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Different blending ratios of Eri silk and cotton fibres were prepared. The optimum bleaching condition
chosen for the blends containing 0–25% silk content was the oxidative bleaching method, whereas the
blends at 50–100% should be bleached using the two-stage bleaching method (oxidative bleaching
followed by reductive bleaching). These conditions did affect the force–displacement characteristics of
the fibres with no yield point. X-Ray diffraction results showed that the percentage of crystallinity of the
cotton yarn tended to increase after bleaching, whereas the percentage of crystallinity of the Eri yarn
decreased marginally. Dyeing properties of the blended yarns were investigated using warm-dyeing
reactive dyes. Percentage exhaustion and the colour yield of the blends tended to decrease with the
increasing silk content. Shade variation was observed on the yarns at different blend ratios. This was
expected to be caused by the different physical nature of Eri silk and cotton fibres. Consequently, the
dye uptake and visual shade of each dye on the two fibres were different.
Introduction or Eri silk with other fibre blends [9,10]. Bleaching of Eri
silk was studied using H2O2 but, for the blended yarn of
Eri silk is a wild silk, being brought to textile uses as a
Eri silk and other fibres, an optimal bleaching method
spun silk fibre. It cannot be reeled out using the normal
should be studied. Moreover, there have also been a few
reeling process such as that used for mulberry silk. Eri
papers published regarding the relationship of the
silk was reported to be capable of blending, as a staple
structure and dyeing properties of silk fibres after dyeing
fibre, with other fibres such as wool and cellulosic fibres.
with acid dyes [9,11,12] or reactive dyes [13,14]. To our
There is no complication in bleaching and dyeing of Eri
knowledge, no article has been reported about the dyeing
silk ⁄ wool blends because they are both protein fibres.
properties of the blends of wild silk with cotton. As
However, once Eri silk is taken to blend with cellulosic
compared with other silk fibres, Eri silk has a lower dye
fibres, for example cotton, a complication arises in the
uptake despite having lower crystallinity, density and
wet processing conditions, namely bleaching and dyeing,
orientation. This may be because of its high molecular
because of the different nature of the two fibres. As a
weight, which leads to profuse entanglement, making the
result of the difference in dyeability, these two fibres
path of dye diffusion more difficult, thus resulting in a
must be dyed separately using fibre or sliver dyeing
reduction in dye uptake [9].
processes before being brought to the blending process. If
In this study, the effect of bleaching conditions on the
yarn dyeing is to be attempted the optimum conditions
mechanical properties of Eri silk ⁄ cotton blends was
for bleaching and dyeing this fibre blend must first be
investigated. After bleaching, the blended yarn was dyed
investigated. Hydrogen peroxide (H2O2) for oxidative
with warm-dyeing reactive dyes so as to investigate the
bleaching is the preferred bleaching agent and can be
effect of the blending ratio on dyeing and mechanical
used for cellulose and protein fibres [1,2]. Bleaching
properties.
conditions used for Eri silk should be more vigorous than
those being used for cotton because of the higher
crystallinity of Eri silk [3]. Also for the wild silk, the Experimental
yellowish colouring of silk fibroin is considerably more Materials
intensive. That is why the wild silk may be bleached by The cotton used in this study is derived from the crossing
oxidation as well as reduction methods, or using a of varieties Dora 11 (Gossypium hirsutum L.) and the Thai
combination of both methods [3]. cotton variety, which was developed by Kasetsart
To date, a few research articles have been published on University (Thailand). Eri (Philosamia ricini) cocoons
the structure and mechanical properties of wild silk fibre, were prepared into a spun silk fibre at a cut length of
especially Eri silk fibre [4–8]. A previous study of Eri 30 mm. Each fibre was opened and cleaned into slivers in
silk ⁄ cotton blending has been reported about the effect of an industrial cotton card. The Eri and cotton blended
fibre properties, the blending process and fibre migration slivers were pre-drawn to obtain an equilibrium silver
on the physical properties of the blended yarn [7,8]. count before blending at different ratios of 0 ⁄ 100, 25 ⁄ 75,
There are few publications about the bleaching of Eri silk 50 ⁄ 50, 75 ⁄ 25 and 100 ⁄ 0 for draw-frame blending. The
42 ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 42–47
Chollakup et al. Dyeing properties of Eri silk ⁄ cotton blended yarn
blended fibres were spun into yarn with a linear density used here for the study with 5 g of each skein sample.
of 50 tex using the ring spinning method according to our Three Remazol dyes (Remazol Yellow RR, Remazol Red
previous study [8]. RR, Remazol Blue RR) were used for dyeing the yarns.
