Abstract
In this present research, a novel microwave hydrothermal method was applied to cotton fabrics to develop a superhydrophobic surface by rapid synthesis of aligned ZnO nanorods on the surface of the cotton fabric. A two-step approach was used to grow the ZnO nanorods. Firstly, the cotton fabric was coated by a seed layer of ZnO nanocrystals, synthesized using the microwave-assisted sol gel method. Secondly, the ZnO nanorods were grown rapidly on the seeded cotton fabrics using the microwave hydrothermal method. Moreover, a layer of non-fluorinated silane was applied on the as-grown nanorods to fabricate a superhydrophobic surface. Non-fluorinated silane was selected as it is less harmful to the skin than fluorinated silanes. The effect of the zinc nitrate hexahydrate (Zn(NO3)2·6H2O) concentration, reaction time and microwave power on the growth of ZnO nanorods was investigated in detail using scanning electron microscopy. The surface topography and roughness of the nanorods grown on the fabrics were studied using atomic force microscopy. EDS analysis and X-ray diffraction techniques were used to study the structural properties of the ZnO nanorods. The ultraviolet protection properties were investigated by a UV–Vis-NIR spectrophotometer. The ZnO nanorods grown on the cotton fabrics exhibited excellent UV blocking properties. A maximum UPF value of 114 was observed for the ZnO nanorods grown on the cotton fabric with 100 mM of zinc nitrate hexahydrate (Zn(NO3)2·6H2O). The superhydrophobic properties were examined based on contact angle and roll-off angle measurements, where a maximum water contact angle of 170.2° and a minimum roll-off angle of 1° were found for 25 mM of zinc nitrate hexahydrate. The ZnO-OTMS coated fabrics were evaluated for superhydrophobic durability against mechanical abrasion, laundering, chemical and UV action. Moreover, the ZnO-OTMS coated fabrics showed excellent potential for separation of floating and underwater oil layers or an oil–water mixture.
Graphic abstract

This is a preview of subscription content, access via your institution.














References
Afzal S, Daoud WA, Langford SJ (2014) Superhydrophobic and photocatalytic self-cleaning cotton. J Mater Chem A 2:18005–18011. https://doi.org/10.1039/C4TA02764G
Ahmad F, Idrees F, Fazal-e-Aleem IF (2018) Recent advancements in microwave-assisted synthesis of NiO nanostructures and their supercapacitor properties: a comprehensive review. Curr Nanomater 3:5–17. https://doi.org/10.2174/2405461503666180305161202
Aminayi P, Abidi N (2013) Imparting super hydro/oleophobic properties to cotton fabric by means of molecular and nanoparticles vapor deposition methods. Appl Surf Sci 287:223–231. https://doi.org/10.1016/j.apsusc.2013.09.132
Ashraf M, Campagne C, Perwuelz A et al (2013) Development of superhydrophilic and superhydrophobic polyester fabric by growing zinc oxide nanorods. J Colloid Interface Sci 394:545–553. https://doi.org/10.1016/j.jcis.2012.11.020
Ashraf M, Champagne P, Campagne C et al (2014a) Study the multi self-cleaning characteristics of ZnO nanorods functionalized polyester fabric. J Ind Text 45:1440–1456. https://doi.org/10.1177/1528083714562086
Ashraf M, Dumont F, Campagne C et al (2014b) Development of antibacterial polyester fabric by growth of ZnO nanorods. J Eng Fiber Fabr 9:15–22
Ates ES, Unalan HE (2012) Zinc oxide nanowire enhanced multifunctional coatings for cotton fabrics. Thin Solid Films 520:4658–4661. https://doi.org/10.1016/j.tsf.2011.10.073
Bae GY, Min BG, Jeong YG et al (2009) Superhydrophobicity of cotton fabrics treated with silica nanoparticles and water-repellent agent. J Colloid Interface Sci 337:170–175. https://doi.org/10.1016/j.jcis.2009.04.066
