NiOx Nanoflower Modified Cotton Fabric for UV Filter and Gas

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NiOx Nanoflower Modified Cotton Fabric for UV Filter and Gas Sensing Applications Dinesh Kumar Subbiah, Jayanth Babu Karanam, Apurba Das, and John Bosco Balaguru Rayappan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b04682 • Publication Date (Web): 14 May 2019 Downloaded from http://pubs.acs.org on May 14, 2019

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ACS Applied Materials & Interfaces

NiOx Nanoflower Modified Cotton Fabric for UV Filter and Gas Sensing Applications

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1Dinesh

Kumar Subbiah, 1K. Jayanth Babu, 2Apurba Das and 1John Bosco Balaguru Rayappan*

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1Centre

for Nanotechnology & Advanced Biomaterials (CeNTAB) and

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School of Electrical & Electronics Engineering (SEEE),

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SASTRA Deemed to be University, Thanjavur 613 401, India

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2Depatment

of Textile Technology, Indian Institute of Technology Delhi, New Delhi – 110 016 [email protected]

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* Corresponding author

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Prof. John Bosco Balaguru Rayappan, Ph.D.

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Centre for Nanotechnology & Advanced Biomaterials (CeNTAB) &

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School of Electrical & Electronics Engineering

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SASTRA Deemed to be University

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Thanjavur – 613 401

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India

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Phone: +91 4362 264 101; Ext: 2255

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Fax: +91 4362 264120

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E-mail: [email protected] 1 ACS Paragon Plus Environment

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Abstract

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Integration of multifunctional nanomaterials with textiles could be a significant value addition to the bright

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future of the growing technology “Technical Textiles”. Development of textiles with anti-electromagnetic

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radiation and in particular anti-ultraviolet features could be one of the best solutions to the ozone depletion

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induced ultraviolet pollution of the environment, which is a major concern in the context of surging skin cancer

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cases. In this background, multifunctional nanoflower structured partially hydroxide nickel oxide (NiOx) was

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grown on cotton fabric using chemical bath deposition technique for the development of UV filter and flexible

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gas/chemical sensor. X-ray diffraction patterns of bare and NiOx modified cotton fabrics confirmed the micro

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and poly-crystalline nature respectively. Field emission scanning electron microscopic images revealed the

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growth of 3D green button chrysanthemum flower-like morphology on the surface of cotton fabric. In-

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addition, X-ray photoelectron spectra revealed the presence of Ni, carbon, oxygen elements in the NiOx

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modified cotton cellulose. The increase in hydrophobic nature of surface treated fabric was observed using

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Goniometer. Differential scanning calorimeter trace for bare and surface modified cotton fabrics exhibited an

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endothermic behavior at the characteristic onset temperature. The results of thermogravimetric analysis

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revealed the enhanced thermal stability of up to 800ºC for the surface treated fabric compared to bare cotton.

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Further, Ultraviolet Protection Factor (UPF) of the NiOx nanoflower modified cotton fabric was measured

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using an in-vitro method following the AATCC 183:2004 standard using UV transmittance analyzer. The

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enhanced absorbance of ultraviolet rays at 388 nm resulted in the UPF of 2000. The chemical/gas sensing

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features of the surface modified textile samples were investigated using the home-made gas testing chamber.

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NiOx modified fabric showed a selective response of 12431 towards trimethylamine at room temperature.

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Keywords: Technical textiles, NiOx Nanostructures, UV filter, Gas sensor

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1. Introduction

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In the last few decades, researchers and scientists have focused on the reasons leading to depletion of ozone

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layer, resultant elevation of ultraviolet radiation (UVR) and its threat. UV spectrum lies between 290 and 400

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nm and it has a total incident of 8%1 on the earth’s surface. Even though, UVR has less proportion compared

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to visible and IR radiation, its higher energy compared with other radiations2 is a major concern. Excessive

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exposure to UVR can cause several adverse effects such as eye damage, skin cancer3, suppression of immune

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system4, sunburn5, tanning6, genetic damage to cells7 and aging of the skin3. Centers for Disease Control and

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Prevention has predicted a steep increase in the number of skin cancer cases to 1.9 million by 20208. As a

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consequence, governments9 and researchers have started exploring the development of technical textiles to

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protect UVR induced skin cancer cases.

