CN116218367B

CN116218367B - Biologically initiated liquid repellent coating with lubricity and mechanochemical stability

Info

Publication number: CN116218367B
Application number: CN202211715325.9A
Authority: CN
Inventors: 班青; 卜鑫瑜; 刘利彬
Original assignee: Qilu University of Technology
Current assignee: Qilu University of Technology
Priority date: 2022-12-28
Filing date: 2022-12-28
Publication date: 2023-12-01
Anticipated expiration: 2042-12-28
Also published as: CN116218367A

Abstract

The invention discloses a ray-receiving skin heuristic coating (MSC). The hemispherical structure designed and formed by the silicon-containing material and simulating the surface of the solar ray skin endows the MSC with a transparent and firm smooth surface, the surface hardness of the MSC can reach 0.94GPa, and the friction coefficient is only 0.076.MSC has excellent adhesion on various substrates and has different surface tension (21.2-72.8 mN.m ^‑1 ) Different viscosities (0.8-1499 mPa.s) ^‑1 ) Exhibits excellent repellency properties. The coating can withstand 1000 wear cycles under a 250g load and still maintain high transparency and excellent lyophobic properties after 32 days of standing at extremely high/low temperatures. MSC has higher solid surface lubricating capability and mechanochemical stability, and has good long-term durability.

Description

Biologically initiated liquid repellent coating with lubricity and mechanochemical stability

Technical Field

The invention belongs to the field of new materials, relates to research of surface functional materials, and in particular relates to a biological initiated liquid-repellent coating with lubricity and mechanochemical stability, and a preparation method and application thereof.

Background

Surfaces with liquid repellent properties are critical in our daily life and industrial process because of their water-collecting, anti-fouling, anti-corrosion, anti-icing and anti-bioadhesion properties. By combining low surface energy materials with special roughness structures (re-entrant or double-entrant structures), superhydrophobic/amphiphobic surfaces with very low roll angles can be prepared. This strategy relies on coarse micro/nanostructures that can effectively support the liquid and maintain the presence of an air layer beneath the liquid. However, these surface micro/nanostructures are very fragile and cannot withstand physical damage caused by external stress, resulting in a transition from the cassie state (metastable state) built up from such surface structures to the winze state (thermodynamically stable).

As an alternative strategy, ultra-slippery surfaces have been proposed to address the drawbacks of ultra-hydrophobic/amphiphobic surfaces, as their liquid repellency is not necessarily dependent on roughness. To date, ultra-slippery surfaces can be broadly divided into three types. The first type is the lubrication liquid injection porous surface (SLIPS) proposed by Aizenberg et al in 2011, which converts the solid-liquid interface into a liquid-liquid interface, which repels liquid from the surface by means of the high surface mobility of the lubrication liquid surface. However, the practical use of SLIPS is limited by the stability of the lubricant, which may be lost by evaporation, external shear stress, or by the "shadowing effect". The second type of ultra-slippery surface is one that repels liquids by covalently grafting a flexible polymeric brush like PDMS or perfluoropolyether onto the smooth surface. However, chemical grafting relies on a complex and time-consuming preparation process, limiting the realization of industrialization. The third type of spray coating consisting of low surface energy polymeric materials, which solves the problems of stability of lubricating fluids and mass production, has received a great deal of attention in recent years. For example, liu et al use siloxane oligomers to prepare oil repellent supramolecular silicone coatings that can exclude liquids with low surface tension and have some self-healing capabilities. Silicon-containing polymers or elastomers are often selected as materials for making ultra-slippery surfaces because of their excellent chemical inertness and low surface energy that make them liquid repellent.

CN202210862292.4 discloses a method for preparing a self-adhesive super-slip coating rich in coil-shaped liquid-like brushes, which comprises the steps of preparing liquid-like polymer nanoemulsion by adopting an ultrasonic and compatibilizer-assisted method; then, diluting the liquid-like polymer nano emulsion, and coating the diluted liquid-like polymer nano emulsion on the surface of a substrate; and then adopting a unidirectional electrostatic field auxiliary and gradient heating mode to realize the microscopic gradient structures of the coil-shaped liquid-like brush and the coating adhesion layer-harmonizing layer-antifouling layer on the surface of the coating on the substrate, and improving the fastness of the liquid-like brush and simultaneously endowing the coating substrate with adhesion and suitability.

CN202210563602.2 discloses a method for improving the wear resistance of a super-slip coating, which realizes the improvement of the wear resistance of the super-slip surface by injecting functional antifriction super-slip nano-fluid into the surface of a porous matrix. The method for improving the wear resistance of the ultra-smooth coating comprises the steps of preparing and using antifriction ultra-smooth nano fluid; mixing the organic long chain modified nanoparticle dispersion with a perfluorinated ligand to perform ligand exchange, so as to form a nano-fluid with the perfluorinated ligand coated with the nanoparticles; the friction coefficient of the surface is reduced by injecting the functionalized nano-fluid into the porous surface, so that the wear resistance of the ultra-smooth surface is improved.

However, such polymer coatings have low surface hardness, low overall structural strength, and poor abrasion resistance. Therefore, it would be very promising to develop a super-slip surface that can be prepared by spray methods while having mechanochemical stability (e.g., high hardness and strong adhesion to different substrates).

Disclosure of Invention

The invention aims at overcoming the defects of the prior art and provides a liquid-repellent coating with antifouling and drag-reducing performances, and a preparation method and application thereof.

In nature, many organisms' skin has excellent antifouling drag reduction properties as it evolves, which provides a concept for us to design ultra-slippery surfaces. For example, the skin of ray is hard and abrasion resistant, mainly because lime deposits on the scale forming a convex hemispherical morphology (fig. 1 a).

The invention is realized by the following technical scheme:

a method for preparing ultra-smooth coating (MSC) for stimulating skin of Hepialus ray comprises the following steps

S1, adding glycidoxypropyl polyhedral silsesquioxane (GPOSS), EPFS, HPS and a solvent into a reaction container, and fully mixing; the solvent is absolute ethyl alcohol;

s2, stirring the mixed solution obtained in the step 1) for 1 to 3 hours at the temperature of between 40 and 80 DEG C

S3, the obtained suspension can be applied to various base materials by spraying, spin coating, paint spraying and the like,

s4, solidifying in an oven to obtain MSC; the curing temperature is 90-110 ℃.

For the mixed suspension, GPOSS-co-HPS particle size was 10-20nm and EPFS-co-HPS particle size was 5-12nm. The particle size of the MSC suspension is 10-15nm.