Becheri A, Durr M, Lo Nostro P, Baglioni P (2008) Synthesis and characterization of zinc oxide nanoparticles: application to textiles as UV-absorbers. J Nanoparticle Res 10:679–689. https://doi.org/10.1007/s11051-007-9318-3
Boscher ND, Vaché V, Carminati P et al (2014) A simple and scalable approach towards the preparation of superhydrophobic surfaces-importance of the surface roughness skewness. J Mater Chem A 2:5744–5750. https://doi.org/10.1039/c4ta00366g
Brahma S, Rao KJ, Shivashankar S (2010) Rapid growth of nanotubes and nanorods of würtzite ZnO through microwave-irradiation of a metalorganic complex of zinc and a surfactant in solution. Bull Mater Sci 33:89–95. https://doi.org/10.1007/s12034-010-0027-7
Cheng D, He M, Li W et al (2019) Hydrothermal growing of cluster-like ZnO nanoparticles without crystal seeding on PET films via dopamine anchor. Appl Surf Sci 467–468:534–542. https://doi.org/10.1016/j.apsusc.2018.10.177
Das A, Deka J, Rather AM et al (2017) Strategic formulation of graphene oxide sheets for flexible monoliths and robust polymeric coatings embedded with durable bioinspired wettability†. ACS Appl Mater Interfaces 9:42354–42365. https://doi.org/10.1021/acsami.7b14028
Dedova T, Acik IO, Krunks M et al (2012) Effect of substrate morphology on the nucleation and growth of ZnO nanorods prepared by spray pyrolysis. Thin Solid Films 520:4650–4653. https://doi.org/10.1016/j.tsf.2011.11.068
Edalati K, Shakiba A, Vahdati-Khaki J, Zebarjad SM (2016) Low-temperature hydrothermal synthesis of ZnO nanorods: effects of zinc salt concentration, various solvents and alkaline mineralizers. Mater Res Bull 74:374–379. https://doi.org/10.1016/j.materresbull.2015.11.001
Ennaceri H, Wang L, Erfurt D et al (2016) Water-resistant surfaces using zinc oxide structured nanorod arrays with switchable wetting property. Surf Coat Technol 299:169–176. https://doi.org/10.1016/j.surfcoat.2016.04.056
Feng L, Li S, Li Y et al (2002) Super-hydrophobic surfaces: from natural to artificial. Adv Mater 14:1857–1860. https://doi.org/10.1002/adma.200290020
Fujita S, Bhanage BM, Arai M et al (2010) Microwave-assisted additive free synthesis of nanocrystalline zinc oxide. Powder Technol 203:415–418. https://doi.org/10.1016/j.powtec.2010.05.036
Gao X, Wen G, Guo Z (2018) Durable superhydrophobic and underwater superoleophobic cotton fabrics growing zinc oxide nanoarrays for application in separation of heavy/light oil and water mixtures as need. Colloids Surf A Physicochem Eng Asp 559:115–126. https://doi.org/10.1016/j.colsurfa.2018.09.041
Ghamsari MS, Alamdari S, Han W, Park HH (2017) Impact of nanostructured thin ZnO film in ultraviolet protection. Int J Nanomed 12:207–216. https://doi.org/10.2147/IJN.S118637
Ghayour H, Rezaie HR, Mirdamadi S, Nourbakhsh AA (2011) The effect of seed layer thickness on alignment and morphology of ZnO nanorods. Vacuum 86:101–105. https://doi.org/10.1016/j.vacuum.2011.04.025
Grozea CM, Rabnawaz M, Liu G, Zhang G (2015) Coating of silica particles by fluorinated diblock copolymers and use of the resultant silica for superamphiphobic surfaces. Polymer (UK) 64:153–162. https://doi.org/10.1016/j.polymer.2015.03.041
Gurav AB, Latthe SS, Vhatkar RS et al (2014) Superhydrophobic surface decorated with vertical ZnO nanorods modified by stearic acid. Ceram Int 40:7151–7160. https://doi.org/10.1016/j.ceramint.2013.12.052
Gustafsson E, Larsson PA, Wågberg L (2012) Treatment of cellulose fibres with polyelectrolytes and wax colloids to create tailored highly hydrophobic fibrous networks. Colloids Surf A Physicochem Eng Asp 414:415–421. https://doi.org/10.1016/j.colsurfa.2012.08.042
Hasanpoor M, Aliofkhazraei M, Delavari H (2015) Microwave assisted synthesis of zinc oxide nanoparticles. Procedia Mater Sci 8:320–325. https://doi.org/10.1016/j.mspro.2015.11.101
