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Introducing covalent and ionic cross-linking into cotton through polycarboxylic acids and nano TiO2 a
b
Ali Nazari , Majid Montazer & Mohammad Bameni Moghadam a
c
Art & Architectural Department, Yazd Branch, Islamic Azad University, Yazd, Iran
b
Department of Textile Engineering, Amirkabir University of Technology (Tehran Polytechnic), Tehran, Iran c
Department of Statistics, Allameh Tabatabai’ University, Tehran, Iran
Version of record first published: 01 Feb 2012
To cite this article: Ali Nazari, Majid Montazer & Mohammad Bameni Moghadam (2012): Introducing covalent and ionic crosslinking into cotton through polycarboxylic acids and nano TiO2 , Journal of The Textile Institute, 103:9, 985-996 To link to this article: http://dx.doi.org/10.1080/00405000.2011.646678
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The Journal of The Textile Institute Vol. 103, No. 9, September 2012, 985–996
Introducing covalent and ionic cross-linking into cotton through polycarboxylic acids and nano TiO2 Ali Nazaria*, Majid Montazerb and Mohammad Bameni Moghadamc a
Art & Architectural Department, Yazd Branch, Islamic Azad University, Yazd, Iran; bDepartment of Textile Engineering, Amirkabir University of Technology (Tehran Polytechnic), Tehran, Iran; cDepartment of Statistics, Allameh Tabatabai’ University, Tehran, Iran
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(Received 12 October 2011; final version received 1 December 2011) In this study, cationized cotton (CC) fabrics were treated with polycarboxylic acids and nano titanium dioxide (NTO) to produce fabrics with enhanced cross-linking property. The CC cross-linking with butane tetra carboxylic acid and citric acid in the presence of sodium hypophosphite catalyst and NTO co-catalyst under different curing methods were optimized using a statistical approach. The central composite design was used for variables based on Design of Expert software. The appropriate models to create optimum dry crease recovery angle were obtained for each condition. The results show that the covalent and ionic linkages lead to the cross-linking improvement of CC. X-ray diffraction and scanning electron microscopy were also applied to indicate the NTO particles on the cotton surface with the size of nano particles and their crystallinity. Keywords: cotton; cationized; cross-linking; nano TiO2; curing methods
Introduction In order to improve the characteristics of cellulosic fabrics, different parameters have been applied in cationic treatment during the recent decade, among which are cationizing methods and the optimizing of other variables such as temperature and time (Hashem, Hauser, & Smith, 2003), the increase in the affinity of synthetic and natural dyes using cationized cotton (CC) in the absence of electrolytes (Kamel, El-Shishtawy, Youssef, & Mashaly, 2007; Montazer, Malek, & Rahimi, 2007; Soares et al., 2008; Wang, Fang, & Ji, 2007; Wang, Ma, Zhang, Teng, & Yang, 2009). The use of higher concentrations of electrolytes (such as sodium chloride and sodium sulfate) causes the reduction of dyes solubility. Therefore, the reason for using the CC is to reduce the amount of water and energy consumed in the dyeing processes (Hauser & Tabba, 2001). Much availability and environment-friendly factor of polycarboxylic acids leads to their application in the modification of cotton fabric. Some of these usages include the enhancement of cross-linking property (Lam, Kan, & Yuen, 2010), antibacterial activity (Orhan, Kut, & Gunesoglu, 2009), and simultaneous finishing of antimicrobial and cross-linking (Montazer & Gorbanali Afjeh, 2007) properties. *Corresponding author. Email:
[email protected] ISSN 0040-5000 print/ISSN 1754-2340 online Copyright Ó 2012 The Textile Institute http://dx.doi.org/10.1080/00405000.2011.646678 http://www.tandfonline.com
