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Carbohydrate Polymers 138 (2016) 106–113

Contents lists available at ScienceDirect

Carbohydrate Polymers

j ourna l ho me pa g e: www.elsev ier .com/ locate /carbpol

otton fabric with plasma pretreatment and ZnO/Carboxymethylhitosan composite finishing for durable UV resistance andntibacterial property

hunxia Wanga,b,c,∗, Jingchun Lva, Yu Rend, Qingqing Zhoua, Jiayi Chena, Tian Zhia,henqian Lua,b,c, Dawei Gaoa,b,c, Zhipeng Maa, Limin Jine

College of Textiles and Clothing, Yancheng Institute of Technology, Jiangsu 224051, ChinaCollaborative Innovation Center for Ecological Building Materials and Environmental Protection Equipments, Jiangsu 224051, ChinaKey Laboratory for Advanced Technology in Environmental Protection, Jiangsu 224051, ChinaSchool of Textile and Clothing, Nantong University, Jiangsu 226019, ChinaShanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China

r t i c l e i n f o

rticle history:eceived 31 August 2015eceived in revised form 20 October 2015ccepted 17 November 2015vailable online 19 November 2015

eywords:lasma pretreatmentnO/Carboxymethyl chitosan composite

a b s t r a c t

ZnO/carboxymethyl chitosan (ZnO/CMCS) composite was prepared and confirmed by Fourier transforminfrared spectroscopy (FTIR), X-ray diffraction (XRD), Ultraviolet–visible (UV–vis) spectroscopy, Scan-ning electron microscope (SEM), Transmission electron microscope (TEM). The combination of plasmapretreatment and ZnO/CMCS composite finishing was applied to provide durable UV resistance andantibacterial activity for cotton fabric. Cotton fabric was pretreated by cold oxygen plasma and theZnO/CMCS composite finishing was carried out by pad-dry-cure. Cotton fabric was characterized by SEM,FTIR, UV resistance, antibacterial activity and Thermogravimetry (TG). SEM and FTIR analysis demon-strated the presence of ZnO/CMCS composite on cotton fabric and the increasing loading efficiency of

otton fabricV resistancentibacterial activityurability

ZnO/CMCS composite owing to plasma treatment. UV resistance and antibacterial activity of the finishedcotton fabric were greatly improved, which increased with the increasing concentration of ZnO/CMCScomposite. TG analysis indicated that the combined finishing of cotton fabric with plasma pretreatmentand ZnO/CMCS composite could improve its thermal property. The finished cotton fabric exhibited anexcellent laundering durability in UV resistance and antibacterial activity.

. Introduction

Cotton fiber has a large range of applications due to its superiorroperty, especially widely used for summer textiles and medi-al textiles. With the improvement of people’s living standard, theigher requirements on cotton fiber property have been put for-ard. These fields are increasingly subject to ultraviolet protection

nd antibacterial activity and so on, so that there is a need for mul-ifunctional finishing of cotton fiber (Vigneshwaran, Kumar, Kathe,aradarajan, & Prasad, 2006; Yadav et al., 2006).

Now, the commonly used antibacterial agent is generallyivided into three types: natural agent, organic agent and inorganicgent. Naturally antibacterial agent is environmentally friendly

∗ Corresponding author at: College of Textiles and Clothing, Yancheng Institute ofechnology, Jiangsu 224051, China. Tel.: +86 0515 88298132;ax: +86 0515 88298262.

E-mail address: cxwang@mail.dhu.edu.cn (C. Wang).

ttp://dx.doi.org/10.1016/j.carbpol.2015.11.046144-8617/© 2015 Elsevier Ltd. All rights reserved.

© 2015 Elsevier Ltd. All rights reserved.

and safe to human body. However, most of them influence fab-ric shade due to their poor resistance to washability and havea narrow application range. Organically antibacterial agent hasobvious antibacterial effect and a wide antibacterial range. How-ever, most of them are toxic to humans and cannot be easilydegraded in nature. The antibacterial activity of inorganic agentmainly comes from metals such as silver, zinc, copper and so on.It has some characteristics of high safety, high efficiency, broadspectrum, good chemical stability and heat resistance, weatherresistance and no drug resistance. Thus inorganic antibacterialagent has been increasing people’s attention (El-Shafei, Fouda,Knittel, & Schollmeyer, 2008; Lv, Zhou, Liu, Gao, & Wang, 2014).