To obtain a structure similar to hemispherical dense packing of the skin surface of a ray of Hepialus, hyperbranched amine-rich polysiloxane (HPS) was formed by polycondensation reaction using a small molecular aminosilane coupling agent N- [3- (trimethoxysilyl) propyl ] ethylenediamine (KH-792). Hard segment GPOSS (glycidoxypropyl polyhedral silsesquioxane) has a cage-like silica-rich molecular structure to provide structural rigidity to the coating. The highly flexible structure of EPFS (epoxy modified poly (3, 3-trifluoropropyl methyl siloxane)) with fluorinated side chains is selected to provide repellency to external liquids. The rich amino groups on HPS as the core of the reaction can react with the epoxy groups on GPOSS and EPFS (fig. 1 b), forming denser globular clusters. The photo of the bats and the partial enlarged view of the skin of the bats are shown in figure 1 a. The 3D map of the synthetic clusters in ethanol solvent is shown in fig. 1 b.

Preferably, in step S1, the mass ratio of HPS, GPOSS and EPFS is (0-9): (0-9): (1-7), the ratio of the addition of the solvent to the total mass of the monomers is (2.82-11.28): 1. preferably, the mass ratio of HPS, GPOSS and EPFS is (0-3): (1-8): (3-7).

Preferably, in step S1, 0.8g GPOSS, 0.1g EPFS and 0.5g HPS are mixed with 10mL (7.893 g) solvent absolute ethanol in a 100mL round bottom flask.

Preferably, in step S2, stirring is carried out at 60℃for 2 hours.

Preferably, in step S3, the substrate is selected from glass, wood, PMMA sheet, various metals, and the like.

Preferably, in step S4, the MSC is obtained after curing for 8-10 hours in an oven at 100 ℃.

Preferably, the preparation method of the hyperbranched amino-rich polysiloxane (HPS) comprises the following steps:

a) Adding N- [3- (trimethoxy silicon based) propyl ] ethylenediamine (KH-792), absolute ethyl alcohol and deionized water into a reaction vessel, and stirring at 40-80 ℃ for 4-12 hours;

b) Absolute ethanol was removed by rotary evaporation under vacuum to give a colorless viscous liquid, HPS.

Preferably, in step a), the volume ratio of KH-792, absolute ethanol and deionized water is (1-15): (1-15): (0-2), more preferably, the volume ratio of KH-792, absolute ethanol and deionized water is 10:10:1; preferably, in step a), stirring is carried out at 60℃for 10 hours.

Preferably, the preparation method of the epoxidized poly (3, 3-trifluoropropyl methyl siloxane) (EPFS) comprises the following steps:

1) Poly (3, 3-trifluoropropyl methyl siloxane) (PTFMS) and (3-Glycidoxypropyl) Dimethylethoxysilane (GDES) were added to a reaction vessel and stirred;

2) Tetramethyl ammonium hydroxide solution (THAM) was added and air was vented with inert gas;

3) Sealing and reacting for 4-8 hours;

4) After the reaction was completed, THAM and methanol were removed. The resulting pale yellow transparent viscous material was EPFS.

Preferably, in step 1), the mass ratio of poly (3, 3-trifluoropropyl methyl siloxane) (PTFMS) to 3-glycidyl propyl trimethoxysilane (GDES) is 1: (0.1-1)

Preferably, the reaction temperature in step 1) is 60 to 90 ℃.

Preferably, in step 1), 1g of poly (3, 3-trifluoropropyl methyl siloxane) (PTFMS) and 0.3mL (3-Glycidoxypropyl) Dimethylethoxysilane (GDES) are stirred in a 100mL round bottom flask in a 80℃water bath.

Preferably, in step 2), the amount of tetramethylammonium hydroxide solution (THAM) added is 0.1mL, and the reaction system is adjusted to a pH of about 10 to 11;

preferably, in step 2), the inert gas is nitrogen or argon.

Preferably, in step 2), 0.1mL of tetramethylammonium hydroxide solution (THAM) is added and the flask is continuously flushed with N2 to vent the air thoroughly.

Preferably, in step 3), the closed reaction environment is stirred for a further 6 hours.

Preferably, in step 4), the THAM and methanol are removed by vacuum rotary evaporation.

The invention also provides a super-slip coating (MSC) prepared by the method.

A superslide coating (MSC) for stimulating skin of a ray of a Hepialus is prepared by agglomerating EPFS, GPOSS and HPS, wherein EPFS chains and GPOSS cages are combined with HPS to form spherical clusters, and the distance between HPS and EPFS isAnd the distance between the HPS and the epoxy group on GPOSS is about +.>GPOSS is glycidoxypropyl polyhedral silsesquioxane, EPFS is epoxy modified poly (3, 3-trifluoropropyl methyl siloxane), and HPS is hyperbranched amino-rich polysiloxane.

The surface morphology and internal structure of MSCs were characterized. High magnification Atomic Force Microscopy (AFM) showed that hemispherical clusters of 15-20nm in size appeared densely arranged on the surface (FIG. 4 b). The diameter of the hemispheres was consistent with the particle size in the MSC suspension particle size test (fig. 10). The height of the protrusions is only about 4nm (fig. 4b inset).

The cross-sectional SEM images showed that the thickness of the MSCs was about 50 μm (fig. 4c inset). The elemental distribution image shows that fluorine migrates to the surface (fig. 4 c) due to the relatively high solidification temperature, which is critical for the liquid repellent properties of the MSC surface.

A coating composition comprising 20 to 30% by mass of HPS, 60 to 70% by mass of GPOSS and 10% by mass of EPFS, a coating composition comprising 0 to 30% by mass of HPS, 50 to 80% by mass of GPOSS and 20% by mass of EPFS, a coating composition comprising 0 to 20% by mass of HPS, 50 to 70% by mass of GPOSS and 30% by mass of EPFS, a coating composition comprising 0 to 10% by mass of HPS, 50 to 60% by mass of GPOSS and 40% by mass of EPFS, a coating composition comprising 0 to 20% by mass of HPS, 10 to 30% by mass of GPOSS and 70% by mass of EPFS, and a sliding angle of less than 10 °. More preferably, a coating consisting of 20-30% HPS, 70-60% GPOSS and 10% EPFS by mass fraction gives a minimum SA of 7.06 DEG + -0.06 deg.