Dyeing was carried out at 1 and 3% owf depths of shade
Effect of bleaching on the physical properties of the at 50 C and a liquor ratio of 20:1 in sealed stainless-steel
blended yarns dye pots surrounded by aqueous media in a laboratory
All blended yarns were firstly scoured using alkaline for dyeing machine. The amount of Glauber’s salt used for
30 min at a temperature of 95 C using 1 g ⁄ l sodium 1% and 3% owf depths of shade was 50 and 80 g ⁄ l,
hydroxide (NaOH) and 1 g ⁄ l scouring agent. The blended respectively, whereas soda ash was used at 10 and 12 g ⁄ l,
yarns were then bleached in hank form using different respectively. Degree of exhaustion (%) of the dyes was
bleaching methods as shown in Table 1. Colour determined by measuring the absorbance of the dyebath
measurements (L* value, CIE whiteness) of the blended before and after dyeing, using an ultraviolet–visible (UV–
yarns were carried out with a Lovibond RT100 vis) spectrophotometer (Hitashi, Japan). The reflectance of
Reflectance Tintometer (Tintometer Ltd, UK) before and the dyed yarns was measured using a Louvibond
after bleaching. The crystallinity of the bleached yarns Reflectance Tinnometer Colorimeter. The reflectance
compared with the unbleached yarns was characterised values were used to calculate the colour yield (K ⁄ S) using
using X-ray diffraction (XRD). The XRD pattern was taken the Kubelka–Munk equation [15].
on an X’Pert Philips diffractometer with a run rate of
3 ⁄ min. Also, the mechanical properties (tenacity and
percentage elongation) were characterised following the Results and Discussion
method of ISO 2062-1993 (E) using Autograph 500KN Effect of bleaching on the physical properties of the
(Shimadzu, Japan). This method is used for determination blended yarns
of single-end breaking force and elongation at break for From the previous results [10], the physical properties of
yarn. The gauge length and cross-head speed were the blended yarn after peroxide bleaching were varied
500 mm and 500 mm ⁄ min, respectively. Optimum depending on the fibre blend ratios. Because of the
bleaching conditions were investigated for each blended different fibre lengths, finenesses and strengths between
yarn. Eri silk and cotton, their fibre distribution at different
ratios provided different physical properties [8,16]. In this
Dyeing properties of the blended yarns dyed with warm- study, the colour (L* and whiteness) (Figure 1) and
dyeing reactive dyes mechanical properties (Figure 2) of the blended yarn after
The blended yarns were dyed with warm-dyeing reactive bleaching under different conditions were investigated.
dyes provided by DyStar (Thailand). Skein dyeing was Before bleaching, the L* and whiteness values of the
(a) 94 (b) 80
93 70
92
60
91
50
Whiteness
90
L* value
89 40
88 30
87
20
86
85 10
84 0
0 25 50 75 100 0 25 50 75 100
Silk content, % Silk content, %
Figure 1 Colour properties of the blended yarns before and after bleaching at different conditions: (a) L* value; (b) whiteness
ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 42–47 43
Chollakup et al. Dyeing properties of Eri silk ⁄ cotton blended yarn
%Elongation
12.0
11.5 15
11.0 10
10.5
5
10.0
9.5 0
0 25 50 75 100 0 25 50 75 100
Silk content, % Silk content, %
Before bleaching Bleaching I Bleaching II Bleaching III Bleaching IV
Figure 2 Mechanical properties of the blended yarns before and after bleaching under different conditions: (a) tenacity; (b) percentage
(%) elongation
blended yarns increased with the increasing silk content bleaching of the cotton fibre, the yarn tenacity tends to
(Figure 1a and b). increase (Figure 2a). This may be attributable to the
After bleaching under the conditions in method no. I removal of waxes and grease during the bleaching
(representing mild conditions), only the yarns containing process, which could explain an increase in strength.
