A non-fluorinated mechanochemically robust volumetric superhydrophobic nanocomposite

doi:10.1016/j.jmst.2020.06.029

Abstract

Abstract:

The widespread use of water-repellent superhydrophobic surfaces is limited by the inherent fragility of their micro- and nanoscale roughness, which is prone to damage and degradation. Here, we report a non-fluorinated volumetric superhydrophobic nanocomposites that demonstrate mechanochemical robustness. The nanocomposites are produced through the addition of microscale diatomaceous earth and nanoscale fumed silica particles to high-temperature vulcanized silicone rubber. The water-repellency of the surface and bulk of nanocomposites having 120 phr of filler was determined based on the water contact angle and contact angle hysteresis. We compared the water-repellency of nanocomposites of differing diatomaceous earth to fumed silica mass ratios. Increasing the amount of diatomaceous earth enhanced the water-repellency of the nanocomposite surface, whereas an increased amount of fumed silica improved the water-repellency of the bulk material. Moreover, increasing the diatomaceous earth/fumed silica mass ratio improved the cross-linking density and hardness values of the nanocomposite. Despite being subjected to a range of mechanical durability tests, including sandpaper abrasion, knife scratching, tape peeling, water jet impact, and sandblasting, the nanocomposite maintained a water contact angle of 163° and contact angle hysteresis of 2°. When the water-repellency of the prepared nanocomposites eventually deteriorated, we restored their superhydrophobicity by removing the upper surface of the nanocomposite. This extraordinary robustness stems from the embedded low surface energy micro/nanostructures distributed throughout the nanocomposite. We also demonstrated the chemical stability, UV resistance, and self-cleaning abilities of the nanocomposite to illustrate the potential for real-life applications of this material.

Key words: Volumetric superhydrophobic, Nanocomposite, Diatomaceous earth, Hierarchical micro/nanostructure, Mechanical robustness, Chemical stability, Self-cleaning

E. Vazirinasab, G. Momen, R. Jafari. A non-fluorinated mechanochemically robust volumetric superhydrophobic nanocomposite[J]. J. Mater. Sci. Technol., 2021, 66: 213-225.

Figures/Tables 11

Fig. 1. Schematic illustration of the fabrication of the volumetric SH nanocomposite.

Table 1 Chemical composition and wettability properties of the HTV-SR nanocomposites.

Type	HTV-SR (phr)	DE (phr)	FS (phr)	WCA of the surface (°)	CAH of the surface (°)	WCA of the bulk material (°)	CAH of the bulk material (°)
HTV-SR	100	0	0	110.0 ± 1.7	49.1 ± 2.9	112.5 ± 2.1	48.9 ± 2.2
D30F90	100	30	90	152.1 ± 1.2	19.4 ± 0.9	155.8 ± 0.9	8.7 ± 1.5
D40F80	100	40	80	156.6 ± 1.0	12.3 ± 1.3	158.4 ± 1.0	5.9 ± 0.7
D50F70	100	50	70	159.8 ± 0.8	7.6 ± 1.1	160.2 ± 1.2	3.1 ± 0.8
D60F60	100	60	60	160.7 ± 0.6	6.2 ± 0.7	161.3 ± 0.6	4.2 ± 0.4
D70F50	100	70	50	163.1 ± 0.5	3.7 ± 0.5	159.3 ± 0.8	7.1 ± 0.9
D80F40	100	80	40	164.2 ± 0.7	2.8 ± 0.6	155.9 ± 1.0	18.4 ± 1.6
D90F30	100	90	30	163.1 ± 0.8	5.1 ± 0.4	152.0 ± 0.8	23.9 ± 1.2

Fig. 2. (a) The effect of diatomaceous earth (DE) concentration on the WCA and CAH of the HTV-SR nanocomposite surface and bulk material; (b) a water droplet showing the WCA and CAH of a pristine HTV-SR and a nanocomposite D70F50; (c) SEM image of DE particles (×1000); (d) demonstration of the mirror-like phenomenon on the surfaces of the submerged bulk nanocomposite D70F50; (e) demonstration of the Moses effect around the intact and cut surfaces of nanocomposite D70F50, showing a water meniscus of approx. 5 mm (red arrows illustrate the meniscus). The blue water droplets illustrate the superhydrophobicity of the surfaces.