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On the other hand, detection of toxic gases and volatile organic compounds (VOCs) in the working ambient

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is a concern in the context of growing industrial sectors. Especially, emission of VOCs from industries10 like

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paint11 have serious implications on the environment12. For this instance, Trimethylamine (TMA), which is a

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short-chain tertiary aliphatic amine, an air pollutant emitted from chemical industries, fishery industries and

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exhaust from vehicles13,14 need to be monitored and controlled. Inhalation of TMA leads to neuro and heart

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diseases15,16,17.

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In this context, development of wearable suits by modifying the surface of textiles with nanomaterials has

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gained a significant momentum. For these kinds of modifications, suitable fabrics have been identified based

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on the unique factors such as fiber structure, type of fabric, configuration of warp and weft of thread18–20. In

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particular, nanostructured inorganic materials have been used for the manufacturing of multifunctional fabrics

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due to their tunable electrical, mechanical, thermal, chemical, optoelectronic and magnetic properties21–26.

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Further, adding various functionalities to the fabrics by the process of surface modification have enabled the

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fabrication of smart textiles for UV-blocking27, self-cleaning28, gas sensing29, water repellent30, anti-

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microbial31, flame-retardant32 applications. 3 ACS Paragon Plus Environment

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Nanostructured metal oxide materials like ZnO33, WO334, TiO235, NiO33 have been used for fabricating functional textiles for UV blocking and gas sensing applications. Mohamed Rehan et al.,36 developed in-situ incorporated ZnO and Ag nanoparticles on cellulose for enhancing UV blocking characteristics. The developed fiber exhibited an UPF of 442. Ibrahim et al.,37 prepared multifunctional cotton fabrics modified with ZnO, ZrO and TiO2 nanoparticles using padding technique to study flame retardant, antibacterial and UV blocking functions. TiO2 modified fabrics showed UV blocking factor of 101. Wang et al.,27 embedded dumbbell shaped ZnO on cotton fabric via dip-pad-cure method and revealed that the curing temperature (170℃) plays an important role in-turn better UPF of 786.7. TiO2 incorporated cotton fabrics employing ultrasonic acoustic method exhibited self-cleaning and anti-microbial properties with a UPF of 63.13. Jiang et al.,38 deposited aluminum-doped ZnO (AZO) on polyester fabric using magnetron sputtering and also evaluated UPF (362), water repellency and infrared emissivity with respect to the thickness of modified fabrics. Tungsten oxide modified polyester fabrics prepared using two-roll padding technique achieved a UPF of 108.1 in the UVB region39. Our group has recently developed nanostructured ZnO modified cotton fabrics using sol-gel and seed layer enhanced sol-gel technique for UV filter and gas sensing applications. This fabric showed a UPF of 378 with a selective detection of acetaldehyde vapour at room temperature29. In similar line, another wide bandgap metal oxide material namely NiO/NiOx with high electrocatalytic activity has been considered for the fabrication of multifunctional cotton fabrics. NiOx has been considered as a UV blocking candidate due to its wide bandgap40, large refractive index33, tunable catalytic41 and environment friendly features42. Interestingly the four different phases of NiOx namely α-Ni(OH)2, β-NiOOH, β-Ni(OH)2 and γNiOOH have motivated us to modify the cotton fabric to enhance the UV protection capability employing chemical bath technique. Since, metal hydroxide is one of the promising candidates for gas sensing applications43 and in particular 3D flower-like nanostructures have been an interesting candidate for sensing applications because of its enhanced surface area, different energy levels, enormous number of interior contact sites, multiple scattering points or 4 ACS Paragon Plus Environment

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junctions44 and tunable transport properties suitable for variety of applications involving surface phenomena45, the sensing characteristics of 3D green button chrysanthemum flower-like NiOx modified cotton fabric were investigated and reported.

2. Experimental section 2.1 Materials A white colored cotton cellulose fabric (warp and weft count of 40x40 picks per inch) was brought from Department of Textile Technology Delhi, Indian Institute of Technology, New Delhi. Sodium hydroxide (NaOH), nickel (II) sulfate hexahydrate (NiSO4.6H2O), potassium persulfate (K2S2O8) were procured from Alfa-Aesar, USA. Ammonium hydroxide solution (30-33% of NH3 in H2O) was purchased from Sigma Aldrich, USA.

2.2 Synthesis of NiOx flowers on cotton fabric 2.2.1 Pretreatment of cotton fabric Mercerisation technique46 was adopted to remove the impurities and additives such as fats, waxes, pectin, proteins, coloring, moistures and mineral from textile surface. Pretreatment promotes the oxidation / reduction rate of metal oxide compounds and increase the absorbance rate on the surface of cotton substrates. 1 M of sodium hydroxide pellets were dissolved in 200 mL of deionized water and maintained at 90°C. Cotton fabric was cut in to samples of 20 cm x 20 cm size and treated with preheated NaOH solution. Then the NaOH treated samples were washed thoroughly with doubly-deionized water and dried at 120°C for 2 h in a hot air oven prior to deposition.

