阅读说明：本技术 一种纳米ZrO2/Al2O3复合材料的制备方法及其应用 (Nano ZrO2/Al2O3Preparation method and application of composite material ) 是由 王威 张现峰 孟晓林 王传虎 于 2021-09-05 设计创作，主要内容包括：本发明公开一种纳米ZrO-(2)/Al-(2)O-(3)复合材料的制备方法及其应用,包括以下步骤：S1：按0.05mol/100mL的比例将四氯化锆溶解于去离子水中,制出ZrCl-(4)-ZrOCl-(2)混合溶液；S2：向ZrCl-(4)-ZrOCl-(2)混合溶液中加入等体积的pH值为12的氨水溶液,搅拌至产生白色絮状沉淀时,得到母液；S3：向S2所得母液中加入一定量的纳米氧化铝,充分搅拌至形成均匀的悬浮液,并移至聚四氟乙烯内衬的反应釜中,200℃水热反应2-6h,再自然冷却至室温,真空抽滤后,用去离子水和丙酮洗涤,再抽滤,得到湿样品；S4：将所得湿样品置于马弗炉内,110℃干燥24h。本发明以四氯化锆为原料,一步水热法直接制出了纳米ZrO-(2)/Al-(2)O-(3)复合颗粒,无需高温煅烧,方法简便易操作,表面改性后Al-(2)O-(3)粉体的断裂韧性、耐酸碱性能得到显著提升。(The invention discloses a nano ZrO 2 /Al 2 O 3 The preparation method and the application of the composite material comprise the following steps: s1: zirconium tetrachloride is dissolved in deionized water according to the proportion of 0.05mol/100mL to prepare ZrCl 4 ‑ZrOCl 2 Mixing the solution; s2: to ZrCl 4 ‑ZrOCl 2 Adding an ammonia water solution with the pH value of 12 and the same volume into the mixed solution, and stirring until white flocculent precipitate is generated to obtain mother liquor; s3: adding a certain amount of nano alumina into the mother liquor obtained in S2, fully stirring to form uniform suspension, transferring to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 2-6h, naturally cooling to room temperature, carrying out vacuum filtration, washing with deionized water and acetone, and carrying out vacuum filtration to obtain a wet sample; s4: the resulting wet sample was placed in a muffle furnace and dried at 110 ℃ for 24 h. The invention takes zirconium tetrachloride as raw material and directly prepares nano ZrO by a one-step hydrothermal method 2 /Al 2 O 3 The composite particles do not need high-temperature calcination, the method is simple and easy to operate, and the surface modified Al 2 O 3 The fracture toughness and acid and alkali resistance of the powder are obviously improved.)

1. Nano ZrO₂/Al₂O₃A process for the preparation of a composite material, characterized in thatThe method comprises the following steps:

s1: zirconium tetrachloride is dissolved in deionized water according to the proportion of 0.05mol/100mL to prepare ZrCl₄-ZrOCl₂Mixing the solution;

s2: to ZrCl₄-ZrOCl₂Adding an ammonia water solution with the pH value of 12 into the mixed solution, and stirring until white flocculent precipitate is generated to obtain mother liquor;

s3: adding a certain amount of nano alumina into the mother liquor obtained in S2, fully stirring to form uniform suspension, transferring to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 2-6h, naturally cooling to room temperature, carrying out vacuum filtration, washing with deionized water and acetone, and carrying out vacuum filtration to obtain a wet sample;

s4: placing the obtained wet sample in a muffle furnace, and drying at 110 ℃ for 24h to obtain the nano ZrO₂/Al₂O₃A composite material.

2. The nano ZrO 2 of claim 1₂/Al₂O₃The preparation method of the composite material is characterized in that ZrCl is adopted₄-ZrOCl₂The dosage ratio of the mixed solution, the ammonia water solution and the nano alumina is 100 mL: 100mL of: (0.15-0.25) mol.

