Facile fabrication of fluoro-polymer self-assembled ZnO nanoparticles mediated, durable and robust omniphobic surfaces on polyester fabrics
Graphical abstract
Introduction
Omniphobic surfaces have gained great deal of attention due to their special properties such as oil-water separation [1], self-cleaning [2], anti-corrosion [3,4], water repellency [5] and mechanical robustness [6]. Omniphobic property can be used especially with textile materials for various functional applications such as coats, rainwear, shoes, umbrellas and table clothes. Generally, a surface with a static water contact angle>150° is defined as a superhydrophobic surface [7]. The water contact angle (WCA) of a surface depends on two major properties: 1) surface roughness and 2) low surface energy [3,[7], [8], [9]]. The surface roughness can be achieved by fabricating a micro and nano-structured layer on the surface [10]. The low surface free energy can be realized by applying a low surface free energy substance on top of the nanostructured layer [10]. There are various reported methods available to fabricate superhydrophobic surfaces such as electrochemical deposition [11], self-assembly layer by layer method [2], hydrothermal synthesis [12], chemical vapor deposition, phase separation, wet chemical reaction [13], dip coating [7], spin coating, electrospinning and sol-gel processing [14]. Most of these methods are multi-step processes that require special equipment or chemicals, moreover they are expensive to implement at large scale and even the coatings are not transparent. As water has high surface tension (72.1 mN/m), superhydrophobic surfaces can be produced easily and also available in nature. However to repel low surface tension-liquids such as ethanol, a surface with lower surface free energy is usually required.
Fluoropolymers have lower surface free energy, high chemical and thermal stability, outstanding adhesive and oil-repellent properties, low refractive indices and low dielectric constants. These properties can be attributed to the high electronegativity of fluorine, strong fluorine-carbon bond and large Van der Waals radii [[15], [16], [17], [18], [19]]. Omniphobic textiles have been prepared using various fluoropolymers such as 1H, 1H, 2H, 2H-perfluorodecanethiol [13], 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane and perfluorododecyl -1H, 1H, 2H, 2H-triethoxysilane [14]. However, these methods are highly time consuming and the modifications therein change the fabric color or leave a slippery surface.
In our work, we developed a method to modify polyester fabric to make it omniphobic. The method involves first depositing a seed layer on the fabric followed by a polymer layer. In a typical experiment, the polyester fabric is first coated with ZnO seed layer and the low surface free energy was realized using TDM. First ZnO and TiO2 both were used to deposit the seed layer as they are less expensive, easily available, easy to handle and environment-friendly. Out of the two, ZnO turned out to be the best as the TiO2 seed layer detached from the fabric during fluoropolymer application indicating weak interaction with the fabric compared to ZnO. When the most optimized method is used, interestingly no color change or slippery surfaces were observed. More importantly this method is less time-consuming, low cost and easy to process [18,19].
Section snippets
Materials and characterization techniques used
3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl methacrylate(C12H19F13O2, 98%), sodium hydroxide (NaOH, 98%), sodium persulfate (Na2S2O8, 98%), zinc nitrate hexahydrate ((Zn(NO3)2.6H2O, 99%), titanium(IVI isopropoxide (Ti[OCH(CH3)2]4, 97%) (TTIP), hexamethylene tetraamine (HMT) (C6H12N4, 99%) and absolute ethanol (100%) were purchased from Sigma-Aldrich and used without further purification. Polyester fabric was purchased from a local store (Technical parameters of the fabric: Fabric type- woven,
Morphological and elemental characteristics
Achieving the omniphobic property, as described before, mainly depends on the careful construction of the modified surface. In this regard, surface morphological characterization is very important. SEM characterization was carried out to analyze the surface morphology of the non-treated polyester fabric (NT) (Fig. 1a), fluoropolymer applied fabric without any seed layer (FP) (Fig. 1b), ZnO seed layer applied fabric (ZO) (Fig. 1c), fluoropolymer applied fabric on top of the ZnO seed layer (Fig. 1
Conclusions
Polyester fabric surface was successfully modified to achieve robust omniphobic property using a novel and simple method. The fabric with the ZnO seed layer showed better superhydrophobicity (WCA 152°) compared to the fabric without a seed layer (142°). The modified omniphobic fabric showed higher durability over 50 cycles of abrasion and over 1.5 h of washing (three washing cycles). The treated fabric also made contact angle of 132° with oil and even after 50 cycles of abrasion the contact
Declaration of Competing Interest
The authors declare that there is no conflict of interest. All authors have reviewed and agreed to publish the manuscript in the Journal of Fluorine Chemistry.
Acknowledgements
The authors are grateful to Ms. A. Senthilnathan and Ms. G. T. D. Chandrakumara for their kind support during this research.
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