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2.2.2 Chemical bath deposition of NiOx on pretreated cotton fabric 150 mL of 0.5 M nickel sulfate hexahydrate and 0.09 M potassium persulfate were mixed at room temperature. 11.24 mL of ammonium hydroxide solution (30-35%) was added to the prepared precursor solution under vigorous stirring condition. As the end of reaction process, the colour of the solution was changed from light green to dark blue and solution became viscous47. This could be due to the replacement of ammonia with the coordinated water molecules in the precursor solution48. The treated cotton cellulose samples were dipped into the prepared precursor solution. The dipped cotton fabric was kept undisturbed for 96 h and then it was dried at 80±6°C for 1 h using hot air oven. Then the dried samples were washed several times with deionized water and dried at room temperature for further analysis.

2.3 Methods XRD patterns were recorded in the diffraction angle ranging from 5° to 80° on a D8 Focus X-ray Diffractometer, Bruker, Germany with Cu Kα radiation. The crystallite size of NiOx modified fabric was estimated using the Debye-Scherrer formula as given in Eq. 1, 𝐷 = 𝑘𝜆(𝛽𝑐𝑜𝑠ϴ) ―1

(1)

where, λ represents the wavelength (λ = 1.5406 Å) of the incident X-ray, k is the shape factor constant (0.89), βℎ𝑘𝑙 represents the full width at half- maximum of the diffraction peak, and θ denotes the diffraction angle. Field Emission Scanning Electron Microscope (JSM6701F, JEOL, Japan) was used to observe the morphological features of unmodified and modified fabrics. Fourier Transform Infra-red (FTIR) (Alpha-T, Bruker, Germany) spectrometer was used to examine the functional groups of the bare and surface modified samples in the wavenumber range of 400-4000 cm-1. Thermogravimetric analyzer (SDT Q600, TA Instruments, USA) was used under the nitrogen atmosphere in the temperature range of 30 and 800°C at a heat flow rate of 10°C min-1 for observing the thermal stability of the modified samples. Differential Scanning Calorimeter (DSC 214 Polyma, NETZSCH, USA) was used in the temperature range of 298 to 673 K at a 6 ACS Paragon Plus Environment

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heating rate of 10 K min-1 for studying the exothermic or endothermic behaviour of the surface modified textile samples. The percentage change in latent heat of fusion was calculated using the Eq. 2, % 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑓𝑢𝑠𝑖𝑜𝑛 =

[∆𝐻𝑁𝑖𝑂𝑥 𝑚𝑜𝑑𝑖𝑓𝑖𝑒𝑑 𝑓𝑎𝑏𝑟𝑖𝑐 ― ∆𝐻𝐶𝑜𝑛𝑡𝑟𝑜𝑙𝑙𝑒𝑑 𝑓𝑎𝑏𝑟𝑖𝑐] [∆𝐻𝐶𝑜𝑛𝑡𝑟𝑜𝑙𝑙𝑒𝑑 𝑓𝑎𝑏𝑟𝑖𝑐]

(2)

where, ∆Htreated cotton fabric and ∆Hcontrolled fabric are the latent heat of fusion of treated and controlled cotton samples respectively. Surface area and porosity analyzer (ASAP 2020, Micrometrics, USA) was used to measure the adsorption isotherms and specific surface area of bare and NiOx modified fabrics. Stiffness analyzer (WIRA Instruments, UK) was used to measure the stiffness of the bare and NiOx modified fabrics. Analytical balance instrument (Amkette Analysis Ltd, India) under ASTM D3776 M-Option 3:2017 was used to measure the weight of the bare and NiOx cotton cellulose. Static water contact angle measurement was carried out on standard goniometer equipment integrated with high-resolution camera and imaging software (Model 250, Rame-Hart Instruments, USA) using 30 µL distilled water droplet. X-ray photoelectron spectrometer (Model K-Alpha, Thermo Scientific, USA) was utilized to analyze the surface of the modified fabric. UV transmittance analyzer (UV2000F, Labsphere Inc., USA) under AATCC 183:2010 standard was used to measure the Ultraviolet Protection Factor (UPF) of the modified fabrics in the wavelength range of 280-410 nm. The computerized formula for the calculation of UPF value is given as follows (Eq. 3,4): 𝑈𝑃𝐹 =