Nanotechnology, a high-tech science and technology rapidlydeveloped in the late 1980s, has been widely used in many fieldssuch as raw material, chemical, textile, medicine, traffic, energy

and so on. In recent years, many dyeing and finishing auxil-iaries with special function and new textiles with high effectivefunction have been produced due to the nanotechnology applica-tion in textile industry. With the development of nanotechnology,

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he nano material synthesis by biological molecules or organismsecome an important branch of nanotechnology research becausef mild reaction condition, good controllability of production pro-ess, degradability of reaction products (Kathirvelu, Louis D’Souza,

Dhurai, 2008; Raveendran, Fu, & Wallen, 2003). Compared withrdinary ZnO, nano ZnO, as a new functional material, has somepecial properties and applications in many fields such as light,lectricity, magnetism sensitivity, UV shielding and so on. NanonO, with broad-spectrum bacteriostatic and bactericidal property,hows good antibacterial activity against pathogens including Kleb-iella pneumoniae (K. pneumoniae) and Staphylococcus aureus (S.ureus) and so on. In many countries, nano ZnO has been widelysed as an antimicrobial factor in the manufacturing of hygieneroducts. However, it is difficult for pure nano ZnO to evenly dis-erse and it is easy to agglomerate in solution, which will result inoor finishing effects. (Selvam & Sundrarajan, 2012; Tang, Cheng,a, Pang, & Zhao, 2006; Taubert & Wegner, 2002).Chitosan (CS) has attracted the attention of researchers because

f its availability, biodegradability, biocompatibility, antimicrobialctivity and non-toxicity (Abdel-Halim, Abdel-Mohdy, Al-Deyab, &l-Newehy, 2010; Kim et al., 2008; Ravi Kumar, 2000; Muzzarelli,985). It is a promising polymer matrix and a powerful chelatinggent (Muzzarelli et al., 2001). It can enhance the dispersion andtability of nanoparticles by forming various chemical bonds withransition or heavy metals in composite material (El-Shafei & Abou-keil, 2011). However, the application of CS in textile is limitedue to its solubility only in weak acid (Lim & Hudson, 2004a). Theater-soluble CMCS has been extensively used as drug delivery

arrier, flocculating agent, biomaterial, metal ion chelating agent,extile chemical and so on (Chen & Park, 2003; Lim & Hudson, 2004;

uzzarelli, Tanfani, Emanuelli, & Mariotti, 1982; Sun & Wang,006; Upadhyaya, Singh, Agarwal, & Tewari, 2013; Wang & Wang,008).

There are few research reports on ZnO/CMCS composite fin-shing on cotton fabric. In addition, plasma treatment is annvironmental friendly technique and an effective way of improv-ng surface adhesion without affecting their bulk properties. It waseported that plasma treatment could enhance loading efficiencyf particles on substrate due to the effect of physical etching andhemical modification (Wang et al., 2015; Haji, Barant, & Qavamnia,013; Zheng, Chen, & Qi, 2012). Therefore, the goal of this studyas to develop a combined finishing with plasma pretreatment

nd ZnO/CMCS composite on cotton fabric for durable UV resis-ance and antibacterial property. Cotton fabrics were detected byhe changes in structure and properties before and after finishing.he UV resistance, antibacterial activity and thermal property wereharacterized by Ultraviolet protection factor (UPF), sterilizationate and TG analysis. Surface morphology and chemical composi-ion were analyzed by SEM and FTIR.

. Materials and methods

.1. Materials and chemicals

CS, with the molecular weight of 100,000 and the deacetylationegree of 85%, was provided by Zhejiang Golden-Shell Biochem-

cal Co. Ltd. (China). ZnSO4·7H2O was supplied by Tianjin Kemiuhua Chemical Reagent Co. Ltd. (China). All chemicals were ofnalytic grade and presented by Sinopharm Chemical Reagent Co.td. (China). Cotton fabric was supplied by Wujiang Fuhua Weavingo. Ltd. (Jiangsu, China).

