Development of multifunctional linen fabric using chitosan film as a template for immobilization of in-situ generated CeO2 nanoparticles

Accepted Manuscript Development of multifunctional linen fabric using chitosan film as a template for immobilization of in-situ generated CeO2 nanoparticles

Rohit Tripathi, Aadesh Narayan, Indrajit Bramhecha, Javed Sheikh PII: DOI: Reference:

S0141-8130(18)33847-9 doi:10.1016/j.ijbiomac.2018.10.067 BIOMAC 10718

To appear in:

International Journal of Biological Macromolecules

Received date: Revised date: Accepted date:

25 July 2018 13 October 2018 14 October 2018

Please cite this article as: Rohit Tripathi, Aadesh Narayan, Indrajit Bramhecha, Javed Sheikh , Development of multifunctional linen fabric using chitosan film as a template for immobilization of in-situ generated CeO2 nanoparticles. Biomac (2018), doi:10.1016/ j.ijbiomac.2018.10.067

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ACCEPTED MANUSCRIPT Development of Multifunctional Linen Fabric using Chitosan film as a template for immobilization of in-situ generated CeO2 Nanoparticles Rohit Tripathi, Aadesh Narayan, Indrajit Bramhecha and Javed Sheikh* Dept. of Textile Technology, Indian Institute of Technology (I.I.T.), Delhi, India

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Abstract

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Linen fabric lacks functional properties which can be imparted using CeO2 nanoparticles;

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however, the efficiency and durability against the repeated washing is always a big limitation. Wash-durable functionalization thus can be achieved by surface modification using chitosan-

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based recipes which can also impart additional functional properties to linen. In the present work, the modification of linen fabric was achieved using a chitosan-based recipe followed by

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in-situ synthesis of CeO2 nanoparticles on chitosan-treated fabrics. The modified fabric was characterised using FTIR, TGA, SEM and EDX techniques and further evaluated towards

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functional properties. The modified linen displayed highly effective antibacterial activity

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against S. aureus and E. coli bacteria. The additional functional properties like wrinkle resistance, UV protection and flame retardancy were also achieved using such dual

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modification. Most of the functional properties were retained in satisfactory level after five subsequent washes. The modified linen thus can be claimed as a suitable candidate for

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functional apparels and technical textiles. Keywords: Linen, Chitosan, CeO2 nanoparticles, Functional properties

*Corresponding Author: Dr. Javed Sheikh, [email protected]

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ACCEPTED MANUSCRIPT 1. Introduction In textile industry, use of nanotechnology is expanding rapidly owing to its characteristic and invaluable nature. There are substantial possibilities for utilization of nanotechnology commercially in textiles sector. Exploring nanotechnology can profitably add multiple-valued properties to textile products and its processing. Functional fabrics with special functions like

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antibacterial, UV protective, flame retardant, anti-odor etc. can be produced using

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nanotechnology [1-10]. Some studies regarding simultaneous coloration and functionalization

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of textiles using nanomaterials are also available in literature [11-12]. Nanomaterials have excellent magnetic, optical, catalytic and electronic properties, owing to this, they are used

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across a wide range of new generation industries and in advanced technologies. Mainly structure, shape, and size decides the properties of nanomaterials [13].

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In order to achieve durability of functional properties on textile materials, various attempts have been made to achieve wash-fast immobilization of nanoparticles on the textile materials.