The abrasion experiments further demonstrate an optimal component content with 30% HPS, 60% GPOSS and 10% EPFS by mass fraction. The coating remained at a slip angle of less than 10 ° after 800 taber abrasion cycles according to ASTM test standard load of 250g weight (fig. 12).

Since the size of the clusters is smaller than the wavelength of visible light, the average transmittance of the MSCs reaches 92%.

MSCs can also withstand extreme high and low temperatures. After one month of standing at a high temperature of 120 ℃ and a low temperature of-25 ℃ respectively, the sliding angle of water on the surface of MSC was still 7.34 ° ± 0.96 °, the transparency was substantially the same as the original transparency (fig. S15, S16), indicating the stability of the coating structure and chemical composition.

The average coefficient of friction of the MSC surface was measured as low as 0.0756 (fig. 13 f), after 1000 wear cycles, the water droplets could slide off the coating surface without any residue, although the sliding angle increased to 15.73 ° ± 1.43 °. Meanwhile, the average visible light transmittance of the coating is kept above 85%.

The adhesion of MSC on stainless steel substrate can reach 9.47±0.32MPa and even on teflon surface can reach 0.81±0.2MPa (fig. 13 j).

The application of the ultra-smooth coating (MSC) inspired by the skin of the bata ray can be used as an antifouling, oil-proof and anti-fog coating, and has wide application scenes.

The present invention has developed a smooth surface with high hardness and has the ability to repel liquids with a wide range of surface tension and viscosity. The coating suspension comprises hyperbranched rich amine polysiloxane (HPS), glycidoxypropyl polyhedral silsesquioxane (GPOSS) and epoxy modified poly (3, 3-trifluoropropyl methyl siloxane) (EPFS), target clusters are synthesized in ethanol solvent, and a compact stacking structure similar to the surface of the Hepialus ray fish skin is obtained after spray curing.

MSC has excellent adhesion on various substrates and has excellent rejection performance for liquids with different surface tension (21.2-72.8 mN.multidot.m < -1 >) and different viscosity (0.8-1499 mPa.multidot.s < -1 >). The coating can withstand 1000 wear cycles under a 250g load and still maintain high transparency and excellent lyophobic properties after 32 days of standing at extremely high/low temperatures. MSC realizes the ultra-low sliding angle of the solid ultra-sliding coating to liquids with different surface tension and different viscosities, and the sliding performance is obviously superior to that of the reported solid ultra-sliding coating.

Thanks to a reasonable design and the formation of spherical clusters aggregates, MSCs have a transparent and strong ultra-slippery surface with a hardness of about 0.94GPa and a friction coefficient of only 0.076.MSC pairs having 21.2 to 72.8 mN.m ^-1 The liquids having a surface tension and a viscosity of 0.8 to 1499 mpa.s exhibit extraordinary repellency. MSC has long-term durability, and the coating can still maintain high transparency and excellent lyophobic performance after 1000 abrasion cycles under 250g load or after being placed for 32 days at extremely high/low temperature. In addition, the adhesion of ice to the MSC surface is only 8.9kPa, and a large area of ice can be easily removed from the MSC surface by a slight external force (wind or slight vibration). The MSC also protects metals from harsh environments, for example, it can withstand 500 hours of copper ion accelerated acid salt spray (CASS) corrosion testing.

Drawings

FIG. 1 a) Hepialus ray photograph and Hepialus ray an enlarged view of the skin is partially formed. b) 3D maps of clusters were synthesized in ethanol solvent.

Figure 2 GPOSS density profile simulated by solvent (ethanol) Molecular Dynamics (MD). The red region is a low aggregation density region, and the blue region is a high aggregation density region.

FIG. 3 is a graph of MD simulation results for solvent (ethanol). Red molecules represent GPOSS, blue molecules represent HPS, green molecules represent EPFS, and grey molecules represent ethanol. Pictures of simulation going to 0, 200, 400, 600, 800, 1000ps, respectively.

Figure 4 a) schematic diagram of MSC preparation process. b) Atomic Force Microscope (AFM) characterization of MSC surfaces. c) Cross-sectional elemental plot of MSC, purple represents fluorine distribution. The inset is a cross-sectional SEM image of the MSC. d) The Sliding Angle (SA) of water varies with different curing times and curing temperatures, respectively. e) SA trend of water with different mass fractions of HPS, EPFS and GPOSS. f) Hardness varies with mass fractions of different HPS, EPFS and GPOSS. g) Transmission of MSC coated glass and original glass. The inset is a photograph of an MSC coated glass sample (45 cm. Times.40 cm). The inset is a photograph of an MSC coated glass sample (45 cm. Times.40 cm).

FIG. 5 shows a schematic diagram of HPS molecules when MD simulation is performed with solvent (ethanol), a) in the initial state and b) in the final state. The volume of the HPS molecules is simply represented by an oval green shade, the blue dotted line representing the X-axis, the red dotted line representing the Y-axis, the purple dotted line representing the Z-axis, and the corresponding color number representing the length in units ofThe volume of the HPS molecule is simply indicated by the oval green shade, the blue dotted line indicates the X-axis, the red dotted line indicates the Y-axis, the purple dotted line indicates the Z-axis, and the corresponding color number indicates its length in>

FIG. 6 scheme of HPS molecules in MD simulation in vacuum, a) is the initial state, b) is the final state. The volume of the HPS molecules is simply represented by an oval green shade, the blue dotted line representing the X-axis, the red dotted line representing the Y-axis, the purple dotted line representing the Z-axis, and the corresponding color number representing the length in units ofIt can be seen that the molecular structure is more extended without ethanol.

Figure 7 GPOSS density profile simulated by Molecular Dynamics (MD) in vacuum. The red region is a low aggregation density region, and the blue region is a high aggregation density region.

Fig. 8 is a graph of MD simulation results in vacuum. Red molecules represent GPOSS, blue molecules represent HPS, and green molecules represent EPFS.

FIG. 9 Radial Distribution Function (RDF) graphs of GPOSS-HPS (red) and EPFS-HPS (blue). Data from MD simulations under a) solvent system and b) vacuum system, respectively. RDF shows that the distance between HPS and EPFS is mainly concentrated in solvent-borne systemsWithin a range of about +.A distance between HPS and epoxy on GPOSS>This may be caused by steric hindrance of the GPOSS. These results of MD simulations indicate that EPFS chains and GPOSS cages can combine with HPS to form different globular clusters. EPFS is in the near range +.>The ratio of the average density g (r) within is significantly greater, indicating that EPFS and HPS are better able to combine without solvent effects. However, the RDF curve of GPOSS does not change significantly, indicating that the steric effect impedes the intermolecular interactions to some extent even in the absence of solvent.