3. Nano ZrO produced by the production method according to any one of claims 1 to 2₂/Al₂O₃The composite material is applied to the glass wear-resistant coating material.

4. Use according to claim 3, characterized in that it comprises the following steps:

s1: into nano ZrO₂/Al₂O₃Dripping functional silane coupling agent-absolute ethyl alcohol solution into the composite material, controlling the solid-to-liquid ratio to be 1g/mL, stirring for 1-3h, evaporating the absolute ethyl alcohol at 85-95 ℃ to obtain the treated nano ZrO₂/Al₂O₃A composite material;

s2: the treated ZrO₂/Al₂O₃Composite material and friction reductionAdding the solvent into a benzyl alcohol diluent, stirring and dispersing, adding into the organic fluorine-silicon modified epoxy resin, and fully stirring to obtain a mixed component;

s3: adding a polyamide 650 curing agent into the mixed component obtained in the step S3, and uniformly stirring to obtain a glass wear-resistant coating material; after the treatment of ZrO₂/Al₂O₃The mass ratio of the composite material, the friction reducer, the benzyl alcohol diluent, the organic fluorine-silicon modified epoxy resin and the polyamide 650 curing agent is (0.2-0.3): (0.05-0.15): (0.3-0.5): 1: (0.8-1);

s4: after washing and drying the glass substrate, uniformly brushing the glass wear-resistant coating material on the surface of the glass substrate according to a dip-coating method, standing for 6-12h at 40-50 ℃, and then curing and reacting for 8h at 65-75 ℃ to form the wear-resistant coating.

5. The use according to claim 4, wherein the mass fraction of the functional silane coupling agent in the functional silane coupling agent-absolute ethanol solution is 5-10%.

6. Use according to any of claims 4-5, wherein the functional silane coupling agent comprises one of an aminosilane coupling agent or an epoxysilane coupling agent.

7. The use according to claim 6, wherein the aminosilane coupling agent comprises one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl ] ethylenediamine or N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.

8. The use according to claim 6, wherein the epoxysilane coupling agent comprises one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, or 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

9. Use according to claim 4, wherein the friction reducer is prepared from polytetrafluoroethylene micropowder and a fluorine-containing silane in a ratio of 1: (0.4-0.8) by mass ratio.

10. Use according to claim 4, wherein the fluorine-containing silane comprises one or more of tridecafluorooctyltriethoxysilane, trifluoropropylmethylcyclotrisiloxane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane.

Technical Field

The invention belongs to the field of nano materials, and particularly relates to nano ZrO₂/Al₂O₃A preparation method and application of the composite material.

Background

With the continuous development of high and new technologies, the surface corrosion and abrasion of engineering machinery, equipment and parts become the main failure modes of the equipment parts in the long-term use process. The surface adhesion coating technology is a technology based on functional coating, has the characteristics of simplicity, convenience, rapidness, low cost, suitability for field operation and the like, is a surface repair and reinforcement technology with wide application prospect, and is key to preparing high-performance wear-resistant functional coating. Practice shows that the surface adhesion coating technology is one of effective means for repairing and strengthening the surface layer of the non-steel material component.

The wear-resistant coating mainly comprises a polymer matrix, a reinforcement and other auxiliary agents, and the performance of the wear-resistant coating is mainly determined by the matrix, the reinforcement and the interface action between the matrix and the reinforcement. The alumina powder has excellent characteristics such as high strength, high hardness, abrasion resistance and wear resistance, and has a special application to a polymer-based wear-resistant coating, but the alumina powder is directly used, the interface bonding with the polymer matrix is weak, the alumina is equiaxed grains, and atomic bonds formed by aluminum ions and oxygen ions in the crystal form are mostly covalent bonds, ionic bonds and mixed bonds, so that the interatomic bonding energy is very high and has strong directionality, and the alumina material has large brittleness, low fracture toughness and small plastic deformation. Therefore, the surface modification of the alumina powder body by adopting the traditional surface treatment technology cannot fundamentally solve the inherent morphological defects of the powder surface, and the defects are easy to become weak points in the composite material in a microscopic way, which is one of the reasons for causing the failure of the composite material. Research shows that the surface state of the powder can be effectively improved by adopting a surface nano-modification method, and on one hand, nano particles cannot be effectively and uniformly attached to parent particles by adopting a traditional physical compounding method and other similar methods, and most of the compounding methods are simple physical attachments, have small binding force and are easy to fall off from the surfaces of the parent particles; on the other hand, the energy consumption is large in industrial production, which causes energy waste, for example, a sol method using metal alkoxide as a raw material can prepare tightly combined composite particles, but the preparation process is complex, high-temperature calcination is generally required, and the preparation period is long.

