A protective film, a method of manufacturing the same, and a fan blade using the same

Abstract

The present disclosure relates to a protective film and a preparation method thereof and a fan blade using the same, the preparation method of which cures a vulcanized rubber layer, an adhesive and a ceramic diaphragm into a three-layer structure of the protective film, wherein the vulcanized rubber layer plays a role of shock absorption, the adhesive has high bonding strength, and the ceramic diaphragm has high strength and high toughness. The protective film of the present disclosure has both hard wear resistance and shock absorption and impact resistance, while maintaining good elasticity, and can not only prevent the front edge of the fan blade from being worn by wind sand and corroded by rainwater, but also absorb most of the energy of wind impact to reduce the possibility of cracking of the front edge of the blade.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a protective film, in particular, to a protective film and a preparation method thereof and a fan blade using the same. BACKGROUND

[0002] Affected by the natural environment, the fan blade is inevitably worn by wind sand, rainwater and other factors in continuous high-speed rotation, the damage to the leading edge of the blade is the most intense, which can cause the increase of the rotating resistance of the blade, the decrease of the lift, and further the decrease of the aerodynamic performance of the blade, and directly affect the service life of the fan blade and the wind power generation power. If the corrosion of the leading edge of the blade cannot be treated in time, the corrosion degree will be aggravated with time, the power generation capacity will be continuously reduced, and finally the wind power operator will suffer huge economic losses.

[0003] The maintenance cost of the fan blade is huge, and the personnel, equipment, transportation and other difficulties are very high, and the blade maintenance of offshore wind power is more difficult, therefore, the leading edge of the blade needs to be protected by the protective product, which can improve the service life of the blade, reduce the maintenance cost of the leading edge of the blade, and reduce the operation and maintenance cost.

[0004] The leading edge protective film has high hardness and high wear resistance, and can well protect the fan blade from the impact and corrosion of wind resistance, rainwater, sand and ultraviolet rays in daily life. However, since the leading edge protective film is exposed to the natural environment for a long time, it is easy to be worn and corroded by wind sand and rainwater, and will be quickly worn, aged and even cracked. SUMMARY

[0005] The purpose of the present disclosure is to provide a protective film and a preparation method thereof and a fan blade using the same, which has the properties of hard wear resistance and shock absorption and impact resistance, and maintains good elasticity, can not only protect the leading edge of the fan blade from wind sand wear and rainwater corrosion, but also can absorb most of the energy of wind impact, and reduce the possibility of cracking of the leading edge of the blade.

[0006] In order to achieve the above purpose, the first aspect of the present disclosure provides a preparation method of a protective film, which comprises:

[0007] (1) mixing rubber, vulcanizing agent and first filler to obtain a blended rubber; mixing and vulcanizing the blended rubber to obtain a vulcanized rubber layer;

[0008] (2) contacting resin, acid ester compound, organic amine and second filler to obtain an adhesive;

[0009] (3) mixing high polymer carrier, ceramic particles, third filler and water to obtain a precursor solution; electrospinning the precursor solution to obtain a ceramic fiber layer; drying and calcining the ceramic fiber layer to obtain a ceramic film sheet;

[0010] (4) bonding the vulcanized rubber layer with the ceramic diaphragm through the adhesive, and performing a curing treatment to obtain a protective film.

[0011] Optionally, in step (1), the vulcanizing agent is selected from metal oxides, the metal oxides are selected from one or more of magnesium oxide, zinc oxide and lead oxide, and the first filler is selected from one or more of stearic acid, carbon black, mica and fumed silica; preferably, the vulcanizing agent comprises magnesium oxide and zinc oxide, and the filler comprises stearic acid and carbon black; the blended rubber comprises rubber, magnesium oxide, zinc oxide, stearic acid and carbon black; the content of the magnesium oxide is 1.8-2.2 parts by weight, the content of the zinc oxide is 2.0-5.0 parts by weight, the content of the stearic acid is 0.9-1.1 parts by weight, and the content of the carbon black is 40-55 parts by weight, relative to 90-100 parts by weight of the rubber; the rubber is selected from one or more of chlorinated butyl rubber, butyl rubber, nitrile rubber and polyethylene-butyl rubber blend, and preferably is chlorinated butyl rubber; the weight average molecular weight of the rubber is 100000-600000; more preferably, the blended rubber further comprises a rubber vulcanization accelerator, the rubber vulcanization accelerator comprises a first accelerator and a second accelerator, the content of the first accelerator is 1.8-2.4 parts by weight, and the content of the second accelerator is 0.8-1.2 parts by weight, relative to 90-100 parts by weight of the rubber; wherein the first accelerator is selected from a sulfenamide accelerator, the sulfenamide accelerator is selected from one or more of N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide and N-oxybisdimethylene-2-benzothiazole sulfenamide, and the second accelerator is selected from one or more of tetramethylthiuram disulfide, tetramethylthiuram monosulfide and tetraethylthiuram disulfide.