𝑛𝑚 Σ400 280 𝑛𝑚 𝐸𝜆𝑆𝜆Δ𝜆

(3)

𝑛𝑚 Σ400 280 𝑛𝑚 𝐸𝜆𝑆𝜆T𝜆Δ𝜆 𝜆

𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑈𝑉 𝑡𝑟𝑎𝑛𝑠𝑚𝑖𝑠𝑠𝑖𝑜𝑛 =

∑𝜆2𝑇(𝜆) 1

(𝜆2 ― 𝜆1)

(4)

where, 𝐸𝜆 denotes to the relative erythemal spectral effectiveness, 𝑆𝜆 relates the solar spectral irradiance, 𝛥𝜆is the measured wavelength interval (280 nm ≤ λ ≤ 400 nm), 𝑇𝜆 denotes the average spectral transmittance and λ is the wavelength of radiation. Room temperature chemical/gas sensing performance of the modified fabrics was investigated using a homemade gas sensing unit integrated with high resistance electrometer (Keithley


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6517B, USA)49. Sensing response of the nanostructured modified cotton fabric can be calculated by using Eq. 5, 𝑅𝑎

𝑆 = 𝑅𝑔

(𝑖𝑓 𝑅𝑎 ≫ 𝑅𝑔)

(5)

where, Ra and Rg is the resistance of the sensing material in an ambient air atmosphere and analyte atmosphere respectively.

3. Results and discussion 3.1 Physical characteristics

Fig. 1. Photographs of (a) bare and (b) NiOx modified cotton fabrics.

The photographs of bare (White Color) and NiOx modified (Dark Blue Color) cotton fabrics are shown in Fig. 1. The weight of bare and modified fabrics was measured using the standard test method (ASTM D3776 M-Option 3:2017 standard). The weight of NiOx modified fabric (10.02 (oz/yd2)) was increased by 1.77 oz/yd2 with reference to the bare cotton sample (8.25 oz/yd2). This trend is well within the allowed standard of 2.5 to 13.8 (oz/yd2)50. Bending modulus of the cotton fabric was estimated by the cantilever method using stiffness analyzer (WIRA Instruments, UK). Stiffness of the surface modified cotton fabric was increased to 37.5 mm with reference to 32.5 mm for the bare sample.


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3.2 Crystal phase

Fig. 2. XRD patterns of (a) bare and (b) NiOx modified cotton fabrics.

XRD patterns of bare and NiOx grown cotton fabric samples are shown in Fig. 2. The bare cotton fabric exhibited microcrystalline cellulose structure (Fig. 2(a)) with diffraction peaks corresponding to (110), (110), (200) and (004) planes at 2θ = 14.5°, 16.1°, 22.2° and 33.6° respectively. The observed microcrystalline cellulose structure of bare cotton fabric is in good agreement with the standard JCPDS card no. [03-0226]51. The strong crystalline peak at 2θ = 22.2º denotes the presence of intermolecular hydrogen bonding52. The occurrence of crystal plane (004) could be attributed to the characteristic signatures of microcrystalline cellulose, which is in agreement with the results observed by Wang et al53. Fig. 2(b) shows the XRD pattern of NiOx modified fabric with diffraction planes of (001), (120), (002), (031), (230), (004) and (300) at 2θ= 18.9°, 21.1°, 23.4°, 36.8°, 40.6°, 47.8°, 59.70° respectively. The observed XRD pattern is in good aggreement with the standard JCPDS card no. [14-0117], [40-1179], [22-0444] corresponding to hexagonal, orthorhombic and hexagonal cubic structure of Ni(OH)2, α-3Ni(OH)2.2H2O and Ni2O3H respectively54. The presence of (200) and (004) planes in the NiOx modified fabric (Fig. 2(b)) confirmed the deposition of Ni2O3H on microcrystalline cotton cellulose. Though polycrystalline natured Ni2O3H structure was observed from Fig. 2(b), the crystallinity was observed to be very less in comparison to the bare cotton fabric. This could be due 9 ACS Paragon Plus Environment

