additions are made as reinforcement
after each strip. The bath is generally discarded after
eight lots. Presteeping in lukewarm soap solution for 2
to 12 h improves the lustre of the yarn [30,32].
The addition of alkali to soap solution increases the
rate of degumming [33], and has been found to make the
process economical since the quantity of soap and the
time required are reduced. Leggis has reported that a
high-grade olive oil soap liquor gives a starting pH of 9.2-
9.5, which rapidly drops to 8.5 [34]; addition of alkali
tends to maintain pH at the effective point. Alkalis rec-
ommended for addition to soap solution include sodium
silicate [3537], sodium sesquicarbonate [36],sodium car-
bonate 137,381, sodium phosphate [37], sodium hydrox-
ide [35,37,38] and a buffer mixture of sodium carbonate
and sodium bisulphite (271. It has been observed that
with up to 0.18% free alkali no weakening of the fibre
occurs 1391; however, the resultant silkacquires a yellow-
ish tinge 1401.
Toyoda has concluded that the use of alkalis with soap
seems better than soap alone; silk may remain as long as
1 h in 0.001 mom sodium hydroxide or 0.0033 molfl
sodium carbonate in conjunction with soap without any
injury to the fibre [38].Hillman argues that the efficacy of
an alkali-containing soap degumming bath has been
much exaggerated [35]. According to this investigator
certain electrolytes may, without increasing the pH of the
bath to a point that would be considered dangerous,
have a very deleterious action on the strength of the silk,
e.g. a bath of 0.75% soap and 0.75% sodium carbonate,
having pH 10.2, caused a loss of 30% in the tensile
strength of one sample.
In a recent study Brzezinski and Malinowska reported
that degumming in a liquor containing 4 gfl Marseilles
soap and soda or sodium silicate of pH 9.5-10 for 15 min
at 98°C can be beneficial economically (material, energy
and water consumption, and labour requirement) and in
terms of quality [37].
As stated above, degumming is many times referred to
as 'boiling-off' of silk; however, i t has been observed that
silk degummed at 90°C has a superior colour and feel to
that treated at the boil (261. Fermazin has reported that an
emulsion of pine oil in aqueous soap solution at about
80°C produces a degummed silldacetate blended fabric
having uniform lustre, without affecting the strength of
the substrate [41]. In the case of yarns, a foam method of
degumming has been found to be better, since it requires
less time and eliminates excessive handling of the yarn,
thereby avoiding damage [21].
Degumming of silk with a solution containing 2 @l
soap, 0.5 gfl sodium carbonate and 1 s/l detergent can be
carried out over 30-60 min at 50°C in an electromagnetic
field [42].
Soaps hydrolyse in water at high temperature to give
free alkali and 'acid soap', i.e. the fatty component of the
soap. Hart observed that, when raw silk is immersed in a
solution of soap, there was a marked decrease in the
concentration of alkali in the solution [43]. This was
attributed to sorption of alkali by the substrate and inter-
action of sericin with alkali. Tsunokaye postulated that
the degumming action of soap solution is due to alkali
formed on hydrolysis and that the soaps which hydro-
lyse the most have the greatest degurnming power (Table
4) [44]. Stockhausen has confirmed this observation (451.
Fibroin also absorbs 'acid soap'. The absorbed alkali and
'acid soap', which amount to about 1%of the silk, cause
variation in colour, lustre, elasticity, strength, elongation
and scrooping properties.
In a subsequent study Tsunokaye has shown that
excess alkali in the hydrolysed soap diminishes the lus-
tre, strength and elasticity of degummed silk, i.e. the
soaps that hydrolyse the most also effect the lustre [46].
According to Takahashi absorbed fatty acid (i.e. acid
soap) protects silk from the action of alkali and also
retards the rate of degumming [47]. Retained fatty acids
increase the elasticity of the silk as well. Furthermore,
soaps from unsaturated fatty acids or oils retain a better
REV.PROG.COLORATION
VOLUME22 1992 81
 Table 4 Relationship between degree of hydrolysis of soaps danger of chemical damage rapidly increases. De-
and degumming loss
gumming is very slow and incomplete at pH values
below 8.4 [62].
Degree of Degumming In order to maintain the desired pH, buffer solutions
Kind of soap hydrolysis (%) loss (%) are recommended. Some of the buffers investigated are:
potassium carbonate/sodium bicarbonate [63], sodium
Tallow 51.8 18 38 carbonate/sodium bicarbonate [64,65],sodium hydrogen
Olive oil 60.0 18.60 phosphate/trisodium phosphate (651 and potassium
Coconut oil 28.8 16.77
Caster oil 16.5 13.42 tetraborateboric acid [66,67]. Sodium carbonatehodium
Arachis oil 55.0 18.23 bicarbonate is the most widely investigated buffer and is