[0012] Optionally, in step (1), the mixing is performed on a rubber mixing machine, the temperature of the mixing is 150-250°C, and the time is 10-50 min; the vulcanization treatment comprises filling the blended rubber in a flat mold with a thickness of 1-10 mm, and placing the flat mold on a flat vulcanization machine to perform the vulcanization treatment, the temperature of the vulcanization treatment is 150-170°C, the time is 0.5-1 h, and the pressure is 1.0-10.0 MPa.

[0013] Optionally, in step (2), the content of the acid ester compound is 10-25 parts by weight, the content of the organic amine is 5-10 parts by weight, and the content of the second filler is 20-50 parts by weight, relative to 100 parts by weight of the resin; the temperature of the contacting is 20-35℃, and the time is 20-30 h; wherein the resin is selected from one or more of an epoxy resin, an acrylic resin, a polyethylene resin, and a petroleum resin, and is preferably an epoxy resin; the weight average molecular weight of the resin is 400-500; the acid ester compound is selected from one or more of dibutyl phthalate, propylene glycol alginate phthalate, and dioctyl phthalate, and is preferably dibutyl phthalate; the organic amine is selected from one or more of diethylene triamine, triethylene tetramine, and m-phenylenediamine, and is preferably diethylene triamine; and the second filler is selected from an inorganic metal material and / or an inorganic non-metal material, the inorganic metal material is selected from one or more of aluminum oxide powder, aluminum oxide powder, iron powder, and talc powder, and the inorganic non-metal material is graphite powder.

[0014] Optionally, in step (3), the content of the high polymer carrier is 1-20 g, the content of the third filler is 10-20 g, and the content of water is 20-50 g, relative to 100 g of the ceramic particles; the temperature of the drying treatment is 20-100℃, and the time is 1-24 h; the temperature of the calcination treatment is 200-600℃, the time is 1-2 h, and the heating rate is 2-10℃ / min; wherein the high polymer carrier is selected from one or more of polyvinyl alcohol, polyethylene terephthalate, polyacrylic acid, polyvinyl acetate, and polyvinyl pyrrolidone, and is preferably polyvinyl alcohol; the weight average molecular weight of the high polymer carrier is 100000-300000; the ceramic particles are selected from one or more of zirconium acetate, zirconium oxychloride, aluminum nitrate, and titanium isopropyl alcohol, and are preferably zirconium acetate; the average particle size of the ceramic particles is 0.5-2 μm; and the third filler is selected from one or more of a trivalent cobalt salt, a yttrium compound, a persulfate, and a peroxide, and is preferably yttrium nitrate.

[0015] Optionally, in step (4), the thickness ratio of the vulcanized rubber layer, the adhesive, and the ceramic membrane is 1:(0.05-0.4):(0.5-2), the temperature of the curing treatment is 20-30℃, and the time is 10-30 h; preferably, the thickness of the vulcanized rubber layer is 1-10 mm, and is preferably 2-5 mm; the thickness of the adhesive is 0.5-5 mm, and is preferably 1-2 mm; and the thickness of the ceramic layer is 1-10 mm, and is preferably 2-5 mm.

[0016] The second aspect of the present disclosure provides a protective film prepared by the preparation method of the first aspect of the present disclosure.

[0017] Optionally, the protective film comprises, from bottom to top, a vulcanized rubber layer, an adhesive layer and a ceramic layer; the hardness of the vulcanized rubber layer is 40-80 HA.

[0018] Optionally, the impact strength of the protective film is 8-15 kJ / m 2 , the tensile strength of the protective film at 25℃ is 15-22 MPa, and the elongation at break is 500-700%; the tensile strength of the protective film at low temperature of -30℃ is 10-20 MPa, and the elongation at break is 200-600%; the initial decomposition temperature of the protective film tested by thermogravimetric analysis is 230-260℃, the half-decomposition temperature is 400-440℃, and the maximum thermal weight loss rate temperature is 410-450℃.

[0019] Optionally, the thickness of the vulcanized rubber layer is 1-10 mm, preferably 2-5 mm; the thickness of the adhesive layer is 0.5-5 mm, preferably 0.5-2 mm; and the thickness of the ceramic layer is 1-10 mm, preferably 1-5 mm.

[0020] Optionally, the tensile strength of the vulcanized rubber layer at 25℃ is 12-20 MPa, and the elongation at break is 500-700%; the vulcanized rubber layer comprises one or more of a chlorinated butyl vulcanized rubber layer, a butyl rubber layer, a nitrile rubber layer and a polyethylene-butyl rubber blended rubber layer, preferably a chlorinated butyl vulcanized rubber layer.

[0021] Optionally, the adhesive layer comprises a resin adhesive layer, and the resin adhesive layer comprises one or more of an epoxy resin adhesive layer, an acrylic resin adhesive layer, a polyethylene resin adhesive layer and a petroleum resin adhesive layer, preferably an epoxy resin adhesive layer.

[0022] The third aspect of the present disclosure provides a wind turbine blade, wherein the leading edge portion of the wind turbine blade comprises a blade body and the protective film of the second aspect of the present disclosure, the vulcanized rubber layer of the protective film is in contact with the surface of the blade body, and the thickness of the protective film is 5-50 mm.