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Such immobilization can be achieved using a polymer treatment which can react with cellulose

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and also able to hold nanoparticles. Chitosan is a new-age functional biopolymer which is highly basic polysaccharide containing amino group at C-2 position. It was used to modify

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textile substrates for imparting dyeability as well as to functionalize textile substrates [14-21]. Some reports regarding utilization of chitosan and its derivatives and nanoparticles for

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modification of textile substrates are available in literature. There is a reported study of growing Ag-nanoparticles on chitosan modified cotton fabric. This treatment showed durable and appreciable antibacterial properties on cotton fabric [22]. Non-hydrolytic sol-gel process was used to generate in-situ hybrid chitosan-TiO2 photocatalysts by utilizing tetrabutyl titanate, as a precursor, chitosan as a template, and tert-butanol as solvent. The chitosan-TiO2 nanoparticles are found to be potent in regulating the crystallization process and to limit the NPs aggregate formation during the thermal actions and have also showed good photocatalytic

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ACCEPTED MANUSCRIPT activity in visible-light, even in absence of any thermal treatment [23]. Chitosan/ZnO nanoparticles synthesis was optimized at 0.75% concentration of ZnO for formation of nanoparticles at 60oC. Modified cotton fabric demonstrated good antibacterial properties as well as significant improvement in UV protection, which increased with increasing concentration of nanoparticles of ZnO/chitosan [24]. Carboxymetyl chitosan was utilized for

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surface modification of cotton to bind silver nanoparticles generated by in-situ method [25].

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From the advancement in the recent researches, cerium oxide nanoparticles (Ceria NPs) have gained a spot light for their outstanding catalytic activities, which are derivative of speedy and

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required mutation of the oxidation states among Ce4+ and Ce3+. Cerium can effortlessly and radically fine-tune its electronic configuration to fit its instantaneous environs which results in

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the distinctive catalytic, magnetic and electronic properties [26]. The primary application of Ceria NPs was in the field of catalysis and stems from their unique structure and atomic

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properties compared with other materials [27-30]. In the same way, it is highly efficient in

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absorbing UV radiation to protect photosensitive materials, as an anticorrosive coating material of metals [26, 31]. Recently, Ali et al have synthesized copper/chitosan-cotton nanocomposite

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as a catalyst to reduce toxic dyes like Congo red (CR) dye degradation [32]. Cubical CeO2 NPs with an average size of 4nm were prepared using combination of chitosan, cerium nitrate and

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sodium hydroxide [27]. In situ synthesis of cerium oxide nanoparticles on silica sol coated cotton fabric through low-temperature hydrothermal method was carried out to uniformly covered with approximately 60-90 nm cerium oxide particles. The finished fabric showed an excellent UV hindrance property with UPF values over 50. Also, fabric retains the excellent durable up to 30 washes [33].

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ACCEPTED MANUSCRIPT In the current work, CeO2 nanoparticles were immobilised on chitosan treated linen fabric using the in-situ method of synthesis. The efficacy of functional properties offered by the modified linen was evaluated. The durability of the functional properties against washing was also studied. The mechanism of multifunctional modification of linen fabric using chitosan

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formulations and cerium oxide nanoparticles was explored.

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2. MATERIALS

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Linen fabric (epi=45, ppi=41, GSM=241.5) was procured from Jayshree Textiles, Aditya Birla group, Kolkata, West Bengal, India; Cerium (III) Sulphate from Central Drug House (CDH),

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Vardaan House, Daryaganj, New Delhi; Sodium Hypophosphite from Loba chemie and Citric acid from Thermofisher (Fischer scientific). Above material was used as it was supplied

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without any pretreatment.

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3.1. Fabric pretreatment

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3. METHODS

Linen fabric (Sample 1) was treated with a combination of citric acid (w/v 12%), sodium

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hypophosphite (5%) and chitosan (1%). Aqueous solutions of chitosan were prepared by dissolving chitosan using citric acid by stirring at 60oC for 45mins. Sodium hypophosphite

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(SHP) was also added in the aqueous solution before the fabric samples were padded with the prepared solutions. The fabric was padded with 75±1% expression, dried at 100°C for 3 mins and cured at 140°C for 5mins to get chitosan treated fabric (Sample 2). 3.2. In-situ synthesis of Ceria NPs Cerium oxide NPs were adsorbed on the padded linen fabrics by exhaust method. Sample 2 was made to stand in a 1 % (w/v) solution of cerium sulphate (precursor for NPs) for 45mins. The treated fabric was removed and further treated with 0.1N NaOH under continuous 4

ACCEPTED MANUSCRIPT sonication at 50oC for 30 mins. The modified fabric was removed, washed with cold water and dried to get sample 3.