Hill D, Attia H, Barron AR, Alexander S (2019) Size and morphology dependent surface wetting based on hydrocarbon functionalized nanoparticles. J Colloid Interface Sci 543:328–334. https://doi.org/10.1016/j.jcis.2019.02.058
Hsieh CT, Wu FL, Yang SY (2008) Superhydrophobicity from composite nano/microstructures: carbon fabrics coated with silica nanoparticles. Surf Coat Technol 202:6103–6108. https://doi.org/10.1016/j.surfcoat.2008.07.006
Hu XL, Zhu YJ, Wang SW (2004) Sonochemical and microwave-assisted synthesis of linked single-crystalline ZnO rods. Mater Chem Phys 88:421–426. https://doi.org/10.1016/j.matchemphys.2004.08.010
Huang JY, Li SH, Ge MZ et al (2015) Robust superhydrophobic TiO2@fabrics for UV shielding, self-cleaning and oil–water separation. J Mater Chem A 3:2825–2832. https://doi.org/10.1039/c4ta05332j
Jeong SW, Bolortuya S, Eadi SB, Kim S (2020) Fabrication of superhydrophobic surfaces based on PDMS coated hydrothermal grown ZnO on PET fabrics. J Adhes Sci Technol 34:102–113. https://doi.org/10.1080/01694243.2019.1661609
Kajbafvala A, Zanganeh S, Kajbafvala E et al (2010) Microwave-assisted synthesis of narcis-like zinc oxide nanostructures. J Alloys Compd 497:325–329. https://doi.org/10.1016/j.jallcom.2010.03.057
Karunakaran RG, Lu C, Zhang Z, Yang S (2011) Highly transparent superhydrophobic surfaces from the coassembly of nanoparticles ( e 100 nm ). Langmuir 27:4594–4602
Khan MZ, Baheti V, Militky J et al (2018) Superhydrophobicity, UV protection and oil/water separation properties of fly ash/trimethoxy(octadecyl)silane coated cotton fabrics. Carbohydr Polym 202:571–580. https://doi.org/10.1016/j.carbpol.2018.08.145
Khan MZ, Baheti V, Militky J et al (2020) Self-cleaning properties of polyester fabrics coated with flower-like TiO2 particles and trimethoxy (octadecyl)silane. J Ind Text 50:543–565. https://doi.org/10.1177/1528083719836938
Küçük M, Öveçoğlu ML (2019) Fabrication of SiO2–ZnO NP/ZnO NR hybrid coated cotton fabrics: the effect of ZnO NR growth time on structural and UV protection characteristics. Cellulose 2:1773–1793. https://doi.org/10.1007/s10570-019-02891-2
Latthe SS, Rao AV (2012) Superhydrophobic SiO2 micro-particle coatings by spray method. Surf Coat Technol 207:489–492. https://doi.org/10.1016/j.surfcoat.2012.07.055
Li R, Che J, Zhang H et al (2014) Study on synthesis of ZnO nanorods and its UV-blocking properties on cotton fabrics coated with the ZnO quantum dot. J Nanoparticle Res. https://doi.org/10.1007/s11051-014-2581-1
Li S, Huang J, Chen Z et al (2017) A review on special wettability textiles: theoretical models, fabrication technologies and multifunctional applications. J Mater Chem A 5:31–55. https://doi.org/10.1039/c6ta07984a
Li S, Huang J, Ge M et al (2015) robust flower-like TiO2@cotton fabrics with special wettability for effective self-cleaning and versatile oil/water separation. Adv Mater Interfaces 2:1500220. https://doi.org/10.1002/admi.201500220
Li X, Chen X, Yi Z et al (2019) Fabriction of ZnO nanorods with strong UV absorption and different hydrophobicity on foamed nickel under different hydrothermal conditions. Micromachines. https://doi.org/10.3390/mi10030164
Liu H, Gao SW, Cai JS et al (2016) Recent progress in fabrication and applications of superhydrophobic coating on cellulose-based substrates. Materials (Basel) 9:124. https://doi.org/10.3390/ma9030124
Lu Y, Sathasivam S, Song J et al (2015) Robust self-cleaning surfaces that function when exposed to either air or oil. Science 347:1132–1135. https://doi.org/10.1126/science.aaa0946
Mirzaei A, Neri G (2016) Microwave-assisted synthesis of metal oxide nanostructures for gas sensing application: a review. Sens Actuators B Chem 237:749–775. https://doi.org/10.1016/j.snb.2016.06.114
Motshekga SC, Pillai SK, Sinha Ray S et al (2012) Recent trends in the microwave-assisted synthesis of metal oxide nanoparticles supported on carbon nanotubes and their applications. J Nanomater 2012:15. https://doi.org/10.1155/2012/691503
