Macromol. Chem. Phys.

2001, 202, 949–955 949

Full Paper: Tendering of cotton cellulose caused by the samples resulting from Fe2+ and Fe3+ ions are identical and
presence of Fe2+ and/or Fe3+ ions during bleaching with the maximum tendering was observed when the fabric
H2O2 using the exhaustion method and the pad-steam samples were contaminated with 0.3 mg/g fabric Fe2+ and/
method were studied. This was carried out by staining the or Fe3+ ions. The catalytic degradation is much higher
cotton fabric samples with different concentrations of Fe2+ when the cotton samples were bleached with the pad-
or Fe3+ ions then subjecting these samples to bleaching. steam than with the exhaustion method. The ceasing of
Ceasing of cotton tendering resulting from Fe2+ and/or such catalytic tendering could be achieved by pretreat-
Fe3+ during bleaching with H2O2 by pretreatment of the ment of the cotton fabrics with a bath containing 1% oxa-
fabric by oxalic acid were also studied under a variety of lic acid at 40 8C for 1 min. The pretreated fabrics have
conditions. The onset of this pretreatment on the proper- higher degree of polymerization, whiteness index, tensile
ties of the cotton fabric compared to the untreated fabric strength and lower Eisenhut’s tendering factor compared
are discussed. The samples were monitored for degree of with the untreated fabrics. The state of the fabric (i. e.,
polymerization, Eisenhut’s tendering factor, whiteness grey, desized, scoured) does not play any significant role
index, tensile strength and elongation at break. Results in such pretreatment.
obtained show that the catalytic degradation of the cotton

A New Method for Preventing Catalytic Degradation of

Cotton Cellulose by Ferrous or Ferric Ions During
Bleaching with Hydrogen Peroxide
A. Hebeish,* M. Hashem, A. Higazy
National Research Centre, Dokki Cairo, Egypt

Introduction brown to deep brown but reddish because it is rich in iron

Hydrogen peroxide offers technical and ecological advan- containing minerals; a point which explains the reddish
tages over other bleaching agents, e. g., sodium hypo- tinge of grey cotton. A high wind occurring in certain
chlorite and sodium chlorite. In the bleaching reaction, countries also increases the fiber contamination with
the ecological clean decomposition products, water and heavy metal ions. In this case the fibers become heavily
oxygen, are formed. contaminated with dust. Modern cultivation of cotton
The mechanism of hydrogen peroxide bleaching was fiber, harvesting, processing and packing method incor-
extensively studied.[1, 2] Textile bleaching with hydrogen porate further abraded metals. A high proportion of husks
peroxide is a well-established process in the textile indus- also considerably changes the metal content of the fibers.
try. However, the presence of metal ions catalyzes the Nowadays, in order to produce high yield crops, all cot-
rapid decomposition of the perhydroxy anion to molecu- ton fields are sprayed with greater or lesser amounts of
lar oxygen, which has no bleaching action, and water. insecticides, fungicides and herbicides, which contain fer-
The vigorous decomposition of the peroxide in contact rous or ferric ions. A further problem exists in the distri-
with such catalytic ions causes catalytic damage, which bution of the metal in the materials. It may happen that
can range from very low degree of polymerization (DP) heavy metal contaminates in cotton – which is spun by
to actual holes in the textile materials.[3] It has also been the open end method – accumulate in the rotor under the
reported that the extent of such damage is largely depend- influence of its centrifugal forces and re-accumulate in
ent on the type of heavy metal.[4, 5] the form of compact particles on the yarn as it is being
Raw cotton can exhibit widely different contents of spun. This situation is a typical cause of catalytic damage
heavy metal ions relying on its origin. In the final cotton in the subsequent bleaching treatments and also leads to
goods, the higher metal content is attributed to several increased thread breaks during rewinding.
factors.[6 –9] Among these factors are weather conditions Metals cannot be removed by the normal washing or
and the geological factors of the region where the cotton alkali treatments. Metal ions can be removed by treat-
is grown. In many parts of the world the earth is not light ments with inorganic acids. However the use of inorganic

