doi: 10.1111/j.1478-4408.2007.00088.

Enhanced PAA bleaching of cotton by incorporating a cationic bleach activator

Pavla Krizman Lavric,a,* Franci Kovac,b Petra Forte Tavcer,a Peter c c Hauser and David Hinks
a

Department of Textiles, Faculty of Natural Sciences and Engineering, University of Ljubljana, Snezniska 5, 1101 Ljubljana, Slovenia Email: pavla.krizman@ntf.uni-lj.si Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, 1000 Ljubljana, Slovenia

College of Textiles, North Carolina State University, Raleigh, NC 27695, USA

Received: 9 February 2007; Accepted: 8 May 2007

Peracetic acid is a well-known alternative to hydrogen peroxide as a bleaching agent for cotton. In this study, a novel cationic bleach activator, N-[4-(triethylammoniomethyl)benzoyl]butyrolactam chloride, was used in combination with peracetic acid to investigate the enhancement of cotton bleaching efciency. The effects of temperature, pH and concentrations of activator and peracetic acid on the bleaching performance were studied using a statistical design of experiment. Adding activator to a peracetic acid bleaching bath improved the resultant whiteness of the substrate and at optimal conditions produced less bre damage than when peracetic acid was used alone. In addition, the bleaching performance of both peracetic acid and hydrogen peroxide in the presence of activator was compared. In the absence of activator, the peracetic acid performance was considerably superior to a conventional hydrogen peroxide bleach system in which no bleach activator is present. However, addition of activator to the hydrogen peroxide bath increased the whiteness to a level comparable to peracetic acid.

Introduction
Key drivers for change in textile wet-processing include reduction in processing costs, reduction in environmental impact and improvement in quality. These drivers continue to encourage research into new chemicals and processes, including the development of new bleaching agents and processes, as bleaching is a critical part of the textile preparation. Among the alternatives to conventional bleaching for cotton, which is currently dominated by hydrogen peroxide (HP) bleaching, peracetic acid (PAA) and other peracids are interesting because they are efcient oxidising agents and are relatively environmentally benign. Commercial PAA solutions contain some acetic acid and HP owing to an equilibrium reaction (Eqn 1). CH3 COOH H2 O2 CH3 COOOH H2 O 1

Spontaneous decomposition of PAA, mainly to acetic acid and oxygen, is facilitated by high temperature, high pH values or heavy metal ion catalysis, especially when single-electron transfers are possible [1]. These decomposition reactions are undesirable as they lead to the formation of species that are not involved in the bleaching process. The bleaching action of PAA is mainly the result of epoxidation of the double bonds present in unwanted coloured compounds [2]. Even at optimal conditions for bleaching, only a small fraction of PAA is consumed and a large part of both oxidants (PAA and HP) remains unused [3]. In this process (60 C, pH 7.5), HP is inactive and does not inuence the nal bleaching [4].
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By adding bleaching activators, bleaching can be enhanced by converting inert HP into active peracids. The most common peracid bleach activator currently used is tetraacetylethylenediamine (TAED). Even though it is cost-effective, relatively environmentally benign and provides effective bleaching at temperatures as low as 40 C [5], the search for alternatives to TAED has been going on since the late 1970s. One drawback is the low solubility of TAED. In a series of recent reports [610], the development of new bleach activators was presented. A new activator, N-[4-(triethylammoniomethyl)benzoyl]caprolactam chloride (TBCC) was found to reduce signicantly bleaching time and temperature while providing equivalent whiteness and less bre damage than when the bleach activator was not included in the bleach recipe. It was found that in the presence of peroxide and alkali, the bleach activator facilitates the formation of peracid, giving a potentially more efcient bleaching system than plain HP. It is hypothesised that the cationic peracids formed exhibit increased substantivity for the negatively charged cotton surface in aqueous alkaline media. Hence, increased substantivity to cotton increases the bleaching effect. However, peracid formation is dependent on pH, temperature and concentrations of peroxide and activator in the bleaching bath. In aqueous solutions, TBCC was found to be sensitive to hydrolysis. To increase hydrolytic stability, the structure was modied and a butyrolactam-based activator, N-[4-(triethylammoniomethyl)benzoyl]-butyrolactam chloride (TBBC), was found to exhibit near equivalency

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 Krizman Lavric et al. Enhanced PAA bleaching of cotton

in whiteness, but signicantly higher hydrolytic stability [610]. In the present study, the performance of TBBC was studied by following the consumption of PAA and HP and the formation of peracids during cotton bleaching. The bleaching effect was assayed by measuring whiteness degree and bre damage. Bleaching experiments were conducted using a statistical design of experiment.