[0023] By the technical scheme, the present disclosure provides a protective film, a preparation method thereof and a fan blade using the same. The preparation method cures a vulcanized rubber layer, an adhesive and a ceramic diaphragm into a protective film with a three-layer structure. The vulcanized rubber layer plays a shock-absorbing role, the adhesive has high bonding strength, and the ceramic diaphragm has high strength and high toughness. The protective film prepared by the preparation method has the characteristics of hardness, wear resistance, shock absorption and impact resistance. The protective film is attached to the fan blade. The protective film can not only better protect the blade from the impact and corrosion of wind resistance, rainwater, dust and ultraviolet rays, but also has good elasticity, can play a shock-absorbing effect, reduce the impact force on the inside of the blade, can also absorb most of the energy of the wind impact, reduce the possibility of cracking of the leading edge of the blade, prolong the service life and maintenance cycle of the blade, reduce the operation and maintenance cost of the leading edge of the wind power blade, and improve the economic performance.

[0024] Other features and advantages of the present disclosure will be described in detail in the following specific embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0025] The accompanying drawings are included to provide a further understanding of the present disclosure and constitute a part of the specification, and are used together with the following specific embodiments to explain the present disclosure, but do not constitute a limitation on the present disclosure. In the drawings:

[0026] Figure 1 is a scanning electron microscope image of the flexible ceramic fiber layer prepared in Example 1 of the present disclosure. DETAILED DESCRIPTION

[0027] The specific embodiments of the present disclosure are described in detail below in conjunction with the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, and do not limit the present disclosure.

[0028] The first aspect of the present disclosure provides a preparation method of a protective film, the preparation method comprising:

[0029] (1) mixing rubber, vulcanizing agent and first filler to obtain a blended rubber; mixing and vulcanizing the blended rubber to obtain a vulcanized rubber layer;

[0030] (2) contacting resin, acid ester compound, organic amine and second filler to obtain an adhesive;

[0031] (3) mixing a polymer carrier, ceramic particles, a third filler and water to obtain a precursor solution; electrospinning the precursor solution to obtain a ceramic fiber layer; drying and calcining the ceramic fiber layer to obtain a ceramic diaphragm;

[0032] (4) bonding the vulcanized rubber layer and the ceramic diaphragm by the adhesive, and performing curing treatment to obtain a protective film.

[0033] The preparation method provided by the present disclosure cures the vulcanized rubber layer, the adhesive and the ceramic diaphragm into a three-layer protective film, wherein the vulcanized rubber layer plays a shock-absorbing role, the adhesive has high bonding strength, and the ceramic diaphragm has high strength and high toughness, the prepared protective film has both hard wear resistance and shock-absorbing and impact resistance performance, and meanwhile maintains good elasticity, can not only prevent the front edge of the fan blade from being worn by wind sand and corroded by rainwater, but also can absorb most of the energy of wind impact, thereby reducing the possibility of cracking of the front edge of the blade.

[0034] In an embodiment of the present disclosure, in step (1), the vulcanizing agent is selected from metal oxides, the metal oxides are selected from one or more of magnesium oxide, zinc oxide and lead oxide, and the first filler is selected from one or more of stearic acid, carbon black, mica and fumed silica; preferably, the vulcanizing agent comprises magnesium oxide and zinc oxide, and the filler comprises stearic acid and carbon black; the blended rubber comprises rubber, magnesium oxide, zinc oxide, stearic acid and carbon black; relative to 90-100 parts by weight of rubber, the content of the magnesium oxide is 1.8-2.2 parts by weight, the content of the zinc oxide is 2.0-5.0 parts by weight, the content of the stearic acid is 0.9-1.1 parts by weight, and the content of the carbon black is 40-55 parts by weight; the rubber is selected from one or more of chlorinated butyl rubber, butyl rubber, nitrile rubber and polyethylene-butyl rubber blend, and preferably is chlorinated butyl rubber; and the weight average molecular weight of the rubber is 100000-600000. In the above embodiment, the use of the preferred components and proportions of the blended rubber is beneficial to the synthesis of the vulcanized rubber layer with high cross-linking degree, thereby improving the shock-absorbing effect of the protective film.

[0035] In a preferred embodiment, the blended rubber further comprises a rubber vulcanization accelerator, the rubber vulcanization accelerator comprises a first accelerator and a second accelerator, relative to 90-100 parts by weight of rubber, the content of the first accelerator is 1.8-2.4 parts by weight, and the content of the second accelerator is 0.8-1.2 parts by weight; wherein the first accelerator is selected from a sulfenamide accelerator, the sulfenamide accelerator is selected from one or more of N-cyclohexyl-2-benzothiazole sulfenamide (CBS, CAS No. 95-33-0), N-tert-butyl-2-benzothiazole sulfenamide (TBBS, CAS No. 95-31-8) and N-oxydiethylene-2-benzothiazole sulfenamide (NOBS, CAS No. 102-77-2), and the second accelerator is selected from one or more of tetramethylthiuram disulfide (TMTD, CAS No. 137-26-8), tetramethylthiuram monosulfide (TMTM, 97-74-5) and tetraethylthiuram disulfide (TETD, CAS No. 97-77-8).