Macromol. Chem. Phys. 2001, 202, No. 6 i WILEY-VCH Verlag GmbH, D-69451 Weinheim 2001 1022-1352/2001/0603–0949$17.50+.50/0
950 A. Hebeish, M. Hashem, A. Higazy

acids in the demineralization of cellulosic fabrics Staining the Fabrics With Ferrous and/or Ferric Ions
involves a number of serious disadvantages. For this, a Fabric samples were stained independently with a calculated
number of special products based on phosphonic acid amount of ferrous ammonium sulfate as a source of Fe2+ ions
have been devised.[6] and ferric ammonium sulfate as a source of Fe3+ ions. The
The present work is undertaken with a view to tackle samples were dried at ambient conditions and left 24 h
the pin-hole problem arising from the presence of ferrous before bleaching with H2O2.
(Fe2+) and/or ferric (Fe3+) ions in cotton fabrics. This pro-
blem constitutes a serious burden on the textile manufac-
turing. To achieve the goal, the following points are stud- Bleaching
ied: (a) tendering of cotton caused by the presence of Fe2+ Two bleaching methods were used, namely, the pad-steam
and/or Fe3+ ions after cotton bleaching using H2O2 as per and the exhaustion methods. In the pad-steam method, the
the exhaustion method and the pad-steam method; (b) sample was padded in solution containing H2O2 (15 g/l) and
removal of Fe+2 and/or Fe+3 ions by treatment with oxalic sodium silicate (5 g/l) at pH 10.3 (adjusted by NaOH). The
acid at various conditions; and the onset of this on proper- fabric was then squeezed to a wet pick up of 100% and
stored in closed cups at 100 8C for 1 h. After bleaching, the
ties of the cotton fabric compared to the untreated fabric.
sample was washed several times by hot water, then by cold
These properties embrace the degree of polymerization water and finally dried at ambient conditions.
(DP), Eisenhut’s tendering factor (T.F.), whiteness index In the exhaustion method, the bleaching bath was prepared
(W.I.) tensile strength (T.S.) and elongation at break; and containing H2O2 (5 g/l) and sodium silicate (2 g/l). The pH
(c) application of oxalic acid treatments on the loom- was adjusted to 10.3 using aqueous NaOH solution. Material
state, desized and scoured cotton fabrics. to liquor ratio 1 : 50 was used and the bleaching process was
carried out at 90 8C for 1 h. The sample was then washed
several times with hot water then washed with cold water
Experimental Part and finally dried at ambient conditions.
Materials
Cotton Fabric Testing and Analysis
Grey cotton fabric was kindly supplied by El-Naser Com- The degree of polymerization (DP) of cotton fabrics was
pany for Spinning, Weaving and Dyeing, Mehala El-Kubra, determined as described elsewhere.[10] Eisenhut’s Tendering
Egypt. The fabric is 100% cotton sized with hydrolyzed factor (T.F.) was calculated as follows:
starch and has the following specification: weaving normal
1/1, width 135 cm, weight 230 g/m2.  
1 2000 2000
T:F ¼ N log ÿ þ1
log2 DPx DPtx
Chemicals Used
where DPtx = DP value after bleaching and DPx = DP value
Sodium hydroxide, oxalic acid, ferrous ammonium sulphate,
ferric ammonium sulphate, cupper sulphate, sodium sulphite, before bleaching. DP of grey cotton fabric was determined
and found equal 3 120; after desizing and scouring, the DP
ammonium hydroxide (25%), potassium permanganate were
of analytical grade chemicals. Hydrogen peroxide (50%), amounts to 2 886. The latter value will be taken as the value
of DP before bleaching (DPx). The Whiteness Index of the
sodium silicate, Egyptolm (non-ionic wetting agent), Aspy-
conm (anionic wetting agent), Diastaze enyme were of techni- cotton fabric was determined according to a reported method
described elsewhere.[11] The Tensile Strength (T.S.) and elon-
cal grade chemicals.
gation at break were determined according to a standard
method.[12]
Desizing
Grey cotton fabric was desized by padding the fabric in solu-
tion containing Diastaze enzyme (2 g/l), Egyptolm (1 g/l). The Results and Discussion
sample was then squeezed to a wet pick up of 100% and stored
at room temperature for 8 h. The sample was washed several At the outset, a systematic investigation into the catalytic
times with hot water, then washed with cold water and dried. degradative action of Fe2+ and Fe3+ ions on cotton during
After desizing the sample undergoes 6.2% loss in weight. bleaching with H2O2 was undertaken. Thus samples of
desized and scoured cotton fabric were stained through
Scouring deposition of Fe2+ and Fe3+ ions at different concentra-
Desized fabric was treated with an aqueous solution contain-
tions followed by drying and bleaching with H2O2 as
ing NaOH (30 g/l), Egyptolm (1 g/l) and Aspyconm (1 g/l) described in the experimental section. The samples so
using material to liquor ratio, 1 : 30, at 95 8C for 30 min. The obtained were monitored for degree of polymerization
sample was then washed several times with hot water and (DP) and Eisenhut’s Tendering Factor (T.F.). Results of
cold water and finally dried. After scouring, the sample this investigation are given below along with their appro-
shows 18% loss in weight. priate discussion.
A New Method for Preventing Catalytic Degradation of Cotton Cellulose ... 951