The invention takes zirconium tetrachloride as raw material and adopts a hydrothermal method to prepare Al₂O₃The nano-zirconia particles are deposited on the surface of the powder in situ, and the nano-ZrO is directly formed in one step₂/Al₂O₃The composite particles do not need high-temperature calcination, and the method is simple, convenient and easy to operate; the composite particle is applied to a wear-resistant coating taking organic silicon modified epoxy resin as a matrix, so that Al can be ensured₂O₃Plays a role in enhancing abrasion resistance and further improves the abrasion resistance of the composite abrasion-resistant coating.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide nano ZrO₂/Al₂O₃A preparation method and application of the composite material.

The technical scheme of the invention is summarized as follows:

nano ZrO₂/Al₂O₃The preparation method of the composite material comprises the following steps:

s1: according to 0.05mol/10Dissolving zirconium tetrachloride in deionized water in a proportion of 0mL to prepare Zr Cl₄-ZrOCl₂Mixing the solution;

s2: to ZrCl₄-ZrOCl₂Adding an ammonia water solution with the pH value of 12 into the mixed solution, and stirring until white flocculent precipitate is generated to obtain mother liquor;

s3: adding a certain amount of nano alumina into the mother liquor obtained in S2, fully stirring to form uniform suspension, transferring to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 2-6h, naturally cooling to room temperature, carrying out vacuum filtration, washing with deionized water and acetone, and carrying out vacuum filtration to obtain a wet sample;

s4: placing the obtained wet sample in a muffle furnace, and drying at 110 ℃ for 24h to obtain the nano ZrO₂/Al₂O₃A composite material.

Preferably, the ZrCl₄-ZrOCl₂The dosage ratio of the mixed solution, the ammonia water solution and the nano alumina is 100 mL: 100mL of: (0.15-0.25) mol.

The nano ZrO prepared by the preparation method₂/Al₂O₃The composite material is applied to the glass wear-resistant coating material.

The application comprises the following steps:

s1: into nano ZrO₂/Al₂O₃Dripping functional silane coupling agent-absolute ethyl alcohol solution into the composite material, controlling the solid-to-liquid ratio to be 1g/mL, stirring for 1-3h, evaporating the absolute ethyl alcohol at 85-95 ℃ to obtain the treated nano ZrO₂/Al₂O₃A composite material;

s2: the treated ZrO₂/Al₂O₃Adding the composite material and the friction reducer into a benzyl alcohol diluent, stirring and dispersing, adding into the organic fluorine-silicon modified epoxy resin, and fully stirring to obtain a mixed component;

s3: adding a polyamide 650 curing agent into the mixed component obtained in the step S3, and uniformly stirring to obtain a glass wear-resistant coating material; after the treatment of ZrO₂/Al₂O₃Composite material, friction reducer, benzyl alcohol diluent and organic fluorine-silicon modifierThe mass ratio of the epoxy resin to the polyamide 650 curing agent is (0.2-0.3): (0.05-0.15): (0.3-0.5): 1: (0.8-1);

s4: after washing and drying the glass substrate, uniformly brushing the glass wear-resistant coating material on the surface of the glass substrate according to a dip-coating method, standing for 6-12h at 40-50 ℃, and then curing and reacting for 8h at 65-75 ℃ to form the wear-resistant coating.