Table 2 Crosslinking measurements obtained from the swelling test and hardness values obtained for the pristine HTV-SR and the produced nanocomposites.

Type	Swelling ratio	Crosslinking density (mol cm^-3) × 10^-4	M_C (g mol^-1)	Hardness (Shore A)
HTV-SR	1.485 ± 0.002	1.63 ± 0.02	7076 ± 109	62.8 ± 0.7
D30F90	0.848 ± 0.006	1.16 ± 0.06	9943 ± 452	92.0 ± 0.6
D40F80	0.765 ± 0.005	1.35 ± 0.05	8519 ± 360	91.2 ± 0.9
D50F70	0.668 ± 0.004	1.65 ± 0.04	6974 ± 278	92.1 ± 0.5
D60F60	0.639 ± 0.003	1.76 ± 0.03	6540 ± 163	94.8 ± 0.6
D70F50	0.595 ± 0.004	1.95 ± 0.04	5896 ± 271	96.1 ± 0.4
D80F40	0.550 ± 0.002	2.18 ± 0.02	5263 ± 102	97.0 ± 0.4
D90F30	0.562 ± 0.004	2.12 ± 0.04	5427 ± 265	97.2 ± 0.9

Fig. 3. Surface profiles and roughness values of (a) pristine HTV-SR and the nanocomposites (b) D60F60, (c) D70F50, and (d) D80F40; FESEM images of the surface of (e) the pristine HTV-SR and the nanocomposites (f) D60F60, (g) D70F50, and (h) D80F40; FESEM images of the cross-section of (i) the pristine HTV-SR and the nanocomposites (j) D60F60, (k) D70F50, and (l) D80F40. All images (e-l) are at ×1000 magnification.

Fig. 4. FESEM images of the surface of nanocomposites (a) D60F60, (b) D70F50, and (c) D80F40; FESEM images of the cross-section of nanocomposites (d) D60F60, (e) D70F50, and (f) D80F40. All images (a-f) are at ×10000 magnification.

Fig. 5. (a) FTIR spectra of the pristine HTV-SR and nanocomposite D70F50 (inset shows the FTIR spectra of FS and DE); (b) TGA curve of the pristine HTV-SR and nanocomposite D70F50.

Fig. 6. (a)-(c) Sandpaper abrasion of the nanocomposite D70F50; (a) an image of the sandpaper abrasion apparatus; (b) WCA and CAH of the nanocomposite abraded by #160, #320, and #800 sandpaper after 250 abrasion cycles at a 5 kPa abrasion force; (c) WCA and CAH of the nanocomposite abraded by #160, #320, and #800 sandpaper after 250 abrasion cycles at a 25 kPa abrasion force; (d) knife scratching test; (e) tape peeling test; (f) WCA and CAH of the nanocomposite after multiple cycles of tape peeling; (g) water jet impact test; (h) sandblasting test; (i) WCA and CAH of the nanocomposite after several repeated cycles of ultrasonication and abrasion. Insets demonstrate the wettability of the nanocomposite after the associated tests.

Fig. 7. Schematic illustration of the volumetric superhydrophobic nanocomposite containing DE and FS particles.

Fig. 8. (a) Changes in WCA and CAH of the nanocomposite D70F50 over time during its immersion in deionized water and in the acidic and alkaline solutions; (b) contact angle of droplets of deionized water and the acidic and alkaline solutions during the droplet evaporation test (inset images show the WCA during evaporation of the water droplet); (c) WCA of the nanocomposite and pristine HTV-SR after heating for 2 h at different temperatures; (d) hydrophobic recovery of the nanocomposite following each cycle of plasma treatment; (e) WCA and CAH of the nanocomposite relative to the pristine HTV-SR as a function of the duration of UV irradiation; (f) water uptake of the pristine HTV-SR and SH nanocomposite in relation to the duration of the sample immersion.

Fig. 9. The self-cleaning ability of the volumetric superhydrophobic nanocomposite D70F50. (a) SiC particles having an average diameter of 50 μm and (b) SiC particles having an average diameter of 18 μm were dispersed on the surface and cleaned using several water droplets. A clean surface is observed in the final images of the rows.

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