Soya bean oil 60.0 18.71 sometimes prepared by mixing soda ash with a calcu-
Cotton seed oil 61 .O 18.24
Chrysalis oil 53.0 18.03
lated amount of sodium bisulphite.
Sodium caprylate 0.75 3.09 It has been reported that the rate of degumming de-
Sodium laurate 1.25 7.15 pends not only on the pH but also on the total concentra-
Sodium myristate 14.25 7.51 tion of electrolytesin thebuffersolution [64].For instance,
Sodium palmitate 38.0
Sodium stearate 59.75 19.44 it takes 20 min to degum silk at a temperature of 95°C in
Sodium arachidate 62.50 20.30 a 0.05 moVl carbonatebicarbonate solution with a pH of
Sodium oleate 42.40 19.30 10.0, while for a 0.025 mom solution the time required is
Sodium ricinoleate 10.30 12.10
30 min and for a 0.01 mom solution it is 60 min. Decorn-
position of fibroin also increases with increase in normal-
ity of the carbonatehicarbonate solution at the same pH.
lustre on the silk than do soaps produced from saturated Degumming with alkalis alone results in silk with very
fatty acids. Olive oil soap is considered particularly suit- poor wetting properties. However, if a nonionic surface-
able for silk degumming because of its low degree of active agent is introduced along with the alkalis the
hydrolysis, which gives better lustre. wetting properties improve considerably without affect-
ing the rate of degumming [65]. Either the surface-active
Degumming with alkalis agent is sorbed by the substrate or it removes the wax and
Boiling in aqueous solution of (alkaline) ash of certain fatty matter, thereby improving the wetting. This aspect
woods was perhaps one of the most common methods of has not been thoroughly investigated (68,691. However,
degumming before soap became available. Soaps score various workers have recommended the use of synthetic
over alkalis because of their surface-active properties. surface-active agents with alkalis, including: alkyl aryl
However, as stated earlier, soap-based methods are rela- sodium sulphonate [36,51,52], ethylene oxide conden-
tively expensive. The alkali-based methods improve sate (Geropon BPM) (611, polyoxyethylene alkyl ethers
labour productivity and machine efficiency by cutting (54,701, polyethylene glycol ethers (C8-Clh) [55].
the cost of chemicals as well as by reducing the time of The presence of salts in water enhances the degrada-
treatment from 90-120 min to 10-30 min. tion of silk being treated with alkalis owing to the distri-
Alkalis should not be used alone in boiling-off silk bution of ions in external and internal phases according
since they leave the stock dirty yellowish, thin and harsh to Donnan membrane theory. Addition of salt to an
[48).The best compromise is achieved by using mixture alkaline solution in which negatively charged fibroin is
of soap and alkalis. Developments in synthetic surface- present increases the concentration of hydroxyl groups
active agents has revived interest in alkali-based in the internal phase, which in turn attack the fibroin.
degumming processes and agents. Lowering of viscosity of silk is more pronounced in the
Various alkalis have been investigated for use as presence of calcium salts [61].Addition of metal-chelating
degumming agents. They include sodium hydroxide agents such as sodium hydrogen pyrophosphate pre-
[37,49-511, sodium carbonate [36,37,48,51-561, potassium vents the damage of the silk during degumming with
carbonate [50], sodium silicate [36,37,51,57], trisodium alkalis [71]. The effect of sodium pyrophosphate, sodium
phosphate [37,49,53,54,56,58], sodium pyrophosphate tripolyphosphate and EDTA as degumming aids has
[59], sodium bicarbonate [60), borax [49], ammonia [49] been evaluated by Lee, Song and Chung [72].
and salts of weak acids, such as silicic, boric (611 and Thus a specially formulated composition for de-
stannicacid. Hall has observed that the rate of degumming gumming silk comprises a liquid alkaline mixture con-
decreases in the following order: caustic soda > sodium taining synthetic polymer, protective agent for silk,
carbonate > sodium silicate > trisodium phosphate > sequestrant, wetting or emulsifying agent, buffer salts,
borax > sodium bicarbonate [a]. Sodium carbonate was alkali and water (731. Miltopan SE (Henkel) is reported to
the most preferred alkali. be based on the above-mentioned composition [74]. It
Mosher established that the pH of the boil-off bath in penetrates the sericin very quickly and evenly, and hy-
alkaline degumming should be maintained between 9.5 drolyses it completely while additives present protect the
and 10.5 (481. Below pH 9.5 the rate of degumming is too fibroin. It is claimed that the degurnming bath can be
slow, with a risk of mechanical damage; above 10.5 the reused several times, and that one-bath degumming and