In recent years, there is growing interest in the applications of nanoparticles due to their unique and valuable properties. This is because of the creation of multi-functional properties for textile fabrics. The properties imparted to textiles using nanotechnology include water repellence, soil resistance, antimicrobial (Son, Youk, & Park, 2006), antistatic and UV-protection (Yuen, Kan, & Wong, 2009), wrinkle resistance, flame retardation, decrease of photo yellowing (Montazer, Pakdel, & Moghadam, 2010), self-cleaning of cellulosic (Bozzi, Yuranova, Guasaquillo, Laub, & Kiwi, 2005; Meilert, Laub, & Kiwi, 2005; Vero, Hribernik, Andreozzi, & Sfiligoj-Smole, 2009; Veronovski, Rudolf, Smole, Kreže, & Geršak, 2009; Yuranova, Mosteo, Bandara, Laub, & Kiwi, 2006), protein (Tung & Daoud, 2008) and synthetic (Mihailović et al., 2010; Yuranova, Laub, & Kiwi, 2007) fibers. The use of nano titanium dioxide (NTO) as a photocatalyst in the presence of maleic anhydride as crosslinker to improve the crease recovery properties of the silk fabrics has been reported (Wang & Chen, 2005b). Wang and Chen (2005a, 2005b) have reported the application of four different carboxylic acids, named, butane tetra carboxylic acid (BTCA), maleic acid, citric acid (CA), and succinic acid (SUA) as
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cross-linking agents to treat cotton fabrics in the presence of nanometer titanium dioxide (TiO2) as catalyst under UV irradiation and electronic field. They represent that dry crease recovery angles (DCRA) and wet crease recovery angles of treated samples increased with the increase of polycarboxylic concentrations and irradiation time of ultraviolet (UV), whereas in all the cases, tensile strength retention decreased. Chen and Wang (2006) have investigated the cross-linking of cotton cellulose with SUA in the presence of TiO2 nanocatalyst under UV irradiation. Besides, as a result of photocatalytic effect of NTO, cross-linking mechanism of cellulosic via SUA under UV irradiation was revealed. Yuen and colleagues (2009) have studied the wrinkle-resistant treatment of cotton fabric during two stages using BTCA, sodium hypophosphite (SHP), and NTO. They have demonstrated that the addition of NTO could enhance the wrinkle resistance and decrease the bending length of the cotton fabric. In addition, wool treatment with CA and NTO was investigated in order to reduce the photo yellowing (Montazer & Pakdel, 2010) and improve the anti-UV properties (Hsieh, Zhang, & Li, 2006). The application of central composite design (CCD) attracted the attention of many researchers in their recent scientific studies in order to optimize the variables, including optimization of wool dyeing with madder and liposome (Montazer, Taghavi, et al., 2007), modification of wool surface by liposome for dyeing with weld (Montazer, Zolfaghari, Toliat, & Bameni Moghadam, 2009), photocatalytic decolorization of the azo dye reactive black 5 (Secula, Suditu, Poulios, Cojocaru, & Cretescu, 2008), extraction process of polysaccharides from poria cocos (Yongjiang, Zhong, Jianwei, Minger, & Xueqian, 2009), and dried longan pulp (Zhong & Wang, 2010), electrochemical treatment (Körbahti, 2007), protease production (Dutta, Dutta, & Banerjee, 2004), and more recently self-cleaning of conventional and CC (Nazari, Montazer, Moghadam, & Anary-Abbasinejad, 2011). We have also studied and indicated the effects of NTO particles on the simultaneous cross-linking and antimicrobial finishing of different cotton fabrics (Nazari, Montazer, & Rahimi, 2009) and the suggested mechanism of cotton cellulose cross-linking which leads to an ester bond formation between cotton cellulose and polycarboxylic acid (Nazari, Montazer, Rashidi, et al., 2009). Afterwards, in 2010, the optimization of DCRA values of bleached cotton with polycarboxylic acids, SHP catalyst, and NTO photocatalyst using CCD approach was illustrated in our work (Nazari, Montazer, Rashidi, Yazdanshenas, & Moghadam, 2010). In the present study, the ionic and ester crosslinking of CC fabric was investigated in the presence of