[0036] In an embodiment of the present disclosure, in step (1), the mixing is performed on a rubber mixing machine, the temperature of the mixing is 150-250 DEG C, and the time is 10-50 min; the conditions of the vulcanization treatment include: the blended rubber is filled in a flat mold with a thickness of 1-10 mm, and the flat mold is placed on a flat vulcanization machine for vulcanization treatment, the temperature of the vulcanization treatment is 150-170 DEG C, the time is 0.5-1 h, and the pressure is 1.0-10.0 MPa. In the above embodiment, the flat mold with a preferred thickness and the vulcanization conditions are selected, which is beneficial to obtain a vulcanized rubber layer with a suitable thickness, the vulcanized rubber layer can fully absorb impact energy, and the shock-absorbing effect is achieved, thereby avoiding long-term stress fatigue of the fan blade.

[0037] In an embodiment of the present disclosure, in step (2), the content of the acid ester compound is 10-25 parts by weight, the content of the organic amine is 5-10 parts by weight, and the content of the second filler is 20-50 parts by weight, with respect to 100 parts by weight of the resin; the temperature of the contacting is 20-35 DEG C, and the time is 20-30 h; wherein the resin is selected from one or more of an epoxy resin, an acrylic resin, a polyethylene resin, and a petroleum resin, and is preferably an epoxy resin; the weight average molecular weight of the resin is 400-500; the acid ester compound is selected from one or more of dibutyl phthalate, propylene glycol alginate, and dioctyl phthalate, and is preferably dibutyl phthalate; the organic amine is selected from one or more of diethylene triamine, triethylene tetramine, and m-phenylenediamine, and is preferably diethylene triamine; and the second filler is selected from an inorganic metal material and / or an inorganic non-metal material, the inorganic metal material is selected from one or more of aluminum oxide powder, aluminum oxide powder, iron powder, and talc powder, and the inorganic non-metal material is graphite powder. In the above embodiment, the preferred raw materials and contacting conditions are selected, which is beneficial to obtain an adhesive with high bonding strength, the adhesive can firmly connect different materials together, and has good performance, high mechanical strength, medium resistance, aging resistance, and good electrical insulation after curing.

[0038] In one embodiment of this disclosure, in step (3), relative to 100g of the ceramic particles, the content of the polymer carrier is 1-20g, the content of the third filler is 10-20g, and the content of water is 20-50g; the drying temperature is 20-100℃, and the time is 1-24h; the calcination temperature is 200-600℃, the time is 1-2h, and the heating rate is 2-10℃ / min; wherein, the polymer carrier is selected from polyvinyl alcohol and polyethylene terephthalate. The polymer carrier is selected from one or more of alcohol esters, polyacrylic acid, polyvinyl acetate, and polyvinylpyrrolidone, preferably polyvinyl alcohol; the weight-average molecular weight of the polymer carrier is 100,000 to 300,000; the ceramic particles are selected from one or more of zirconium acetate, zirconium oxychloride, aluminum nitrate, and titanium isopropoxide, preferably zirconium acetate; the average particle size of the ceramic particles is 0.5 to 2 μm; the third filler is selected from one or more of trivalent cobalt salts, yttrium compounds, persulfates, and peroxides, preferably yttrium nitrate. In the above embodiments, the selection of a polymer carrier with a preferred molecular weight is beneficial for obtaining a fiber membrane with uniform thickness and appropriate density during electrospinning; the selection of ceramic particles with a preferred average particle size is beneficial for the ceramic fiber layer to obtain excellent flexibility and resistance to wind erosion and rainwater erosion.

[0039] In a preferred embodiment, the electrospinning conditions include: drawing an appropriate amount of the prepared precursor solution with a syringe, fixing it on the electrospinning machine support, adjusting the receiving distance to 14 cm, controlling the ambient temperature to 25±2℃ using an air conditioner, controlling the ambient humidity to 50±5% using a dehumidifier, setting the spinning negative voltage to -1.5 kV and the positive voltage to 0–17 kV; setting the injection speed to 0.1–0.3 mm / min and the receiving roller speed to 80 r / min. In the above embodiment, the preferred electrospinning process facilitates the fabrication of a flexible ceramic fiber layer. The fibers in this flexible ceramic fiber layer are cylindrical, with a diameter on the order of nanometers, within the range of 250–30 nm. Its scanning electron microscope image is shown below. Figure 1 As shown, the fiber is more likely to slip when the ceramic layer is deformed by impact, allowing the impact energy to propagate and dissipate along the fiber's slippage. When the energy is transferred to the next fiber layer, the impact energy is further dissipated because the fibers in the next layer also slip. Therefore, the ceramic layer exhibits superior flexibility and impact resistance, which is beneficial for wind turbine blades to withstand harsh environmental conditions such as wind, rain erosion, and low temperatures without affecting the aerodynamic shape of the blades.