VOLUME
82 REV.PROC.COLORATION 22 1992
bleaching or degumming and dyeing is feasible. As com-
pared with soap, Miltopan SE offers following advan-
tages [75,76]:
(a) Degumming time is reduced to between a quarter
and a fifth
@ j Despite the higher pH value (11.0-11.5) as compared
with soap, the fibroin is not damaged
(c) Processing cost is considerably reduced
(d) Hard water up to 26"German can be used.
Another commercial degumming product, P-400, was
originally developed in the early 1970s in the Silk Re-
search Laboratory in Lyons and later patented and mar-
keted by Hepatex AG. It is based on a synthetic soap and
is claimed to offer the same benefits over conventional
soap as those advanced for Miltopan SE [77,78]. Other
commercial products found suitable for degumming of
silk are Sopajet L (Indifar), Setafin (Henkel), Idrosolvan
9 0 (Bozzeto) and Serilan PCS (ROTA) [79].
Initially it was thought that alkaline degumming con-
sists of the following stages [47]:
1. Glutinisation, whereby the sericin particles become
hydrated and charged with hydroxyl ions
2. Dispersion of the glutinised particles by the repul-
sion of similarly charged particles
3. Secondary albuminate formation in which dispersed
particles were further stabilised by hydrolysis.
Subsequently Wolf and Hougen stated that the de-
gumming of silk is a chemical reaction, rather than one
depending principally upon absorption and diffusion
[80]. During degumming alkali is absorbed by sericin.
The resultant alkali-sericin compound undergoes pro-
gressive decomposition in combination with more alkali.
According to these investigators the mechanism of silk
degumming in soap or alkaline solutions may be repre-
sented by Eqn 2:
dS/dt = -(C + kA)S (2)
whereS is the sericin content of silk, expressed in g per g
dry silk; t is the time elapsed in min; A is the g equivalent
of alkali present in the bath per g dry silk; C is the
degumming coefficient in water alone and k is the
degumming coefficient due to the presence of soap or
alkali. The coefficient k is dependent on temperature,
yarn size, degree of agitation, watedsilk ratio and nature
of soap or alkali.
The equation of Wolf and Hougen has been applied
mainly to the first phase of degumming, in which the
sericin combines with alkali. The results therefore largely
reflect the comparative behaviour of soap and various
alkalis. The alkali absorbed by the fibroin or consumed
during hydrolysis was not taken into account by Wolf
and Hougen, which is a limitation of their study.
Alkalis hydrolyse proteins by attacking peptide bonds.
The reaction is nonspecific. The chief amino acids af-
fected are cystine, serine, threonine and arginine [81].
Degumming in acidic solutions
Since degumming is traditionally carried out in alkaline
solutions, the process in acidic solutions has not received
much attention. A process of degumming with dilute
hydrochloric acid was patented in 1886 (BP 1896)[4] and
later investigated by Takahashi [82]. Investigations car-
ried out by Viktorov and co-workers have shown that
organic acids (acetic, formic, lactic) are not effective in
eliminating sericin, and therefore only strong mineral
acids (sulphuric and hydrochloric) are suitable for this
purpose [83].They concluded that complete degumming
of silk with these acids cannot be achieved without
considerable harm to the fibroin.
Mosher has observed that two phases of effective
degumming occur at different pH values: an alkaline
plateau between 9.5 and 10.5 and an acidic sector be-
tween 1.5 and 2 [%]. He has also pointed out that drastic
alkaline treatments may prove harmful to silk, while
acidic treatments are comparatively safe. It has been
claimed that degumming at pH 1.0-2.9 gives a product
superior in tensile properties to that obtained by soap
degumming [84].
Recently Flensberg and Hammers have reported that
acid degumming is being carried out on a commercial
scale [74]. These investigators degummed silk with tar-
taric and citric acid, and observed that these treatments
gave very good results in terms of tensile strength and
elongation of the silk.
Studies in degumming of silk yarn and fabric with ten
organic acids at a concentration of 0.05 mol/l for 1 h at the
boil have been carried out by the author and co-workers
[18]. From the data given in Table 5, it can be observed
that, irrespective of the strength of the acid (pK, value),
the weight loss is almost the same. However, a good
correlation has been observed between pH and tenacity,
as well as between pH and flexural rigidity of the
degummed samples. In terms of weight loss and tenacity,
the best results were obtained with succinic acid fol-
lowed by tartaric and monochloroacetic acids.
Dilute acids are specific in their hydrolytic attack on
proteins and are known to break peptide bonds linking
aspartic and glutamic acid [85]. Blackburn and Lee have
proposed the mechanism shown in Scheme 1 for acid
hydrolysis [86].
f FH2COOH
-NH-C-CH-NH-C-
f ' FH,COOH
CH2C00H
I -NH-C-CH-NH + HOOC-
-NH2 + HOOC-CH-NH-E- I
0
Scheme 1
REV.PROG.COLORATION 22 1992 83
VOLUME
 Table 5 Treatment conditions and observed responses for yarns degummed with organic acids