SHP catalyst and NTO co-catalyst under different curing methods (UV, high temperature [high temp], and UV-temperature [UV-temp]. The CCD approach was employed to optimize DCRA values. The pretreatment influence of cationization of cotton fabric on DCRA values was measured and reported. Accordingly, the best treatment conditions to optimize the DCRA properties of the cationized samples were represented. Experimental Material BTCA and CA, sodium hydroxide and SHP were supplied by Merck Chemical Co., Darmstadt, Germany. Nonionic detergent (Rucogen DEN) composed of fatty alcohol ethoxylate was obtained from Rudolf Chemie Co. (Tehran, Iran). NTO was employed as the photocatalyst with the anatase crystalline structure and an average particle size of 21 nm from Degussa Chemie Co., Duisburg, Germany. The desized, scoured, and bleached plain weave 100% cotton fabric was used with wrap density 32 yarn/cm, weft density 30 yarn/cm, and fabric weight 118 g/m2. Instrument Finishing compounds were prepared and dispersed using an ultrasonic bath (200 V, 50 W, 40 KHz). Thermal oven was used to dry and cure the samples. Some treated samples were exposed to the UV irradiation of an HPA 400S lamp (400 W, Philips, Belgium). Scanning electron microscopic (SEM) observations on specimens of treated fabrics was carried out using an LEO 440i electron microscope (Cambridge, UK). An X-ray diffractometer type 3003 PTS, SEIFERT, Ahrensburg, Germany (k = 1.54060Å, at 40 kV, and 30 mA) with Cu Ka irradiation was used to identify the crystalline phase and also crystal size, using the Scherrer method (Wang, Wu, & Xu, 2005). Method The cotton fabric samples were prepared in 14 5 cm2 swatches. Bleaching treatment of cotton fiber was performed using 3.5% hydrogen peroxide and 2% sodium hydroxide (based on weight of fabric: OWF) at a liquor ratio of 8:1 under the boiling condition for 90 min. The bleached cotton fabric was cationized based on pad-batch method, using 25 g/L 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (Quat-188) and 10 g/L sodium hydroxide (based on weight of bath: OWB) with 90% wet pick up. These samples were placed in closed bags for 24 h in ambient temperature. The aqueous finishing dispersion was prepared by the mixtures of carboxylic acid cross-linking agents
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The Journal of The Textile Institute
CA and BTCA and SHP with the amount of 60% CA or BTCA and NTO (based on weight of bath: OWB) and required percentage of distilled water in ultrasonic bath for 15 min. The cotton fabrics were padded with 90% wet pick up by freshly prepared aqueous solutions. Padded fabrics were dried at 60°C for 3 min to remove mobile water. The treated samples were cured with different conditions: UV (15 min UVA irradiation), high temp (150°C, 5 min for CA, and 180°C, 2 min for BTCA) and UV-temp (UVA irradiation and high temp). Then, the finished samples were washed at 70°C for 30 min using a solution containing 2 g/L Na2CO3 and 1 g/L nonionic detergent (Rucogen DEN), and finally dried at ambient conditions. The process of treatment on CC samples is shown in Scheme 1. DCRA of warp (w) plus filling (f) of the treated cotton fabrics was evaluated using the AATCC test method 66-2003. Specimens were prepared in 40 15 mm swatches and 500 ± 5 g of weight was
Raw Cotton Fabric
BTCA or CA
987
loaded on the folded specimens for 5 min ± 5 s. The recorded vertical angle guidelines were aligned and the recovery angles were measured. Experimental design The CCD used for experimental plan with four variables is shown in Table 1. Four variables including the amounts of BTCA, CA, NTO, and different curing methods were studied. The ranges of these variables are shown in Table 1. Details of the CCD for crosslinking the bleached cotton fabric with CA and BTCA in the presence of NTO are presented in Table 2. Also, the influence of the variable on the results Y (CRA) was adjusted using the following second-order polynominal function: Y ¼ b0 þ iPj
Bleaching
X
bi Xi þ
X
bij Xi Xj þ
i; j ¼ 1; 2; 3
Cationizing
Sonicating
SHP and NTO
Padding
Drying
Curing
UV-A
High Temp
UV-A + High Temp
Normal Washing
Scheme 1. The process of cotton treatment with BTCA and CA under different curing methods.
X
ci Xi2 ;
(1)
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Table 1. Range of variables.
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Variable
Lower limit
Upper limit
CA concentration (g/L) BTCA concentration (g/L) NTO (%) Curing method
50.96 50.96 .12
In this equation, b0 is an independent term according to the mean value of the experimental plan, bi are regression coefficients that explain the influence of the variables in their linear form, bij are regression coefficients of the interaction terms between variables, and ci are the coefficients of quadratic form of the variables.