[0040] In one embodiment of the present disclosure, in step (4), the thickness ratio of the vulcanized rubber layer, the adhesive and the ceramic membrane is 1:(0.05-0.4):(0.5-2), the curing treatment is performed at a temperature of 20-30°C for 10-30 hours; preferably, the thickness of the vulcanized rubber layer is 1-10 mm, preferably 2-5 mm; the thickness of the adhesive is 0.5-5 mm, preferably 1-2 mm; and the thickness of the ceramic layer is 1-10 mm, preferably 2-5 mm. In the above embodiment, the preferred weight ratio and curing conditions are used to facilitate the preparation of the three-layer structure, hard and wear-resistant protective film.

[0041] The second aspect of the present disclosure provides a protective film prepared by the preparation method of the first aspect of the present disclosure.

[0042] In one embodiment of the present disclosure, the protective film comprises a vulcanized rubber layer, an adhesive layer and a ceramic layer stacked in order from bottom to top; and the hardness of the vulcanized rubber layer is 40-80 HA.

[0043] In one embodiment of the present disclosure, the impact strength of the protective film is 8-15 kJ / m 2 , the tensile strength of the protective film at 25°C is 15-22 MPa, and the elongation at break is 500-700%; the tensile strength of the protective film at low temperature of -30°C is 10-20 MPa, and the elongation at break is 200-600%; the initial decomposition temperature of the protective film tested by thermogravimetric analysis is 230-260°C, the half-decomposition temperature is 400-440°C, and the maximum thermal weight loss rate temperature is 410-450°C. The protective film of the present disclosure has good tensile strength and elongation at break at room temperature and low temperature, has good resilience and toughness, can greatly eliminate mechanical vibration, reduce the damage caused by impact to the fan blade, and can absorb most of the energy of wind impact, reducing the possibility of cracking of the leading edge of the blade.

[0044] In one embodiment of the present disclosure, the thickness of the vulcanized rubber layer is 1-10 mm, for example, 2 μm, 4 μm, 6 μm, 8 μm or 10 μm, preferably 2-5 mm; the thickness of the adhesive layer is 0.5-5 mm, for example, 1 μm, 2 μm, 3 μm, 4 μm or 5 μm, preferably 0.5-2 mm; and the thickness of the ceramic layer is 1-10 mm, for example, 1 μm, 3 μm, 5 μm, 7 μm or 9 μm, preferably 1-5 mm. In the above embodiment, the vulcanized rubber layer, the adhesive layer and the ceramic layer with the preferred thickness are selected to further improve the shock-absorbing and impact-resistant performance of the protective film.

[0045] In an embodiment of the present disclosure, the tensile strength of the vulcanized rubber layer at 25℃ is 12-20 MPa, and the elongation at break is 500-700%; the vulcanized rubber layer comprises one or more of a chlorinated butyl vulcanized rubber layer, a butyl rubber layer, an nitrile butyl rubber layer, and a polyethylene-butyl rubber blended rubber layer, and is preferably a chlorinated butyl vulcanized rubber layer. In the above embodiment, the vulcanized rubber layer with the preferred structure is selected, which is beneficial to obtaining good elasticity and recovery rate, absorbing the energy of external impact, and preventing the leading edge of the blade from cracking under stress.

[0046] In an embodiment of the present disclosure, the adhesive layer comprises a resin adhesive layer, and the resin adhesive layer comprises one or more of an epoxy resin adhesive layer, an acrylic resin adhesive layer, a polyethylene resin adhesive layer, and a petroleum resin adhesive layer, and is preferably an epoxy resin adhesive layer.

[0047] The third aspect of the present disclosure provides a wind turbine blade, wherein the leading edge portion of the wind turbine blade comprises a blade body and the protective film according to the second aspect of the present disclosure, the vulcanized rubber layer of the protective film is in contact with the surface of the blade body, and the thickness of the protective film is 5-50 mm. The protective film provided by the present disclosure has the characteristics of high strength, corrosion resistance, hardness, wear resistance, shock absorption and impact resistance. It not only can better protect the blade from the impact and corrosion of wind resistance, rainwater, sand and dust, and ultraviolet rays in daily life, but also has good elasticity, can reduce the impact force on the inside of the blade, can absorb most of the energy of wind impact, and can reduce the possibility of cracking of the leading edge of the blade.

[0048] The present disclosure will be further described by examples, but the present disclosure is not limited in any way by the examples.

[0049] In the examples and comparative examples of the present disclosure, the raw materials used are commercially available materials.

[0050] The morphology of the flexible ceramic fiber layer prepared by electrospinning is observed by observing the microscopic image, and the testing instrument is a field emission scanning electron microscope;

[0051] The molecular weight distribution is determined by measuring the residence time of molecules in a gel column, and the testing instrument is a gel permeation chromatograph;

[0052] The hardness of the material is tested by the indentation hardness test method, and the testing instrument is a Rockwell hardness tester;

[0053] The particle size of the material is tested by the method of diffraction and scattering affected by the size of the particles, and the testing instrument is a laser particle size analyzer;

[0054] The thickness of the material is tested by the mechanical contact measurement method, and the testing instrument is a thickness gauge.