Preferably, the mass fraction of the functional silane coupling agent in the functional silane coupling agent-absolute ethyl alcohol solution is 5-10%.

Preferably, the functional silane coupling agent includes one of an aminosilane coupling agent or an epoxysilane coupling agent.

Preferably, the aminosilane coupling agent comprises one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl ] ethylenediamine or N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.

Preferably, the epoxysilane coupling agent includes one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, or 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

Preferably, the friction reducer is prepared from polytetrafluoroethylene superfine powder and fluorine-containing silane according to the weight ratio of 1: (0.4-0.8) by mass ratio.

Preferably, the fluorine-containing silane comprises one or more of tridecafluorooctyltriethoxysilane, trifluoropropylmethylcyclotrisiloxane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane.

The invention has the beneficial effects that:

1. the invention takes zirconium tetrachloride as raw material and adopts a hydrothermal method to prepare Al₂O₃The zirconia nano particles are grown on the surface of the powder in situ, and the nano ZrO is directly prepared by one step₂/Al₂O₃The composite particles are not required to be calcined at high temperature, energy is saved, carbon is low, and the method is simple, convenient and easy to operate; meanwhile, as the nano ZrO₂Has high toughness and excellent chemical stability, and can be used for treating nano Al₂O₃Surface modification of Al₂O₃The fracture toughness and acid and alkali resistance of the powder are obviously improved; compared with the traditional physical mixing method or physical doping method, the nano ZrO prepared by the method₂Can be stably bonded or adhered to Al₂O₃Increasing the nano-ZrO on the surface of the powder₂/Al₂O₃The composite stability of (1).

2. The nano ZrO prepared by the invention₂/Al₂O₃The composite material is used as a reinforcement in a glass wear-resistant coating material, so that wear resistance is enhanced, and the wear resistance and mechanical strength of the composite wear-resistant coating are further improved.

3. The nano ZrO of the invention₂/Al₂O₃When the composite material is applied to the glass wear-resistant coating, the nano ZrO is coupled by using the silane coupling agent containing amino or epoxy₂/Al₂O₃The surface of the composite material is modified, and the nano ZrO is treated under the action of a polyamide 650 curing agent₂/Al₂O₃The composite material utilizes amino or epoxy group and nano ZrO on the surface₂Surface hydroxyl (hydrothermal method can synthesize nano ZrO)₂A large number of active hydroxyl groups on the surface) and the organic fluorine-silicon modified epoxy resin to generate cross-linking reaction, thereby further leading the nano ZrO to be₂/Al₂O₃The composite material is stably grafted in epoxy resin molecules, so that nano ZrO is formed₂/Al₂O₃The composite material is stably embedded into the three-dimensional network structure of the wear-resistant coating material, and the ZrO content is remarkably improved₂/Al₂O₃The interface bonding strength of the composite material and the organic fluorine-silicon modified epoxy resin matrix.

4. According to the invention, benzyl alcohol is used as a diluent, and a rigid benzene ring structure is grafted into an organic fluorine-silicon modified epoxy resin molecular chain by utilizing the ring-opening addition of hydroxyl and epoxy, so that the mechanical property, the mechanical property and the wear-resistant strength of the glass wear-resistant coating material are further improved.

5. The friction reducer prepared by the polytetrafluoroethylene superfine powder and the fluorine-containing silane is utilized to further improve the self-lubricating property of the glass wear-resistant coating and reduce the friction factor, thereby achieving the effects of reducing friction and resisting wear; in addition, the antifriction agent also has the functions of improving the hydrophobic and oleophobic properties of the wear-resistant coating and ensuring certain self-cleaning property of the coating.

