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Bioinspired process using anisotropic silica particles and fatty acid for superhydrophobic cotton fabrics

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Abstract

Superhydrophobic cotton fabrics having lotus leaf-like dual scale surface roughness were prepared via a 2-step ‘green’ process. First, silica particles with different shapes were synthesized using a water-in-alcohol emulsion and polyvinyl pyrrolidone (PVP) of different molecular weights (MWs). Lower MW PVP resulted in a combination of spherical and cone-shaped particles while high MW PVP resulted in needle-shaped particles. These anisotropic particles were covalently bonded to the fabrics to create desired permanent surface roughness. Second, fatty acid was grafted using a novel solvent-free grafting process of fatty acid to lower the surface energy of fabrics. Grafting of fatty acid and silica particles onto the fabric surface was confirmed using ATR-FTIR. The facile 2-step process consisting of obtaining surface roughness through silica particles and low surface energy through grafted fatty acid resulted in superhydrophobic cotton fabrics with water contact angles (WCA) above 150°. Fabrics with dual-shaped particles (spherical and cone-shaped) exhibited a higher WCA of 157° while fabrics with single-shaped (needles) particles showed a slightly lower WCA of 153°. Covalent bonding of both particles and fatty acid resulted in highly durable superhydrophobic characteristics. The ‘green’, fluorine-free process developed in this study can be easily scaled up for other cellulosic materials such as viscose rayon, paper, micro-fibrillated cellulose, etc., to expand their applications in self-cleaning surfaces, water-repellent protective coatings, packaging, polymer composites, electronics and others.

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References

  • Afzal S, Daoud WA, Langford SJ (2014) Superhydrophobic and photocatalytic self-cleaning cotton. J Mater Chem A 2:18005–18011

    CAS  Google Scholar 

  • Athauda TJ, Ozer RR (2012) Investigation of the effect of dual-size coatings on the hydrophobicity of cotton surface. Cellulose 19:1031–1040

    CAS  Google Scholar 

  • Bae GY, Min BG, Jeong YG, Lee SC, Jang JH, Koo GH (2009) Superhydrophobicity of cotton fabrics treated with silica nanoparticles and water-repellent agent. J Colloid Interface Sci 337:170–175

    CAS  Google Scholar 

  • Bao L-h, Yun-Jun L (2018) Silicone softener for stain repellent stain release and wrinkle resistance fabric finishing. J Eng Fiber Fabr 13:301–304

    Google Scholar 

  • Brijitta J, Ramachandran D, Rabel A, Raj NN, Viswanathan K, Prasath SS (2017) Evolution of shape isotropy in silica microparticles induced by the base. Colloid Polym Sci 295:1485–1490

    CAS  Google Scholar 

  • Chen K, Yu G, He F, Zhou Q, Xiao D, Li J, Feng Y (2017) A pH-responsive emulsion stabilized by alginate-grafted anisotropic silica and its application in the controlled release of λ-cyhalothrin. Carbohydr Polym 176:203–213

    CAS  PubMed  Google Scholar 

  • Chen T et al (2019) Superhydrophobic and flame retardant cotton modified with DOPO and fluorine-silicon-containing crosslinked polymer. Carbohydr Polym 208:14–21

    CAS  PubMed  Google Scholar 

  • Dankovich TA, Hsieh Y-L (2007) Surface modification of cellulose with plant triglycerides for hydrophobicity. Cellulose 14:469–480

    CAS  Google Scholar 

  • Dashairya L, Barik DD, Saha P (2019) Methyltrichlorosilane functionalized silica nanoparticles-treated superhydrophobic cotton for oil–water separation. J Coat Technol Res 16:1021–1032

    CAS  Google Scholar 

  • David G, Gontard N, Angellier-Coussy H (2019) Mitigating the impact of cellulose particles on the performance of biopolyester-based composites by gas-phase esterification. Polymers 11:200–218