.2. ZnO/CMCS composite preparation

Water-soluble CMCS was prepared from CS as reported in ourrevious research (Lv et al., 2014). CMCS (1 g) was fully dissolved

mers 138 (2016) 106–113 107

in distilled water (167 mL) to prepare CMCS solution with constantstirring. NaOH (1.3 g) was dissolved in distilled water (167 mL) toget NaOH solution. ZnSO4·7H2O (5 g) was added to CMCS solution.After vigorous stirring for 15 min, NaOH solution was added dropwise to the mixture solution of CMCS and ZnSO4 with constantstirring for 20 h at 50 ◦C. Then the resulting solution was decantedand filtered off to obtain ZnO/CMCS powder. It was rinsed 3 times indistilled water to eliminate any impurity and finally dried at 80 ◦Cfor 3 h to convert Zn(OH)2 into ZnO nanoparticle (El-Shafei & Abou-Okeil, 2011; Lv et al., 2014).

2.3. ZnO/CMCS composite characterizations

FTIR spectrum was recorded on a Nexus-670 Fourier TransformInfrared Spectrophotometer (NICOLET, USA) at room temperatureby KBr squashed method. Sample was prepared as a KBr pellet andwas scanned against a blank KBr pellet background. The spectralrange was 400–4000 cm−1.

XRD pattern was carried out using a D8 Advance (Bruker,Germany). The scan range (2�) was 110–168◦ with scanning stepof 0.0001◦ in reflection geometry.

UV–vis spectrum was recorded on a UV-2450 Ultraviolet Spec-trometer (Shimadzu Corporation, Japan). The spectral range was200–600 nm.

SEM and TEM images were taken using a QUANTA 200 scanningelectron microscope (FEI, America) with a VANTANGE 100 energydispersive X-ray (EDX) spectrometer and Tecnai G20 (FEI, America),respectively.

2.4. Plasma treatment

The plasma treatment of cotton fabrics was carried out usingHD-1B low temperature plasma apparatus manufactured byChangzhou Zhongke Changtsi Plasma Processing Apparatus PlasmaTechnology Co., Ltd., (Jiangsu, China). The low temperature plasmawas generated by capacitance coupling glow discharge at lowerpressure than 20 Pa.Cotton fabrics, hung in the cylindrical chamber,were treated by O2 plasma for 2 min at 200 W. The plasma treatedcotton fabrics were immediately placed into a clean plastic bag tominimize potential contamination for ZnO/CMCS finishing (Wanget al., 2015).

2.5. ZnO/CMCS composite finishing

The ZnO/CMCS composite finishing of cotton fabric was carriedout using pad-dry-cure method. ZnO/CMCS composite solutionswith different concentrations of 0.25%, 0.5% and 1.0% were pre-pared. Cotton fabric was immersed in ZnO/CMCS compositesolution for 30 min, padded to pick up 100%, dried at 80 ◦C for3 min and finally cured at 140◦C for 3 min. The cotton fabric with0.25% ZnO/CMCS finishing was designated as ZnO/CMCS-0.25. Thecotton fabrics with plasma pretreatment and ZnO/CMCS com-posite (different concentrations: 0.25%, 0.5% and 1.0%) finishingwere designated as PT-ZnO/CMCS-0.25, PT-ZnO/CMCS-0.5 and PT-ZnO/CMCS-1.0, respectively.

2.6. Cotton fabric characterizations

UPF rating and UV transmittance were measured by a YG(B)912ETextile Ultraviolet Prevention Instrument from Weizhou DarongTextile Instrument Co. Ltd. (Zhejiang, China).

According to AATCC 100-2012, Staphylococcus aureus (S. aureus,Gram-positive bacteria) and Klebsiella pneumoniae (K. pneumoniaegram-negative bacteria) were applied for antibacterial activity test.Sterilizing rate was measured.

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The thermal property test was carried out by a STA449 C Ther-ogravimetric Analyzer (TGA, Germany). The heating rate was

0 ◦C/min under a nitrogen stream from 20 ◦C to 700 ◦C. About0.0 mg of sample was used in each case.

Surface morphology and chemical composition were analyzedy SEM and FTIR.

The laundering durability of the treated cotton fabric was eval-ated according to the AATCC 61(2A)-1996 test method. UPF ratend Sterilizing rate were determined after 10, 20 and 30 washingycles in the presence of a non-ionic detergent.

. Results and discussion

.1. Characterizations of ZnO/CMCS composite

.1.1. FTIR analysisFig. 1 showed the CMCS synthesis, ZnO/CMCS formation and

TIR spectra of CS, CMCS and ZnO/CMCS.The carboxymethylation process of CS for the CMCS synthesis

as illustrated in Fig. 1(A), which was confirmed by FTIR spectrahown in Fig. 1(C).