Experimental
Materials Scoured cotton fabric, 102 g/m2, was obtained from Tekstina (Slovenia). PAA, as a 15% equilibrium solution, was supplied by FMC Corporation. Hydrogen peroxide (35% w/w), acetic acid (99.5%) and sodium carbonate were purchased from Fisher Scientic Co. (USA), and tetrasodium pyrophosphate was purchased from Aldrich Chemical Co. (USA). The wetting agent, Kieralon MFB, was purchased from BASF Corporation (USA). The bleach activator, TBBC, was synthesised and puried to >97% purity, as reported previously [11]. Bleaching Two parallel sets of experiments were undertaken. In the rst set, scoured cotton fabrics were bleached in closed beakers in a laboratory infrared (IR) dyeing machine (Ahiba Nuance, Datacolor International, USA) at a liquor-to-goods ratio of 20:1, at conditions according to the central composite design (CCD). The pH of the mixture was adjusted by adding 0.5 M sodium carbonate. After the addition of samples (10.0 g) to the bleaching solution, the temperature was raised to 40 C. After 5 min at 40 C, the temperature was raised (3 C/min) to the target bleaching temperature (50, 60, 70 or 80 C), and bleaching was performed at the set temperature for 40 min. Then, the bleached samples were washed in hot water, rinsed twice in cold water and dried under ambient conditions. Except for washing and rinsing, distilled water was used for all experiments. Whiteness and bre damage were measured on bleached samples. To study the TBBC performance, PAA and HP consumption and/or formation of peracids were monitored at 40, 60 and 80 C, pH 7.5 with and without the addition of TBBC (0%, 1.5% and 3% owf), over 60 min. Bleaching of scoured cotton fabric was performed in asks in a shaking water bath (SWB25, Thermo Haake, Germany) at a frequency of 85 rpm. A blank bath without fabric was used in a control experiment. For comparison, the second set was performed in the presence of HP using optimal conditions for PAA bleaching. When HP bleaching was performed, the solution contained HP (15 g/l of 35% w/w HP), tetrasodium pyrophosphate as stabiliser and Kieralon MFB as a wetting agent, with and without the addition of TBBC (1.5% owf). Cotton samples (10.0 g) were bleached in the same manner as described above, with a bleach temperature of 60 C, bleaching time 40 min and pH 8. Whiteness and bre damage were measured on bleached samples.

Methods Statistical design of experiments The experimental design and statistical analysis were performed using Design-Expert (v. 6.0.8) statistical software, supplied by Stat-Ease, Inc. (USA). Four factors were evaluated: temperature, pH and concentration of TBBC and PAA. Each factor included ve levels ()2, )1, 0, +1, +2), which were chosen based on preliminary experiments (Table 1), and a total of 30 trial experiments were run, as shown in Table 2. Whiteness The CIE Whiteness Index (WI) value for each sample was calculated from spectrophotometric measurements using a Datacolor Spectraash SF 600 Plus-CT spectrophotometer (Datacolor International) with the following settings: illuminant D65, large area view, specular excluded, UV included and CIE 1964 Supplemental Standard Observer (10 degree observer). Each sample was folded into four layers, the reectance of each sample was measured ve times, averaged and WI values were calculated [12]. Concentration of reactants The PAA and HP concentrations in the bleaching bath were determined via iodometric titration using a method developed in the Laboratory for Peroxide Chemistry in the Faculty of Chemistry and Chemical Technology, University of Ljubljana, to determine the concentration of both oxidants simultaneously [3]. This method is based on the reaction of both PAA and HP with KI as indicated in Eqns 2 and 3, respectively. The concentration of released iodine was determined with standardised sodium thiosulphate (Eqn 4). As both oxidants react with KI at room temperature, the titration provided a value for total oxidant concentration. To determine the PAA concentration, titration with sodium thiosulphate was performed at 0 C, as HP reacts negligibly with KI at this temperature. The calculated difference between total oxidant and PAA concentration was equal to the concentration of HP. All values reported were the average of at least two readings. 2KI CH3 COOOH CH3 COOH ! I2 2CH3 COOK H2 O 2 2KI H2 O2 H2 SO4 ! I2 K2 SO4 2H2 O I2 2Na2 S2 O3 ! 2NaI Na2 S4 O6 3 4

