Scalable and Durable Superhydrophobic RTV

Silicone Rubber Insulator Coatings via

Fluorosilane-modified Silica Nanoparticle
Incorporation
Zijia Shen Feipeng Wang* Gang Wen
State Key Laboratory of Power State Key Laboratory of Power State Key Laboratory of Power
2021 International Conference on Electrical Materials and Power Equipment (ICEMPE) | 978-1-6654-1840-9/21/$31.00 ©2021 IEEE | DOI: 10.1109/ICEMPE51623.2021.9509104

Transmission Equipment & System Transmission Equipment & System Transmission Equipment & System
Security and New Technology Security and New Technology Security and New Technology
Chongqing University Chongqing University Chongqing University
Chongqing, China Chongqing, China Chongqing, China
[email protected] [email protected] [email protected]

Jianpeng Ye
State Key Laboratory of Power
Transmission Equipment & System
Security and New Technology
Chongqing University
Chongqing, China
[email protected]

Abstract—RTV silicone rubber coatings have been widely lengthy, extensive outages as reclosing tends to fail, the
applied to insulators because of their good hydrophobicity and economic loss caused by the former is more than ten times that
anti-fouling performance. However, challenge is presented as of the latter [4].
pollution flashovers frequently occur on the insulators
operating for years along transmission lines due to the Among a series of remedial methods to reduce pollution
hydrophobicity decline and deterioration of their RTV coatings. flashover incidents, coating hydrophobic surfaces (mainly
In this study, superhydrophobic RTV silicone rubber insulator room temperature vulcanizing (RTV) silicone rubber coatings)
coatings were fabricated on glass substrate using PDMS as base or applying silicone rubber composite insulators has been
material and fluorosilane-modified silica nanoparticles as validated to be the most significant enhancement in insulator
hydrophobic fille via simply high-pressure spraying, with 160º pollution performance [5]. RTV silicone coatings have been
contact angle and rolling angle less than 10º. The prepared applied extensively to the glass and porcelain insulators
coating maintains superhydrophobic stability under a harsh without sacrificing the electrical insulation strength and
environment involving six low (-15°C, 24 h) high (80°C, 24 h) mechanical performance of existing facilities while equipping
temperature cycles, and it exhibits excellent acid and alkali them with crucial pollution performance improvement [6].
corrosion resistance. Rather than laboratory research, this Despite their evident achievements for mitigating pollution
presented technique is facile and scalable, capable of large-area flashover, RTV coatings are increasingly incompetent to
superhydrophobic coating production on the complex surface,
prevent pollution flashover occurrences in recent years, as the
thereby boding well for great potentials in practical application.
mounting severe weather events and the ever-rising voltage
Keywords—superhydrophobicity, insulator coatings, RTV level of transmission lines. The common commercial RTV
silicone rubber, fluorosilane surface-modified silicone rubber surface shows a water contact angle (CA) no
bigger than 120° with an undesirable rolling angle (RA),
I. INTRODUCTION allowing water droplets to easily condense in the high-
moisture environment and hence causing corona discharge,
As one of the critical components of overhead
whose long-term development leads to hydrophobicity
transmission lines, insulators play a significant role in
decline as well serious aging and degradation of the insulator,
mechanical support to carry the conductor weight and tension
and eventually results in surface flashover [7]. Thus, it is
load and withstanding voltage stresses. Studies have shown
currently a pressing challenge to improve RTV coating’s
that insulator failure is the leading cause of reliability
hydrophobicity to enhance its performance on anti-pollution
reduction of transmission lines [1]. Once wetting and pollution
flashover by a cost-effective and scalable method, satisfying
accumulation (the latter being inevitable to the insulators
the growing need of demanding external insulation level of
operating for years), the surface of the insulator is likely to
insulators for the safe and stable operation of ultra/extra-high
suffer from leakage current, and arc discharges occur along
voltage power system.
with dry band formation, which can quickly develop to
pollution flashover, a notorious threat to the stable operation Commercial RTV coatings are generally composed of
of the power system [2], [3]. In China, the number of power base material and fillers, prepared by physical and chemical
outages caused by pollution flashover on transmission lines is reaction through the interaction of various components and
only slightly lower than that caused by lightning stroke; functional groups. Polydimethylsiloxane (PDMS) polymer is
however, since pollution flashovers are prone to result in generally used as the base material of RTV silicone rubber