FIG. 10 DLS plots of MSC, GPOSS-co-HPS (in suspension, the number of moles of epoxide groups on GPOSS is equal to the number of moles of active hydrogen on HPS), EPFS-co-HP (in suspension, the number of moles of epoxide groups on EPFS is equal to the number of moles of active hydrogen on HPS), and 100% HPS (pure HPS suspension), 100% EPFS (pure EPFS suspension) and 100% GPOSS (pure GPOSS suspension), respectively; the particle size of the GPOSS suspension is mainly distributed at about 5nm, while the particle size of the EPFS is slightly smaller at about 4nm, mainly due to the different structure of the two molecules (one cage and one chain). For the mixed suspension, the particle sizes of GPOSS-co-HPS and EPFS-co-HPS were mainly distributed at 10-20nm and 5-12nm. The particle size of the MSC suspension is mainly distributed between 10 and 15nm.

Fig. 11 SEM image of MSC surface. The magnification was 50000×.

Fig. 12 sliding angle of control samples 1-4 and MSCs as a function of wear test cycle. The abrasion resistance of MSCs was significantly higher than other comparative samples. The composition details of the four comparative samples are as follows. Control sample 1:20wt% HPS, 50wt% GPOSS and 30wt% EPFS. Control sample 2:10wt% HPS, 60wt% GPOSS and 30wt% EPFS. Control sample 3:10wt% HPS, 70wt% GPOSS and 20wt% EPFS. Control sample 4:20wt% HPS, 70wt% GPOSS and 10wt% EPFS. The composition of the MSC is: has HPS with mass fraction of 30%, GPOSS with mass fraction of 60% and EPFS with mass fraction of 10%.

Fig. 13 a) the state of water droplets photographed by a high-speed camera on the surface of MSC, the substrate inclination angle is 10 °. b) SA of liquids with different surface tension on the MSC surface. The illustrations are optical images of ethanol and water, respectively, at the surface of the MSC. c) SA of liquids of different viscosities on the surface of MSCs, inset is a photograph of MSC coated glass before and after immersion in glycerol. d) With the substrate tilt angle maintained at 15 °, eight different liquids (H2O, ethanol, n-hexadecane, DCM, tween, span-80, castor oil and glycerol) were slid on the MSC surface for 5 cm. e) The contact angle of water (CA) and SA as a function of drop temperature. f) The friction coefficient curve of MSC, red dotted line, is the average friction coefficient calculated from the experimental data. g) Comparison of the coefficient of friction with the work recently reported. h) Comparison of Young's modulus and stiffness of MSC to commercial polymers. i) The average transmittance of water SA (red curve) and MSC (blue curve) as a function of wear test cycle. j) Comparison of adhesion of MSC to coatings prepared with KH-792.

Fig. 14 contact angles of liquids with different surface tension at the MSC surface.

Fig. 15 contact angles of liquids with different viscosities at the MSC surface.

Figure 16 displacement-load curve of nanoindentation test. All five test points come from different locations on the same sample. There were no significant differences between the five sets of data indicating sample surface uniformity.

Detailed Description

The following examples are further illustrative of the invention, but the invention is not limited thereto. The reaction vessel comprises a small reactor (such as a round bottom flask and the like) in experiments and an industrial reaction vessel (such as a reaction kettle and the like). Unless otherwise indicated, all references herein to "reaction vessel" are intended to be given the meaning set forth above.

Reagent material

N- [3- (trimethoxysilyl) propyl ] ethylenediamine (KH-792), 3-glycidylpropyltrimethoxysilane (KH-560) and tetramethylammonium hydroxide solution (THAM) were purchased from Aba Ding Shiji Co., ltd, and glycidoxypropyl polyhedral silsesquioxane (GPOSS) was purchased from Guangzhou New Co., ltd (China). Poly (3, 3-trifluoropropyl methyl siloxane) (PTFMS) was purchased from Wuhan Nara white pharmaceutical chemical Co., ltd. (3-Glycidoxypropyl) Dimethylethoxysilane (GDES) is available from Tourette chemical Co., ltd; absolute ethanol, nitric acid, HCl, naOH are all supplied by national pharmaceutical chemicals limited (china). The molecular structure of GPOSS is as follows:

Characterization:

the tests according to the invention were carried out as follows, unless otherwise indicated.

Scanning electron photomicrographs (SEM)

SEM characterization was performed at SUPRA ^TM 55 thermal field emission scanning electron microscopy (Zeiss, germany). After spraying MSCs on the glass substrate and curing, the samples were quenched with liquid nitrogen and then SEM-characterized for different surfaces and cross-sections of the samples.

Atomic Force Microscope (AFM)

AFM characterization was performed on a Dimension ICON2-SYS atomic force microscope (Bruker, USA). After spraying MSCs on the glass substrate and curing, the samples were quenched with liquid nitrogen and then the different surfaces of the samples were characterized. The test temperature was 25 ℃.

Particle size analysis (dynamic light Scattering, DLS)

Particle size characterization was performed on a Zetasizer Nano ZS nm particle size potentiometric analyzer (Malvern, uk). The diluent solvent tested was ethanol. A four-way cuvette containing pure ethanol is used as a reference cuvette, and the solution to be measured is filled into another cuvette.

Transmittance characterization

Transmittance was performed on a UV-vis spectrophotometer (UV-2600, shimadzu, japan). MSCs were sprayed onto glass slides (7.5 cm x 2.5 cm) and the original glass slides served as control samples. The transmittance of air was set as the baseline for the test. The test wavelength range is 400nm to 800nm.

Wetting characteristics

Contact and sliding angles were measured by a SL250 dynamic/static optical contact angle meter (KINO, usa). MSCs were coated on glass slides (7.5 cm x 2.5 cm) and the liquid volume measured at each time was 10 μl. . When the drop stabilizes, a side view image is taken with a camera. For slip angle measurement, the sample is tilted using a motor-controlled rotatable test platform, and the rotation angle will be fed back in real time on a computer connected to the motor.

Talbot abrasion test

Durability was evaluated using a taber abrasion tester according to ASTM standard test (D4060 standard). Two loading wheels (fromIndustries>Cs-10). Abrasion tests were performed on annular glass substrates having a diameter of 10 cm.