3.3. Characterization and functional properties of the modified linen. The morphology of treated linen fabrics surface was studied using scanning electron

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microscopy (FEI Quanta, USA). To know the elemental composition of treated linen fabrics

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energy dispersive spectroscopy (EDS, attached to the SEM, operating at 20 keV) was used.

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FTIR spectra of fabric samples (n = 3 per group) before and after mineralization were recorded using ATR accessories of Alpha-P spectroscope (Bruker, USA). Fourier self-deconvolution

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(FSD) was used for deconvolution of spectra.

The physical characterization of fabric samples was done by testing different physical

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properties tensile strength (ASTM D-5035) [34], and crease recovery angle using Shirley CR tester with 500gm for 5 min (ASTM-D-1295)[34]at each stage (Sample 1 to Sample 3) for

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comparison between the changes in fabric physical properties before and after treatment.

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The modified linen fabrics were evaluated for antibacterial properties using AATCC-100 test method [35], UV protection factor (UPF) using ANZ standards [36] and flame-retardant

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properties using LOI analysis as per ASTM-D-2863 standard [34].

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4. Results and Discussion

4.1. Predicted Mechanism of Functionalization of Linen The predicted mechanism of functionalization of linen is presented in Figs.1 and 2. In stage 1 of finishing, the base fabric was treated with a mixture of citric acid, chitosan and SHP, wherein the esterification of hydroxyl groups of linen is expected. The film of chitosan citrate thus would get deposited with proper attachment through esterification. In the second stage, the modified linen will absorb Cerium ions, from the precursor solution, because of the presence

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ACCEPTED MANUSCRIPT of some free carboxylic acid groups along with the presence of amino groups of chitosan containing a lone pair of electron. A similar mechanism was reported earlier for the binding of metal ions by cotton fabric containing chitosan [37]. After subsequent treatment with alkali along with sonication, the generated CeO2 nanoparticles got distributed in the film structure

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some free carboxyl and hydroxyl groups of citric acid (Fig. 2).

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and held firmly with the possible attachment with amino and hydroxyl groups of chitosan and

Fig. 1: Mechanism of Ce3+ absorption on Chitosan-treated linen

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Fig. 2: Mechanism of In-situ synthesis and immobilization of CeO2-Nps on chitosan-

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treated fabrics

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4.2.1. ATR-FTIR analysis

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4.2. Characterization of the modified linen

FTIR spectroscopy allows examining the functional groups present on the substrate surface by measuring the vibrational absorption frequency of chemical bonds. It provides the insight into

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functional group identification of nanoparticle and its surrounding. FTIR spectrum of untreated

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(sample 1) and modified linen (sample 3) is presented in Fig 3. The prepared samples show the occurrence of some absorption in the ranges from 400 cm-1 to 4000 cm-1. Broad absorption peaks were detected at 3396, 3209, 1561, and 1351 cm−1.

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Fig. 3: The graph of untreated linen sample (B) with the sample treated with the optimum

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concentration (C) obtained

The first was attributed to the stretching band of a hydroxy group, and the others were for

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asymmetric and symmetric stretching band of the carboxyl group, respectively. The reduction in intensity of hydroxyl band was observed to mark the consumption of OH groups. The small peak

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at 2856cm-1 depicts the presence C-H stretching vibration of aldehyde groups. Small hump at

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3311cm-1 was the N-H stretch peak while the peak between 1400-1600-1 corresponds to N-H bending vibration. C-N bending was showed by the peak at 1171cm-1. The analogous peak rose

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due to the existence of −NH2 group from chitosan and −OH groups due to hydrogen bound hydroxyl ions or due to the molecularly chemisorbed water molecules on CeO2 surface while