Movahedi T, Norouzbeigi R (2019) Synthesis of flower-like micro/nano ZnO superhydrophobic surfaces: additive effect optimization via designed experiments. J Alloys Compd 795:483–492. https://doi.org/10.1016/j.jallcom.2019.04.343
Nandi R, Major SS (2017) The mechanism of growth of ZnO nanorods by reactive sputtering. Appl Surf Sci 399:305–312. https://doi.org/10.1016/j.apsusc.2016.12.097
Nosonovsky M, Bhushan B (2009) Superhydrophobic surfaces and emerging applications: non-adhesion, energy, green engineering. Curr Opin Colloid Interface Sci 14:270–280. https://doi.org/10.1016/j.cocis.2009.05.004
Pan C, Shen L, Shang S, Xing Y (2012) Preparation of superhydrophobic and UV blocking cotton fabric via sol–gel method and self-assembly. Appl Surf Sci 259:110–117. https://doi.org/10.1016/j.apsusc.2012.07.001
Pandiyarasan V, Suhasini S, Archana J et al (2017) Fabrication of hierarchical ZnO nanostructures on cotton fabric for wearable device applications. Appl Surf Sci 418:352–361. https://doi.org/10.1016/j.apsusc.2016.12.202
Pant HR, Bajgai MP, Nam KT et al (2011) Electrospun nylon-6 spider-net like nanofiber mat containing TiO2 nanoparticles: a multifunctional nanocomposite textile material. J Hazard Mater 185:124–130. https://doi.org/10.1016/j.jhazmat.2010.09.006
Parbat D, Gaffar S, Rather AM et al (2017) A general and facile chemical avenue for the controlled and extreme regulation of water wettability in air and oil wettability under water. Chem Sci 8:6542–6554. https://doi.org/10.1039/c7sc02296d
Polefka TG, Meyer TA, Agin PP (2011) Effects of solar radiation on the skin. J Cosmet Dermatol 11:134–143. https://doi.org/10.1111/j.1473-2165.2012.00614.x
Polsongkram D, Chamninok P, Pukird S et al (2008) Effect of synthesis conditions on the growth of ZnO nanorods via hydrothermal method. Phys B Condens Matter 403:3713–3717. https://doi.org/10.1016/j.physb.2008.06.020
Preda N, Enculescu M, Zgura I et al (2013) Superhydrophobic properties of cotton fabrics functionalized with ZnO by electroless deposition. Mater Chem Phys 138:253–261. https://doi.org/10.1016/j.matchemphys.2012.11.054
Qi G, Zhang H, Yuan Z (2011) Superhydrophobic brocades modified with aligned ZnO nanorods. Appl Surf Sci 258:662–667. https://doi.org/10.1016/j.apsusc.2011.06.167
Rather AM, Manna U (2017) Stretchable and durable superhydrophobicity that acts both in air and under oil. J Mater Chem A 5:15208–15216. https://doi.org/10.1039/c7ta04073c
Riaz S, Ashraf M, Hussain T et al (2019) Fabrication of robust multifaceted textiles by application of functionalized TiO2 nanoparticles. Colloids Surf A Physicochem Eng Asp 581:123799. https://doi.org/10.1016/j.colsurfa.2019.123799
Shinde VR, Gujar TP, Noda T et al (2010) Growth of shape- and size-selective zinc oxide nanorods by a microwave-assisted chemical bath deposition method: effect on photocatalysis properties. Chem Eur J 16:10569–10575. https://doi.org/10.1002/chem.200903370
Shirgholami MA, Shateri Khalil-Abad M, Khajavi R, Yazdanshenas ME (2011) Fabrication of superhydrophobic polymethylsilsesquioxane nanostructures on cotton textiles by a solution-immersion process. J Colloid Interface Sci 359:530–535. https://doi.org/10.1016/j.jcis.2011.04.031
Skompska M, Zarȩbska K (2014) Electrodeposition of ZnO nanorod arrays on transparent conducting substrates—a review. Electrochim Acta 127:467–488. https://doi.org/10.1016/j.electacta.2014.02.049
Taghizadeh SM, Lal N, Ebrahiminezhad A et al (2020) Green and economic fabrication of zinc oxide (ZnO) nanorods as a broadband UV blocker and antimicrobial agent. Nanomaterials 10:1–12. https://doi.org/10.3390/nano10030530