Table 1 Actual values of variables Variables A B C D Name (unit) Temperature (C) TBBC (% owf) pH PAA (ml/l) )2 40 0 6.5 5 )1 50 0.75 7 10 0 60 1.5 7.5 15 1 70 2.25 8 20 2 80 3 8.5 25

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 Krizman Lavric et al. Enhanced PAA bleaching of cotton

Table 2 Central composite design for PAA bleaching Factor 1 (temperature, C) 50 70 50 70 50 70 50 70 50 70 50 70 50 70 50 70 40 80 60 60 60 60 60 60 60 60 60 60 60 60 Factor 2 (TBBC, % owf) 0.75 0.75 2.25 2.25 0.75 0.75 2.25 2.25 0.75 0.75 2.25 2.25 0.75 0.75 2.25 2.25 1.5 1.5 0.0 3.0 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Factor 4 (PAA, ml/l) 10 10 10 10 10 10 10 10 20 20 20 20 20 20 20 20 15 15 15 15 15 15 5 25 15 15 15 15 15 15

Trial 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

Factor 3 (pH) 7 7 7 7 8 8 8 8 7 7 7 7 8 8 8 8 7.5 7.5 7.5 7.5 6.5 8.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5

Response WI 68.0 81.7 68.9 83.5 73.8 82.2 76.4 84.2 76.0 86.2 77.1 86.6 78.8 87.3 78.8 87.3 68.2 87.1 79.0 81.7 77.6 81.8 71.9 83.2 81.1 81.5 81.8 81.3 81.7 81.7

Damage to substrate Fibre damage was determined by measuring the degree of polymerisation (DP values) via a viscosimetric method [13]. For this purpose, bres were dissolved in cuoxam. The adequacy of the process was assessed by calculating Eisenhuts tendering factor (TF) [13].

Eqn 5 and Table 3. It is clear that temperature had the greatest effect on whiteness followed by PAA concentration and pH, while TBBC concentration had the least effect, as seen from the coefcient estimate. The effect of each of the input factors on whiteness is illustrated in Figure 1 as contour lines. Before bleaching, the whiteness value of the scoured fabric was 15.9. When TBBC was added to the bleaching bath, better whiteness was achieved with higher temperature, higher concentration of PAA and higher initial pH regardless of TBBC concentration. When comparing other factors at constant TBBC concentration, it can be seen that TBBC effectiveness is T, pH and PAA concentration dependent. Hence, the reaction between TBBC and HP to form peracids is highly temperature dependent. The performance of TBBC was more pronounced at lower temperatures (<60 C) and at lower PAA concentrations, which is in agreement with the previous results [10]. Optimal pH depends on the temperature and PAA concentration used. At lower pH values, higher temperature and more PAA are needed to obtain a better whiteness. An optimal bleaching recipe can be predicted using the mathematical model. For example, to reach a WI value of 85, a number of recipe formulations are possible. Table 4 shows the comparison between the original recipe used in previous research [4], and used as a reference in this study, and the optimised recipe predicted by the CCD model. The nal step in a statistically designed experiment is to predict the response at the optimal settings and in this case WI can be predicted for any xed variable input, such as a desired temperature or concentration of oxidant or activator. In this way, the model predicts a WI output and associated condence interval. Concentration of reactants To assay the inuence of TBBC on bleaching performance with PAA, the concentrations of both oxidants (PAA and HP) during the bleaching process were measured as a function of time and the kinetics compared with a blank bath in which no cotton sample was present (Figures 2 and 3). The recipe derived from the CCD centre point conditions (15 ml/l of PAA at 60 C and pH 7.5) was used in all kinetic measurements. Consumption of both oxidants, PAA and HP, increased with time in the blank as well as in the bleaching bath (Figures 2 and 3). The addition of TBBC resulted in a
Table 3 Effect and signicance of model terms after ANOVA (R2 0.9840) Model terms A B C D A2 D2 AC Coefcient estimate 4.96 0.59 1.23 2.58 )0.82 )0.83 )0.93 Probability > F <0.0001 0.0089 <0.0001 <0.0001 0.0005 0.0004 0.0015