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synthesis or due to the cellulosic –OH groups. There is no peak in the rage of 1600s which confirms the modification of C=O bonds environment in citric acid. Further bands around 1171–1000 and 960–850 cm−1 were mostly associated with the presence of lingering organic or the formation of “carbonate-like” species on the ceria surface. A strong band at 717 cm−1 which was due to the shielding of the phonon band of the metal oxide (CeO2) network was also observed [29]. The characteristics peaks at wavenumber 538 cm-1 and other peaks below 900 cm−1 were designated to Ce–O stretching vibrations for nanoparticles. This confirms the immobilization of CeO-Nps on linen fabric. 8

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4.2.2. Thermogravimetric analysis CeO2-Nps treated linen (sample 3) and untreated linen (sample 1) were subjected to thermogravimetric analysis (TGA) to get chemical characteristics of sample with varying temperature (Fig. 4). Below 200°C there was no significant change in thermal plot of both the

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samples, which implies no decomposition of the linen samples. After 200°C, there was

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appreciable change in both the plot of treated as well as controlled sample which represents the

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initiation of decomposition of samples. During chitosan coating, there is acidic environment around linen which may degrade the cellulosic content to some extent. This leads to initial

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higher rate of degradation for the treated sample as compared to that of controlled one. CeO2Nps imparts stability to the linen and reduces the decomposition rate of the treated sample.

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Around 350°C, CeO2-Nps showed their activity and stabilized the decomposition of treated as against controlled sample. Melting point of cerium oxide is about 2400°C [38], it does not

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degrade around the temperature near 800°C. Considering the final remaining weight of treated

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(23.7%) and controlled (15.5%) sample as depicted in thermogram, the presence of cerium

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oxide deposition on the linen fabric was confirmed.

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ACCEPTED MANUSCRIPT Fig.4: Thermograms of unfinished and finished linen 4.2.3. SEM analysis Morphology, porosity, surface chemistry, conformation and topography of samples were characterized by different techniques to gain insight into their potential relevance to the extent of induced mineralization. The SEM photographs of sample 1, 2 and 3 are presented in Fig. 5.

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A comparison between the SEM images of samples 1, 2 and 3 reveals the induction of

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mineralization in the fabrics due to the treatment. However, the main problem that was faced

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during the SEM imaging was that the maximum magnification that could be deployed on the samples was around 8-10KX, above which the samples started burning and developed cracks

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due to the intensity of the electron beam being focused in that area.

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Fig. 5: A) SEM images of the Sample 1 at 5KX B) Sample 2 C) Sample 3

Chitosan pretreated structures (Sample 2) appeared rough due to the presence of pores. The

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company of some small sized, low-diameter particles on surface of both samples showed the presence of interfacial deposition which was spread in a disorderly fashion but convincingly appeared more in some areas. Two distinctive patterns of ceria deposition were visible; elliptically shaped spheres and large aggregates, probably formed by the consequent fusion of nano-particles. Though the magnification being used was 10KX and therefore this cannot be used as measurement of dimensions of CeO2-Nps; however, their presence can be seen clearly in the SEM image of sample 3.

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4.2.4. EDX analysis The data obtained in EDX analysis of the samples is summarized in Table 1which clearly indicates the introduction of CeO2-Nps on the sample 3. After subsequent washing, the overall concentration of the cerium decreased; however, even after 5 cycles, the retention of cerium

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content was quite high, and thus it is safe to assume that the CeO2-Nps have been incorporated

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in the fabrics. Their dimensions, size and properties induced however can’t be directly inferred

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from these results. Even though EDX analysis gives elemental composition of the scanned area on the fabric, especially surface, it can be treated as method for confirming the presence of

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CeO2-Nps rather than the actual elemental analysis of the complete fabric.