Purity Concn Initial Final pK, Weight loss Flexural rigidity Tenacity
Acid (yo) (gii) PH PH x 10-3 (yo) (g/cm2 x (gldenier)

Lactic 88 3.963 2.65 3.05 3.85 21.82 0.3470 2.91

Tartaric 99 7.42 2.30 2.45 3.02 21.08 0.3382 3.38
Citric 99.5 10.44 2.35 2.50 21.57 0.3065 2.75
Oxalic 99 6.23 1.87 1.90 1.2 20.6 0.3224 2.99
Malonic 99 5.00 2.25 2.40 2.82 21.27 0.3314 3.12
Succinic 99 5.84 2.88 3.25 4.18 21.15 0.3292 3.45
Trichloroacetic 99 8.08 1.79 5.4 0.70 20.96 0.9190 3.13
Dichloroacetic 99 6.38 1.79 1.85 1.48 23.21 0.3139 3.13
Monochloroacetic 99 4.67 2.25 2.50 2.82 21.75 0.3483 3.23
Glacial acetic 99.5 2.985 3.22 3.80 4.74 15.12 0.5988 3.49

Dilute acids are used at a concentration just sufficient
to maintain the p carboxyl group of aspartic acid residues
in the undissociated state. In this way aspartic acid peptide
bonds are preferentially cleaved at a rate at least 100times
faster than other bonds [87].
The data of amino acid content of sericin and fibroin in
Table 2 show that sericin contains about 16.71 mol %
aspartic acid and 4.42 mol % glutamic acid, while silk has
only 1.3mol%asparticand l.Omol% glutamicacid.Since
dilute acids preferentially attack peptide bonds linking
aspartic and glutamic acid, it can be concluded that the
degumming of silk in acidic solutions may be brought
about by the hydrolysis of sericin and its subsequent
dissolution in water. However, this hypothesis has yet to
be experimentally confirmed.
Enzymatic degumming
Enzymatic methods, also known as biological methods,
were used long before the nature of enzymes was fully
understood, and it is only during the past few decades
that enzymatic degumming of silk has been developed
along scientific lines [4].
Enzymatic degumming is considered to have a mild
action on the fibres and is claimed to produce uniformly
degummed material with a soft handle [88-931. Many
investigators have reported that the enzymatic method
of sericin removal produces better results, particularly in
terms of reduced lousiness, than the classical boiling-off
methods in acid or alkaline media (94-1001. Since
degumming by this method is carried out at a compara-
tively low temperature under mildly alkaline or acid
conditions, the natural wax, soil and twisting oil are not
completely eliminated [92].A short pretreatment with an
alkaline solution swells the sericin on the surface of the
fabric (and may eliminate wax and oil) and results in
better degummed silk [91,100-1081.
Various studies have indicated that proteolytic en-
zymes react at a limited number of sites in the polypeptide
substrate. It is an advantage when an enzyme has a
specific mode of action, and the specificity of some of the
common enzymes is shown in Table 6 [109].
Minagawa has reviewed the application of protease in
various degumming and scouring processes [110]. The
effect of varying conditions on degumming of silk fabrics
with protease hasalsobeen discussed. Forthedegumming
of silk three main types of enzymes have been used:
trypsin, papain and bacterial enzymes.
Tryysin
This is a serine protease which is most active in the pH
range 7-9. Ammonium bicarbonate (0.1 moM) is consid-
ered to be a good buffer. For tryptic digestion an enzyme/
substrate ratio of 1 or 2% for 1-4 h at 37°C is considered
appropriate.
Trypsin is the proteolytic enzyme secreted by the
pancreas, and a degumming process in which pancreatic
secretions could be used was patented by Soltau in 1895
[4].Subsequently Rohm and Haas patented processes for
treatment of raw silk with pancreatin in the presence of
soap and alkali (41. A recent patent has claimed that
treatment with a liquid containing 4% 0.w.f. mixture of
sodium bicarbonate sodium carbonate and sodium sul-
phate at a 2:2:1 weight ratio, and 0.3%alkali protease for
10-20 min at 5040°C gives good uniform results com-
pared with those obtained with a liquid containing only
sodium carbonate and protease [lll].Pretreatment with
weakly alkaline solutions of sodium silicate [91,100],so-
dium carbonate or borax I1121 followed by degumming
with pancreatin enzyme has also been claimed to give
improved results.
A detailed investigation of the effect of trypsin concen-
tration, temperature and time of treatment on the re-
moval of sericin from silk by hydrolysis has been carried
out by Krysteva et al. [98]. According to these investiga-
tors a 1% solution of trypsin completely hydrolysed
sericin in 10 h at 37"C, while the amount of sericin
removed by a 4 h treatment with 1 and 8% trypsin
solution were 26.4% and 28.7% respectively. Further-
more, the tensile strength of silk fibres conventionally
treated with sodium carbonate was less than that of
trypsin-treated fibres. Similar studies have been recently
carried out by Lee, Song and Chung [lo€!]. A combined
degumming and scouring process by which not only
sericin but fat and other impurities are also removed has
also been patented [107]. In this process an alkali
pretreatment is followed by fermentation for 1.5-2 h at