Friction test

The friction test was performed in a reciprocating mode on a UMT-2MT wear tester (CETR, USA). The test was performed at room temperature with a load of 800 μN, a test frequency of 30 millimeters per minute and a test time of 30 minutes.

Adhesion test

To test the adhesion of the coating to different substrates, AB glue was used to bond the center shaft to the coating. The center shaft was loaded with 200g of weight and then dried at room temperature for 3 days to complete adhesion. The adhesion between the coating and the substrate was tested using an adhesion tester (XH-M, china).

Nano indentation test

The nanoindentation test was performed on a Bruker Hysitron TI980 press equipped with a standard berkovich press. The displacement is used as a control signal. The test procedure included a load (5 seconds) -hold (2 seconds) -unload (1 second) procedure. Five different positions are taken for each sample to reduce errors.

Stability test

i. High temperature stability. MSC coated glass substrates were subjected to high temperature stability testing in an oven at 120 ℃ with contact angle and slip angle measurements taken every 4 days for a total of 32 days.

Stability at subzero temperature. The MSC-coated glass substrates were subjected to a low temperature stability test in a-25 ℃ refrigerator, with contact angle and sliding angle measurements taken every 4 days for a total of 32 days.

High temperature drop test. Drops of water at different temperatures (0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃ respectively) were dropped onto the surface of the MSC, and the contact angle and sliding angle were measured. The inset photograph obtained from the thermal infrared imaging shows the state of water droplets sliding on the MSC surface at 80 ℃.

Thermal infrared photography

Thermal infrared imagers were performed on a handheld UTI160H thermal infrared imager (UNI-T, china). The thermal infrared images are continuously shot under the condition of fixed distance.

Anti-icing test

i. Anti-icing test at varying temperatures. The whole test process is carried out in a refrigeration cycle machine. The original aluminum sheet (10 cm. Times.10 cm) and MSC coated aluminum sheet were placed in a refrigeration cycle machine at an inclination of 10. The initial temperature was 0℃and 2mL of water was added to the test sample at 10℃drops until the temperature reached-70 ℃. At each temperature, deionized water was allowed to freeze completely for 30 minutes. The ice on the sample surface was then weighed.

Anti-icing test at constant temperature. MSCs were coated on 6cm×6cm aluminum sheets, and original aluminum sheets were used as control samples. All test samples were kept at-25 ℃ for 1 hour to allow the samples to cool to the test temperature and remain constant. Flowing water was then applied to the surface of the sample to observe the frozen state of the water.

Deicing test

i. Ice adhesion measurement. The deicing performance of MSCs is characterized by quantifying the force required to deice the surface of an MSC. The force was measured using a MARK-10M3-500 (united states) hand-held load cell. Briefly, ice (1 cm. Times.1 cm. Times.0.2 cm) was stored at various sub-zero temperatures for 2 hours to ensure complete freezing. For different sized ice block tests, water was filled into 1cm wide PDMS molds, with different lengths (1 cm, 2cm, 3cm, 4cm, 6cm, 8cm, 10cm, 15cm and 20 cm) and different thicknesses (2 mm, 4mm, 6mm, 8mm and 10 mm) on the test surface, and frozen in a low temperature chamber at-50 ℃ for more than 2 hours to ensure complete freezing. After removal of the soft PDMS mold, the load cell probe (1 cm wide) was parallel to the ice cubes tested. During the test, a continuous external force is applied until the ice pieces are completely moved, from which the peak force required to remove the ice pieces can be obtained on the load cell.

Large scale deicing test. Ice of size 40cm x 30cm was frozen on the surface of MSC Al using a mold which was kept at-50 ℃ for 12 hours to be completely frozen. The sample was then immediately removed and tested.

Copper accelerating acetate fog (CASS)

5% sodium chloride solution and an appropriate amount of acetic acid were added to a salt spray corrosion tester (Lai St. Equipment Co., ltd.) to adjust the pH to about 3. Adding proper amount of anhydrous copper chloride (concentration: 0.26. 0.26g L) ^-1 ) (ASTM B368) to induce strong corrosion. The test temperature was 50 ℃. Under the CASS test, the corrosion speed is 2-3 times faster than that of the acetate fog test. This is an extremely severe environment. The samples were tested for changes at different times. Furthermore, in order to quantitatively evaluate the corrosion resistance of the coating (Δm, Δm= |m) ₀ -m _t I), where m ₀ Is the initial mass of the sample, m _t Is the mass of the sample at different test times.

Electrochemical measurement

Electrochemical measurements of the coating were performed in a CASS (ASTM B368) environment. The coatings were electrochemically measured at a stable open circuit voltage using a CHI 660D electrochemical workstation (Shanghai morning glory, china). The scan rate of the polarization curve was 1mV s _-1 Electrochemical impedance spectrum is thatIs performed in the frequency range of 5mV. Each test is repeated for more than three times to ensure the accuracy of the experimental result.

The following specific examples are provided to further illustrate the present invention, but the present invention is not limited thereto.

EXAMPLE 1 Synthesis of starting Compounds

Preparation of hyperbranched amino-rich polysiloxanes (HPS)

Into a 100mL round bottom flask was added 10mL KH-792, 10mL absolute ethanol, and 1mL deionized water, and stirred at 60℃for 10 hours. After the completion of the reaction, absolute ethanol was removed by rotary evaporation under vacuum to obtain colorless viscous liquid as HPS.

Preparation of epoxidized poly (3, 3-trifluoropropyl methyl siloxane) (EPFS)

1g of PTFMS and 0.3mL of GDES in a 100mL round bottom flask were stirred in a 80℃water bath. Then, 0.1mL THAM was added and N was used ₂ The flask was continuously flushed to thoroughly vent the air, and the reaction environment was then closed and stirred for an additional 6 hours. After the reaction was completed, THAM and methanol were removed by vacuum rotary evaporation. The resulting pale yellow transparent viscous substance.

Example 2

The other points are the same as in example 1, except that the reaction conditions are changed.