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to the increased distance between the molecular chains (O-H) and damaged crystallite sites of Ni-O metal complexes influenced by interfacial gradient forces acting between the metal oxide matrix and the surface of cotton23. The formation of Ni2O3H phase could be due to the role of oxidization agent as it partially hydrolyzed nickel oxide (NiOx) for catalytic process55. The diffraction peak at 2θ = 6.3° might be due to the inherent presence of montmorillonite (MMT)56,57 in the cotton cellulose and the same has been suppressed after the modification of cotton surface with NiOx. Major peak found at 22.2° with an increased intensity and decreased fullwidth half maximum might be due to the increase in crystallite size with secondary wall cellulose. Absence of change in the crystallinity of (002) plane after hydrolysis revealed the presence of active amorphous region in cotton cellulose58. XRD pattern showed that nanoparticles are localized on the inward construction of the absorbent fabric. The observed peak shift after the modification of nanoparticles might be due to the interfacial forces playing between the nickel nanoparticles and cotton cellulose23. The average crystallite size of NiOx modified cotton fabric from (300) plane was 40 nm.

3.3 Morphological analysis and growth mechanism (a)

(b)

Fig. 3. FE-SEM images of (a) bare and (b) NiOx modified cotton fabrics. 10 ACS Paragon Plus Environment

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FE-SEM images of bare and NiOx modified cotton fabrics are shown in Fig. 3(a & b). The bare cotton fabrics showed the ordered arrangement of cellulose structure whereas NiOx modified cotton fabrics showed the growth of 3D green button chrysanthemum flower like structure on the cotton fabric. The formation of this structure on the cotton fibers mainly depends on the concentration of precursor solution with suitable oxidizing agents and growth duration. Growth of NiOx on the cotton fabric could be realized through the following mechanism: (i)

Potassium persulfate (K2S2O8) in the precursor acts as a strong oxidizing /structure directing agent and it generates more active sites on the surface of the cotton fabric. S2O82- ions from K2S2O8 react with Ni(OH)2 and gets oxidized. Composition of Ni decides the transformation of Ni(H2O)62+ to Ni(NH3)62+ as it depends on the concentration of ammonium hydroxide in the precursor solution. As the pretreated cotton fabric was dipped in to the precursor solution, Ni2+ ions from precursor solution get bonded with 𝑂𝐻 ― ions and lead to the formation of homogeneous Ni(OH)2. As an initial growth stage, the Ni nucleation sites from Ni(OH)2 get uniformly distributed over the surface of cotton fabrics.

(ii)

As a next stage, it was reduced to NiOOH as a sequence of color indication observed during the CBD process. As the Ni2+ nucleation sites grew further, the degree of supersaturation increases as a function of growth duration. This results in the formation of nickel oxy-hydroxide or nickel oxide hydroxide or nickel hydroxide. The possible formation reactions are given in equations (6–10) as reported by S.-Y. Han et al.,55

𝑁𝑖𝑆𝑂4 + 𝑥𝐾2𝑆2𝑂8― + 2(1 + 𝑥)𝑂𝐻 ― →𝑁𝑖𝑂1 + 𝑥 + 𝑥𝐾2𝑆𝑂4 + (1 + 𝑥)𝑆𝑂24 ― + (1 + 𝑥)𝐻2𝑂 𝑁𝑖𝑂1 + 𝑥 + 2𝑥/3𝑁𝐻3→𝑁𝑖𝑂 + 𝑥/3𝑁2 + 𝐻2𝑂

(6) (7)

𝑁𝑖2 + + 2𝑂𝐻 ― →𝑁𝑖(𝑂𝐻)2

(8)

𝑁𝑖(𝑂𝐻)2 + 𝑆2𝑂8― →2𝑁𝑖𝑂𝑂𝐻 + 2𝑆𝑂24 ― + 2𝐻 +

(9)

(or) 11 ACS Paragon Plus Environment


(10)

𝑁𝑖𝑂𝑂𝐻 + 𝐻2𝑂→𝑁𝑖(𝑂𝐻)2 +𝑂𝐻 (iii)

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Further the negatively charged cotton cellulose surface enhanced the binding nature of Ni2+ ions inturn facilitates the growth of 3D green button chrysanthemum flower like structure under drying temperature of 353 K (Fig. 4). The petals of flower were grown on the surface of each thread spreading in all the directions59.

Fig. 4. Schematic representation for the growth process of the NiOx on cotton cellulose.