84 REV.PROG.COLORATION
VOLUME
22 1992
3740°C in a bath containing 2% trypsin/lipase/amylase protease that has been extensively investigated for
mixture in the ratio 72:10:18 at pH 7-8. degumming of silk. Bromelin, a similar enzyme from
Trypsin catalyses the hydrolysis of the peptide bond pineapple, has also been tried and found suitable [101,116].
between the carboxylic acid group of lysine, or the Pioneering work in the application of papain to silk
carboxylic acid group of arginine and amino group of the degumming has been carried out by Wallerstein and
adjacent amino acid (1131, as shown in Table 6. Cleavage associates, whose methods are covered by patents (117-
take place slowly when the basic residue is adjacent in 1261. Originally the use of papain at 50-70°C in the
sequence to an acidic residue and does not occur at all presence of potassium cyanide or hydrogen sulphide
when the residue is followed by proline (Scheme 2) was suggested; later other less poisonous activators, e.g.
[ 114,115). sodium hydrosulphide, sodium sulphoxylate or sodium
Since sericin is a polar, less crystalline protein with a sulphite, were also recommended.
relatively high lysine and arginine content, it is easily The degumming of raw silk by activated papain has
hydrolysed by trypsin. On the other hand, fibroin is not been covered by other patents (127-1291. The process of
affected by this enzyme, due to the lysine and arginine degumming with papain and the properties of the
present in its structure. degummed silk substrates have been studied by various
investigators [88,95,99,108,116,130-1341. Munch has re-
Table 6 Specificty of proteases ported that sodium thiosulphate and a mixture of
thiosulphate and hydrosulphide can act as satisfactory
Optimum Major Minor activators (1321.
Enzyme PH cleavages cleavage sites Papain exhibits a wide specificity in its action towards
polypeptides. Peptide bonds formed by the carboxyl
Highly specific
Trypsin 7-9
+
-Lys-x-;
groups of arginine and lysine residues are highly suscep-
tible to attack by papain. In addition, cleavage occurs
+ +
Arg-X; Aec-X-
readily at the carboxylic acid group of histidine, and also
at glycine, glutamic acid, glutamine, leucine and tyrosine.
4 4 The mechanism of action of papain on sericin has yet to
S. aureus V8 protease 4 ,7 , 8 -Glu-X -Asp-X- be elucidated.
Less specific
Chymotrypsin 7-9 +
-H-X-(R) Bacterial enzymes
Degumming can be achieved by treatment with bacteria.
Pepsin 2
i +
-x-H-y-(bb The Schapping process used for waste silk is an example
++
-X-GIU-Y -
of bacterial degummingof silk.A bacterial enzyme alkalase
marketed by Novo has been found to be very effective in
hydrolysing sericin [96,108,135]. Lee, Song and Chung
Papain 5-7.5 Phe-X-Y
4 have found this enzyme to be more effective than trypsin
and papain (108).It can completely hydrolyse sericin in 1
Elastase 7-9 h at 60°C and pH9. The physico-mechanical properties of
alkalase-treated fabrics have been found to be better than
(a) H = Try, Phe, Trp. Leu
the conventional soap'soda-boiled silk. Treatment of raw
(b) H = aromatic or large aliphatic silk fabric with 0.05% alkalase under ultrasound at 24
(c) N = Ser, Ala, Gly,Val, Leu kHz has been claimed to yield better results at lower
temperature (1351.
0 Other alkali-stable proteases found suitable for de-
-NH-CH-C?
I NH-CH-C'
7 NH-
gumming of silk include degummase [136], thermo-
p 2 1 4 *O
I degummase (1351, esperase [137), sauinase [137],
NH2
I proteolytic enzyme S114 (1381 and proteinase (1391. Iida
(1401 has found that cations of calcium, magnesium and
barium act as enzyme activators while iron(a), iron(~n),
aluminium, silver and mercury(1) are deactivators. An-
ionic surfactants inhibit degumming while oxidants with
NH2 reducing power d o not affect the process of degumming
Scheme 2 with alkali-stable protease.