    PubMed Central  Google Scholar 

  • Deng B et al (2010) Laundering durability of superhydrophobic cotton fabric. Adv Mater 22:5473–5477

    CAS  Google Scholar 

  • Duan W, Xie A, Shen Y, Wang X, Wang F, Zhang Y, Li J (2011) Fabrication of superhydrophobic cotton fabrics with UV protection based on CeO2 particles. Ind Eng Chem Res 50:4441–4445

    CAS  Google Scholar 

  • Ebert D, Bhushan B (2012) Wear-resistant rose petal-effect surfaces with superhydrophobicity and high droplet adhesion using hydrophobic and hydrophilic nanoparticles. J Colloid Interface Sci 384:182–188

    CAS  PubMed  Google Scholar 

  • Feng L, Zhang Y, Xi J, Zhu Y, Wang N, Xia F, Jiang L (2008) Petal effect: a superhydrophobic state with high adhesive force. Langmuir 24:4114–4119

    CAS  PubMed  Google Scholar 

  • Gashti MP, Alimohammadi F, Shamei A (2012) Preparation of water-repellent cellulose fibers using a polycarboxylic acid/hydrophobic silica nanocomposite coating. Surf Coat Tech 206:3208–3215

    CAS  Google Scholar 

  • Guerrero-Martínez A, Pérez-Juste J, Liz-Marzán LM (2010) Recent progress on silica coating of nanoparticles and related nanomaterials. Adv Mater 22:1182–1195

    PubMed  Google Scholar 

  • Hagemans F, van der Wee EB, van Blaaderen A, Imhof A (2016) Synthesis of cone-shaped colloids from rod-like silica colloids with a gradient in the etching rate. Langmuir 32:3970–3976

    CAS  PubMed  Google Scholar 

  • Hoefnagels H, Wu D, De With G, Ming W (2007) Biomimetic superhydrophobic and highly oleophobic cotton textiles. Langmuir 23:13158–13163

    CAS  PubMed  Google Scholar 

  • Huang W, Song Y, Xing Y, Dai J (2010) Durable hydrophobic cellulose fabric prepared with polycarboxylic acid catalyzed silica sol. Ind Eng Chem Res 49:9135–9142

    CAS  Google Scholar 

  • Huang W, Xing Y, Yu Y, Shang S, Dai J (2011) Enhanced washing durability of hydrophobic coating on cellulose fabric using polycarboxylic acids. Appl Surf Sci 257:4443–4448

    CAS  Google Scholar 

  • Ji B, Zhao C, Yan K, Sun G (2016) Effects of acid diffusibility and affinity to cellulose on strength loss of polycarboxylic acid crosslinked fabrics. Carbohydr Polym 144:282–288

    CAS  PubMed  Google Scholar 

  • Jiang C, Liu W, Yang M, Liu C, He S, Xie Y, Wang Z (2018) Facile fabrication of robust fluorine-free self-cleaning cotton textiles with superhydrophobicity, photocatalytic activity, and UV durability. Colloids Surf A 559:235–242

    CAS  Google Scholar 

  • Jonoobi M, Harun J, Mathew AP, Hussein MZB, Oksman K (2010) Preparation of cellulose nanofibers with hydrophobic surface characteristics. Cellulose 17:299–307

    CAS  Google Scholar 

  • Khalil-Abad MS, Yazdanshenas ME (2010) Superhydrophobic antibacterial cotton textiles. J Colloid Interface Sci 351:293–298

    Google Scholar 

  • Korhonen JT, Kettunen M, Ras RH, Ikkala O (2011) Hydrophobic nanocellulose aerogels as floating, sustainable, reusable, and recyclable oil absorbents. ACS Appl Mater Interfaces 3:1813–1816

    CAS  PubMed  Google Scholar 

  • Kyrychenko A, Korsun OM, Gubin II, Kovalenko SM, Kalugin ON (2015) Atomistic simulations of coating of silver nanoparticles with poly (vinylpyrrolidone) oligomers: effect of oligomer chain length. J Phys Chem C 119:7888–7899