It appears that with the UV-temp curing method, both cross-linking mechanisms of cotton fabric based on UV and high temp occurred. The details of the mentioned mechanisms have been reported in our previous study (Nazari, Montazer, Rashidi, et al., 2009). Therefore, the treated fabrics cured with UV or high temp methods show lower DCRA compared to those cured with UV-temp. At the concentration of 99.04 g/ L of both polycarboxylic acids, there is a higher increase in the value of treated fabrics’ DCRA based on the UV method as compared with the high temp method. This can be due to the higher availability of polycarboxylic acids to react with particle sizes of NTO and pairs of electrons and holes formed through UV irradiation. As shown in Table 2, the increase of NTO concentration helps improve the DCRA due to higher possibility of the cross-linking of the cotton cellulose. However, the higher concentration of NTO causes the decrease of DCRA. This can be considered as a result of particles agglomeration of NTO that is caused by the preventive effect for producing cross bonds via BTCA and CA in cellulose chains. Also, under similar conditions, CC samples have higher DCRA values than bleached samples in our previous study (Nazari et al., 2010). This could be related to the cationized samples containing Quat-188 that form ionic and covalent bonds with polycarboxylic acids, while these bonds are considered to be only covalent in the bleached samples. The addition of ionic bonds to the ester ones leads to the more crosslinking of cellulosic cotton fabric and therefore to the increase of DCRA values of cationized samples. Furthermore, cross-linking of cotton fabrics with CA is effectively promoted by NTO and SHP (Scheme 3). As it is also shown, CA can maintain NTO particles. There is an ionic interaction between carboxylate anionic groups related to polycarboxylic acid and NTO cation. This kind of interaction has been previously reported (Yuranova et al., 2007).
Results and discussion Cross-linking properties The reaction mechanism of Quat-188 and CA with cotton is proposed in Scheme 2. First, intermediate anhydride cycles were formed as shown in reaction I. The cotton was cationized through reaction II. CA was bonded to cotton by Quat-188 via ionic linkage by reaction III. The binding of cotton with CA was continued via ester linkage through reactions IV and V. On the other hand, one other free carboxylic group of CA could bond to NTO via strong electrostatic interactions through reaction VI (Yuranova et al., 2007). Table 2 lists the DCRA of CC fabrics treated with BTCA and CA under different conditions. Table 2 shows the increase in values of DCRA with increasing the concentration of the cross-linking agent. However, the increase of NTO concentration increases the value of DCRA and further increase of the NTO decreases the DCRA. This may be caused by the agglomeration on NTO in the solution bath or on the fabric and/or inhibiting the action of the cross-linking agent on cotton under higher concentrations of NTO. Based on Table 2, in similar conditions samples treated will BTCA have higher DCRA values as compared to the samples treated with CA. This is because of simultaneous formation of two cyclic anhydride intermediates via BTCA with four carboxylic groups. Consequently, it was suggested that four carboxylic groups on BTCA allowed bond formation more readily (Lee & Broughton, 2007). Three curing methods including UV irradiation (UV), high temp, and the combination of these two methods (UV-temp) have been used in this study. As shown in Table 2, the order of decrease in DCRA for these three methods is: UV-temp > high temp > UV. However, for high concentrations of both CA and BTCA (99.04 g/L), the order of decrease in DCRA is: UV-temp > UV > high temp.