Catalytic Degradative Effect of Fe2+ and Fe3+ Ions on 3.11 in the case of the pad-steam method and 1.34 in the
Cotton Cellulose During its Bleaching With H2O2 case of the exhaustion method. In other words, a lower
material to liquor ratio would enhance the catalytic effect
Table 1 depicts the relationship between the concentra-
of Fe2+ or Fe3+ ions.
tion of Fe2+ and Fe3+ ions deposited on the unbleached
The above findings conclude, in accordance with pre-
fabric and the DP and T.F. of the fabric after being
vious reports,[1 – 3, 13] that the presence of Fe2+ or Fe3+ ions
bleached with H2O2 using the exhaustion and the pad-
in cotton has a detrimental effect on cotton. Fe2+ or Fe3+
steam method. The results feature four main points. First,
ions seem to catalyze degradation of cotton with H2O2 as
the catalytic degradation effects of Fe2+ ions and Fe3+ ions
shown by the following reaction scheme:
are very comparable, this is evidenced by the almost
equal values of DP and T.F. obtained in both cases. Sec-
ond, the DP decreases significantly with increasing the Fe2+ + H2O2 ggs Fe3+ + HO9 + HO– (1)
concentration of Fe2+ and Fe3+ ions up to 0.3 mg/g fabric.
Third, this decrease in DP is much higher with the pad- Fe3+ + HOO– ggs HOO9 + Fe2+ (2)
steam method than with the exhaustion method. Fourth,
at Fe+2 and Fe3+ ion concentrations higher than 0.3 mg/g HO9 + H2O2 ggs HOO9 + H2O (3)
fabric the magnitude of the decrease in DP is lessened
considerably. For instance the bleached fabric derived HOO9 + H2O2 ggs HO9 + H2O + O2 (4)
from unbleached cotton having 0.15 mg Fe2+ or Fe3+ ion/g
fabric exhibits a DP of 460 using the pad-steam method The hydroxy radical (HO9) and the perhydroxy radical
and a DP of 1 025 using the exhaustion method. These (HO92) formed as per Equation (1)–(4) are strong oxidiz-
values are against DPs of 985 and 1117 when the ing species for cotton and would account for the decrease
unbleached cotton fabric containing 0.9 mg Fe2+ or Fe3+ in DP and the increase in T.F. Meanwhile, the relatively
ion/g fabric was bleached using the pad-steam method lower fall in DP and higher T.F. at higher concentration
and the exhaustion method, respectively. of Fe2+ ions suggest that the latter participate in deactiva-
T.F. was calculated from DP. Table 1 reveals that max- tion of the said oxidizing species as shown by Equation
imum tendering was observed at Fe2+ or Fe3+ion concen- (5) and (6).
trations of 0.3 mg/g fabric. The T.F. in this case reached
HO9 + Fe2+ ggs Fe3+ + HO – (5)