[0055] Example 1

[0056] (1) Put 100 parts by weight of chlorinated butyl rubber (rubber, weight average molecular weight 200000) into an internal mixer and plasticize for 2-10 min, then add magnesium oxide 2.0 parts by weight (vulcanizing agent), zinc oxide 5.0 parts by weight (vulcanizing agent), stearic acid 1.0 parts by weight (first filler), high wear-resistant carbon black 50 parts by weight (filler), N-tert-butyl-2-benzothiazole sulfenamide 2.2 parts by weight (TBBS, first accelerator), tetramethylthiuram disulfide 1.0 parts by weight (TMTD, second accelerator), and blend for 20 min to obtain a blended rubber. The blended rubber is mixed on an open mill, the mixing temperature is 170℃, the mixing time is 30 min, and the rubber is thin-passed and bagged three times. After uniform mixing, the rubber is sheeted and stored for 24 h, and then it is ready for use. The mixed blended rubber is placed in a 2mm thick flat mold, and the flat mold is placed on a flat vulcanizing machine at 170℃ and 10MPa for 35 min to obtain a solid chlorinated butyl vulcanized rubber layer;

[0057] (2) Take E-44 epoxy resin 100 parts by weight (resin, weight average molecular weight 500), dibutyl phthalate 15 parts by weight (acid ester compound), diethylenetriamine 8 parts by weight (organic amine), and aluminum oxide powder 30 parts by weight (second filler), and uniformly mix the four components at a temperature of 25℃ for 24 h to obtain an adhesive;

[0058] (3) 2.533g of polyvinyl alcohol (PVA, high polymer carrier, weight average molecular weight 200000), 100g of zirconium acetate (ceramic particles, average particle size 1μm), 12.597g of yttrium nitrate hexahydrate (third filler), and 50ml of water are mixed and stirred at room temperature for 5h using a magnetic stirrer to prepare a uniform precursor solution; an appropriate amount of the prepared precursor solution is extracted using a syringe, fixed on the support of an electrospinning machine, and electrospun with a receiving distance of 14cm, an environmental temperature controlled at 25±2℃ by an air conditioner, an environmental humidity controlled at 50±5% by a dehumidifier, a negative voltage of the spinning set at -1.5KV, a positive voltage set at 20kV, and a push injection speed set at 0.25mm / min, and the receiving roller speed set at 80r / min. The scanning electron microscope image of the flexible ceramic fiber layer obtained by the above spinning is shown in FIG. 1, and the flexible ceramic fiber layer is placed in a vacuum drying oven at 80℃ for 24h, and then calcined in a muffle furnace at a temperature rising rate of 5℃ / min to 600℃, and kept for 2h to obtain a ceramic membrane; Figure 1

[0059] ​(4) uniformly spin-coating the adhesive on the surface of the chlorinated butyl vulcanized rubber layer, and bonding the ceramic membrane with the adhesive, the thickness ratio of the vulcanized rubber layer, the adhesive and the ceramic membrane is 1:0.4:1, curing at 25℃ for 24h, to obtain a protective film, the protective film has a vulcanized rubber layer, an adhesive layer and a ceramic layer stacked from bottom to top, and the structural characteristics are shown in Table 1.

[0060] The prepared protective film is attached to the leading edge part of the fan blade to play a protective and shock-absorbing impact role. The vulcanized rubber layer of the protective film is in contact with the blade body, and the thickness of the protective film is 12mm.

[0061] Comparative Example 1

[0062] The same as Example 1, the difference is only that in step (1), no vulcanization treatment is performed, and the blended rubber is mixed and used as a rubber layer for curing in step (4), and finally a comparative protective film is prepared, and the structural characteristics are shown in Table 1.

[0063] Comparative Example 2

[0064] The same as Example 1, the difference is only that in step (2), no organic amine substance is added, and finally a comparative protective film is prepared, and the structural characteristics are shown in Table 1.

[0065] Comparative Example 3

[0066] The same as Example 1, the difference is only that in step (3), no electrospinning is performed, and the precursor solution is directly dried and calcined, and finally a comparative protective film is prepared, and the structural characteristics are shown in Table 1.

[0067] Table 1

[0068]

[0069] Test Example 1

[0070] The impact resistance of the protective films prepared in Examples 1 and Comparative Examples 1-3 is tested by a pendulum impact tester. The pendulum impact tester converts gravitational potential energy into kinetic energy through the circular motion of the pendulum, and breaks the test piece when the pendulum moves to the lowest point. According to the principle of energy conservation, the difference in energy possessed by the pendulum before and after breaking the test piece is the energy absorbed by the test piece (without considering friction loss). If this difference can be measured, the energy absorbed by the sample can be known, and the strength H of the sample can be calculated. The test results are shown in Table 2.

[0071] Test Example 2

[0072] The tensile strength and elongation at break of the protective films prepared from Example 1 and Comparative Examples 1-3 were tested by a universal tensile testing machine. The mechanical properties of the protective films and comparative samples were studied on a Zwick / Roell Z005 universal tensile machine with a 5 kN load cell at room temperature. The tensile strength and elongation at break were tested according to GB / T 528-2009. The 2 mm sheets were cut into dumbbell shapes of 10 mm x 4 mm x 2 mm by a punch. Five tensile strength tests were performed for each material, with a tensile rate of 5 mm / min, and the test temperature was 25℃ and -30℃, respectively. The test results are shown in Table 2.