According to the literature (Vigneshwaran et al., 2006), it waseported that in the aqueous synthesis of ZnO nanoparticles, thenitial precipitate was Zn(OH)2, which by subsequent modificationsroduced ZnO nanoparticles. The possible chemical reaction wasiven as follows:

n(NO3)2·6H2O + 2NaOH → Zn(OH)2 + 2NaNO3 + 6H2O (1)

n(OH)2 + 2H2O → Zn2+ + 2OH− + 2H2O → Zn(OH)42− + 2H+

(2)

ig. 1. Schematic illustrations of (A) CMCS synthesis and (B) ZnO/CMCS formation,nd (C) FTIR spectra of (a) CS, (b) CMCS and (c) ZnO/CMCS.

mers 138 (2016) 106–113

Zn(OH)42− → ZnO + H2O + 2OH− (3)

The ZnO/CMCS formation was illustrated in Fig. 1(B). Thesimultaneous presence of CMCS in the reaction medium quicklyprevented ZnO from agglomerating because of the polymers’ heli-cal form, resulting in the formation of ZnO/CMCS nanocomposites.Subsequent heat treatment at 80 ◦C for 3 h helped the completeconversion of Zn(OH)2 to ZnO.

For CS as shown in Fig. 1(a), the characteristic peaks of3431 cm−1, 2922 cm−1, 1656 cm−1 and 1603 cm−1 were ascribed tothe stretching vibrations of OH/N H, C H, C O (amide I) and thescissoring vibration of N H2 (amide II), respectively (Brugnerottoet al., 2001). In comparison with the FTIR spectrum of CS, CMCSdisplayed the new absorption peaks at 1599 cm−1 and 1412 cm−1

corresponding to COOH as shown in Fig. 1(b) (Chen & Park, 2003).The FTIR spectrum of ZnO/CMCS was similar to that of CMCS andbut the new absorption peaks appeared at 600 cm−1 and 442 cm−1,which were attributed to O Zn O. Compared with the FTIR spec-trum of CMCS, the characteristic bands of OH, C H and COOH werefound the shifts to higher wavenumber of 3416 cm−1, 2928 cm−1

and 1608 cm−1 in ZnO/CMCS spectrum as shown in Fig. 1(c), whichresulted from the formation of hydrogen bonds between ZnO andCMCS (El-Shafei & Abou-Okeil, 2011; Rajendran & Sivalingam,2013).

3.1.2. XRD analysisFig. 2 presented the XRD patterns of CS, CMCS, ZnO and

ZnO/CMCS.As shown in Fig. 2(a) the characteristic peaks of CS appeared

at 10.2◦ and 19.9◦, indicating the higher crystallinity of CS dueto the existence of intramolecular hydrogen bonds (Rajendran &Sivalingam, 2013; Zhang, Du, Yu, & Zhang, 2001). However, asshown in Fig. 2(b), the two strong crystalline peaks practically dis-appeared, demonstrating the lower crystallinity of CMCS becausethe introduction of carboxymethyl groups increased the distancebetween molecular chains and destroyed the crystalline state. TheXRD pattern of ZnO (Fig. 2(c) showed the peaks at 31.9◦, 34.6◦, 36.4◦,47.6◦, 56.7◦, 62.9◦, 66.6◦, 68.0◦ and 69.2◦, which could be assignedto (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2) and

(2 0 1) crystal planes of ZnO with hexagonal wurtzite structure. Thelines well matched the normal value reported by JCPDS (No. 36-1451), respectively (Li, Deng, Deng, Liu, & Xin, 2010; Salehi, Arami,Mahmoodi, Bahrami, & Khorramfar, 2010). As shown in Fig. 2(d),

Fig. 2. XRD patterns of (a) CS, (b) CMCS, (c) ZnO and (d) ZnO/CMCS.

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ZnO/CMCS composite (Popescu, Muresan, & Grigoriu, 2011). There-

Fig. 3. UV–vis spectra of (a) CS, (b) CMCS,(c) ZnO and (d) ZnO/CMCS.

he peak at 2� less than 24◦ may be attributed to the presence ofMCS (Swarthmore, 1972) and the broad peak at 2� from 31◦ to6◦ was related to ZnO crystalline (Swarthmore, 1988). This broad-ning may be ascribed to the presence of Zn in coordination witharboxyl groups in CMCS moieties (El-Shafei & Abou-Okeil, 2011).