Table 1. Relationship between Fe2+ or Fe3+ ion concentration HOO9 + Fe2+ ggs Fe3+ + HOO– (6)
deposited on the cotton fabric and the degradation expressed as
degree of polymerization and tendering factor after bleaching of The oxidation of hydroxyl groups in a cellulose chain
the fabric with H2O2. Conditions used: Samples of cotton fabric
can occur by attack of a free radical:
were desized, scoured and stained with Fe2+ or Fe3+ then
bleached either by the pad-steam or the exhaustion method as
described in the Experimental Part.
H
0
HO9 + R1C 1OH ggs R1C9 1OH + H2O (7)
Fe2+ or Fe3+ Bleaching Fe2+ Fe3+ 0 0
Concentration Method R– R–
—————
mg/g fabric DP T.F. DP T.F.
R1C9 1OH + HOOH ggs R1C 2O + H2O (8)
a)
0.0 PS 1 715 0.56 1 715 0.56 0 0
Exb) 1 782 0.51 1 782 0.51 R– R–
0.075 PS 1 270 0.91 1 268 0.92 The carbonyl groups can be formed in this way on a
Ex 1 570 0.66 1 570 0.66 number of monomeric units of the chain. It has been pos-
0.15 PS 460 2.21 463 2.21 tulated[13] that hydrogen peroxide in alkaline solutions
Ex 1 025 1.18 1 560 0.67 adds to aldehyde groups of carbohydrate forming hydro-
0.3 PS 241 3.11 246 3.10 peroxide adduct (Equation (9)). The latter will decom-
Ex 880 1.34 901 1.34 pose either by a free radical mechanism (Equation (10))
0.6 PS 720 1.60 702 1.63 or ionic mechanism (Equation (11)).
Ex 963 1.26 960 1.26
OOH
0.9 PS 985 1.23 991 1.22 0
Ex 1117 1.07 1112 1.06 R1C 2O + HOOH ggs R1C 1OH (9)
0 0
a)
R– R–
PS = Pad-steam method.
b)
Ex = Exhaustion method. Acyclic adduct
952 A. Hebeish, M. Hashem, A. Higazy