TABLE 1 preparation conditions of hyperbranched amino-rich polysiloxanes (HPS)

Reaction conditions					Product(s)
						KH-792: absolute ethyl alcohol: deionized water	10:10:1	1:1:0	8:8:1	15:15:2	Colorless viscous liquid
Stirring temperature (. Degree. C.)	40	50	60	80	Colorless viscous liquid
						Stirring time (h)	12	10	4	6	Colorless viscous liquid

TABLE 2 preparation conditions of epoxidized Poly (3, 3-trifluoropropyl methyl siloxane) (EPFS)

Example 3

Preparation of ultra-smooth coating (MSC) inspired by skin of Hepialus ray

In a 100mL round bottom flask, 0.8g GPOSS, 0.1g EPFS and 0.5g HPS were mixed with 10mL (7.893 g) solvent absolute ethanol and stirred at 60℃for 2 hours. The obtained suspension can be applied to various base materials by spraying, spin coating, paint spraying and the like, and then is solidified in a baking oven at 100 ℃ for 8-10 hours to obtain the MSC.

Molecular Dynamics (MD) simulation

The model is built from non-unit cell modules of Materials Studio software. In the solvent model, the molar ratio of each component was HPS: GPOSS: EPFS: ethanol=1:6:3:100. In the vacuum model, the molar ratio of the individual components is HPS: GPOSS: epfs=1:6:3. MD simulations were performed using Forcite Plus of Materials Studio software (Biovia inc.). The temperature was controlled by a Nose Hoover thermostat at 298K. A canonical ensemble (NVT) is then applied to each system using a velocity Verlet algorithm. The force field is COMPASS II and the time step is set to 1fs. Van der Waals interactions are calculated by an atom-based method with a cut-off distance ofElectrostatic interactions are calculated by a group-based method, which requires a long time, but is accurate for long-distance interactions. Finally, a 1000ps simulation was performed for each system to reach an equilibrium state.

Molecular Dynamics (MD) simulations confirm the formation of globular clusters. To accurately assess molecular and structural evolution of MSCs, a system consisting of 1 HPS molecule, 6 GPOSS molecules, 3 EPFS molecules and 100 ethanol molecules (n=1 in the repeat unit of EPFS) was used in the simulated space (volume) MD simulations were performed. MD simulations of the proportion of each component in MSC at concentrations comparable to our experiments (30% HPS, 60% GPOSS and 10% EPFS, respectively) were used as a preliminary computational assessment of experimental design. In a solventIn the existing system, HPS finally stabilizes at a volume of approximately +.> Is an ellipsoidal structure (fig. 5).

GPOSS and HPS (E) _GPOSS-HPS :135.35kcal·mol ^-1 ) And interaction energy of EPFS and HPS (E _EPFS-HPS :42.11kcal·mol ^-1 ) Is far lower than the interaction energy (E _GPOSS-EPFS :301.51kcal·mol ^-1 ) (Table 3), which causes the GPOSS and EPFS to gradually aggregate toward HPS to form polymer clusters, in FIG. 2 red represents the GPOSS aggregate low density region and blue represents the GPOSS aggregate high density region (blue). When the equilibrium state was reached, both the red GPOSS molecules and the green EPFS molecules clearly aggregated around the blue HPS molecules, representing spherical clusters in the size range of 2.98-3.65nm (fig. 3).

Table 3. Interaction energies (vacuum and ethanol solvents, respectively) between different components in different MD simulation environments.

EXAMPLE 4MSC preparation

The other points are the same as in example 3, except that the reaction conditions are changed. The MSC preparation process is schematically shown in FIG. 4a, and the preparation conditions are shown in Table 4.

TABLE 4 preparation conditions of ultra-smooth coating (MSC) inspired by the skin of ray of Hepialus

Reaction conditions
							HPS:GPOSS:EPFS	3:6:1	2:7:1	3:5:2	1:6:3	1:5:4	2:1:7
Solvent: monomer mass	2.82：1	4:1	6:1	8:1	10:1	11.28:1
							Stirring temperature (. Degree. C.)	60	50	60	40	70	80
Stirring time (h)	3	2	2	2	2	1
							Curing temperature (. Degree. C.)	100	90	90	100	100	110
Curing time (h)	9	10	8	9	9	8

More GPOSS: EPFS: HPS ratio experiments are shown in tables 5 and 7.

After spraying and high temperature curing, a densely packed structure of spherical clusters is formed on a microscopic level, and the coating surface exhibits excellent mechanical stability and liquid repellency while ensuring high overall transparency (fig. 4 a). During the curing process, the volatilization of the solvent ethanol causes the spherical clusters in the coating to be more densely packed. The spatial domain image of MD shows that in solvent-removed systems, HPS molecules are more extended in vacuo than in ethanol systems (fig. 6, 5). This exposes more reactive functional groups on the HPS, provides more reactive sites and promotes molecular aggregation.

In addition to MD confirmed molecular aggregation behavior, the surface morphology and internal structure of MSCs were characterized. High magnification Atomic Force Microscopy (AFM) showed that hemispherical clusters of 15-20nm in size appeared densely arranged on the surface (FIG. 4 b). The diameter of the hemispheres was consistent with the particle size in the MSC suspension particle size test (fig. 10). The height of the protrusions is only about 4nm (fig. 4b inset).

In addition, SEM images showed very smooth macroscopic surfaces with little macroscopic roughness being visible (fig. 11). The cross-sectional SEM images showed that the thickness of the MSCs was about 50 μm (fig. 4c inset). The elemental distribution image shows that fluorine migrates to the surface (fig. 4 c-4 c) due to the relatively high solidification temperature, which is critical for the liquid repellent properties of the MSC surface. In addition, the different curing temperatures and curing times also affect the lubricating properties (fig. 4 d). Curing temperatures of 100 ℃ for 8 hours ensure a stable Slip Angle (SA) of less than 10 °, which is the optimal curing condition selected during MSC preparation.

The different amounts of components in the MSC also affect the lyophobicity and hardness of the coating. Fig. 4e and table 5 show the effect of different mass ratios of HPS, GPOSS and EPFS in the coating on slip angle. Increasing the content of GPOSS and EPFS promotes the reaction between the epoxy resin and the amino groups, which helps to reduce the surface free energy and improve the surface lubricity of the coating.

As can be seen from Table 5, the coating composition of 20 to 30% by mass of HPS, 60 to 70% by mass of GPOSS and 20% by mass of EPFS, the coating composition of 0 to 30% by mass of HPS, 50 to 80% by mass of GPOSS and 20% by mass of EPFS, the coating composition of 0 to 20% by mass of HPS, 50 to 70% by mass of GPOSS and 30% by mass of EPFS, the coating composition of 0 to 10% by mass of HPS, 50 to 60% by mass of GPOSS and 40% by mass of EPFS, the coating composition of 0 to 20% by mass of HPS, 10 to 30% by mass of GPOSS and 70% by mass of EPFS, had a lower sliding angle, and the sliding angle was lower than 10 °. More preferably, by adjusting the different contents of the three components to a coating consisting of 20 to 30% by mass of HPS, 70 to 60% by mass of GPOSS and 10% by mass of EPFS, a minimum SA of 7.06 DEG + -0.06 DEG is obtained.