.1.3. UV–vis spectroscopy analysisFig. 3 illustrated the UV–vis spectra of ZnO, CS, CMCS, and

nO/CMCS.As shown in Fig. 3(a) and (b), the absorption peaks of CS and

MCS were not evident due to the lack of conjugated double bondsn CS and CMCS molecules. Compared with CS and CMCS, thebsorption bands of ZnO and ZnO/CMCS were observed at about00–310 nm indicating the appearance of ZnO in CMCS, whichroved the growth of ZnO crystals on CMCS). However, it was

ower than that of macrocrystalline ZnO at about 370–380 nm inhat absorption peak would have a blue-shift with the decreasingize of ZnO particle (Selvam & Sundrarajan, 2012). Therefore, ZnO

Fig. 4. SEM images of (a) CMCS and (b) ZnO/CMCS, (c) EDX sp

mers 138 (2016) 106–113 109

particles in ZnO/CMCS would be nanometric, which was congruentwith the XRD analysis.

3.1.4. SEM and TEM observationFig. 4 displayed the SEM images of CMCS and ZnO/CMCS and the

EDX spectrum and TEM image of ZnO/CMCS.It could be seen that some ZnO evenly dispersed in CMCS while

some ZnO agglomerated into patches shown in Fig. 4(b). As shownin Fig. 4(c), the presence of Zn demonstrated the successful prepara-tion of ZnO/CMCS. There was a little S element because of the ZnSO4used for the preparation of ZnO/CMCS composite. As shown inFig. 4(d), the ZnO/CMCS particles were composed of heterogeneousclusters. ZnO (black dots) and CMCS particles were homogeneouslyspherical with the particle size of about 30 nm and 200 nm, respec-tively. CMCS may be a stabilizer or a template of the formation ofZnO particles through the formation of coordination bonds withZn2+ due to the carboxyl groups in CMCS (Raveendran et al., 2003;Taubert & Wegner, 2002).

3.2. Characterizations of cotton fabric

3.2.1. SEM observationFigs. 5 and 6 showed the SEM images of cotton fabrics.The control had a relatively smooth surface shown in Fig. 6(a)

while the plasma treated cotton fiber had a rougher surface withmicro-cavities shown in Fig. 6(f). It could be seen that there wasa very small particles on the surface of ZnO/CMCS-0.25 (Figs. 5(b)and 6(b)), whereas the number of fine particles on the surface ofPT-ZnO/CMCS became larger and larger with the increasing concen-tration of ZnO/CMCS composite (Figs. 5(c–e) and 6(c–e)). This maybe the etching effect of plasma treatment before ZnO/CMCS com-posite finishing (Haji, Rahbar, & Shoushtari, 2015; Martin, Mouret,Davies, & Baley, 2013). The much rougher surface would facili-tate the deposition of much more ZnO/CMCS particles on cottonfabric, which also increased with the increasing concentration of

fore, the most deposition of ZnO/MCS composite on cotton fabricshown in Figs. 5(e) and 6(e) could be easily found on the surface ofPT-ZnO/CMCS-1.0.

ectrum of ZnO/CMCS and TEM image of (d) ZnO/CMCS.

110 C. Wang et al. / Carbohydrate Polymers 138 (2016) 106–113

Fig. 5. SEM images (×100) of (a) control, (b) ZnO/CMCS-0.25, (c) PT-ZnO/CMCS-0.25, (d) PT-ZnO/CMCS-0.5 and (e) PT-ZnO/CMCS-1.0.

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Fig. 6. SEM images (×5000) of (a) control, (b) ZnO/CMCS-0.25, (c) PT-ZnO

.2.2. FTIR analysisFig. 7(A) showed the FTIR spectra of cotton fabrics. The absorp-

ion spectrum of the plasma treated cotton fabric had the similarharacteristic bands to that of the control. Comparing the spec-ra of the control and ZnO/CMCS composite finished cotton fabrics,he new absorption bands were found at 1730 cm–1 and 432 cm–1

orresponding to CMCS and ZnO, respectively. With the plasmaretreatment and as the concentration of ZnO/CMCS increased, theeaks at 1730 cm–1 and 432 cm–1 showed a slight increase in trans-ission. Plasma treatment could introduce some polar groups,hich would facilitated the chemical bonding between ZnO/CMCS

nd cotton fabric (Haji, Semnani Rahbar, & Mousavi Shoushtari,014; Li, Moyo, Ding, Shan, & Qiu, 2013; Wang et al., 2015).