Free Radical Mechanism: Pretreatment With Oxalic Acid

In the previous section, it has been disclosed that maxi-
H mum degradation of H2O2 bleached cotton fabric occurs
0 H
HO1O1C1OH l9OH 0 at 0.3 mg/g fabric Fe2+ or Fe3+ ions concentration. This
0 gggs O2C1OH was observed when the Fe2+ or Fe3+ ions contaminated
H1C1O1H
0 fabric was bleached using the pad-steam or the exhaus-
R– Formic acid tion method but with the certainty that the former method
exerts higher degradation than the latter.
+ H1C 2OH + H2O (10) In this section the research is designed to establish the
0 most appropriate conditions for ceasing the catalytic
R– degradation effect of Fe2+ or Fe3+ ions during bleaching
Lower aldoses the cotton fabric with H2O2, by pretreatment of the fabric
with oxalic acid. Thus, desized and scoured cotton fabric
Ionic Mechanism: was stained with Fe2+ or Fe3+ ions at a concentration of
0.3 mg/g fabric. The fabric was then pretreated with oxa-
H
0 H lic acid under a variety of conditions including oxalic
HO1O1C1OH l OH 0
– acid concentration as well as the time and temperature of
0 gggs O2C1OH the pretreatment. The pretreated fabric samples were
H1C1O1H
0 bleached using H2O2 as per the pad-steam method and the
R– Formic acid exhaustion method. These samples were monitored for
DP, T.F., W.I., T.S. and elongation at break.
+ H1C 2OH + H2O (11)
0
R– Oxalic Acid Concentration
Lower aldoses Table 2 shows the effect of oxalic acid concentration on
DP, T.F., W.I., T.S. and elongation at break of the cotton
The process is then repeated until complete degradation fabric after bleaching using the pad-steam (PS) and
of cellulose to glucose and finally to formic acid. The fact exhaustion method (EX). Results obtained with the
that the ferrous ions and ferric ions significantly enhances untreated sample (i.e oxalic acid concentration = 0) are
the oxidation of the most hexoses indicate that the free set out in the same table for comparison. It is seen (Table
radical mechanism is operative, but the ionic mechanism 3) that pretreatment of the fabric with oxalic acid permits
is not excluded. It should be noted here that at lower tem- the bleached fabric to retain much of its original DP,
perature, oxygen will be produced as follows: depending on the concentration of oxalic acid and to a
much lesser extent on the method of bleaching used. In
OOH OH
0 0 this regard, the effect is achieved at 1% oxalic acid using
R1C 1OH + –OOH ggs R1C 1O9 + 9O2– + H2O (12) the exhaustion method.
0 0 The results in Table 2 signify also (a) that T.F.
R– R–
decreases as the concentration of oxalic acid increases (b)
OOH OH that W.I. of the bleached cotton fabric increases with the
0 0 increase in the concentration of oxalic acid upto 1% then
R1C 1OH + 9O2– ggs R1C 1O9 + O2 + –OH (13)
0 0 becomes almost constant (c) that T.S. in warp and weft
R– R– directions sharply increases as the oxalic acid concentra-
tion increases, (d) elongation at break exhibits higher
OH values with increasing oxalic acid concentration.
0
R1C 1O9 + H2O2 ggs R1C OOH + 9OH (14) It is as well to emphasize that the tensile strength and
0 0 elongation at break of Fe2+ or Fe3+ ion-stained and
R– R–
bleached fabric samples could not be measured because
In this way a high concentration of hydroxyl radical of the severity of degradation. The same holds true for
will be produced and the sugar will catalyze the H2O2 the sample pretreated with 0.25% oxalic acid. This
decomposition with evolution of oxygen. The latter implies that it is advisable to use oxalic acid at a concen-
would explain the catalytic effect of the cotton on the tration of at least 0.75% in the pretreatment to overcome
decomposition of H2O2. It might also explain the sorption the catalytic degradation of cotton by Fe2+ or Fe3+ ions
of H2O2. This sorption was found to decrease with during bleaching with H2O2.
increase in pH, presumably by the more rapid decomposi- Oxalic acid reacts with the Fe2+ or Fe3+ ions to form the
tion of the hydrogen peroxide at higher alkalinity.[13] corresponding oxalate salt. The latter is soluble in water
A New Method for Preventing Catalytic Degradation of Cotton Cellulose ... 953

Table 2. The effect of oxalic acid concentration on the properties of cotton fabric containing Fe2+ or Fe3+ ions after bleaching the
fabric with H2O2. Pretreatment conditions: Samples of cotton fabric were treated with solutions containing oxalic acid at 30 8C for
2 min.

Oxalic Acid Bleaching DP T.F. W.I. T.S. Elongation

Conc. Method —— ————
————— kg N f %
%
Warp Weft Warp Weft

Zero PSa) 243 (243)c) 3.10 (3.10) 35 (35) – – – –

Exb) 280 (280) 2.90 (2.90) 41 (40) – – – –
0.25 PS 360 (360) 2.56 (2.56) 59 (60) – – – –
Ex 364 (364) 2.54 (2.54) 55 (62) – – – –
0.50 PS 804 (806) 1.49 (1.48) 71 (72) 17 (19) 14 (17) 7 (5) 4 (6)
Ex 804 (804) 1.49 (1.49) 71 (72) 25 (25) 14 (12) 7 (4) 5 (6)
0.75 PS 1 805 (1 805) 0.50 (0.50) 85 (85) 51 (51) 47 (47) 20 (21) 19 (19)
Ex 1 822 (18 22) 0.49 (0.49) 80 (82) 51 (52) 48 (48) 20 (20) 19 (19)
1.0 PS 1 890 (1 892) 0.45 (0.45) 88 (86) 51 (52) 49 (48) 21 (22) 18 (18)
Ex 1 897 (18 97) 0.45 (0.45) 84 (84) 52 (52) 51 (51) 20 (20) 18 (18)
1.5 PS 1 892 (1 892) 0.45 (0.45) 88 (88) 50 (52) 52 (51) 20 (20) 18 (18)
Ex 1 897 (1 898) 0.45 (0.45) 84 (84) 52 (54) 51 (52) 20 (21) 19 (18)