Papain
Papain is a sulphydryl enzyme isolated from papyrus
latex. It is readily available from a number of sources. It is
most active between p H 5 and 7.5 at 7&9OoC and requires
activation by a sulphydryl reagent. It is the only plant
ANALYTICAL INVESTIGATIONS OF SILK
DEGUMMING
Analytical investigations of silk degumming are carried
out to assess qualitatively as well as quantitatively the

REV.PROG. COLORATION VOLUME 22 1992 85

residual sericin and the damage caused to silk on
degumming.
The extent of degumming is most simply assessed by
measuring weight loss. This method does not give infor-
mation about the residual sericin, because after the initial
rapid weight loss the curve becomes asymptotic since the
degumming agents start attacking the silk.
Komatsu has used U.V.absorption at 280 nm as a
measure of the dissolution of sericin removed by treat-
ment with hot water, alkali and protease (81. A linear
relationship between weight loss and absorbance at 275
nm of the liquid remaining after degumming with tar-
taric acid has been observed [141]. Both tyrosine and
tryptophan absorb in this region, although tryptophan is
much the stronger absorber (1421.
Qualitative information about residual gum is ob-
tained by staining. Initially the use of ruthenium red for
distinguishing fibroin and sericin was suggested. On
immersion of silk in an aqueous solution of this dye the
gum acquires a deeper crimson shade than does the
fibroin. However, the differentiation is not very good
[143]. Wagner used picrocarmine and observed that the
gum is stained an intense red, the fibroin yellow [144].
Herzog found that a cold saturated solution of quinoline
blue, diluted to twice its volume with water and then
with one-third of the total volume of glycerine, stained
the residual gum blue in spun silk [145]. The fibroin
remained almost colourless. According to Wagner, when
raw silk threads are immersed for 24 h in a cold solution
of litmus, the gum is stained deep blue, whilst the fibroin
remains unstained [144].
Denham and Dickinson examined the suitability of
numerous dyes for distinguishing between fibroin and
silk gums and found CI Direct Red 2, CI Direct Red 61, CI
Direct Green 9, CI Acid Violet 19 and certain others to be
suitable (1431. Dyes that have also been used for this
purpose include CI Direct Red 80 [20], CI Reactive Violet
2 [36], CI Direct Blue 22 [I461 and Durazol Blue 2RS (ICI,
CI Direct Blue 71) [147].
It has been observed that the K1S values of silk dyed
with Durazol Blue 2RS for 1 min at 100°C show a linear
relationship with weight loss, which can be used to
quantify the extent of degumming (1471.
Pauly reagent, diazotised sulphanilic acid, has also
been recommended [3]. The diazobenzene sulphonic
acid undergoes a coupling reaction with selected phen-
olic amino acid components of the polypeptide chain
(e.g. tyrosine) to form a red azo dye as shown in Scheme
3. The gum turns orange-red with Pauly reagent, whereas
degummed silk turns yellow. Mechanically damaged silk
fabric also assumes a reddish colour on contact with this
reagent. Hence the practical application of this reaction
requires a certain amount of experience.
The degree of fibre damage in degumming has been
assessed by determining the viscosity and the primary
amino group content of silk. Excessive fibre damage also
leads to loss in tensile strength.
A method for assessing the damage by determining
86 REV.PROC.COLORAT~ON
VOLUME
22 1992
+ NENCI -
y 2 I
Q SO,H
Diazotizalion
S0,Na
Sulphanilic acld
#
Scheme 3
the viscosity of silk in zinc chloride solution has been
standardised by Trotman [148,149]. Cupriethylene
diamine and a 60% solution of calcium chloride and
ethanol at ratio of 491371 have also been used as solvents
for viscosity measurement [20].
Since sericin has a greater proportion of lysine than
has fibroin, the degumming can be monitored through
degradation of (a + E ) amino group content. If the
degumming is carried out in too strong an alkali or over
too long a duration, a marginal increase in amino group
content is exhibited as hydrolytic degradation. Knott,
Freddi and Belly have monitored the change in amino
group content of differently degummed silk using the
ninhydrin-based method of determining amino groups
[150,151] and found evidence for degradation of silk (201.
The extent of degumming can be qualitatively as-
sessed by viewing the degummed fibres under the scan-
ning electron microscope. Residual sericin appears as
lumps on the surface of the fibre. The extent of fibre
damage can also be assessed by this method [3].
The splittingof fibresintominute fibrillae is frequently
observed in silk. This has been attributed to the mechani-
cal injury of the fibre caused by chafing and rubbing
during degumming. The fibrillation of silk is also due to
the particular fineness of the fibroin threads, which are
locked within the surrounding gum and are termed
secondary threads. During degumming these are re-
leased and roll up to form small balls or pills. As a result
the silk fabric does not appear clean, particularly when
dyed in dark shades. If the degumming process is too
long, the balling-up of secondary strands into pills can
become acute.
The mechanical damage of silk during degumming is
also referred to as soap marks, friction marks, mildew
marks or lousiness. By using a degumming machine that
reduces friction, the formation of these marks can be
avoided to a large extent.
DEGUMMING MACHINES
Silk is degummed both in yarn and fabric form. Since silk
/’’ 3 ?