.2.3. UV resistance

Table 1(A) showed the UVA transmittance and UPF of cotton

abrics. The UV transmittance and UPF of the treated samples wereower and higher than that of the control, and also decreasednd increased with the plasma treatment and the increasing

-0.25, (d) PT-ZnO/CMCS-0.5, (e) PT-ZnO/CMCS-1.0 and (f) plasma treated.

concentration of ZnO/CMCS composite in the range studied asshown in Table 1(A). This finding may result from the increasingZnO particles due to the more deposition of ZnO/CMCS on cottonfabric consistent with the SEM observation and FTIR analysis. ZnOabsorbs photons under UV irradiation. The excited electrons jumpfrom the valence band to the conduction band forming the holeswith positive charges. In quite short time of one billionth second,about 90% hole–electron pairs recombine. Therefore, the longerwavelength light is emitted or the energy is released. The energyband of ZnO at room temperature is 3.37 eV and its absorption peakis at about 380 nm, which has good absorption effect on UVA (longwave 320–400 nm and UVB (medium wave 280–320 nm). All thesecontributed to the good UV resistance of the ZnO/CMCS finishedcotton fabric.

3.2.4. Antibacterial activityTable 1(B) showed the results of colony forming units (CFU) after

18 h and sterilization rate of cotton fabrics. It was clearly shown thatthe sterilization rate of all the treated samples was quite higher

C. Wang et al. / Carbohydrate Polymers 138 (2016) 106–113 111

Fig. 7. (A) FTIR spectra and (B) degradation profiles of (a) control, (b) plasma treated, (c) ZnO/CMCS-0.25, (d) PT-ZnO/CMCS-0.25, (e) PT-ZnO/CMCS-0.5 and (f) PT-ZnO/CMCS-1.0.

Table 1Properties of cotton fabrics: (A) UV transmittance and UPF, (B) Colony forming units after 18 h and sterilization rate, and (C) UPF and sterilization rate after different washingcycles.

(A)

Samples UVA (%) UVB (%) UPF

Control 8.08 5.6 16.9ZnO/CMCS-0.25 3.39 2.32 30+PT-ZnO/CMCS-0.25 3.13 2.16 30+PT-ZnO/CMCS-0.5 3.01 2.03 30+PT-ZnO/CMCS-1.0 2.58 1.77 50+

(B)

Samples S. aureus K. pneumoniae

Colony forming units (CFU/cm2) Sterilization rate (%) Colony forming units (CFU/cm2) Sterilization rate (%)

Control 9.8 × 104 – 1.3 × 105 –ZnO/CMCS-0.25 1.6 × 103 98.3 1.0 × 102 99.9PT-ZnO/CMCS-0.25 1.0 × 102 99.9 1.0 × 102 99.9PT-ZnO/CMCS-0.5 1.0 × 102 99.9 1.0 × 102 99.9PT-ZnO/CMCS-1.0 1.0 × 102 99.9 2.0 × 102 99.9

(C)

Samples UPF Sterilization rate (%)

S. aureus K. pneumoniae

10 20 30 10 20 30 10 20 30

ZnO/CMCS-0.25 25.4 20.4 17.2 88.3 40.2 10.5 89.9 42.5 18.8PT-ZnO/CMCS-0.25 30+ 30+ 30+ 98.8 98.0 96.8 99.9 99.4 98.6

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PT-ZnO/CMCS-1.0 50+ 50+ 50+

han that of the control. ZnO plays a bacterial effect on the fin-shed cotton fabric. Free electrons (e−) are generated and the holesh+) with positive charges are left when ZnO is exposed to sun lightspecially to UV radiation. The oxygen can be activated by the holesnto active oxygen [O], which can oxidize various microorganisms.n addition, CMCS is a water-soluble CS derivative. The unsubsti-uted amino groups are positive in acid condition and can combineith molecular groups with negative charges on the bacterial cell

urface. CMCS attaches to the bacterial surface to prevent the nutri-nt substance from transporting to the cells. Therefore, CMCS alsoonduces to the good antibacterial activity of the finished cottonabric.