[0073] Test Example 3

[0074] The protective films prepared from Example 1 and Comparative Examples 1-3 were tested by a thermal gravimetric analyzer (TGA). The sample was heated at a rate of 20℃ / min from 30℃ to 700℃ under a nitrogen atmosphere with a gas flow rate of 20 mL / min, and the sample amount was about 10 mg. The test results are shown in Table 2.

[0075] Table 2

[0076]

[0077] The data of Test Examples 1-2 above show that the protective film of the present disclosure has good shock absorption and impact resistance, while maintaining good elasticity, which can play a shock absorption effect, not only to protect the fan blade leading edge from wind and sand abrasion and rain corrosion, but also to absorb most of the energy of wind impact, reducing the possibility of blade leading edge cracking.

[0078] Test Example 3 tested the initial decomposition temperature and half-decomposition temperature of the protective film during the heating process. The higher the decomposition temperature, the better the thermal stability of the protective film, which can maintain its performance unaffected at higher temperatures and is less likely to decompose or degrade in a high-temperature environment. As shown by the initial decomposition temperature and half-decomposition temperature in Table 2, the decomposition temperature of the protective film prepared from Example 1 is higher than that of the comparative protective films prepared from Comparative Examples 1-3, indicating that the protective film prepared by the preparation method of the present disclosure has higher thermal stability, which is beneficial to prolonging the blade life and maintenance cycle, reducing the operation and maintenance cost of the wind turbine blade leading edge, and improving the economic performance.

[0079] The preferred embodiments of the present disclosure are described in detail above in combination with the drawings, but the present disclosure is not limited to the specific details in the above-described embodiments. Within the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0080] It should be further noted that various specific technical features described in the above specific embodiments can be combined in any suitable manner, and the disclosure will not be repeated here for various possible combinations.

[0081] In addition, various different embodiments of the disclosure can also be combined with each other as long as they do not contradict the idea of the disclosure, and they should also be considered as disclosed by the disclosure.

Claims

1. A method for producing a protective film, characterized by, The preparation method comprises: (1) mixing rubber, vulcanizing agent and first filler to obtain a blended rubber; mixing and vulcanizing the blended rubber to obtain a vulcanized rubber layer; wherein the rubber is selected from one or more of chlorinated butyl rubber, butyl rubber, nitrile rubber and polyethylene-butyl rubber blend, and the vulcanizing agent is selected from metal oxide; (2) contacting resin, acid ester compound, organic amine and second filler to obtain an adhesive; (3) mixing high polymer carrier, ceramic particles, third filler and water to obtain a precursor solution; electrospinning the precursor solution to obtain a ceramic fiber layer; drying and calcining the ceramic fiber layer to obtain a ceramic membrane; wherein the high polymer carrier is selected from one or more of polyvinyl alcohol, polyethylene terephthalate, polyacrylic acid, polyvinyl acetate and polyvinylpyrrolidone, the ceramic particles are selected from one or more of zirconium acetate, zirconium oxychloride, aluminum nitrate and titanium isopropyl alcohol, and the third filler is selected from one or more of trivalent cobalt salt, yttrium compound, persulfate and peroxide; (4) bonding the vulcanized rubber layer and the ceramic membrane through the adhesive and performing curing treatment to obtain a protective film.

2. The production method according to claim 1, characterized by, In step (1), the metal oxide is selected from one or more of magnesium oxide, zinc oxide and lead oxide, and the first filler is selected from one or more of stearic acid, carbon black, mica and fumed silica; The rubber is chlorinated butyl rubber; and the weight average molecular weight of the rubber is 100000-600000.

3. The preparation method according to claim 2, characterized in that, The vulcanizing agent comprises magnesium oxide and zinc oxide, and the first filler comprises stearic acid and carbon black; the blended rubber comprises rubber, magnesium oxide, zinc oxide, stearic acid and carbon black; relative to 90-100 parts by weight of rubber, the content of magnesium oxide is 1.8-2.2 parts by weight, the content of zinc oxide is 2.0-5.0 parts by weight, the content of stearic acid is 0.9-1.1 parts by weight, and the content of carbon black is 40-55 parts by weight.

4. The preparation method according to claim 3, characterized in that, The blended rubber further comprises a rubber vulcanization accelerator, the rubber vulcanization accelerator comprises a first accelerator and a second accelerator, and relative to 90-100 parts by weight of rubber, the content of the first accelerator is 1.8-2.4 parts by weight, and the content of the second accelerator is 0.8-1.2 parts by weight; wherein the first accelerator is selected from a sulfenamide accelerator, and the sulfenamide accelerator is selected from one or more of N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide and N-oxybisdimethylene-2-benzothiazole sulfenamide, and the second accelerator is selected from one or more of tetramethylthiuram disulfide, tetramethylthiuram monosulfide and tetraethylthiuram disulfide.