Ul Hassan Sarwar Rana A, Kang M, Kim HS (2016) Microwave-assisted facile and ultrafast growth of ZnO nanostructures and proposition of alternative microwave-assisted methods to address growth stoppage. Sci Rep 6:1–13. https://doi.org/10.1038/srep24870
Unalan HE, Hiralal P, Rupesinghe N et al (2008) Rapid synthesis of aligned zinc oxide nanowires. Nanotechnology 19:255608. https://doi.org/10.1088/0957-4484/19/25/255608
Wahab R, Kim YS, Lee K, Shin HS (2010) Fabrication and growth mechanism of hexagonal zinc oxide nanorods via solution process. J Mater Sci 45:2967–2973. https://doi.org/10.1007/s10853-010-4294-x
Wang J, Geng G, Wang A et al (2015) Double biomimetic fabrication of robustly superhydrophobic cotton fiber and its application in oil spill cleanup. Ind Crops Prod 77:36–43. https://doi.org/10.1016/j.indcrop.2015.08.044
Xiong D, Liu G, Hong L, Duncan EJS (2011) Superamphiphobic diblock copolymer coatings. Chem Mater 23:4357–4366. https://doi.org/10.1021/cm201797e
Xu B, Cai Z (2008) Fabrication of a superhydrophobic ZnO nanorod array film on cotton fabrics via a wet chemical route and hydrophobic modification. Appl Surf Sci 254:5899–5904. https://doi.org/10.1016/j.apsusc.2008.03.160
Xu B, Cai Z, Wang W, Ge F (2010) Preparation of superhydrophobic cotton fabrics based on SiO2 nanoparticles and ZnO nanorod arrays with subsequent hydrophobic modification. Surf Coat Technol 204:1556–1561. https://doi.org/10.1016/j.surfcoat.2009.09.086
Xu F, Lu Y, Xie Y, Liu Y (2009) Controllable morphology evolution of electrodeposited ZnO nano/micro-scale structures in aqueous solution. Mater Des 30:1704–1711. https://doi.org/10.1016/j.matdes.2008.07.024
Yan YY, Gao N, Barthlott W (2011) Mimicking natural superhydrophobic surfaces and grasping the wetting process: a review on recent progress in preparing superhydrophobic surfaces. Adv Colloid Interface Sci 169:80–105. https://doi.org/10.1016/j.cis.2011.08.005
Zhang H, Yang D, Ma X et al (2006) Straight and thin ZnO nanorods: hectogram-scale synthesis at low temperature and cathodoluminescence. J Phys Chem B 110:827–830. https://doi.org/10.1021/jp055351k
Zhang M, Wang C, Wang S, Li J (2013) Fabrication of superhydrophobic cotton textiles for water–oil separation based on drop-coating route. Carbohydr Polym 97:59–64. https://doi.org/10.1016/j.carbpol.2012.08.118
Zhang ZH, Wang HJ, Liang YH et al (2018) One-step fabrication of robust superhydrophobic and superoleophilic surfaces with self-cleaning and oil/water separation function. Sci Rep 8:1–12. https://doi.org/10.1038/s41598-018-22241-9
Zhou Z, Zhao Y, Cai Z (2010) Low-temperature growth of ZnO nanorods on PET fabrics with two-step hydrothermal method. Appl Surf Sci 256:4724–4728. https://doi.org/10.1016/j.apsusc.2010.02.081
Zhu T, Li S, Huang J et al (2017) Rational design of multi-layered superhydrophobic coating on cotton fabrics for UV shielding, self-cleaning and oil–water separation. Mater Des 134:342–351. https://doi.org/10.1016/j.matdes.2017.08.071
Zhu X, Zhang Z, Ge B et al (2014) A versatile approach to produce superhydrophobic materials used for oil–water separation. J Colloid Interface Sci 432:105–108. https://doi.org/10.1016/j.jcis.2014.06.056
Acknowledgments
This work was supported by the Technology Agency of the Czech Republic—Project No. TH03020534. The authors are also thankful to the student grant competition 21312 provided by the Technical University of Liberec.
Author information
Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Khan, M.Z., Militky, J., Baheti, V. et al. Growth of ZnO nanorods on cotton fabrics via microwave hydrothermal method: effect of size and shape of nanorods on superhydrophobic and UV-blocking properties. Cellulose 27, 10519–10539 (2020). https://doi.org/10.1007/s10570-020-03495-x
Received:
Accepted:
Published:
Issue Date:
Keywords
- Superhydrophobic
- Cotton fabrics
- Nanorods
- Contact angle
- UV protection