Drawings

FIG. 1 shows nano ZrO of the present invention₂/Al₂O₃A flow chart of a preparation method of the composite material;

FIG. 2 shows a nano ZrO layer of the present invention₂/Al₂O₃Application flow chart of the composite material.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

The present application provides an embodiment of nano ZrO₂/Al₂O₃The preparation method of the composite material comprises the following steps:

s1: zirconium tetrachloride is dissolved in deionized water according to the proportion of 0.05mol/100mL to prepare ZrCl₄-ZrOCl₂Mixing the solution;

s2: to ZrCl₄-ZrOCl₂Adding an ammonia water solution with the pH value of 12 into the mixed solution, and stirring until white flocculent precipitate is generated to obtain mother liquor; said ZrCl₄-ZrOCl₂The dosage ratio of the mixed solution, the ammonia water solution and the nano alumina is 100 mL: 100mL of: (0.15-0.25) mol;

s3: adding a certain amount of nano alumina into the mother liquor obtained in S2, fully stirring to form uniform suspension, transferring to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 2-6h, naturally cooling to room temperature, carrying out vacuum filtration, washing with deionized water and acetone, and carrying out vacuum filtration to obtain a wet sample;

s4: placing the obtained wet sample in a muffle furnace, and drying at 110 ℃ for 24h to obtain the nano ZrO₂/Al₂O₃A composite material.

The scheme also provides the nano ZrO of the embodiment₂/Al₂O₃The application of the composite material in the glass wear-resistant coating material comprises the following stepsThe method comprises the following steps:

s1: into nano ZrO₂/Al₂O₃Dripping functional silane coupling agent-absolute ethyl alcohol solution into the composite material, controlling the solid-to-liquid ratio to be 1g/mL, stirring for 1-3h, evaporating the absolute ethyl alcohol at 85-95 ℃ to obtain the treated nano ZrO₂/Al₂O₃A composite material; the mass fraction of the functional silane coupling agent in the functional silane coupling agent-absolute ethyl alcohol solution is 5-10%; the functional silane coupling agent comprises one of an aminosilane coupling agent or an epoxy silane coupling agent; the amino silane coupling agent comprises gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane and N- [3- (trimethoxysilyl) propyl]One or more of ethylenediamine or N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane; the epoxy silane coupling agent comprises one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane or 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane;

s2: the treated ZrO₂/Al₂O₃Adding the composite material and the friction reducer into a benzyl alcohol diluent, stirring and dispersing, adding into the organic fluorine-silicon modified epoxy resin, and fully stirring to obtain a mixed component; the friction reducer is prepared from polytetrafluoroethylene superfine powder and fluorine-containing silane according to the weight ratio of 1: (0.4-0.8) by mass ratio; the fluorine-containing silane comprises one or more of tridecafluorooctyltriethoxysilane, trifluoropropylmethylcyclotrisiloxane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane;

s3: adding a polyamide 650 curing agent into the mixed component obtained in the step S3, and uniformly stirring to obtain a glass wear-resistant coating material; after the treatment of ZrO₂/Al₂O₃The mass ratio of the composite material, the friction reducer, the benzyl alcohol diluent, the organic fluorine-silicon modified epoxy resin and the polyamide 650 curing agent is (0.2-0.3): (0.05-0.15): (0.3-0.5): 1: (0.8-1);

s4: after washing and drying the glass substrate, uniformly brushing the glass wear-resistant coating material on the surface of the glass substrate according to a dip-coating method, standing for 6-12h at 40-50 ℃, and then curing and reacting for 8h at 65-75 ℃ to form the wear-resistant coating.

Example 1

S1: dissolving 0.25mol of zirconium tetrachloride in 500mL of deionized water to prepare ZrCl₄-ZrOCl₂Mixing the solution;

s2: to 500mL of ZrCl₄-ZrOCl₂Adding 500mL of ammonia water solution with the pH value of 12 into the mixed solution, and stirring until white flocculent precipitate is generated to obtain mother liquor;

s3: adding 0.75mol of nano alumina into the mother liquor obtained in S2, fully stirring to form uniform suspension, transferring the suspension into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 2h, naturally cooling to room temperature, carrying out vacuum filtration, washing with deionized water and acetone, and carrying out vacuum filtration to obtain a wet sample;

s4: placing the obtained wet sample in a muffle furnace, and drying at 110 ℃ for 24h to obtain the nano ZrO₂/Al₂O₃A composite material.