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C

O

(wt %)

(wt %)

(wt %) 65.73

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Sample

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Table 1:- Elemental composition of fabric surface using EDX analysis.

32.84

Finished

52.52

24.60

21.50

After 5 wash

28.33

37.96

32.28

0

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Control

4.3. Functional Properties of the modified linen

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The modified linen was evaluated towards the efficacy of the functional properties and the results are presented in Table 2. Table 2: Functional properties of modified linen Sample No.

CRA

LOI

UPF

Bacterial Reduction S. aureus

E. coli

Sample 1

96

18.5

10.4

N

N

Sample 2

209

20

48.18

82.75

84.50

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205

24.5

71.85

99.90

100

Sample 3-After 5 Wash

170

21.5

44.65

78.60

85.80

N-negligible

Crease recovery angle of control sample was found to be 96 which was improved after finishing using chitosan-citric acid and sodium hypophosphite combinations. The fabrics having CRA

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values close to or higher than 200o are considered as wrinkle resistant fabrics; however, the

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values close to 170 can be taken as moderate level of wrinkle resistance. In general, the crease

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recovery angle can be increased by two mechanisms viz. crosslinking of hydroxyl groups of cotton using suitable crosslinking agent and polymer deposition on the surface. In this case,

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chitosan gets dissolved in citric acid as a result of complex formation between carboxyl group of CA and amino groups of CTS. The remaining two carboxyl groups crosslink cotton, under

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thermal treatment, the extent of which can be increased in presence of esterification catalyst like SHP. Chitosan is a film-forming polymers which results in improved crease recovery of

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cotton. The CRA decreased after 5 washes indicating the hydrolysis of some of the ester

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linkages; however, the retention was CRA was moderate. Linen is highly prone to wrinkle formation during washing and the CRA of 170 can be taken as moderate level of wrinkle

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resistance.

Ceria-nanoparticles modified and controlled linen fabrics were evaluated for antimicrobial

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properties, using Staphylococcus aureus (gram-positive) and Escherichia coli (gram-negative) bacteria. Antimicrobial property is mainly due to the presence of chitosan and cerium cations. Amine groups from chitosan bind with negatively charged residues of the cell surface of bacteria and such interaction causes extensive changes in the cell surface and cell permeability, leading to the leakage of intracellular substances. This inhibits the growth of bacteria. Antimicrobial activity of treated samples was assessed for 0.5%, 1% and 1.5% chitosan treated samples for E. coli and S. aureus bacterial strains. Cerium cation also acts similar mechanism

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ACCEPTED MANUSCRIPT to reduce the microbial growth. The synergistic effect of chitosan and cerium cation makes the treatment more efficient leading to bactericidal effect on microbes. There is regular improvement in antimicrobial property of linen fabric found with S. Aureus and E. Coli bacterium but the BCR% is higher for the gram positive bacterium S. aureus than that for gram negative bacterium E. coli. Further, more than 20% loss in BCR% was obtained

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after 5 washes.

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The untreated linen (sample 1) and CeO2-Nps treated linen fabric (sample 3) were tested for

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flammability using LOI testing. The LOI value of the untreated linen fabric was 18.5 which confirms the susceptibility of linen towards burning in normal air. The LOI value of linen fabric

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showed marked increase after subsequent modifications (sample 3). Even though LOI of 24.5 is not suitable to claim the fabric as flame retardant, the increase in LOI from 18.5 to 24.5 was

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substantial. This may be attributed to the presence of nitrogen rich chitosan along with thermal resistant CeO2-Nps. The LOI value showed significant reduction after 5 washes. The process

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showed a great promise to make flame retardant linen; however, it requires further

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optimization.