    CAS  Google Scholar 

  • Li F, Biagioni P, Bollani M, Maccagnan A, Piergiovanni L (2013) Multi-functional coating of cellulose nanocrystals for flexible packaging applications. Cellulose 20:2491–2504

    CAS  Google Scholar 

  • Li X, Zhou L, Wei Y, El-Toni AM, Zhang F, Zhao D (2014) Anisotropic growth-induced synthesis of dual-compartment Janus mesoporous silica nanoparticles for bimodal triggered drugs delivery. J Am Chem Soc 136:15086–15092

    CAS  PubMed  Google Scholar 

  • Li Y et al (2018) Fabrication of superhydrophobic and superoleophilic polybenzoxazine-based cotton fabric for oil–water separation. Cellulose 25:6691–6704

    CAS  Google Scholar 

  • Lin D, Zeng X, Li H, Lai X, Wu T (2019) One-pot fabrication of superhydrophobic and flame-retardant coatings on cotton fabrics via sol-gel reaction. J Colloid Interface Sci 533:198–206

    CAS  PubMed  Google Scholar 

  • Longbottom BW, Rochford LA, Beanland R, Bon SA (2015) Mechanistic insight into the synthesis of silica-based “matchstick” colloids. Langmuir 31:9017–9025

    CAS  PubMed  Google Scholar 

  • Maity J, Kothary P, O’Rear EA, Jacob C (2010) Preparation and comparison of hydrophobic cotton fabric obtained by direct fluorination and admicellar polymerization of fluoromonomers. Ind Eng Chem Res 49:6075–6079

    CAS  Google Scholar 

  • Maruthamuthu M, Sobhana M (1979) Hydrophobic interactions in the binding of polyvinylpyrrolidone. J Polym Sci 17:3159–3167

    CAS  Google Scholar 

  • Menaa B, Mizuno M, Takahashi M, Tokuda Y, Yoko T (2006) Polycarboxylic acids as network modifiers for water durability improvement of inorganic–organic hybrid tin-silico-phosphate low-melting glasses. J Solid State Chem 179:492–499

    CAS  Google Scholar 

  • Molina R, Teixidó JM, Kan C-W, Jovančić P (2017) Hydrophobic coatings on cotton obtained by in situ plasma polymerization of a fluorinated monomer in ethanol solutions. ACS Appl Mater Interfaces 9:5513–5521

    CAS  PubMed  Google Scholar 

  • Mulyadi A, Zhang Z, Deng Y (2016) Fluorine-free oil absorbents made from cellulose nanofibril aerogels. ACS Appl Mater Interfaces 8:2732–2740

    CAS  PubMed  Google Scholar 

  • Murphy RP, Hong K, Wagner NJ (2017) Synthetic control of the size, shape, and polydispersity of anisotropic silica colloids. J Colloid Interface Sci 501:45–53

    CAS  PubMed  Google Scholar 

  • Onur A, Ng A, Garnier G, Batchelor W (2019) The use of cellulose nanofibres to reduce the wet strength polymer quantity for development of cleaner filters. J Clean Prod 215:226–231

    CAS  Google Scholar 

  • Panwar K, Jassal M, Agrawal AK (2015) In situ synthesis of Ag–SiO2 Janus particles with epoxy functionality for textile applications. Particuology 19:107–112

    CAS  Google Scholar 

  • Patil NV, Netravali AN (2019) Direct assembly of silica nanospheres on halloysite nanotubes for “Green” ultrahydrophobic cotton fabrics. Adv Sustain Syst 1900009

  • Rodionova G, Lenes M, Eriksen Ø, Gregersen Ø (2011) Surface chemical modification of microfibrillated cellulose: improvement of barrier properties for packaging applications. Cellulose 18:127–134