a)
PS = Pad-steam method.
b)
Ex = Exhaustion method.
c)
Values in brackets represent the values obtained for Fe3+ ions.
Table 3. The effect of the temperature of oxalic acid pretreatment on major properties of cotton fabric containing Fe2+ or Fe3+ ion
after the fabric was bleached with H2O2. Pretreatment conditions: Samples of cotton fabric were treated with a 1% aqueous solution
of oxalic acid for 2 min.

Table 3. The effect of the temperature of oxalic acid pretreatment on major properties of cotton fabric containing Fe2+ or Fe3+ ion
after the fabric was bleached with H2O2. Pretreatment conditions: Samples of cotton fabric were treated with a 1% aqueous solution
of oxalic acid for 2 min.

Temp. Bleaching DP T.F. W.I. T.S. Elongation

—— Method ——— ————
8C kg N f %

Warp Weft Warp Weft

30 PSa) 1 895 (1 892)c) 0.45 (0.45) 88 (88) 50 (48) 49 (46) 20 (20) 19 (19)
Exb) 1 912 (1 930) 0.44 (0.43) 82 (82) 46 (47) 50 (50) 15 (16) 14 (15)
40 PS 1 912 (1 914) 0.44 (0.44) 90 (91) 52 (52) 49 (49) 20 (20) 20 (20)
Ex 1 921 (1 935) 0.43 (0.42) 86 (86) 55 (55) 55 (55) 19 (19) 19 (19)
50 PS 1 905 (1 905) 0.44 (0.44) 90 (91) 51 (51) 50 (51) 18 (18) 18 (18)
Ex 1 908 (1 912) 0.44 (0.44) 86 (87) 53 (53) 52 (52) 20 (20) 19 (19)
60 PS 1 895 (1 891) 0.45 (0.45) 89 (88) 48 (48) 47 (47) 20 (21) 19 (19)
Ex 1 890 (1 890) 0.45 (0.45) 87 (87) 52 (52) 50 (51) 18 (18) 18 (18)
70 PS 1 800 (1 808) 0.51 (0.50) 89 (89) 47 (47) 46 (46) 20 (20) 19 (19)
Ex 1 820 (1 822) 0.49 (0.49) 86 (86) 52 (52) 51 (51) 19 (19) 18 (18)

a)
PS = Pad-steam method.
b)
Ex = Exhaustion method.
c)
Values in brackets represent the values obtained for Fe3+ ions.

and removed during washing. Current data suggest that a to convert the Fe2+ or Fe3+ contaminates to the soluble
certain concentration of oxalic acid (ca. 1%) is required salt.
954 A. Hebeish, M. Hashem, A. Higazy

Table 4. The effect of pretreatment time on the properties of cotton fabric containing Fe2+ or Fe3+ ion after bleaching the fabric with
H2O2. Pretreatment conditions: Samples of cotton fabric treated with a 1% aqueous solution of oxalic acid at 40 8C. Zero time repre-
sents the values obtained with untreated fabric.