Results and Discussion

Central composite design A full factorial experimental design was used to determine the optimal conditions for bleaching cotton with PAA in the presence of TBBC, and for the quantication of the effects of temperature, pH and concentrations of PAA and TBBC on nal whiteness. Table 2 shows the variables in the full factorial experiment together with the relevant WI values for each trial. Each factors inuence on nal whiteness was assayed by statistical analysis. A quadratic model was developed and shown to be statistically valid, with R2 0.984 (Eqn 5). WI 197:65 3:02 A 2:77 B 34:57 C 3:78 D 8:15 103 A2 0:03 D2 0:19 AC
2

Evaluation of the results revealed that A, B, C, D, A , A2 and AC were signicant model terms. Factors with P-value >0.05 were insignicant and were excluded from
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 Krizman Lavric et al. Enhanced PAA bleaching of cotton

2.25

8.00

1.88 TBBC, % owf

7.75

1.50

pH

77 78 79 80 81 76

85 82 84 83 7.50

78 79 80 81 77 76

83 82

84

85

1.13

7.25

75 74

0.75 50 55 60 Temperature, C 20.0 87 86 17.5 85 PAA, ml/l 84 15.0 78 77 76 75 74 73 10.0 50 55 60 Temperature, C 20.0 65 70 79 80 81 82 83 65 70

7.00 50 55 60 Temperature, C 8.00 82 7.75 83 65 70

pH

7.50

12.5

7.25 80 7.00 0.75 1.13

81

1.50 TBBC, % owf

1.88

2.25

20.0

84

83 17.5 PAA, ml/l 82 PAA, ml/l 17.5 83 82

15.0 81 12.5 78 10.0 0.75 1.13 79 80

15.0 81 12.5 79 77 78 80

1.50 TBBC, % owf

1.88

2.25

10.0 7.00

7.25

7.50 pH

7.75

8.00

Figure 1 Effect of bleaching factors on whiteness of cotton using TBBC, with contour lines representing WI values; the levels for each parameter are in accordance with their centre point (1.5% owf TBBC, 15 ml/l PAA, 60 C and pH 7.5)

slight decrease in HP concentration, because of peracid formation. Consequently, the cationic PAA concentration increased. Interestingly, the same observation was made in the blank bath. Also, as expected, the concentration of PAA increased with increased TBBC concentration. A slightly smaller difference in PAA concentration after the addition of TBBC was found in the bleaching bath

compared with the blank bath. In this case, the peracid that formed was immediately consumed during bleaching. This supports the hypothesis that newly formed cationic peracids have higher substantivity for the anionic cotton surface [610]. Comparison of the titration curves of PAA and HP in the blank bath and the bleaching bath shows slightly
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 Krizman Lavric et al. Enhanced PAA bleaching of cotton

Table 4 Summary of a predicted optimised bleach recipe at 65 C Temperature (C) 60 65 TBBC (% owf) 0 2 PAA (ml/l) 15 20

Recipe Reference Optimised

pH 7.5 7.5

WI 79 85

0.016

0.012
PAA conc., mol/l

0.008

0.004

0.000 0 15 30 t, min 45 60

higher consumption of both oxidants in the blank bath, indicating that the cotton fabric acts as a stabiliser for HP, which supports the previous ndings [14,15]. For comparison, the same kinetic measurements were performed at 40 (CCD minimum level) and 80 C (CCD maximum level), as differences in whiteness were found to be larger at lower temperatures. The WI values of bleached sample at 40 C after addition of TBBC increased from 62.8 to 68.2 in the presence of TBBC, while WI values only increased slightly when the temperature was increased from 60 to 80 C (from 79.0 to 81.6 at 60 C and from 86.0 to 87.1 at 80 C). Second-order rate constants were obtained under pseudo rst-order conditions and show similar trends for all three temperatures studied (Table 5). The reaction rate for PAA consumption decreased with increasing TBBC concentration in bleaching and blank baths due to the formation of probably more reactive peracid. However, the consumption of PAA increased with temperature and was more rapid in the blank bath than in the bleaching bath. The rate constant for HP consumption increased with higher TBBC concentrations and temperatures, as indicated in Figures 2 and 3. Degree of polymerisation It is well known that increasing the temperature of bleaching produces higher whiteness but at the expense of bre strength. The results of polymerisation degree expressed in DP values (Figure 4) show that similar bre damage (as measured by degree of polymerisation) was found at 40 and 60 C, while at 80 C the bre damage was signicantly higher. Interestingly, even lower bre damage was measured when the concentration of TBBC was increased from 1.5% to 3% owf at 60 C, illustrating the benet of incorporating this bleach activator into the bleach bath. At optimal conditions for PAA bleaching, HP remains inert and does not affect the bleaching in terms of nal whiteness regardless of the temperature used [3,4]. Agnihotri and Parikh observed that in the PAA system, the presence of free peroxide beyond a certain limit leads to degradation of cotton bres [16]. However, by increasing the temperature, a small decrease in DP value was reported previously but no major damage was observed [3]. Figure 1 shows that temperature has a greater impact on TBBC performance than pH of the bleaching bath. In