    CAS  Google Scholar 

  • Sai H, Fu R, Xing L, Xiang J, Li Z, Li F, Zhang T (2015) Surface modification of bacterial cellulose aerogels’ web-like skeleton for oil/water separation. ACS Appl Mater Interfaces 7:7373–7381

    CAS  PubMed  Google Scholar 

  • Samyn P, Schoukens G, Stanssens D, Vonck L, Van den Abbeele H (2013) Hydrophobic waterborne coating for cellulose containing hybrid organic nanoparticle pigments with vegetable oils. Cellulose 20:2625–2646

    CAS  Google Scholar 

  • Sehaqui H, Zimmermann T, Tingaut P (2014) Hydrophobic cellulose nanopaper through a mild esterification procedure. Cellulose 21:367–382

    CAS  Google Scholar 

  • Shang Q, Liu C, Zhou Y (2018) One-pot fabrication of robust hydrophobia and superoleophilic cotton fabrics for effective oil-water separation. J Coat Technol Res 15:65–75

    CAS  Google Scholar 

  • Shimizu M, Saito T, Fukuzumi H, Isogai A (2014) Hydrophobic, ductile, and transparent nanocellulose films with quaternary alkylammonium carboxylates on nanofibril surfaces. Biomacromol 15:4320–4325

    CAS  Google Scholar 

  • Singh AK, Singh JK (2017) Fabrication of durable superhydrophobic coatings on cotton fabrics with photocatalytic activity by fluorine-free chemical modification for dual-functional water purification. New J Chem 41:4618–4628

    CAS  Google Scholar 

  • Song Z, Xiao H, Zhao Y (2014) Hydrophobic-modified nano-cellulose fiber/PLA biodegradable composites for lowering water vapor transmission rate (WVTR) of paper. Carbohydr Polym 111:442–448

    CAS  PubMed  Google Scholar 

  • Tang K-PM, Kan C-W, Fan J-T, Tso S-L (2017) Effect of softener and wetting agent on improving the flammability, comfort, and mechanical properties of flame-retardant finished cotton fabric. Cellulose 24:2619–2634

    CAS  Google Scholar 

  • Wang J, Lu Y (2016) Facitablele synthesis of asymmetrical flower-like silica. Mater Des 111:206–212

    CAS  Google Scholar 

  • Wang X-D, Shen Z-X, Sang T, Cheng X-B, Li M-F, Chen L-Y, Wang Z-S (2010) Preparation of spherical silica particles by Stöber process with high concentration of tetra-ethyl-orthosilicate. J Colloid Interface Sci 341:23–29

    CAS  PubMed  Google Scholar 

  • Wang L, Zhang X, Li B, Sun P, Yang J, Xu H, Liu Y (2011) Superhydrophobic and ultraviolet-blocking cotton textiles. ACS Appl Mater Interfaces 3:1277–1281

    CAS  PubMed  Google Scholar 

  • Wen Q, Guo F, Yang F, Guo Z (2017) Green fabrication of coloured superhydrophobic paper from native cotton cellulose. J Colloid Interface Sci 497:284–289

    CAS  PubMed  Google Scholar 

  • Xue C-H, Jia S-T, Zhang J, Tian L-Q, Chen H-Z, Wang M (2008) Preparation of superhydrophobic surfaces on cotton textiles. Sci Technol Adv Mater 9:035008

    PubMed  PubMed Central  Google Scholar 

  • Xue C-H, Jia S-T, Zhang J, Tian L-Q (2009) Superhydrophobic surfaces on cotton textiles by complex coating of silica nanoparticles and hydrophobization. Thin Solid Films 517:4593–4598

    CAS  Google Scholar 

  • Yang H-C, Pi J-K, Liao K-J, Huang H, Wu Q-Y, Huang X-J, Xu Z-K (2014) Silica-decorated polypropylene microfiltration membranes with a mussel-inspired intermediate layer for oil-in-water emulsion separation. ACS Appl Mater Interfaces 6:12566–12572