At the beginning of growth process, primary source of Ni2+ ions dissolved in potassium persulfate was immediately hydrolyzed. During the interaction with ammonium hydroxide, the generated Ni(OH)2 nuclei having electrostatic driving force and minimized surface energy of cotton cellulose promoted the growth of nanosheets60,61. It is a well-known fact that the higher saturation level benefits the formation and enhancement of nucleation sites, while lower one facilitates the crystal growth. When the reaction time was extended gradually, further nucleation and assembly process enhanced the growth of nanosheets and lead to the formation of nanostructured NiOx 3D green button chrysanthemum flower on cotton fabric. This might be due the gradual self-orientation of nanosheets with lower surface energy. Specific surface area of bare and NiOx modified cotton cellulose was determined from N2 adsorption using Brunauer-Emett-Teller (BET) method (Fig. 5). NiOx modified cotton cellulose showed higher adsorption value of 8.1 cm3/g than bare cotton cellulose (2.6 cm3/g). Subsequently, the specific surface area of the bare and NiOx modified cotton cellulose found to be 2.64 and 3.46 m2/g respectively. The uniform NiOx nanoflower on cotton cellulose resulted in the 12 ACS Paragon Plus Environment

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increased surface area62. Further, to test the possibility of post processing of NiOx modified fabrics with dying, the surface modified samples were dyed with methylene blue and confirmed the same with functional analysis

using FTIR spectrometer (Fig. S1) and presented in supplementary information.

Fig. 5. N2 adsorption-

desorption isotherm of

(a) bare and (b) NiOx

modified cotton fabrics.

3.4

Contact

angle

measurement



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Fig. 6. Contact angle measurement of NiOx modified cotton cellulose.

To determine the wettability nature of bare and NiOx modified cotton fabrics, water contact angle measurement was carried out and the observed result for NiOx modified cloth is shown in Fig. 6. The water contact angle (CA) on NiOx modified cotton fabric was found to be 85.6°, which confirmed the increase in hydrophobic nature with reference to hydrophilic bare cotton fabric. The 3D green button chrysanthemum flower like structure of NiOx modified cotton fabric promotes the water repelling affinity at the edges of cellulose due to the influence of surface roughness63,64. Air plays a vital role in between the solid/liquid interface, which results in tramping of air occurred in-between the NiOx modified cotton fabric and water droplet65.

3.5 Thermogravimetric analysis

Fig. 7. Thermogravimetric analysis of (a) bare and (b) NiOx modified cotton fabrics. 14 ACS Paragon Plus Environment

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Thermogravimetric analysis (TGA) of the bare and modified cotton fabrics are shown in Fig. 7. This analysis was used to estimate the weight loss rate and thermal stability of the cotton fabrics. TGA of the bare cotton cellulose (Fig. 7(a)) comprises of three stages with respect to temperature. In the first stage, (below 275°C) there was an initial weight loss, which could be attributed to the dehydration of the cotton cellulose. Significant weight loss in the second stage (275 to 400°C) might be due to the degradation of crystalline region of bare cotton cellulose (char pyrolysis). With further increase in temperature, the bare cotton entered into the third stage namely pyrolysis region, where the complete sample was burnt. TGA analysis of NiOx modified fabric (Fig. 7(b)) comprises of two stages; first stage (20-275°C) revealed the evaporation of half of water molecules in the crystalline region66 and in the second stage (275-700°C), a sudden drop of weight loss was observed, which might be attributed to the removal of remaining water molecules and thermo oxidative decomposition of NiOx. After 700°C and up to 800°C, the weight percentage was started decreasing slowly and indicated the removal of the hydroxyl group present in cotton cellulose without any additional phases67. Thus, NiOx modified cotton fabric exhibited better thermal stability than bare cotton cellulose. Thermal degradation of NiOx modified fabric process can be represented by Eqn. (11), 𝑁𝑖2 + + 2𝑂𝐻 ―

𝑅𝑇

(11)

𝑁𝑖(𝑂𝐻)2

3.6 Differential scanning calorimetry


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Fig. 8. Differential scanning calorimetry thermogram of bare and NiOx modified fabrics.

Fig. 8 shows the differential scanning calorimetry thermogram of bare and NiOx modified cotton fabrics at a controlled and constant heating rate. Bare and NiOx modified samples showed an intense endothermic behavior throughout the thermograph. Both the samples exhibited the endothermic peaks at 64.5 and 76.4ºC, which are attributed to the carboxyl group and elimination of bounded water compounds in cotton fabrics respectively68. A second endothermic peak at 126.9ºC corresponds to NiOx modified fabric, which could be due to the evaporation of solvents and partial decomposition of nickel group presented in the cotton cellulose 69.

Also, the peaks at 368.8 and 312ºC confirmed the final decomposition of cellulose crystal phase present

in the cotton fabrics68.