99.3 98.6 99.9 99.9 99.299.8 99.2 99.9 99.9 99.9

ZnO was prepared in CMCS solution to prepare ZnO/CMCS com-posite, which imultaneously has good characteristics of ZnO andCMCS. During the formation process of nano ZnO, CMCS can beadsorbed on the surface of zinc ions (Zn2+) to form complexes. Zn2+

is reduced into Zn by NH2, OH and COOH in CMCS molecules.At the same time CMCS itself is oxidized, which plays a stabilizingeffect on ZnO particles. In aqueous solution the intermolecular andintramolecular hydrogen bonds lend to the formation of indepen-

dent space effect on the molecular level, which provides a goodtemplate for the growth of ZnO nanoparticles. CMCS in the manu-facture of ZnO particles are simultaneously used as stabilizers andreducing agents.

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.2.5. Thermal propertyFig. 7(B) presented the degradation profiles of cotton fabrics. It

as obvious that all TG curves exhibited two stages of weight losst 90∼100◦C with a weight loss of 8% and at 380–400 ◦C with aeight loss 80–90%, which was probably due to the evaporation of

he absorbed water and thermal degradation of the polymers. Theotal weight loss of plasma treated cotton fabric was a bit higherhan that of the control while the total weight loss of ZnO/CMCSomposite finished cotton fabric was lower than that of the control.

Compared with the control, the thermal stability of plasmareated cotton fabric slightly decreased due to the plasma etch-ng of fiber surface. It also could be considered that there was nobvious effect of plasma treatment on thermal property of cottonabric because the plasma treatment did not affect bulk propertyf substrate (Wang, Du, & Qiu, 2012; Zhou et al., 2013). However,he thermal stability of ZnO/CMCS composite finished cotton fabricas improved. The plasma treatment and the higher concentra-

ion of ZnO/CMCS composite had a positive effect on the thermaltability of the finished cotton fabric owing to the strong interac-ions between cotton fabric and much more ZnO/CMCS particles,hich could be explained by SEM and FTIR analysis results (Wang

t al., 2015). In general, the finished cotton fabric exhibited betterhermal stability than the control, especially the PT-ZnO/CMCS-1.0.

.2.6. Laundering durabilityTable 1(C) showed the UPF and sterilization rate of the fin-

shed cotton fabrics after 10, 20 and 30 washing cycles. Withhe increasing washing cycles, UPF and sterilization rate of thenO/CMCS-0.25 greatly decreased while there were no significanthanges in UPF and sterilization rate before and after washingor the PT-ZnO/CMCS-0.25, PT-ZnO/CMCS-0.5 and PT-ZnO/CMCS-.0, indicating the excellent laundering durability of the cottonabric with the plasma pretreatment and ZnO/CMCS composite fin-shing. This may be attributed to the higher loading efficiency ofnO/CMCS and the stronger interaction between ZnO/CMCS andlasma treated cotton fabric.

. Conclusions

A novel method was developed to obtain the cotton fabricith durable UV resistance and antibacterial activity through

ombining plasma pretreatment and ZnO/CMCS composite fin-shing. ZnO/CMCS composite was prepared, characterized andeposited on the plasma treated cotton fabric. There was a sig-ificant improvement of UV resistance and antibacterial activity ofhe finished cotton fabric. Plasma pretreatment greatly facilitatedhe loading efficiency of ZnO/CMCS. Even after 30 washing cycles,he improved properties of the cotton fabrics with plasma pre-reatment and ZnO/CMCS finishing remained almost unchanged,howing excellent laundering durability. It was worth to men-ioning that the findings in this research supported the potentialroduction of new environmentally friendly textiles. Thus this newnd facile method may bring a promising and green strategy toroduce series of durably multifunctional textiles.

cknowledgments

The project was supported by National Natural Science Founda-ion of China (No. 11305138), Production, Education & Researchooperative Innovation Fund Project of Jiangsu Province (Nos.Y2014108-07, BY2015057-08, BY2015057-18), National Natu-

al Science Funds of Jiangsu (No. BK20140431). The project waslso supported by the joint research fund between Collaborativennovation Center for Ecological Building Materials and Environ-

ental Protection Equipments and Key Laboratory for Advanced

mers 138 (2016) 106–113

Technology in Environmental Protection of Jiangsu Province (No.GX2015205). The first author acknowledged the financial supportfrom Overseas Training for University Outstanding Young Teachersand Principals of Jiangsu Province.

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