TABLE 5 influence of different mass ratios of HPS, GPOSS and EPFS in the coating on sliding angle

The abrasion experiments further demonstrate an optimal component content with 30% HPS, 60% GPOSS and 10% EPFS by mass fraction. The coating remained at a slip angle of less than 10 ° after 800 taber abrasion cycles according to ASTM test standard load of 250g weight (fig. 12). Importantly, since the size of the clusters is smaller than the wavelength of visible light, the average transmittance of the MSCs reaches 92%, which is almost the same as the transmittance of the original glass (fig. 4 g). Fig. 4g shows an illustration of a representative photomicrograph of MSCs coated on a large size glass substrate (45 cm x 40 cm).

TABLE 6 sliding angle variation with wear test cycle

In addition to lyophobic properties, coatings of different component content were tested for hardness according to the ASTM D3363-00 pencil hardness test method (FIG. 4f, table 7). As the content of GPOSS increases, the hardness of the coating may increase to 9H due to the rigid structure of GPOSS. Preferably, the hardness of the coating is 8-9H.

TABLE 7 hardness of coatings of different component contents

Lubricating properties and mechanochemical stability of MSC

To observe the super-slip performance of MSCs in a more specific way, we used a high-speed camera of 7400 frames per second to characterize the dynamic process of water droplet slip, where at the moment the water droplet contacts the MSC surface, the droplet starts to slip and spread out simultaneously. At the position of During sliding, the surface spreads into a wafer shape with the largest diameter within 15 milliseconds, similar to the bouncing behavior of water droplets on the super-amphiphobic coating. The droplet then continues to slide and moves about 1 cm in 300 milliseconds (fig. 13 a). MSC also has excellent repellency to liquids of different surface tension (fig. 13 b). For example, ethanol (21.2 mN.m) ^-1 ) The sliding angle of (a) was only 1.98 deg. + -0.08 deg., the contact angle was 48.54 deg. + -1.77 deg., and the water (71.8 mN.m) ^-1 ) The sliding angle of (a) is about 7.06 deg. + -0.06 deg., the contact angle is 106.17 deg. + -2.4 deg. (fig. 14).

In addition, the sliding angle was also almost less than 10 ° for liquids of different viscosities (contact angle as shown in fig. 15). Even for glycerol with a viscosity as high as 1499 mPa-s (20 ℃) the slip angle was only 14.7 ° ± 0.44 °, and when the MSC coated glass sheet was immersed in glycerol, left standing and then removed, no residue remained on the surface (fig. 13 c).

To further characterize superlubrication performance, MSC-coated slides were fixed at an inclination angle of 15 ° and the time required for the liquid to slide the same distance over the MSC surface was recorded. The water droplets may slide on the MSC surface for a distance of 5 cm in less than 1 second, in contrast to ethanol, which has a much lower surface tension, which may slide for the same distance in 1.1 seconds. Even for higher viscosity liquids (e.g., glycerol and castor oil), they can slide off the MSC surface in no more than 15 seconds (fig. 13 d). This is due to the special surface characteristics of MSCs, which give them excellent anti-wetting and super-lubricity. The performance enables the coating to be used as an antifouling, oil-proof and anti-fog coating, and has wide application fields.

In addition to use in a normal temperature environment, MSCs can also withstand extreme high and low temperatures. After one month of standing at 120℃and-25℃respectively, the sliding angle of water on the MSC surface was still 7.34.+ -. 0.96 °, the transparency was substantially the same as the original transparency, indicating the stability of the coating structure and chemical composition.

The MSC is also able to reject high temperature fluids (fig. 13 e), which is not possible with some conventional anti-wetting coatings, because the increase in temperature results in an increase in the surface tension of the liquid. At an inclination angle of 15 deg., it is also possible to slide 4 cm on the MSC surface within 1.5 seconds for a water droplet at 80 deg. (figure 13e inset). These excellent superlubricity properties benefit from the tribological properties of the MSC surface. The super-lubrication performance of the MSC is evaluated more strictly by quantifying tribological parameters such as friction coefficient and the like. The average coefficient of friction at the MSC surface was measured as low as 0.0756 (fig. 13 f), comparable to the polymer ultra-slip coating already reported, while being much lower than the graphene oxide and epoxy-based composite coating (fig. 13 g).

MSCs have excellent mechanical durability both at the coating surface and inside the coating. The presence of the rigid molecule GPOSS increases the hardness of the coating, whereas HPS with hyperbranched amino groups increases the structural strength within the coating. We characterized the surface hardness of the coating by nanoindentation test (figure 16). The hardness of the coating measured at five different locations was about 0.94.+ -. 0.05GPa (FIG. 13 h), 2 times that of Polyethylene (PE), 1.5 times that of Polystyrene (PS), and higher than most reported polymer coatings. The high hardness and high Young's modulus enable the coating to be effective against external physical damage. We tested the abrasion resistance of MSCs by measuring the sliding angle change and average visible light transmittance of water droplets on the surface of the MSCs under a 250g abrasion load according to ASTM-D4060 standard (fig. 13 i). After 1000 wear cycles, the water droplets could still slide off the coating surface without any residue, although the sliding angle increased to 15.73 ° ± 1.43 °. Meanwhile, the average visible light transmittance of the coating is kept above 85%. The excellent mechanical properties of the coating are also reflected in excellent adhesion to different substrates. The adhesion of MSC on stainless steel substrate can reach 9.47±0.32MPa and even on teflon surface can reach 0.81±0.2MPa (fig. 13 j).

To further demonstrate the superiority of incorporating HPS in MSCs, the adhesive strength of coatings prepared by directly using the same molar amount of KH-792 to different substrates was also measured. The data indicate that KH-792 produced MSCs with weaker adhesive strength than MSCs produced by the introduction of HPS (FIG. 13 j). This suggests that the presence of HPS increases the structural strength of the coating and provides strong adhesion to various substrates.