Time Bleaching DP T.F. W.I. T.S. Elongation

—— Method ——— ————
s kg N f %

Warp Weft Warp Weft

Zero PSa) 243 (243)c) 3.10 (3.10) 35 (35) – – – –

Exb) 280 (280) 2.90 (2.90) 41 (40) – – – –
20 PS 1 822 (1 880) 0.45 (0.45) 77 (76) 36 (33) 35 (32) 15 (16) 15 (15)
Ex 1 902 (1 898) 0.44 (0.44) 70 (66) 40 (40) 40 (40) 17 (15) 15 (16)
45 PS 1 932 (1 934) 0.43 (0.42) 85 (85) 45 (45) 41 (41) 17 (17) 18 (18)
Ex 1 934 (1 936) 0.42 (0.42) 83 (82) 49 (49) 46 (47) 18 (18) 18 (18)
60 PS 1 941 (1 937) 0.41 (0.41) 90 (90) 52 (50) 51 (52) 17 (18) 19 (18)
Ex 1 950 (1 941) 0.40 (0.41) 86 (80) 56 (57) 54 (53) 20 (20) 21 (21)
90 PS 1 929 (1 928) 0.43 (0.43) 91 (90) 51 (50) 50 (51) 19 (18) 18 (19)
Ex 1 930 (1 928) 0.43 (0.43) 88 (83) 55 (55) 55 (55) 20 (20) 19 (19)

a)
PS = Pad-steam method.
b)
Ex = Exhaustion method.
c)
Values in brackets represent the values obtained for Fe3+ ions.

Temperature of the Pretreatment 40 8C for 60 s. This time also enables achieving maxi-
Table 3 shows the properties of the cotton fabric stained mum W.I., T.S. and elongation at break.
with Fe2+ or Fe3+ ions then pretreated with aqueous solu- It is further observed that prolonging the pretreatment
tion of oxalic acid (1%) at different temperatures for time has no effect on fabric properties.
2 min. The properties include DP, T.F., W.I., T.S. and elon- Based on the above, it may be concluded that pretreat-
gation at break. ment of the cotton fabrics stained with Fe2+ or Fe3+ ions in
The results reveal that raising the temperature of the an aqueous bath containing 1% oxalic acid at 40 8C for
oxalic acid pretreatment bath from 30 8C to 40 8C brings 60 s before the bleaching with H2O2, ceases completely
about bleached fabrics with higher DP and lower T.F. the catalytic degradation of cotton cellulose.
indicating lower degradation of the cotton fabric. In
accordance with this is T.S. and elongation at break. W.I.
increases also by raising the temperature from 30 8C to State of the Fabric
40 8C. Carrying out the pretreatment at temperatures Pin-holes and razor cuts are usually encountered with cot-
higher than 40 8C exerts a marginal effect on the magni- ton fabric contaminated with heavy metal ions; Fe2+ or
tude of cotton degradation expressed as DP, T.F., T.S. and Fe3+ ions in particular. These ions catalyze the decompo-
elongation at break. Hence, it may be concluded that sition of H2O2 and localized fiber damage and tendering
40 8C constitutes the optimal temperature for the said pre- in places where the ions are deposited. It is shown above
treatment of desized and scoured cotton fabric which is that pretreatment of the fabric with oxalic acid provides a
contaminated by Fe2+ or Fe3+ ions. good means to overcome this problem.
It is envisioned that the state of the fabric could play a
role in this pretreatment. Hence the pretreatment was car-
Time of Pretreatment ried out using grey, desized and scoured fabrics.
Table 4 shows the effect of pretreatment time on the prop- The scoured fabric was stained with Fe2+ or Fe3+ ions
erties of cotton fabric under investigation. The pretreat- (0.3 mg/g fabric) and referred to as substrate III. The grey
ment was carried out using oxalic acid (1%) at 40 8C for fabric was treated with aqueous solution of oxalic acid
different time intervals. The cotton fabric used was (1%) at 40 8C for 60 s followed by desizing, scouring and
stained with either Fe2+ or Fe3+ ions (0.3 mg/g fabric) then bleaching as described in the experimental section and
bleached with H2O2 under the conditions described in the referred to as substrate I. Similarly the desized fabric was
experimental section. It is observed that high DP and stained with Fe2+ or Fe3+ ions then treated with oxalic
minimum T.F. values are obtained when the fabric was acid, scoured and finally bleached with H2O2 (substrate
pretreated with oxalic acid (1% aqueous solution) at II). The fabrics so obtained were evaluated for DP, T.F.,
A New Method for Preventing Catalytic Degradation of Cotton Cellulose ... 955

Table 5. The effect of the state of the fabric on Fe2+ or Fe3+ ion removal using oxalic acid as a pretreatment in bleaching with H2O2.
Pretreatment conditions: Samples of cotton fabric treated with a 1% aqueous solution of oxalic acid at 40 8C for 1 min.