99.04 99.04 5.02 UV, high temp, UV-temp
Statistical analysis For treated samples with CA, the analysis of variance (ANOVA) is given in Table 3. According to the ANOVA results, the fitted models of crease recovery angle by using CA are shown in Equations (2)–(4), respectively,
The Journal of The Textile Institute CH3
OH Cl
CH2
CH
+
CH2
N
+ CH
N
CH2
O
CH
CH2
HO
Cell
Cell
CH
CH3Cl + NaCl
(I)
CH
CH2
O
CH3
-
+ N
CH2
CH3Cl +
+ N
CH2
CH3 CH2
+ N
CH3Cl
(II)
CH3
HOOC
CH2
HOOC
C
HOOC
CH2
OH
(III)
( CA )
OH CH2
+
(Cellulose)
CH3
O
N
OH CH3Cl +
OH
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CH2
CH3
CH3
Cell
CH
CH3
O
Cell
CH2
CH3
(Quat-188)
CH2
CH3
O
CH3Cl + NaOH
989
_ ( CH3 ) 3
CH2
OOC
Ionic HOOC linkag HOOC
C
OH
CH2
OH SHP
Cell
O
CH2
CH
CH2
+ N
_ ( CH3 ) 3
OOC
(IV)
CH2
OC
C
OC
CH2
OOC
CH2
OH
O OH Cell OH
Cell
O
CH2
CH
CH2
+ N
_ ( CH3 ) 3
HOOC Cell
OOC
C
(V) OH
CH2
Ester linkage OH NTO Cell
O
CH2
CH
CH2
+ N
_ ( CH3 ) 3 O2 Ti
4+
Cell
OOC _ O C O OOC
(VI)
CH2 C
OH
CH2
Scheme 2. Suggested linkage mechanism of cationized cotton with CA and NTO.
DCRA(UV) ¼ þ192:58526 þ :33959CA 1:89180NTO;
DCRA(Temp) ¼ þ188:89295 þ :33959CA (2)
1:89180NTO;
(3)
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Table 2. Central composite design for DCRA cationized samples with CA, BTCA, SHP, and NTO cured with different methods.
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Run
Factors
Run
C: DCRA (W + F)
Numbers
D: BTCA (g/L)
E: NTO (%)
150 172
Control Blank 1
0 0
0 2.57
209
Blank 2
75
0
224 209 226 236 190 207 232 211 203 195
1-BTCA 2-BTCA 3-BTCA 4-BTCA 5-BTCA 6-BTCA 7-BTCA 8-BTCA 9-BTCA 10BTCA 11BTCA 12BTCA 13BTCA 14BTCA 15BTCA 16BTCA 17BTCA 18BTCA 19BTCA 20BTCA 21BTCA 22BTCA 23BTCA 24BTCA 25BTCA 26BTCA 27BTCA 28BTCA 29BTCA 30BTCA
58.00 75.00 99.04 75.00 75.00 75.00 92.00 75.00 75.00 75.00
Numbers
A: CA (g/L)
B: NTO (%)
Control Blank 1
0 0
0 2.57
Blank 2
75
0
1-CA 2-CA 3-CA 4-CA 5-CA 6-CA 7-CA 8-CA 9-CA 10-CA
58.00 75.00 99.04 75.00 75.00 75.00 92.00 75.00 75.00 75.00
4.30 2.57 2.57 2.57 5.02 .12 .84 2.57 2.57 2.57
– UV-temp (c) UV-temp (c) UVa UVa UVa UVa UVa UVa UVa UVa UVa UVa
11-CA
50.96
2.57
UVa
194
12-CA
58.00
.84
UVa
227
13-CA
92.00
4.30
UVa
216
14-CA
58.00
.84
196
15-CA
58.00
4.30
16-CA
99.04
2.57
17-CA
75.00
2.57
18-CA
75.00
.12
19-CA
75.00
2.57
20-CA
92.00
.84
21-CA
75.00
2.57
22-CA
50.96
2.57
23-CA
75.00
5.02
24-CA
75.00
2.57
25-CA
92.00
4.30
26-CA
75.00
2.57
27-CA
75.00
2.57
High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb UV-tempc
28-CA
75.00
2.57
UV-tempc
213
.12
UV-temp
c
UV-temp
c
29-CA 30-CA
75.00 92.00
4.30
Curing method
Response
200 222 218 210 222 203 201 197 210 203 217 223 220
212 214
Factors
Response Curing method
F: DCRA (W + F) 150 173
4.30 2.57 2.57 2.57 5.02 .12 .84 2.57 2.57 2.57
– UV-temp (c) UV-temp (c) UVa UVa UVa UVa UVa UVa UVa UVa UVa UVa
50.96
2.57
UVa
212
58.00
.84
UVa
241
92.00
4.30
UVa
206
58.00
.84
219
58.00
4.30
99.04
2.57
75.00
2.57