Figure 2 Change in concentration of PAA with time in the blank bath ( 0%, 1.5%, 3%) and the bleaching bath () 0%, h 1.5%, n 3%) with 15 ml/l of PAA at 60 C and pH 7.5, with the addition of different concentrations of TBBC (0%, 1.5% and 3% owf)

0.14

HP conc., mol/l

0.12

0.10

0.08 0 15 30 t, min 45 60

Figure 3 Change in concentration of HP with time in the blank bath and the bleaching bath with 15 ml/l of PAA at 60 C and pH 7.5, with the addition of different concentrations of TBBC (0%, 1.5% and 3% owf); for key see Figure 2

Table 5 Calculated second-order rate constants (k) of PAA and HP consumption as a function of TBBC concentration at 40, 60 and 80 Ca k40 C Baths Blank TBBC (% owf) 0 1.5 3 0 1.5 3 PAA 2.90 2.19 1.38 1.94 1.84 1.09 10)2 10)2 10)2 10)2 10)2 10)2 HP 1.27 1.54 1.80 1.99 2.46 1.37 10)4 10)4 10)4 10)4 10)4 10)4 k60 C PAA 5.73 4.82 3.67 3.16 2.86 2.93 10)2 10)2 10)2 10)2 10)2 10)2 HP 1.75 2.76 3.34 1.41 2.21 2.36 10)4 10)4 10)4 10)4 10)4 10)4 k80 C PAA 1.57 1.51 1.84 8.40 8.13 9.83 10)1 10)1 10)1 10)2 10)2 10)2 HP 3.44 4.82 4.80 2.60 3.79 3.81 10)4 10)3 10)3 10)4 10)4 10)4

Bleaching

a Correlation coefcient (R2) was in the range 0.920.99

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 Krizman Lavric et al. Enhanced PAA bleaching of cotton

2700 2600 2500 DP

0%

1.5%

3%

0.25 0.20 0.15 TF 0.10 0.05 0.00

100 80 60
WI

0%

1.5%

2400 2300 2200

40 20 0 PAA HP

2100 2000 40 C 60 C 80 C

Figure 4 Degree of polymerisation (DP) and Eisenhuts tendering factor (shown on bars) for samples bleached with 15 ml/l of PAA at different temperatures (40, 60 and 80 C) and pH 7.5, with and without the addition of TBBC (0%, 1.5% and 3% owf)

Figure 5 Effect of 1.5% TBBC addition to PAA and HP on WI values compared to the performance without TBBC; 60 C, pH 7.5 for PAA and pH 8 for HP, 40 min

our case, this means that the rate of perhydrolysis is more temperature-dependent than pH-dependent, as reported in previous work [7]. Higher temperatures increase perhydrolysis with the maximum being reached at 60 C, while at temperatures lower and higher than 60 C other competing reactions appear to prevail. Calculation of Eisenhuts TF showed that there was little bre damage in comparison with unbleached material (DPunbleached 2845), which makes this process

adequate. All values are below 0.4 (Figure 4), which, according to the standard, means that higher temperatures could be used. A comparison between PAA and HP bleaching performance Cotton was bleached with HP using similar, PAA optimal, bleaching conditions. HP and PAA bleaching performance were compared to appraise TBBCs ability of activating HP.