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3.7 X-ray photoelectron spectroscopy

Fig. 9. XPS (a) survey, (b) carbon 1s, (c) Ni 2p, and (d) Oxygen 1s spectra of the NiOx modified cotton cellulose. To investigate the NiOx modified surface on cotton fabric, XPS analysis was carried out and the survey spectra (Fig. 9(a)) confirmed the presence of various states of nickel, carbon and oxygen elements. Survey spectra showed the characteristic existence of NiO with Ni (2s, 2p, 2d, 3s & 3p), O (1s) and core level C 1s. Auger transition characteristics were also observed for Ni (LMM and O KLL). The C 1s peak was deconvoluted into two components (Fig. 9(b)) namely C-O/C-O-C and C=O/O-C=O at 285.4 and 288.5 eV70 respectively. Presence of Ni2+ and Ni3+ (Fig. 9(c)) was confirmed through the spin-orbit coupling of Ni 2p spectra. Ni 2p 17 ACS Paragon Plus Environment


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spectra was observed with Ni 2p3/2 and Ni 2p1/2 peaks at the binding energy range of 850-865 eV and 870885 eV71 respectively. In the present case, Ni 2p3/2 and Ni 2p1/2 peaks were observed at 856.5 and 874.2 eV respectively55. The shake-up satellites correspond to Ni2+ 2p3/2 and Ni3+ 2p1/2 were observed at 862 and 879.5 eV respectively. O 1s peak at 531.9 eV confirmed the appearance of oxygen in defect states in the adsorbed oxygen or hydroxide or oxygen crystal (Fig. 9(d)).

3.8 UV blocking property In electromagnetic spectrum, UV region has been classified into three bands such as UV-C (200-290 nm), UV-B (290-320 nm) and UV-A (320-400 nm) respectively. Whereas, UV-A and UV-B rays are considered to be harmful due to the maximum possibility of penetrating the skin surface and causing several human illnesses. The UV radiation blocking property of the NiOx modified fabrics depends on the type, thickness, inter-pore yarn size, color of the fabric and existence of UV absorbing agent18–20. An UPF rating represents the amount of UV rays is being blocked by the material. A fabric with a UPF rating of 50 would only allow 1/50th of the hazardous rays on its surface to pass through it, and hence UV rays exposure will be reduced by a factor of 50. Based on the UPF rating, fabrics quality can be classified as bad (50) respectively72. The UV blocking measurement of NiOx nanostructured fabric was tested as per the AATCC 183:2010 using UV transmittance analyzer. UPF measurement was carried out in the wavelength range of 290 to 450 nm for 5 times at different locations on the NiOx modified cotton fabric and the mean value was found to be 2000. When the surface modified NiOx fabric was kept in ambient atmosphere, oxygen molecules from the atmosphere adsorb the electrons from the conduction band of NiOOH and forms O2- depletion layer on the modified surface. Under UV exposure, photo-activated electron and hole pairs are generated. Subsequently, the photogenerated holes reacts with chemisorbed oxygen ions and release oxygen molecules. The chemisorption of oxygen species and reaction with photoactivated holes progressing continuously, which effectively block the UV rays. The redox reaction of the nickel oxide hydroxide modified 18 ACS Paragon Plus Environment

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fabric under UV illumination is expressed in the Eq. (12) 𝑁𝑖𝑂𝑂𝐻 + 𝑒 ― ↔𝑁𝑖𝑂 + 𝑂𝐻 ―

(12)

Also, the 3D green button chrysanthemum flower-like structure of NiOx modified cotton fabric promotes more active sites, which facilitates the multiple scattering and reflection phenomena44 in-turn enhance the UV filtering capacity. This enhanced UPF factor could be due to the influence of thickness, deeper coloration and NiOx nanoparticles present in the cotton fabric73. The UV-A and UV-B blocking capacity of NiOx modified fabrics were observed to be 99.90% and 99.93% respectively.

3.9 Gas sensing studies 3.9.1 Selectivity

Fig. 10. Selectivity of NiOx modified fabric towards 100 ppm of acetaldehyde, ammonia, formaldehyde, methanol, ethanol, isopropanol and trimethylamine vapours.

Selectivity of NiOx modified fabric was studied towards different gases such as trimethylamine, ammonia, ethanol, methanol, isopropanol, formaldehyde and acetaldehyde in which it showed selective response of 12431 towards 100 ppm of trimethylamine at room temperature as shown in Fig. 10. This selective response might be due to the lower bond dissociation energy of trimethylamine (351.456 kJ.mol-1) in comparison with 19 ACS Paragon Plus Environment

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other gases such as acetaldehyde (364 kJ.mol-1), ethanol (436 kJ.mol-1), formaldehyde (364 kJ.mol-1), methanol (436.8 kJ.mol-1) and ammonia (368 kJ.mol-1). Also, trimethylamine has weaker interaction with NiOx than other gases due to its Gibbs free energy ( △ 𝑓𝐺 ⋄ )13.