75.00
.12
75.00
2.57
92.00
.84
75.00
2.57
50.96
2.57
75.00
5.02
75.00
2.57
92.00
4.30
75.00
2.57
75.00
2.57
High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb High tempb UV-tempc
75.00
2.57
UV-tempc
259
.12
UV-temp
c
239
UV-temp
c
219
75.00 92.00
4.30
235 224 195 238 217 208 215 230 217 225 232
222 232 229 223 241 259 208 220 223 222 259 239 263
(Continued)
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Table 2 (Continued)
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Run
Factors Curing method
Response
Run
C: DCRA (W + F)
Numbers
Numbers
A: CA (g/L)
B: NTO (%)
31-CA
58.00
4.30
UV-tempc
213
32-CA
92.00
.84
UV-tempc
230
3-CA 34-CA
58.00 75.00
.84 2.57
UV-tempc UV-tempc
230 202
35-CA
75.00
2.57
UV-tempc
213
36-CA
75.00
5.02
UV-tempc
198
37-CA
50.96
2.57
UV-tempc
207
38-CA
75.00
2.57
UV-tempc
230
39-CA
99.04
2.57
UV-tempc
231
Factors
31BTCA 32BTCA 3-BTCA 34BTCA 35BTCA 36BTCA 37BTCA 38BTCA 39BTCA
D: BTCA (g/L)
E: NTO (%)
Response Curing method
F: DCRA (W + F)
58.00
4.30
UV-tempc
212
92.00
.84
UV-tempc
246
58.00 75.00
.84 2.57
UV-tempc UV-tempc
231 233
75.00
2.57
UV-tempc
227
75.00
5.02
UV-tempc
212
50.96
2.57
UV-tempc
229
75.00
2.57
UV-tempc
247
99.04
2.57
UV-tempc
252
Notes: aUVA irradiation for 15 min. bHeating (at 150 °C, 5 min for CA, and 180 °C, 2 min for BTCA). cUVA irradiation for 15 min and then heating (at 150 °C, 5 min for CA, and 180 °C, 2 min for BTCA).
Figure 1(a)–(c) shows the response surface of the model. By using the Design of Expert software, the optimum design point with desirability of .774 is for CA with concentration of 92 g/L, NTO .84%, and curing method of (a) UV, (b) high temp, and (c) UV-temp. The ANOVA of treated cotton with BTCA is given in Table 4. According to the ANOVA results, the fitted models of DCRA using BTCA are shown in Equations (5)–(7), respectively.
Conventional Cellulosic Chain 4+
O2 Ti
O
O
O
O C
C Citric Acid
C
OH O
O
Conventional Cellulosic Chain 4+
O2 Ti
O
O
O
O C
C Citric Acid OH
C O
O
DCRA(UV) ¼ þ199:46608 þ :38423BTCA
CH3 CH3 + N CH3
3:19324NTO;
(5)
Cationized Cellulosic Chain
4+
O2 Ti
O
O
O
O
+ N
C
C
C O
DCRA(temp) ¼ þ209:88915 þ :38423BTCA
CH3
3:19324NTO
CH3
Citric Acid OH
CH3
O
CH3 CH3 + N CH3
DCRA(UVtemp) ¼ þ215:61992 þ :38423BTCA
Cationized Cellulosic Chain
3:19324NTO:
Scheme 3. Formation of ester and ionic linkages between CA and cellulosic chains and electrostatic linkages between CA and NTO.
DCRA(UVtemp) ¼ þ195:96987 þ :33959CA 1:89180NTO:
(6)
(4)
(7)
Besides, Figure 2 shows the response surface of the model. By using the Design of Expert software, the optimum design point with desirability of .778 is about the BTCA concentration of 92 g/L, the NTO concentration of .84%, and curing method of (a) UV, (b) high temp, and (c) UV-temp.
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Figure 1. Design of Expert plot for treated cotton with CA, SHP, NTO and (a) UV, (b) high temp, (c) UV-temp curing methods.