UV-guarding capacity of the modified linen sample was evaluated. The sample 2 also showed

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improved UV protection (UPF-48.18). The heavy crosslinking occurred with the formation of ester linkages might be a reason behind this. The yellowness imparted after the treatment

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indicates the generation of unsaturated groups (esters) which would be capable of absorbing UV light to some extent. A remarkable reduction in diffusion of UV region rays was detected and transmission was curtailed to almost zero under 350nm wavelength, which shows the linen modified with CeO2-Nps is resistant to UV irradiation than controlled linen fabric. There are probably two causes for this, first is the excitation of CeO2 valence electrons that causes a good UV absorption. The other likely reason is efficient UV scattering of CeO2 nanoparticles on the fabric surface because of the larger refractive index.

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4.2 Tensile strength tests The tensile strength testing of the samples showed a significant reduction in strength after the treatment (Fig. 6). Tensile Strength (N)

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1200

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800 600 400

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Tensile strength (N)

1000

0 Sample 1

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200

Sample 2

Sample 3

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Sample No.

Fig 6: The tensile strength of the Sample 1, Sample 2, and sample 3

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The tensile strength reduced approximately by 40% in case of sample 2 (12% citric, 5% SHP,

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1% chitosan) in comparison to untreated linen sample 1. This might be attributed to the degradation of cellulose in presence of SHP in order to make active sites for grafting of citric acid on linen. The degradation of cellulose in strongly acidic pH under the influence of temperature was evident from the tensile strength. The crosslinking of cellulose using citric acid also prevents the H-bonding with the neighboring cellulose chain also results in strength loss. No significant difference was observed in the tensile strength after generation of CeO2 nanoparticles (sample 3). As nanoparticles are expected to be immobilized on the chitosan and

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ACCEPTED MANUSCRIPT cellulose backbone without reacting with them, the mechanical properties are expected to be unaltered.

CONCLUSION The linen fabric was successfully modified for imparting multiple functionalities like wrinkle

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resistance, UV protection, antibacterial activity and flame retardancy using chitosan, citric acid,

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SHP and CeO2 nanoparticles. The modified linen displayed efficient functional properties most

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of which, except CRA, were retained in the excellent scale after 5 washes. Modification of linen with Ce-NPs develops antimicrobial property against gram-positive bacterium, S. aureus

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and gram-negative bacterium, E. coli. The loss in tensile strength was in acceptable levels. Thus, the finishing of linen fabric with ceria-nanoparticles via intermediate treatment with

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chitosan-based formulations opens up the possiblity of multi-functionality property and such modified products can be used as protective textiles.

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Acknowledgement

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Authors gratefully acknowledge Science and Engineering Research Board (SERB, India) for ECRA funding (project File no. ECR/2017/001041).

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References

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1. H. E. Emam, N. S. El-Hawary, H. B. Ahmed, Green technology for durable finishing of viscose fibers via self-formation of AuNPs, Int. J. Biol. Macromol., 96 (2017), 697705.

2. A.K. Jha, K. Prasad, , Green synthesis and antimicrobial activity of silver nanoparticles onto cotton fabric: An amenable option for textile industries, Adv. Mater. Lett., 7 (1) (2016), 42-46. 3. J.Y. Chen, L. Sun, W.Jiang, V.M. Lynch, Antimicrobial regenerated cellulose/nanosilver fiber without leaching, J. Bioact. Compat. Polym., 30 (1) (2015), 17-33 15

ACCEPTED MANUSCRIPT 4. M. Sheshama, H. Khatri, M. Suthar, S. Basak, W.Ali, , Bulk vs. Nano ZnO: Influence of fire retardant behavior on sisal fibre yarn, Carbohydr. Polym.,175 (2017), 257-264. 5. X.-Z. Sun, D.H. Bremner, N. Wan, X. Wang, , Multifunctional properties of cotton fabrics coated with in situ synthesis of zinc oxide nanoparticles capped with date seed extract, Carbohydr. Polym., 181 (2018), 307-316.