0, 25 and 50% silk content were found to be whiter. The Note that, after bleaching, all blended yarns tended to be
yellowness of the blended yarns was enhanced with the more extensible with an increase in the silk content
increasing silk content. This is because of yellowing of (Figure 2b). This may be as a result of the reduction of
the silk fibre after bleaching. As stated by Kobayashi [17], the crystallinity of Eri silk yarn after bleaching, a finding
the silk yarn appeared more yellow because of the confirmed by XRD analysis in the previous study [10]. In
formation of chromophoric compounds containing addition, yarn shrinkage was observed and a decrease of
carbonyl groups from tyrosine, glycine, alanine and serine yarn twist (data not shown here) after bleaching, which
which are present in the silk [3]. An increase in bleaching lead to higher elongation.
time (from 30 to 180 min) in oxidation method no. II From the results described above, it is recommended
rendered more effective bleaching. Meanwhile, the that the blended yarns containing a 0–25% silk content
tenacity of the blended yarns at 0–75% of silk content should only be bleached using the oxidative bleaching
(Figure 2a) tended to increase and no significant method no. I, whereas the blended yarns containing more
difference was exhibited among each of the blend ratios. than a 50% silk content should be bleached using the
Harsher oxidative bleaching (method no. III) imparted two-stage method of bleaching no. V. The physical
higher whiteness of the blended yarns, but deteriorated characteristics of each blended yarn after bleaching under
the yarn strength. In addition, the reductive bleaching their optimum conditions are summarised in Table 2.
using sodium sulfite (Na2SO3, method no. IV) improved The force–displacement curves of Eri silk yarn before
the whiteness of the blended yarn, but this bleaching bleaching (Figure 3a) exhibited a non-distinct yield
deteriorated the fibre strength, especially for cotton, as plateau and a strain region similar to those of Eri silk
compared with the unbleached yarn. Thus, the double fibres or filaments [6], being different from Bombyx mori
bleaching was used for the blended yarn (bleaching silk. This may be caused by lower crystallinity and
method nos V–VII). Oxidative bleaching followed by imperfect crystallites or entanglement, which initially
reductive bleaching (bleaching method no. V) provided offer resistance until yield stress but later allow easy
higher values of L* and greater whiteness of the blended deformation in the amorphous regions until strain
yarns. hardening occurs [18]. Inclusion of cotton fibre in the
The tenacity of the Eri silk yarn was not significantly blends slightly diminished a yield plateau and reduced
different from that of the cotton yarn (Figure 2a). extensibility of the yarns as compared with Eri silk yarn.
Meanwhile, the tenacity of the blended yarns did not At 50 ⁄ 50 silk and cotton blended yarn, it presented the
significantly reduce, with the exception of the 50 ⁄ 50
blended yarn. This may be attributed to the negative Table 2 Physical properties of the blended yarns after bleaching
effect of reductive bleaching on the strength of the cotton at their optimum conditions
fibre in the blended yarn. But for the last two bleaching
methods (the reduction and then the oxidation bleaching, After bleaching I for 0–25% and bleaching V for 50–100%
nos VI and VII), the whiteness of the blended yarns
Eri
containing a high Eri silk content were not improved. The silk Tenacity Elongation
results obtained here do not correspond to the previous (%) L* value Whiteness (cN ⁄ tex) (%)
study of silk bleaching [2], which reported that a high
degree of whiteness of silk was obtained after treatment 0 91.50 0.19 66.08 0.71 12.56 1.04 8.28 1.20
by reductive bleaching with sodium sulfite followed by 25 90.91 0.79 48.52 2.52 12.65 0.97 14.35 1.16
50 91.35 0.75 52.95 2.09 10.08 1.46 14.25 1.38
oxidative bleaching with hypochlorite. It is sulfite that
75 90.84 0.48 42.78 1.85 10.86 1.11 18.72 1.91
this difference is because of the diversity of the Eri silk 100 89.65 0.17 44.83 1.63 13.14 0.83 26.43 1.20