    CAS  PubMed  Google Scholar 

  • Yang M, Liu W, Jiang C, He S, Xie Y, Wang Z (2018a) Fabrication of superhydrophobic cotton fabric with fluorinated TiO 2 sol by a green and one-step sol-gel process. Carbohydr Polym 197:75–82

    CAS  PubMed  Google Scholar 

  • Yang M, Liu W, Jiang C, Liu C, He S, Xie Y, Wang Z (2018b) Facile preparation of robust superhydrophobic cotton textile for self-cleaning and oil-water separation. Ind Eng Chem Res 58:187–194

    Google Scholar 

  • Yasim-Anuar TAT, Ariffin H, Norrrahim MNF, Hassan MA, Tsukegi T, Nishida H (2019) Sustainable one-pot process for the production of cellulose nanofiber and polyethylene/cellulose nanofiber composites. J Clean Prod 207:590–599

    CAS  Google Scholar 

  • Yi D, Zhang Q, Liu Y, Song J, Tang Y, Caruso F, Wang Y (2016) Synthesis of chemically asymmetric silica nanobottles and their application for cargo loading and as nanoreactors and nanomotors. Angew Chem 55:14733–14737

    CAS  Google Scholar 

  • Yu M, Gu G, Meng W-D, Qing F-L (2007) Superhydrophobic cotton fabric coating based on a complex layer of silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent. Appl Surf Sci 253:3669–3673

    CAS  Google Scholar 

  • Zhang J, Liu H, Wang Z, Ming N (2008a) Au-induced polyvinylpyrrolidone aggregates with bound water for the highly shape-selective synthesis of silica nanostructures. Chem Eur J 14:4374–4380

    CAS  PubMed  Google Scholar 

  • Zhang X, Shi F, Niu J, Jiang Y, Wang Z (2008b) Superhydrophobic surfaces: from structural control to functional application. J Mater Chem 18:621–633

    CAS  Google Scholar 

  • Zhao Y, Tang Y, Wang X, Lin T (2010) Superhydrophobic cotton fabric fabricated by electrostatic assembly of silica nanoparticles and its remarkable buoyancy. Appl Surf Sci 256:6736–6742

    CAS  Google Scholar 

  • Zhao Y, Xu Z, Wang X, Lin T (2012) Photoreactive azido-containing silica nanoparticle/polycation multilayers: durable superhydrophobic coating on cotton fabrics. Langmuir 28:6328–6335

    CAS  PubMed  Google Scholar 

  • Zhong Y, Netravali AN (2016) ‘Green’surface treatment for water-repellent cotton fabrics. Surf Innov 4:3–13

    Google Scholar 

  • Zimmermann J, Reifler FA, Fortunato G, Gerhardt LC, Seeger S (2008) A simple, one-step approach to durable and robust superhydrophobic textiles. Adv Funct Mater 18:3662–3669

    CAS  Google Scholar 

  • Zulfiqar U, Hussain SZ, Awais M, Khan MMJ, Hussain I, Husain SW, Subhani T (2016) In-situ synthesis of bi-modal hydrophobic silica nanoparticles for oil-water separation. Colloids Surf A 508:301–308

    CAS  Google Scholar 

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Acknowledgments

The authors would like to acknowledge the use of Cornell Center for Materials Research (CCMR) shared facilities supported through the NSF MRSEC program (DMR-1719875).

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  1. Department of Fiber Science and Apparel Design, Cornell University, 37 Forest Home Dr, Ithaca, NY, 14853, USA

    Namrata V. Patil & Anil N. Netravali

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  1. Namrata V. Patil
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Correspondence to Anil N. Netravali.

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Patil, N.V., Netravali, A.N. Bioinspired process using anisotropic silica particles and fatty acid for superhydrophobic cotton fabrics. Cellulose 27, 545–559 (2020). https://doi.org/10.1007/s10570-019-02811-4

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