State of Bleaching DP T.F. W.I. T.S. Elongation

the fabric Method ——— ————
kg N f %

Warp Weft Warp Weft

Grey PSa) 1 933 (1 934)c) 0.42 (0.42) 95 (93) 52 (53) 52 (53) 20 (20) 19 (21)
(I) Exb) 1 930 (1 931) 0.42 (0.42) 92 (92) 55 (56) 55 (56) 22 (21) 22 (23)
Desized PS 1 930 (1 934) 0.42 (0.42) 90 (91) 53 (54) 53 (54) 18 (16) 19 (17)
(II) Ex 1 929 (1 929) 0.43 (0.43) 82 (88) 55 (53) 55 (53) 18 (18) 20 (20)
Scoured PS 1 935 (1 935) 0.42 (0.42) 90 (92) 51 (51) 51 (51) 17 (18) 19 (18)
(III) Ex 1 932 (1 931) 0.42 (0.42) 88 (88) 54 (54) 54 (54) 20 (20) 21 (21)

a)
PS = Pad-steam method.
b)
Ex = Exhaustion method.
c)
Values in brackets represent the values obtained for Fe3+ ions.

W.I., T.S. and elongation at break. Results of this investi- 1% oxalic acid at 40 8C for 1 min. Such pretreatment
gation are set out in Table 5. Obviously, the state of the enhances the whiteness index, degree of polymerization,
fabric does not play any significant role as far the DP, tensile strength and decreases the tendering-factor com-
T.F., T.S. and elongation at break are concerned since the pared with the untreated fabric.
values of these properties for the three substrates under
investigation are comparable. With W.I., on the other
hand, substrate I displays higher values than the other Received: February 10, 2000
two substrates. It seems likely that pretreatment with oxa- Revised: September 8, 2000
lic acid prior to desizing and bleaching facilitates the
desizing process. Most probably partial removal of the
size as well as other foreign matter occurs during oxalic [1] J. Dannacher, W. Schlenker, Textilchem. Color. 1996, 28,
acid pretreatment thereby contributing to fabric purifica- 11, 24.
[2] M. Spiro, W. P. Griffth, Textilchem. Color. 1997. 29, 11, 12.
tion.
[3] M. Lewin, S. Sello, “Chemical Processing of Fibers and
Fabrics, Fundamental and Preparations”, in: Handbook of
Conclusions Fiber Science and Technology, Marcel Dekker, Inc., New
York 1984, Vol. 1, Part B, p. 193.
Catalytic degradation of cotton cellulose resulting from [4] U. Meyer, P. P. Kokot, R. Weber, J. Zurcher-Vogt. Textilver-
the contamination of the fabric with Fe2+ and Fe3+ ions edlung 1987, 22, 185.
during bleaching with H2O2 is comparable. Maximum [5] E. Reister, Melliand Textilberichte 1985, 10, 734.
[6] H. Behnk, Textilveredlung 1994, 29, 117.
catalytic degradation is observed when the fabric was [7] P. Wurster, Text.-Prax. Int. 1986, 12, 1231.
contaminated with 0.3 mg/g fabric Fe2+ and Fe3+ ions. [8] U. Strahm, Textilveredlung 1984, 19, 123.
The catalytic tendering of the cotton was much higher [9] P. Wurster, Textilveredlung 1987, 22, 230.
when the bleaching was performed according to the pad- [10] A. Kantouch, I. Geczy, Eur. Polym. J. 1965, 1, 207.
steam method than the exhaustion method. Ceasing of the [11] M. H. Rowe, Textilchem. Color. 1978, 10, 215.
[12] ASTM Standard Test Method, “Breaking Load and Elon-
catalytic degradation of the cotton cellulose caused by the gation of Textile Fabrics” (1964), D-1682-64.
presence of Fe2+ and/or Fe3+ ions could be achieved by [13] H. S. Isbell, M. L. Frush, R. Naves, P. Suntracharden, Car-
pretreatment the fabric with aqueous solution containing bohydr. Res. 1981, 90, 111.