processing is largely carried out in the small-scale opera-

tions, manual methods have been popular. More re-
cently machines with electronic controls have been
developed.
Yarn degumming is mostly carried out in the hank
form. In the traditional method an open beckis used. The
hanks are hung on polished wood or metal rods, which
are submerged in the bath and turned manually. The
foam method proposed by Schmid offers a significant
improvement (1521. In this process the silk hanks are
hung in the upper part of the vessel on rotating arms so
that they donot comeintocontactwith the soap liquorin I
6
thebottom of thevesselbut with the foam that constantly
1 Closing hood
rises from the liquor (Figure 1). The splitting of the fibre 2 Inlet valve for washing water from net
is less and the lustre and handle are better. 3 Regulalion valve for the liquor in the arms
4 Pump delivery valve
5 Liquor recirculation valve
I 6 Liquor circulation pump
I 7 Addition pot
8 Drain valve
9 Hank displacing rod
10 Heating coil
11 Perforated tube supporting hank

Figure 2 Mezzera model TMB

A
level

‘ I

‘d

Figure 1 Foam degumming machine

A different type of machine was invented by Magelin

[153]. It consists of a fixed hollow perforated tube to
support the skeins. A rotary pump forces the liquor
through these holes, whence it trickles down over the
skeins. A hank-displacing rod is given a complete turn
around the tube from time to time, thus presenting
another part of the skein to the holes and evening up the
action. The liquor falling from the skeins is collected in
the tank, which supplies the pump. Mezzera’s T M B
machine (Figure 2) is based on this principle. This ma-
chine can also be used for dyeing.
Degumming of silk fabrics is mostly carried out by a
discontinuous method, although continuous degumming
machines are also available. The most common method
of boiling-off flat crepes is by the so-called skein method
(Figure 3A) [154]. A piece of fabric is wound on a collaps-
ible reel, the selvages on the extreme end of which are
stitched to the selvages of the fold beneath it, and the reel
is collapsed. The silk is taken off the reel; two bent rods
are inserted in the centre of the rolled-up silk and the
Figure 3 Skein-type fabric degumming
fabric is submerged in the boiling-off bath. One stick is
used as a support for the silk, while the other is used to
help turn it every 10-15 min. In a variation of this method
(Figure 3B) the fabric is hung on a stick with strings so
that it remains submerged in the bath [155]. Despite the
greatest care, faults repeatedly occur with this method,
particularly in the form of chafe marks or irregularities
that show up as spots. The layers of fabric may cling
together, particularly at the bottom, and zones with
residues may form during degumming or rinsing.
For degumming delicate articles where the prime con-
sideration is perfect production quality, star machines
are used (Figure 4) [156]. These are mainly simple vertical