PT

6. M. Rehan, M. E. El-Naggar, H.M. Mashaly, R. Wilken, Nanocomposites based on

RI

chitosan/silver/clay for durable multi-functional properties of cotton fabrics,

SC

Carbohydr. Polym., 182 (2018), 29-41,

7. A. B. Rezaie, M. Montazer, and M. M. Rad, Antibacterial, UV Protective and Ammonia

NU

Sensing Functionalized Polyester Fabric through in situ Synthesis of Cuprous Oxide Nanoparticles, Fibers Polym., 18(7) (2017), 1269-1279.

MA

8. A. Yadav, V. Prasad, A. A. Kathe, S. Raj, D. Yadav, C. Sundaramoorthy, N. Vigneshwaran, Functional finishing in cotton fabrics using zinc oxide nanoparticles,

D

Bull. Mater. Sci., 29 (6) (2006), 641-645.

PT E

9. S. Kathirvelu, L. D’souza, and B. Dhurai, UV protection finishing of textiles using ZnO nanoparticles. Indian J. Fibre Text. Res., 34(2009), 267-273.

CE

10. S. Shahidi, A. Jamali, S. S. Dalal, H. Ghomi, In-situ synthesis of CuO nanoparticles on cotton fabrics using spark discharge method to fabricate antibacterial textile, J. Nat.

AC

Fibers, In-press.

11. M. Rehan, H.M. Mashaly, S. Mowafi, A. Abou El-Kheir, H.E. Emam, Multi-functional textile design using in-situ Ag NPs incorporation into natural fabric matrix, Dyes Pigm., 118 (2015), 9-17. 12. P. Velmurugan, J. Shim, K.-S. Bang, B.-T. Oh, Gold nanoparticles mediated coloring of fabrics and leather for antibacterial activity, J. Photochem. Photobiol., B, 160 (2016), 102-109.

16

ACCEPTED MANUSCRIPT 13. R. Mahmud, and F. Nabi, Application of Nanotechnology in the field of Textile. IOSR Journal of Polymer and Textile Engineering, 4(1) (2017), 2348–181. 14. J. Sheikh, I. Bramhecha, Multifunctional modification of linen fabric using chitosanbased formulations,

Int. J. Biol. Macromol. 118 (2018) , 896-902.

15. A. E. Sunder, G. Nalankilli and N. K. Swamy, Multifunctional finishes on cotton

PT

textiles using combination of chitosan and polycarboxylic acids. Indian J. Fibre Text.

RI

Res., 39(2014), 418-424.

SC

16. M.D. Teli, Javed Sheikh, Parag Bhavsar, Multifunctional finishing of cotton using chitosan extracted from bio-waste, Int. J. Biol. Macromol., 54 (2013), 125-130.

NU

17. A. Haji, , Improved natural dyeing of cotton by plasma treatment and chitosan coating; optimization by response surface methodology. Cellul. Chem. Technol., 51(9-10)

MA

(2017), 975-982.

18. I.F.Cernat, L. Ciobanu, R. Mureşan, D. Abramiuc, T. Stamate, C.V. Denis,

D

S.C.Hanganu, Medical efficiency of antibacterial wound dressings. Ind. Text.

PT E

(Bucharest, Rom.), 66(3)(2015), 131-135. 19. A. Danko, C. Popescu, S. Dunca, A. Mureşan, Improving cotton textile materials

CE

properties by treating with chitosan and metallic salts. Ind. Text. (Bucharest, Rom.), 64(4) (2013), 204-209.

AC

20. A. Haji, S.S. Qavamnia, F.K. Bizhaem, Salt free neutral dyeing of cotton with anionic dyes using plasma and chitosan treatments. Ind. Text. (Bucharest, Rom.), 67(2) (2016), 109-113. 21. A. Haji, M. Khajeh Mehrizi, S. Hashemizad, Plasma and chitosan treatments for improvement of natural dyeing and antibacterial properties of cotton and wool. Vlakna Text., 23(3) (2016), 86-89.