978-0-7381-3212-9/21/$31.00 ©2021 IEEE

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coatings because of its excellent hydrophobicity, good film- prepared. Next, the nanoparticle/resin dispersion was prepared
forming performance, and strong adhesion. Silica nanoparticle by mixing fluorosilane-modified silica nano-sol (5g) and
as a reinforcing filler has distinct advantages in improving anhydrous ethanol (50 mL) under stirring for 1 h. Then, the
weatherability and electrical properties of RTV coatings; fluorosilane modified dispersion was stirred by a magnetic
meanwhile, it shows excellent dispersibility when it is stirrer for 15 min and then sprayed onto the substrate surface
prepared by simple sol-gel method. Therefore, in this paper, by a spray gun with pressure 0.1 to 0.15 MPa. The
PDMS and silica nanoparticles were chosen as the base superhydrophobic coatings were finally prepared after 1-h
material and filler, respectively, to prepare superhydrophobic curing in a drying oven.
coatings.
B. Characteristics
According to the Wenzel model and the Cassie-Baxter The surface morphology and the structure of the samples
model [8], a surface’s wettability depends on both surface
were studied by field-emission scanning electron microscope
energy and surface roughness. Low surface energy and dual
micro-nano hierarchical rough structure have been revealed to (SEM, JEOL 7800) and atomic force microscopy (AFM, Park
be the two decisive factors to fabricate superhydrophobic Systems XE7), respectively. The static water CA and RA of
coatings. The hydrophobic methyl group -CH3 with a surface the coating were measured by taking an average of 5 random
energy of 24 mJ/m2 is the reason for RTV coating’s 4 – 30 μL water droplets with ±0.2 μL error range on a
hydrophobicity. Notably, the surface energies of hydrophobic contact angle tester (SDC-100) at ambient temperature. Acid-
fluorosilane groups incorporated in this work – -CF3 and -CF2- alkali resistances were tested by measuring static water CA
– are far lower than that of -CH3, which are only 6 mJ/m2 and of the coating after samples being soaked at different pH
15 mJ/m2, respectively [9]. The extremely electronegativity of values (1 to 14) for 24 h. Weatherability of the coating was
fluorine atoms compels them to capture electrons from other
atoms to form a stable structure of the outermost eight determined by six low (-15°C, 24 h) high (80°C, 24 h)
electrons, which blocks reaction with other groups again by temperature cycles: the hydrophobicity changes after each
van der Waals force, and hence resulting in particularly low cycle of three superhydrophobic coatings prepared in the
surface energies of carbon fluoride groups, promising a further same batch were tested simultaneously. A dielectric
increase of coating’s hydrophobicity. Additionally, when spectrometer (Alpha, Novocontrol GmbH) was used to
fluorosilane molecules are grafted on the surface of silica measure relative permittivity with 10-2 – 106 Hz frequency
nanoparticles, the highly stable structure of outermost fluorine range. Surface resistivity was determined by a Keithley 8009
atoms can effectively bind their own electrons, capable of resistivity test fixture at 25°C.
improving the electrical insulation properties of
superhydrophobic coatings. III. RESULTS AND DISCUSSION
Reported here is a facile approach to fabricate A. Surface morphology and roughness
superhydrophobic coating via high-pressure spraying of The surface morphology of the coating is shown in Fig. 1.
PDMS/fluorosilane-modified silica nanoparticles dispersions It can be seen from Fig. 1a, a 104× magnified SEM image
on the glass substrate, which can be employed for the large- with scale length 1 μm, that large amounts of micron and
area and complex surface coating application. The water CA submicron-scale bulges are distributed on the surface of the
of the coating reached 160° with RA less than 10°. This work coating. When zooming in, as displayed by Fig. 1b, a 105×
tested and analyzed the microstructure, hydrophobicity, acid- SEM image with scale length 100 nm, the surface is covered
alkali resistance and weatherability of the superhydrophobic with protrusions less than 100 nm. These micron and nano
coating and compared its insulation properties with common protrusions constitute the dual micro-nano hierarchical rough
RTV silicone rubber coatings used in the power industry. structure of the surface.
II. EXPERIMENTAL SECTION From Fig. 2a, a 3D-AFM image of superhydrophobic
coating with an observed area of 40 × 40 μm2, the uneven
A. Fabrication details surface with random micro-scale contour peaks and nano-
(Heptadecafluoro-1,1,2,2-tetradecyl)trimethoxysilane scale protrusions is clearly shown, indicating dual micro-nano
(FAS-17) was obtained from MREDA, Co., Ltd. (Beijing, rough structure of the coating. Quantified by Fig. 2b AFM
China). Tetraethyl orthosilicate (TEOS) and roughness curve, the peak-to-peak difference of coating is -
Polydimethylsiloxane (PDMS) were purchased from Sigma- 800 – 800 nm, and the root-mean-square roughness reaches
Aldrich Co., Ltd. (St. Louis MO, USA). Aqueous ammonia 385 nm. It is evident from the curve that there are nano
and absolute ethanol were provided by Sinopharm Chemical protrusions and micron hole structure on the surface,
Reagent Co., Ltd. (Shanghai, China). confirming that the prepared superhydrophobic coatings have
the dual micro-nano hierarchical rough texture, a vital factor
Firstly, 30 mL TEOS solution, 20 mL 2 mol/L aqueous for coating being superhydrophobic.
ammonia, and 800 mL of anhydrous ethanol were weighed in
a measuring cylinder and poured into a three-necked flask at a
certain rate, followed by vigorous magnetic stirring at room
temperature for 24 h. The prepared sol solution was then
centrifuged to separate silica nano-gel, from which silica
nanoparticles were obtained by molecular sieve filtration.
Secondly, 3g silica nanoparticles and 10 mL FAS-17 were
added to 50 mL anhydrous ethanol, and then the solution was
mixed with a magnetic stirrer at 150 rpm spinning speed. After
1-h mixing, the silica nano-sol modified by FAS-17 was