3.9.2 Transient studies

(c)

Fig. 11. (a) Transient resistance characteristics towards 100 ppm of trimethylamine vapour, (b) transient response of NiOx modified fabric towards various concentration from 2-200 ppm and (c) response and recovery times trend towards 100 ppm of trimethylamine. Transient response of the NiOx modified cotton fabrics was studied as a function of increasing concentration of trimethylamine from 2-200 ppm as shown in Fig. 11(a & b). The response was increased as a function of increasing concentration of trimethylamine. This behaviour could be due to the excessive presence of chemisorbed oxygen species on the surface of NiOx surface. The response and recovery times of the NiOx 20 ACS Paragon Plus Environment

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modified cotton fabrics were found to be 215 and 138 s respectively. Response and recovery times as a function of concentration are shown in Fig. 11(c).

3.9.3 Sensing mechanism The gas sensing mechanism of metal oxide materials modified cotton surface is based on the model of electron transfer dynamic during oxygen adsorption and desorption processes, which result in the change in surface resistance of the sensing element. When the surface modified cotton fabric is exposed to atmosphere, oxygen molecules get chemisorbed on the surface by trapping electrons from the conduction band of n-type semiconducting NiOx74. This interaction leads to the formation of surface charge region with O2- ions in-turn increases the surface resistance of the modified cotton fabric. The observed steady state surface resistance was fixed as the baseline resistance (Ra) for the sensing studies. The oxygen sorption reaction is given in Eqns. (13 & 14), (13)

𝑂2(𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒)⇋ 𝑂2 (𝑎𝑑𝑠) 𝑂2 (𝑎𝑑𝑠) + 𝑒(―𝑁𝑖𝑂𝑥𝑠𝑢𝑟𝑓𝑎𝑐𝑒)⇋ 𝑂2 ― (ads) + ℎ +

(14)

In the presence of reducing type trimethylamine vapour, its interaction with NiOx modified cotton surface following the reaction given Eqn. (15) resulted in the decrease in its surface resistance from the base line value. During this interaction, electrons released by the target vapour resulted in the desorption of oxygen molecules in-turn increased the number of electrons in the conduction band of NiOx. The resultant steady state resistance is denoted as Rg and the sensing response was calculated using Eqn. 5. The gas-solid interaction scheme12 is shown in Eq. (15), ― →2𝑁2↑ + 12𝐶𝑂2↑ + 18𝐻2𝑂↑ + 21𝑒 ― 4(𝐶𝐻3)3𝑁 + 21𝑂2(𝑎𝑑𝑠)

(15)

4 Conclusion 21 ACS Paragon Plus Environment

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The surface modification process of cotton fabric with NiOx nanostructures was successfully accomplished using chemical bath deposition technique. The 3D green button chrysanthemum flower-like nanostructured NiOx modified cotton fabric exhibited a UPF of 2000. The developed multifunctional fabric showed a selective sensing response of 12431 towards trimethylamine at room temperature. The nanostructured cotton cellulose has good thermal stability and showed an increased hydrophobicity than the unmodified fabrics. This will ensure that the developed technical fabric can be used as protective suit against gas leaks, harmful UV rays, flame retardant and hydrophobic screens.

Acknowledgments The authors are grateful to Nano Mission, Department of Science & Technology, New Delhi for the funding support (SR/NM/NT- 1039/2015) and one of the authors Mr. S. Dinesh Kumar thanks Council of Scientific and Industrial Research, New Delhi for Senior Research Fellowship (09/1095(0035)/18-EMR-1). We also acknowledge SASTRA Deemed University, Thanjavur for extending infrastructure support to carry out the study.

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Highlights  Synthesis and surface modification of NiOx nanoflower on cotton cellulose  Multi-functional cotton fabrics for UV blocking and selective detection of TMA at room temperature  Inorganic modified fabrics showed an enhanced Ultraviolet protection factor of 2000  TMA vapour was detected using surface modified cotton cellulose with response and recovery times of 215 and 138 s  Thermal degradation of NiOx modified fabrics was enhanced up to 800℃


NiOx Nanoflower Modified Cotton Fabric for UV Filter and Gas

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