5. The preparation method according to claim 1, characterized in that, In step (1), the mixing is performed on a rubber mixing machine, the temperature of the mixing is 150-250℃, and the time is 10-50 min. The conditions of the vulcanization treatment include: filling the blended rubber into a flat mold with a thickness of 1-10 mm, and placing the flat mold on a flat vulcanization machine for the vulcanization treatment, the temperature of the vulcanization treatment is 150-170℃, the time is 0.5-1h, and the pressure is 1.0-10.0MPa.

6. The method of claim 1, wherein, In step (2), the content of the acid ester compound is 10-25 parts by weight, the content of the organic amine is 5-10 parts by weight, and the content of the second filler is 20-50 parts by weight, relative to 100 parts by weight of the resin; The temperature of the contact is 20-35℃, and the time is 20-30h; The resin is selected from one or more of an epoxy resin, an acrylic resin, a polyethylene resin and a petroleum resin, and the weight average molecular weight of the resin is 400-500; The acid ester compound is selected from one or more of dibutyl phthalate, propylene glycol alginate acid ester and dioctyl phthalate; The organic amine is selected from one or more of diethylene triamine, triethylene tetramine and m-xylylenediamine; The second filler is selected from inorganic metal materials and / or inorganic non-metal materials, the inorganic metal materials are selected from one or more of aluminum oxide powder, aluminum oxide powder, iron powder and talc powder, and the inorganic non-metal materials are selected from graphite powder.

7. The production method according to claim 6, characterized by, The resin is an epoxy resin; and / or, the acid ester compound is dibutyl phthalate; and / or, the organic amine is diethylene triamine.

8. The method of claim 1, wherein, In step (3), the content of the high polymer carrier is 1-20g, the content of the third filler is 10-20g, and the content of water is 20-50g, relative to 100g of the ceramic particles; The temperature of the drying treatment is 20-100℃, and the time is 1-24h; the temperature of the calcination treatment is 200-600℃, the time is 1-2h, and the heating rate is 2-10℃ / min; The high polymer carrier is polyvinyl alcohol; and the weight average molecular weight of the high polymer carrier is 100000-300000; The ceramic particles are zirconium acetate; and the average particle size of the ceramic particles is 0.5-2μm; The third filler is yttrium nitrate.

9. The method of claim 1, wherein, In step (4), the thickness ratio of the vulcanized rubber layer, the adhesive and the ceramic diaphragm is 1:(0.05-0.4):(0.5-2), the temperature of the curing treatment is 20-30℃, and the time is 10-30h.

10. The method of claim 1, wherein, The thickness of the vulcanized rubber layer is 1-10mm, the thickness of the adhesive is 0.5-5mm, and the thickness of the ceramic diaphragm is 1-10mm.

11. The method of claim 10, wherein, The thickness of the vulcanized rubber layer is 2-5mm, the thickness of the adhesive is 1-2mm, and the thickness of the ceramic diaphragm is 2-5mm.

12. A protective film prepared by the method of any one of claims 1-11.

13. The protective film according to claim 12, characterized in that, The protective film comprises a vulcanized rubber layer, an adhesive layer and a ceramic layer which are sequentially stacked from bottom to top; and the hardness of the vulcanized rubber layer is 40-80HA.

14. The protective film according to claim 13, characterized in that, The impact strength of the protective film is 8-15 kJ / m 2 The tensile strength of the protective film at 25°C is 15-22 MPa, and the elongation at break is 500-700%; the tensile strength of the protective film at low temperature of -30°C is 10-20 MPa, and the elongation at break is 200-600%. The initial decomposition temperature of the protective film is 230-260 DEG C, the half decomposition temperature is 400-440 DEG C, and the maximum thermal weight loss rate temperature is 410-450 DEG C.

15. The protective film according to claim 13, wherein The thickness of the vulcanized rubber layer is 1-10 mm, the thickness of the adhesive layer is 0.5-5 mm, and the thickness of the ceramic layer is 1-10 mm.

16. The protective film according to claim 15, characterized in that, The thickness of the vulcanized rubber layer is 2-5 mm, the thickness of the adhesive layer is 0.5-2 mm, and the thickness of the ceramic layer is 1-5 mm.

17. The protective film according to claim 13, wherein The tensile strength of the vulcanized rubber layer at 25 DEG C is 12-20 MPa, and the elongation at break is 500-700%. The vulcanized rubber layer comprises one or more of a chlorinated butyl vulcanized rubber layer, a butyl rubber layer, a nitrile rubber layer, and a polyethylene-butyl rubber blend rubber layer.

18. The protective film according to claim 17, characterized in that, The vulcanized rubber layer is a chlorinated butyl vulcanized rubber layer.

19. The protective film according to claim 13, wherein The adhesive layer comprises a resin adhesive layer, and the resin adhesive layer comprises one or more of an epoxy resin adhesive layer, an acrylic resin adhesive layer, a polyethylene resin adhesive layer, and a petroleum resin adhesive layer.

20. The protective film according to claim 19, wherein The resin adhesive layer is an epoxy resin adhesive layer.

21. A wind turbine blade, characterised in that The leading edge portion of the fan blade comprises a blade body and the protective film according to any one of claims 12-20, the vulcanized rubber layer of the protective film is in contact with the surface of the blade body, and the thickness of the protective film is 5-50 mm.

Images