Table 8 adhesive strength comparison

	Adhesion with HPS	Adhesion with KH-792
			Iron (Fe)	9.47	8.42
Glass	8.83	7.85
			Cu	6.69	5.64
Al	4.91	4.15
			Polytetrafluoroethylene	0.81	0.67

Claims

1. A method for preparing a super-slip coating inspired by the skin of a ray, comprises the following steps:

s1, adding glycidoxypropyl polyhedral silsesquioxane, epoxidized poly (3, 3-trifluoropropyl methyl siloxane), hyperbranched amino-rich polysiloxane and a solvent into a reaction container, and fully mixing; the solvent is absolute ethyl alcohol;

s2, stirring the mixed suspension obtained in the step S1 for 1-3 hours at the temperature of 40-80 ℃;

s3, the obtained super-slip coating suspension is applied to various base materials by a spray coating and spin coating mode,

s4, curing in an oven to obtain the ultra-smooth coating; the curing temperature is 90-110 ℃;

the preparation method of the hyperbranched amino-rich polysiloxane comprises the following steps:

a) Adding N- [3- (trimethoxysilyl) propyl ] ethylenediamine (KH-792), absolute ethyl alcohol and deionized water into a reaction vessel, and stirring at 40-80 ℃ for 4-12 hours;

b) Removing absolute ethyl alcohol by vacuum rotary evaporation to obtain colorless viscous liquid which is hyperbranched amino-rich polysiloxane;

the preparation method of the epoxidized poly (3, 3-trifluoropropyl methyl siloxane) comprises the following steps:

1) Adding poly (3, 3-trifluoro propyl methyl siloxane) and (3-epoxypropoxy propyl) dimethyl ethoxy silane into a reaction vessel, and stirring;

2) Adding a tetramethylammonium hydroxide solution and exhausting air with an inert gas;

3) Sealing and reacting for 4-8 hours;

4) After the reaction is finished, removing tetramethyl ammonium hydroxide and methanol; the resulting pale yellow transparent viscous material was epoxidized poly (3, 3-trifluoropropyl methyl siloxane).

2. The method for preparing the ultra-smooth coating for ray skin inspiring according to claim 1, wherein in the step S1, the mass ratio of hyperbranched amino-rich polysiloxane, glycidoxypropyl polyhedral silsesquioxane and epoxidized poly (3, 3-trifluoropropyl methyl siloxane) is (0-9): (0-9): (1-7) and not taking 0, wherein the ratio of the total mass of the solvent and the monomer is (2.82-11.28): 1, a step of;

In step S2, stirring for 2 hours at 60 ℃;

in step S3, the substrate is selected from glass, wood, PMMA sheet, various metals;

in the step S4, curing in an oven at 100 ℃ for 8-10 hours to obtain the ultra-smooth coating;

for the mixed suspension, the particle size of glycidoxypropyl polyhedral silsesquioxane-co-hyperbranched amino-rich polysiloxane is 10-20nm, and the particle size of the epoxidized poly (3, 3-trifluoropropyl methyl siloxane) -co-hyperbranched amino-rich polysiloxane is 5-12nm; the particle size of the super slip coating suspension is 10-15nm.

3. The method for preparing the ultra-smooth coating for ray skin inspiring according to claim 1, wherein in the step S1, the mass ratio of hyperbranched amino-rich polysiloxane, glycidoxypropyl polyhedral silsesquioxane and epoxidized poly (3, 3-trifluoropropyl methyl siloxane) is (0-3): (1-8): (3-7) and does not take 0.

4. The method for preparing the ultra-smooth coating for ray skin inspiring according to claim 1, wherein in the step a), the volume ratio of KH-792, absolute ethyl alcohol and deionized water is (1-15): (1-15): (0-2), and not taking 0.

5. The method of claim 1, wherein in step a), the ratio of KH-792, absolute ethanol, and deionized water is 10:10:1 by volume.

6. The method for preparing a skin-inspired ultra-smooth coating of ray of claim 1, wherein in step a), stirring is performed at 60 ℃ for 10 hours.

7. The method for preparing a bate skin inspired ultra-smooth coating as defined in claim 1, wherein in step 1), the mass ratio of poly (3, 3-trifluoropropyl methyl siloxane) to (3-glycidoxypropyl) dimethylethoxy silane is 1: (0.1-1); the reaction temperature in the step 1) is 60-90 ℃.

8. The method for preparing a coating for treating skin irritation of a ray of Hepialus of claim 1, wherein in step 2), the pH of the reaction system is adjusted to 10-11; the inert gas is nitrogen or argon.

9. A ray skin-inspired ultra-slip coating prepared by the method of any one of claims 1-8.

10. The ray of claim 9 a skin-inspired ultra-slip coating, it is characterized in that the method comprises the steps of, hemispherical clusters with the size of 15-20nm are densely arranged on the surface of the ultra-smooth coating, and the height of the protrusions is only 4 nm;

the thickness of the super slip coating layer was 50 μm, and fluorine element was transferred to the surface.

11. The superslip coating for skin elicitation by a ray of bate as in any of claims 9-10, wherein the coating comprises the following composition by mass:

20-30% of hyperbranched amino-rich polysiloxane, 60-70% of glycidoxypropyl polyhedral silsesquioxane and 10% of epoxidized poly (3, 3-trifluoropropyl methyl siloxane), or

0-30% of hyperbranched amino-rich polysiloxane, 50-80% of glycidoxypropyl polyhedral silsesquioxane and 20% of epoxidized poly (3, 3-trifluoropropyl methyl siloxane), wherein the composition mass fraction is not 0; or (b)

0-20% of hyperbranched amino-rich polysiloxane, 50-70% of glycidoxypropyl polyhedral silsesquioxane and 30% of epoxidized poly (3, 3-trifluoropropyl methyl siloxane), wherein the composition mass fraction is not 0; or (b)

0-10% of hyperbranched amino-rich polysiloxane, 50-60% of glycidoxypropyl polyhedral silsesquioxane and 40% of epoxidized poly (3, 3-trifluoropropyl methyl siloxane), wherein the composition mass fraction is not 0; or (b)

0-20% of hyperbranched amino-rich polysiloxane, 10-30% of glycidoxypropyl polyhedral silsesquioxane and 70% of epoxy poly (3, 3-trifluoropropyl methyl siloxane), wherein the composition mass fraction is not 0.

12. Use of the superslip coating for skin elicitation of a ray of a Hepialus of any one of claims 9-11, or of the superslip coating for skin elicitation of a ray of Hepialus of any one of claims 1-8, as an anti-fouling, oil-repellent, anti-fog coating.