raw material used. It can be observed that, after oxidative
44 ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 42–47
Chollakup et al. Dyeing properties of Eri silk ⁄ cotton blended yarn
(a) (b)
7 7
25% 100% 0% 25% 50% 75% 100%
6 75% 6
0%
5 5
Force, N
Force, N
4 50% 4
3 3
2 2
1 1
0 0
0 10 20 30 40 50 60 70 80 90 0 10 20 30 40 50 60 70 80 90 100
Displacement, mm Displacement, mm
Figure 3 Force–displacement curves of the blended with differing silk content (0–100%): (a) before and (b) after bleaching
(a) (b)
1000
Intensity, counts
Intensity, counts
0% 0%
25% 25%
50% 50%
75% 75%
100% 100%
Figure 4 XRD patterns of the blended with differing silk content (0–100%): (a) before and (b) after bleaching
profile of both silk and cotton curves. After bleaching, Table 3 Crystallite size and percentage crystallinity of the cotton
H2O2 oxidised inter-chain bonding (salt bridge) of the and the Eri silk yarns before and after bleaching
side groups of main amino acids, namely alanine 36%
and glycine 29% [18], binding the molecules in the Crystallite size (nm) at 2h
amorphous regions. This was observed as the change of Crystallinity
stress–strain curves of all blended yarns (Figure 3b), Yarn 14.8 16.6–16.9 20.5 22.8 (%)
showing linear relationship without yield point.
The different patterns of force–displacement curves Before bleaching
before and after bleaching indicate the occurrence of Cotton yarn 2.13 2.37 1.93 53.97
morphological changes. This might be caused by breakage Eri silk yarn 1.61 1.65 76.02
of the salt bridge between the amino groups in the After bleaching
amorphous region of the silk, resulting in the occurrence Cotton yarn 1.80 2.34 1.94 62.63
Eri silk yarn 1.74 1.59 74.45
of molecular relaxation. Moreover, yarn shrinkage after
blending can be considered to give more extensibility in
the force–displacement curves.
The results of XRD data of the blended yarns before yarns varied depending on the fibre ratio. Therefore, the
and after bleaching are shown in Figure 4. For the cotton blended yarns with the higher cotton content would
yarn, their scattering curves exhibited three peaks at 2h of exhibit a higher percentage of crystallinity.
14.8, 16.6 and 22.8 both before and after bleaching, all
of which belong to cellulose I [19]. For the Eri silk yarn, Dyeing properties of the blended yarns dyed with
the XRD patterns were composed of only two prominent warm-dyeing reactive dyes
peaks at 2h of 16.9 and 20.5, corresponding to the The bleached yarns were dyed with Remazol RR reactive
reflection from (002) and (201) planes [20]. The XRD dyes and the dyeing properties were evaluated (Figure 5).
pattern of the blended yarns presented the peaks relating The degree of exhaustion and the K ⁄ S values of the
to the fibre blend ratios [21]. blended yarns at 1% owf depth of shade tended to
From Table 3, it is clear the percentage of crystallinity decrease with the increasing silk content, with the
of the cotton yarn increased after bleaching; meanwhile, a exception of those of the Eri silk yarn. It can be
subtle change was observed for that of the Eri silk yarn. interpreted that the dye uptake on cotton was higher than
The similarities of the two patterns (before and after on silk. Among the three Remazol dyes used, Remazol
bleaching) were attributed to a little change in crystal Blue RR exhibited higher colour yield on the blended
size. From these data, the crystallinity of the blended yarns as compared with the other dyes. The three dyes
ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 42–47 45
Chollakup et al. Dyeing properties of Eri silk ⁄ cotton blended yarn
(a) (b)
100 5.0
95 4.5
90 4.0
Exhaustion, %
85 3.5
80 3.0
K/S
75 2.5
70 2.0
65 Yellow 1.5 Yellow
60 Red 1.0 Red
55 Blue 0.5 Blue
50 0.0
0 20 40 60 80 100 0 20 40 60 80 100
Eri silk content, % Eri silk content, %
Figure 5 (a) Percentage exhaustion and (b) K ⁄ S values of the blended yarns dyed with Remazol RR dyes at 1% owf depth of shade
provided more intense colour on cotton as seen from the From these results, it may be explained that the dyeing
higher K ⁄ S values (Figure 5b). conditions used here were not suited for dyeing silk.