H O O O Cl + N C

H O

Cl + N

C N

N OOH

O Cl + N C OOH +

HN

O O

H O O Cl + N H C N O OOH

Cl + N

C N

O Cl + N C OOH N H C O

Scheme 1

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 Krizman Lavric et al. Enhanced PAA bleaching of cotton

2700 2600 2500 DP

0%

1.5%

0.25 0.20 0.15 0.10 0.05 0.00 TF

2400 2300 2200 2100 2000 PAA HP

Figure 6 Effect of 1.5% (owf) TBBC on PAA and HP bleaching performance on degree of polymerisation (DP) and Eisenhuts tendering factor (shown on bars; 60 C, pH 7.5 for PAA and pH 8 for HP, 40 min)

During bleaching with an industrially prepared PAA, both oxidants, PAA and HP, are present in the bleaching bath. While this system produces a highly complex bleaching mechanism at the conditions used for PAA bleaching (pH 7.5), peracetate ions and undissociated HP are expected to be present. Figure 5 shows that HP in the presence of TBBC achieved almost equal whiteness as when PAA was used alone. As HP is mainly undissociated at these conditions, a reaction between HP as a nucleophilic species with TBBC appears likely, ultimately leading to the formation of peracids. Two nucleophilic addition reactions appear possible at pH 7.5, where addition of HP on one of the TBBC carbonyl groups leads to the generation of a peracid (Scheme 1). By comparing DP values of the samples bleached with PAA and HP the addition of TBBC lowered the bre damage in both cases (Figure 6).

Experimental data supported the previously published results that the peracid, formed from the reaction between HP and TBBC, has higher substantivity for the negatively charged surface of cotton than PAA, which leads to a higher level of oxidation on the relevant sites of the substrate in the bleaching bath. A high level of whiteness was achieved in all experiments and determinations of the degree of polymerisation of bleached samples with or without the addition of TBBC show little bre damage in all cases. Peracetic acid and HP bleaching performances at pH 7.5 and 60 C in the presence of TBBC were compared to determine the effect of the bleach activator on the performance of each oxidant. Without adding TBBC, PAA was considerably superior to HP. By adding TBBC to the HP bath, the HP bleaching performance increased to a level comparable to that when PAA was used.

Acknowledgements
The authors gratefully acknowledge the support of the Slovenian Research Agency, applied project, No. L2-72281555, bilateral cooperation project, No. BI-US/06-07-040 and Ad Futura, Science and Education Foundation of the Republic of Slovenia, Public Fund, grant No. 2005/516-02.

References
1. Z Yuan, Y Ni and A R P van Heiningen, Can. J. Chem. Eng., 75 (1997) 37. 2. J Clayden, N Greeves, S Warren and P Wothers, Organic Chemistry (Oxford: Oxford University Press, 2001) 506. 3. P Krizman, F Kovac and P Forte Tavcer, Color. Technol., 121 (2005) 304. 4. P Krizman, F Kovac and P Forte Tavcer, Book of Abstracts, 4th International Conference on Textile Biotechnology, Seoul, Korea (2006) 85. 5. E Menezes and M Chaudhari, Colourage, 52 (1) (2005) 39. 6. N C Gursoy, S-H Lim, D Hinks and P Hauser, Text. Res. J., 74 (2004) 970. 7. N C Gursoy, A El-Shafei, P Hauser and D Hinks, AATCC Rev., 4 (8) (2004) 37. 8. S-H Lim, N C Gursoy, P Hauser and D Hinks, Color. Technol., 120 (2004) 114. 9. J J Lee, S-H Lim, P Hauser and D Hinks, Color. Technol., 121 (2005) 37. 10. S-H Lim, J J Lee, D Hinks and P Hauser, Color. Technol., 121 (2005) 89. 11. A D Willey, G S Miracle, K L Kott, M E Burns, G M A Baillely, N-E Guedira, F E Hardy, L F Taylor and M R Sivik, US5686015 (Procter & Gamble; 1997). 12. AATCC 2006 Technical Manual, Test Method 110-1995. 13. E Siebel, Handbook of Material Analysis. Part V: Textile Analysis (Berlin: Springer-Verlag, 1960). 14. R E Brooks and S B Moore, Cellulose, 7 (2000) 263. 15. J Dannacher and W Schlenker, Text. Chem. Colorist, 28 (11) (1996) 24. 16. V G Agnihotri and D V Parikh, Colourage, 18 (7) (1971) 27.

Conclusions
Development of an activated PAA bleaching system for cotton presents an important step in improving the preparation of this bre. The addition of TBBC increased the efciency of the bleaching process of PAA. An optimised recipe was determined for bleaching using a central composite experimental design, showing that, when TBBC was added, temperature had the greatest effect on PAA performance, followed in turn by the PAA concentration and pH. While increasing concentration of TBBC had the lowest impact on the degree of whiteness, it played an important role in lowering the bre damage. However, at lower temperatures, e.g. 4060 C, and at lower PAA concentrations, a better bleaching performance was achieved by adding TBBC.

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