REV.PROG.COLORATION
VOLUME
22 1992 87

Flgure 4 Horizontal star degurnming machine
star machines, in which the goods are hung from the top.
A pulsating action is provided mechanically. For very
delicate fabrics vertical or horizontal double star type
machines are better suited. In these machines fabrics are
attached on hooks from both sides. Articles with tight
smooth weaves can also be degummed on jigs.
A conveyer-type continuous boil-off machine has been
recommended for certain varieties of fabric [157].How-
ever, this machine has not found much favour with
processors. Recently Mezzera has introduced its VBM
machine (Figure 5)for continuous tensionless open-wid th
pretreatment of silk fabrics. This has been successfully
adopted in Europe and China [156].The standard range
for silk consists of one 8 m VBM unit having 550 m fabric
content, one drum washing unit and one roller washing
unit. This range can run at about 10d m i n . The goods are
hung in loops on rods which remain fully submerged in
the bath and move continuously forward. With appro-
priate synthetic detergents as little as 30-40 min may
suffice for readily removable types of gums; however, 1
h is required in most cases. A similar type of machine is
also available from Noseda in Italy.
Figure 5 Mezzera model VBM for continuous processing of silk
Electrical heating was introduced into the silk indus-
try in the USA in the late 1930s in the form of an electri-
cally heated boil-off kettle [158].This gave a good product
quickly and economically, as well as providing improved
working conditions. In the early 1980s Minagawa, Horii
and Murase carried out the degumming of silk by micro-
wave heating [159].This enabled heat to be transferred to
the interior of the fabric uniformly, hence woven fabrics
made from hard-twist yarn could be evenly degummed.
This method also economised on the amount of
degumming agent required.
Recently Gulrajani and Gupta have designed and
successfully tested a solar degumming machine (Figure
6) (1471, in which the degumming liquor is heated by
solar energy and circulated through the material by
88 REV.PROC.COLORATION
VOLUME
22 1992
Sllrrlng arrangement
Star frame
Hot
water
out
1 Stainless
Selectlvelv
-. -I
AU
\ coated soiar
Figure 6 Solar-energy-baseddegumming machine
thermosiphon cycle, established by the slight tempera-
ture difference between the top and the bottom of the
vessel.
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106. K Komatsu, Nippon Sanshigaku Zasshi, 47 (1) (1978)21;CIiem.Abs.,
89,25913a.
107.Rom. Ro 76 738;Chem. Abs. 99,21404r.
108. Y W Lee, K E Song and I M Chung, Hanguk Chamsa Hakhocchi, 28
(1)(1986)66.
109. Practical protein chemistry - a liaridbook, Ed. A Darbre (New York
John Wiley, 1986)124.
110.M Minagawa, Sen-i To Kogyo, 5 (10(1972)26, Chem. Abs., 77,
49868t.
111.Japanese P 0319 905 (1991).
112.BP 2 213 (1914).
113. M Bergmann and J S Fruton, Adv. Enzymol., 1 (1941)63.
114. C H W Hirs,SMooreand W HStein,]. Biol. Chem.,219(1956)623.
115.E Margoliash et a/., Nature, 192 (1961)1125.
116. H lida, Sen4 Koko, 25 (1973)156; Chcni.Abs., 79,6644r.
117. USP 16 664 764 (1972).
118. USP 1 763 112 (1930).
119. USP 1 855431 (1932).
120. BP 414 778 (1933).
121.French P 756 911 (1933).
122. USP 2 029 350 (1936).
123.USP 2 029 968 (1936).
124.USP 2 029 969 (1936).
125.USP 2 029 970 (1936).
126. USP 2 029 972 (1936).
127.German P 513 373 (1928).
128. BP 468 154 (1936).
129.Japanese P 7242 521 (1972).
130.S Hillman, Text. Color., 54 (1932)457.
131. H Munch, Angew. Chem., 48 (1935)797.
132.H Munch, Melliatid Textilber. English Edn, 9 (1938)37.
133. I Tutiya, Nippotr Shanshigaku Zasshi, 36 (2)(1967)120;Chm. Abs.,
70,12550.
134.Y Fukushima et a/., Kanagawa-Ken Kogyo Shikensho k h y u Hokoku,
(30)(1971)15;Chem. Abs., 76,26303~.
135. Japanese P 63 175 107 (1988).
136. H Katagiri and TNakahama,]. A@. Chon.Soc.japan, 17 (1941)165.
137.Res. Discl., 216 124 (1982);C h m . Abs., 97,73830h.
138. Xiubao Qiu et al., 26 (1) (1986)71;Chem. Abs., 104,208716m.
139.Japanese P 02 261 009 (1990).
140.H Iida, Sen4 Koko, 23 (7) (1971)485;23 (8)(1971)578; Chm.Abs.,
77,153 672k
141.M L Gulrajani and Sheetal Sethi, Unpublished work.
142.D B Wetlaufer, Adv. Protein Chem., 17 (1%2) 304.
143. W B Denham and E Dickinson, I.S.D.C., 51 (1935)93.
144.Wagner, Melliatid Textilber., 6 (1925)43, 118.
145. Herzog, Melliand Textilbcr., 13 (1932)121,181.
146. K Y Chu and J R Provost, Rev. Prog. Coloration, 17 (1987)23.
147.M L Gulrajani and S Gupta, Unpublished work.
148. S R Trotman, I. Soc. Chem. hid., 54 (1935)141T.
149. S R Trotman, 1. SOC.Clicm. lnd., 55 (1936)325T.
150.J Knott, M Grandmaire and J Thelen,]. Textile lnst., 72 (1981)19.
151. J Knott and V Rossback, Angew. Markromol. Chm.,86 (1980)203.
152.J T Marsh, Introduction to textile bleaching (London: Chapman and
Hall, 1946).
153.Amer. Silk. I., 40 (7)(1921)75.
154. P LeBrun, Text. World, 32 (1935)97.
155. F Weber, Melliand Textilber., 19 (1938)76,192.
156. Silkand colour (Basle: Sandoz).
157.P LeBrun, Text. World, 38 (3)(1914)117.
158.G T Perley, Text. World, 37 (5)(1940)64.
159. M Minagawa, T Horii and K Murase, Annual Report ofthe Sciences
of Living (Osaka City University), 30 (1982)97.
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