17

ACCEPTED MANUSCRIPT 22. A. Abou-Okeil. Ag nanoparticles growing onto cotton fabric using chitosan as a template. J. Nat. Fibers, 9(2) (2012), 61-72. 23. Z. Hamden, S. Bouattour, A. M. Ferraria, D. P. Ferreira, L. F. Vieira Ferreira, A. M. Botelho do Rego, and S. Boufi, In situ generation of TiO2 nanoparticles using chitosan as a template and their photocatalytic activity, J. Photochem. Photobiol., A, 321(2016).,

PT

211–222.

RI

24. M. M. AbdElhady, Preparation and characterization of chitosan/zinc oxide

SC

nanoparticles for imparting antimicrobial and UV protection to cotton fabric. Int. J. Carbohydr. Chem., 2012. http://dx.doi.org/10.1155/2012/840591.

NU

25. Q. Xu, X. Ke, L. Shen, N. Ge, Y. Zhang, F. Fu, X. Liu, Surface modification by carboxymethy chitosan via pad-dry-cure method for binding Ag NPs onto cotton fabric,

MA

Int. J. Biol. Macromol., 111 (2018), 796-803.

26. F. Zhang, Q. Jin, and S. W. Chan, Ceria nanoparticles: size, size distribution, and

D

shape. J. of appl. Phys., 95(8) (2004), 4319-4326.

PT E

27. A. B. Sifontes, G. Gonzalez, J. L. Ochoa, L. M. Tovar, T. Zoltan, and E. Canizales, Chitosan as template for the synthesis of ceria nanoparticles. Mater. Res. Bull., 46(11)

CE

(2011), 1794-1799.

28. F. Charbgoo, M. B. Ahmad, and M. Darroudi, Cerium oxide nanoparticles: green

AC

synthesis and biological applications, Int. J. Nanomed., 12(2017), 1401-1413. 29. W. Duan, A. Xie, Y. Shen, X. Wang, F. Wang, Y. Zhang, and J. Li, Fabrication of superhydrophobic cotton fabrics with UV protection based on CeO2 particles. Ind. Eng. Chem. Res., 50(8) (2011), 4441-4445. 30. H. Y. Kim, H. M. Lee, and G. Henkelman, CO oxidation mechanism on CeO2supported Au nanoparticles, J. Am. Chem. Soc., 134(3) (2012), 1560-1570.

18

ACCEPTED MANUSCRIPT 31. A. Younis, D. Chu, and S. Li,. Cerium oxide nanostructures and their applications. In Functionalized Nanomaterials. Ed. M. A. Farrukh, InTech, London. (2016), 53-68. 32. N. Ali, T. Kamal, M. Ul-Islam, A. Khan, S. J. Shah, and A. Zada (2018). Chitosancoated cotton cloth supported copper nanoparticles for toxic dye reduction. Int. J. Biol. Macromol., 111, 832-838.

PT

33. P. Bhavsar, In situ synthesis and application of cerium oxide nanoparticles on cotton

SC

Society of Fiber Science and Technology, (2014).

RI

fabric for UV protection and antibacterial properties (p. Vol. 70). Tokyo, Japan: The

34. ASTM standards manual, ASTM International, West Conshohocken, PA 19428-2959,

NU

United States.

35. AATCC Technical Manual (2007), Research Triangle Park, NC, USA.

MA

36. AS/NZS 4399. Sun protective clothing evaluation and classification; 1996. 37. A. Hebeish, K. Elnagar, M. H. Helal, M. S. Ragab, and M. F. Shaaban, UV/O3

D

preirradiated cotton fabric-containing chitosan for effective removal of heavy metals.

PT E

Mater. Sci. Appl., 5(10) (2014)., 698-707. 38. K.Tsukuma, Mechanical properties and thermal stability of CeO/sub 2/ containing

AC

CE

tetragonal zirconia polycrystals. Am. Ceram. Soc. Bull., 65(10) (1986), 1386-1389.

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