Table 3. ANOVA for response surface quadratic model with CA. Source Model A (CA) B (NTO) C (curing) Residual Lack of fit Pure error Cor. total
Sum of squares 1382.67 799.85 257.07 325.74 4905.77 2615.27 2290.50 6288.44
df 4 1 1 2 34 22 12 38
Mean square 345.67 799.85 257.07 162.87 144.29 118.88 190.88
F value
p-value prob. > F
2.40 5.54 1.78 1.13
.0696 .0245 .1908 .3352
.62
.8381
F value
p-value prob. > F
4.54 5.32 3.80 4.53 – .88 – –
.0048 .0273 .0594 .0181 – .6180 – –
Table 4. ANOVA for response surface quadratic model with BTCA. Source Model D (BTCA) E (NTO) F (curing) Residual Lack of fit Pure error Cor. total
Sum of squares 3500.28 1024.00 732.43 1743.86 6547.30 4041.50 2505.80 10,047.59
df
Mean square
4 1 1 2 34 22 12 38
875.07 1024.00 732.43 871.93 192.57 183.70 208.82 –
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993
Figure 2. Design of Expert plot for treated cotton with BTCA, SHP, NTO and (a) UV, (b) high temp, (c) UV-temp curing methods.
Characterization techniques X-ray diffraction (XRD) analysis The XRD patterns of the sample treated with 99.04 g/ L CA and 2.57% NTO (Figure 3(a)) and the sample treated with 99.04 g/L BTCA and 2.57% NTO (Figure 3(b)) cured under UV-temp method are reported. It can be observed that the major peak of all spectra is anatase (2h = 22.4°), whereas the peak related to rutile phase (2h = 27.5°) could not be observed in XRD spectra (Jung & Park, 1999). Therefore, the coated fabrics with NTO have anatase crystallite phase and can effectively operate under UV irradiation. Scanning electron microscope (SEM) Figure 4(a)–(d) illustrates the SEM images of: NTO powder (a), untreated cotton fabric (b), CA-treated fabric (c), and BTCA-treated fabric (d) (magnification = 3500). Figure 4(b) shows the morphology of
cotton fiber with smooth surface. The morphological changes in the appearance of cotton fibers treated with CA and BTCA in the presence of NTO are shown after padding and UV-temp curing (Figure 4(c) and (d)). These pictures show that, in the same condition or (optimized condition), the surface of the fabric treated with BTCA has a higher number of NTO particles than that of the fabric treated with CA. This may be because higher carboxylic acid groups of BTCA can maintain more particles of NTO. However, these images are proof of the fact that NTO particles were applied on CC fabric by the padding process, but their distribution on fiber surface was not quite even, which has become possible because of the aggregation of some NTO particles. Conclusions The purpose of this study was to improve and optimize of CC cross-linking with polycarboxylic acids using a photocatalyst (NTO) along with a conven-
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Figure 3. XRD patterns of samples 39-CA (a) (99.04 g/L CA, 2.57% NTO, UV-temp) and 39-B (b) (99.04 g/L BTCA, 2.57% NTO, UV-temp).
tional catalyst (SHP) by using statistical models, as polycarboxylic acids CA and BTCA were employed as nonformaldehyde and environment-friendly compounds. Also three different curing methods (UV, high temp, and UV-temp) are applied to compare the crosslinking behavior of cationized cellulose. It can be concluded that at a given polycarboxylic acid concentration, catalyst concentration, and curing method, the DCRA for BTCA is higher than that for CA. Statistical analysis by Design of Expert indicated that the sample treated with 92.00 g/L CA, .84% NTO, and
55.20 g/L SHP and cured with UV-temp shows the optimum DCRA (225.62) with a desirability of .774. The optimum conditions for BTCA with desirability of .778 gave DCRA 248.29 with 92 g/L BTCA, .84% NTO, and 55.20 g/L SHP cured with UV-temp. Polycarboxylic acid compounds of CA and BTCA cause the cross-linking of the inside and surface of the CC, so that they are able to form ionic and ester bonds with large amount of cotton active groups and consequently cause the cross-linking improvement. On the other hand, these compounds are able to react with
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Figure 4. SEM images of the (a) NTO powder, (b) untreated cotton fabric, (c) 92.00 g/L CA, and (d) 92.00 g/L BTCA, treated cotton fabrics in the presence of .84% NTO and UV-temp curing method.
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