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Fig. 1. SEM images of the superhydrophobic coating surface. Photograph of necessary to study coating’s hydrophobic properties after
(a) Zoom in 104 times with 1 μm scale length, and (b) Zoom in 105 times
with 100 nm scale length.
repeated high and low temperature cycles. From Fig.6, it can
be known that the static CA of the coating was 163º before
the test started, and its hydrophobicity was nearly unchanged
after one cycle. Although the hydrophobicity of coating
decreased as the cycle continued, it still maintains
superhydrophobic even after six cycles.

Fig. 2. Roughness of the superhydrophobic coating: (a) Roughness image,

and (b) Roughness curve.

B. Superhydrophobicity

Fig. 3. Water droplets on the coating: (a) Single droplet, and (b) Five random
water droplets.

Fig. 5. Static contact angle of the superhydrophobic coating after being

soaked at various pH bathing for 24 h.

Fig. 4. Superhydrophobicity of the coating with respect to the droplet size.

As demonstrated in Fig. 3a, coating’s superhydrophobicity

allows water droplets to stand on the surface as almost
spherical. Fig. 3b shows that 20 μL water droplets stand at
different locations on the coating under their self-tension and Fig. 6. Stability of the coating in a harsh environment with large temperature
fluctuations.
maintain a tiny contact area with the surface. Fig. 4 describes
the relationship between the droplet size (4 – 30 μL) and static C. Insulation properties
CA, revealing that the CA of the superhydrophobic coating Fig. 7 provides information about the insulation properties
does not change with the size of water droplets in a certain of the superhydrophobic coating. For comparison, the
range, whose value is between 159° and 163°with average commercial RTV silicone rubber coating serves as the
162.5° and RA less than 10°. reference group in each subgraphs. Fig. 7a plots the
As shown in Fig. 5, no obvious deterioration in the relationship between relative permittivity and frequencies of
superhydrophobicity of coating can be found after exposure two coatings. Overall, the relative permittivity of both
coatings decreases with increasing frequency from 10-2 to 106
to various pH (1 – 14) soaking for 24 h – the prepared coating
Hz. Over the whole test range, the relative permittivity of
can still preserve superhydrophobicity with minimum and common RTV coating dropped from 3.21 to 2.58, while that
maximum CAs of 154.4º and 161.1º, respectively. The of the superhydrophobic coating was from 3.04 to 2.46. The
excellent resistance to both acid and alkali of the lower relative permittivity of the superhydrophobic coating
superhydrophobic coating indicates its great potentials for a can effectively reduce not only the electric field distortion at
wide range of pH applications. the interface of coating, metal electrodes and air, to suppress
It is highly likely that the hydrophobic coatings of corona discharge, but also the adhesion between the coating
insulators are exposed to the harsh natural environment in and water droplets to promote the free movement of water
real application, which have to experience the alternating droplets on its surface. Fig. 7b exhibits surface resistivity
under different direct current (DC) voltage. The surface
process of high and low temperature. Therefore, it is

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resistivity of both coatings decreases with the increase of test film-forming agent of coating, and high pressure spraying to
voltage; however, the value of superhydrophobic coating is generate superhydrophobic coating on the glass substrate with
always higher than that of RTV coating. When the DC voltage dual micro-nano rough hierarchical structure has been
increased from 100 V to 1000 V, the surface resistivity of successfully developed. The water CA of coating reaches 160º
superhydrophobic coating decreased from 2.38×1013 to with RA less than 10º. According to the results of acid-alkali
0.79×1013 Ω/cm, and that of RTV silicone rubber coating resistance and weatherability tests, the superhydrophobic
decreased from 2.01×1013 to 0.64×1013 Ω/cm. The results coatings can maintain good superhydrophobic stability under
suggests that the prepared superhydrophobic coating has harsh environments. The insulation property tests show that
superior insulation performance than the RTV coating and both relative permittivity and surface resistivity of the
meets the requirement of surface resistivity for external superhydrophobic coating are superior to common RTV
electrical insulation. silicone rubber coatings. Rather than laboratory research, the
prepared superhydrophobic coating is scalable and durable,
exhibiting large potentials in practical application.
ACKNOWLEDGMENT
The author acknowledges financial support by the
National Key R&D Program of China (2018YFB2100100),
the National Natural Science Foundation of China
(U1866603) and the Project 111 of the Ministry of Education,
China (B08036).
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