The higher silk content in the blend caused a reduction Agarwal et al. [13] reported that the maximum fixation of
in the colour intensity obtained on the dyed yarns. All the bifunctional reactive dyes on silk was optimised in a
three dyes exhausted well onto cotton fibre but, with neutral dyeing medium rather than under the alkali
increasing silk content in the blend, the difference of fixation conditions commonly used for cotton. Thus, this
percentage exhaustion of the three dyes became larger is probably the reason why the reactive dyes used here
(Figure 5a). This implies that the diffusivity towards Eri did not perform well on the blended yarn with a high silk
silk of the three dyes was much different compared with content. Therefore, these Remazol RR dyes were not
that towards cotton. The three dyes exhibited less suited for dyeing Eri silk fibre using the conditions
compatible dyeing properties when dyed onto the silk. studied, even although the Remazol RR dyes are
recommended commercially for dyeing silk ⁄ cotton
(a)
blends.
90 The L*, a* and b* values of the blended yarns dyed
L* a* b*
80 with the three Remazol RR dyes at 1% owf depth of
70 shade are depicted in Figure 6. Shade change was noticed
L*/a*/b* value
60
on the dyed blended yarns as the silk content increased.
50
40 For the blended yarns dyed with the yellow and red dyes
30 (Figure 6), the lightness (L* values) were not significantly
20 different, whilst the a* and b* values decreased relatively
10 with the increasing silk content. A slight increase in L*
0 was observed for those yarns being dyed with the blue
0 25 50 75 100
dye, whereas the a* and b* values did not show a
(b)
60 significant difference (Figure 6c). This result indicates
50 that the blend ratio of cotton and Eri silk affected the
shade of the dyes obtained on the blended yarns.
40
L*/a*/b* value
L*/a*/b* value
25 b*
20 20
10 15
10
0
5
–10 0 25 50 75 100 0
–20 –5 0 25 50 75 100
Eri silk content, % –10
Eri silk content, %
Figure 6 L*, a*, b* values of the blended yarns dyed with the
three Remazol RR dyes at 1% owf depth of shade: (a) Remazol Figure 7 L*, a*, b* values of the blended yarns dyed with the
Yellow RR, (b) Remazol Red RR and (c) Remazol Blue RR three Remazol RR dyes in combination at 3% owf depth of shade
46 ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 42–47
Chollakup et al. Dyeing properties of Eri silk ⁄ cotton blended yarn
The L* values increased, whereas the a* and b* values support and Dr Prapon Boonrumpun for cotton fibre
reduced with the increase in silk content, leading to the support, Shinano Kenshi (Thailand) Co. Ltd and Thairung
change of shade observed on the blended yarns. The Textile (Thailand) Co. Ltd for the spinning process, the
shade variation occurs when the fibre blend ratio Department of Textile Science, Faculty of Agro-Industry,
changes. This study shows that dyeing cotton ⁄ Eri silk Department of Material Engineering, Faculty of
blended yarns with Remazol RR dyes under the Engineering and KAPI, Kasetsart University for bleaching
conditions studied cannot provide a uniform shade onto and dyeing processes and instrument analysis. We also
the blended yarns. deeply thank DyStar (Thailand) Co. Ltd for dyestuff
From this study, it is clear that dyeing Eri silk ⁄ cotton support.
blended yarns with the warm-dyeing Remazol RR dyes
cannot provide a uniform shade onto the yarns. The References
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This work is supported by the Thailand Research Fund (2005) 87.
(TRF). The authors gratefully acknowledge Dr Wirasak 20. K Sen and M K Babu, J. Appl. Polym. Sci., 92 (2004) 1116.
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ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 42–47 47