The scheme also provides the nano ZrO of the embodiment₂/Al₂O₃The application of the composite material in the glass wear-resistant coating material comprises the following steps:

s1: to 100g of nano-ZrO₂/Al₂O₃100mL of N- [3- (trimethoxysilyl) propyl group is dripped into the composite material]Stirring ethylenediamine-absolute ethyl alcohol solution for 1h, evaporating absolute ethyl alcohol at 85 deg.C to obtain processed nano ZrO₂/Al₂O₃A composite material; the N- [3- (trimethoxysilyl) propyl group]N- [3- (trimethoxysilyl) propyl group in ethylenediamine-absolute ethanol solution]The mass fraction of the ethylenediamine is 5 percent;

s2: 60g of the treated ZrO₂/Al₂O₃Adding the composite material and 15g of the friction reducer into 90g of benzyl alcohol diluent, stirring and dispersing, adding into 300g of the organic fluorine-silicon modified epoxy resin, and fully stirring to obtain a mixed component; the friction reducer is prepared from polytetrafluoroethylene superfine powder and tridecafluorooctyltriethoxysilane according to the weight ratio of 1: 0.4 by mass ratio;

s3: adding 240g of polyamide 650 curing agent into the mixed component obtained in S3, and stirring uniformly to obtain the glass wear-resistant coating material;

s4: after washing and drying the glass substrate, uniformly brushing the glass wear-resistant coating material on the surface of the glass substrate according to a dip-coating method, standing for 6h at 40 ℃, and then curing and reacting for 8h at 65 ℃ to form a wear-resistant coating with the thickness of 1 mm.

Example 2

S1: dissolving 0.25mol of zirconium tetrachloride in 500mL of deionized water to prepare ZrCl₄-ZrOCl₂Mixing the solution;

s2: to 500mL of ZrCl₄-ZrOCl₂Adding 500mL of ammonia water solution with the pH value of 12 into the mixed solution, and stirring until white flocculent precipitate is generated to obtain mother liquor;

s3: adding 1mol of nano alumina into the mother liquor obtained in the step S2, fully stirring the mixture until a uniform suspension is formed, transferring the suspension into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 5 hours, naturally cooling the mixture to room temperature, carrying out vacuum filtration, washing the mixture with deionized water and acetone, and carrying out vacuum filtration to obtain a wet sample;

s4: placing the obtained wet sample in a muffle furnace, and drying at 110 ℃ for 24h to obtain the nano ZrO₂/Al₂O₃A composite material.

The scheme also provides the nano ZrO of the embodiment₂/Al₂O₃The application of the composite material in the glass wear-resistant coating material comprises the following steps:

s1: to 100g of nano-ZrO₂/Al₂O₃Dripping 100mL of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane-absolute ethyl alcohol solution into the composite material, stirring for 2h, evaporating the absolute ethyl alcohol at 85-95 ℃ to obtain the treated nano ZrO₂/Al₂O₃A composite material; the mass fraction of the N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane in the N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane-absolute ethyl alcohol solution is 7.5 percent;

s2: 75g of the treated ZrO₂/Al₂O₃Composite materialAdding 30g of friction reducer into 120g of benzyl alcohol diluent, stirring and dispersing, adding into 300g of organic fluorine-silicon modified epoxy resin, and fully stirring to obtain a mixed component; the friction reducer is prepared from polytetrafluoroethylene superfine powder and trifluoropropylmethylcyclotrisiloxane according to the weight ratio of 1: 0.6 by mass ratio;

s3: adding 270g of polyamide 650 curing agent into the mixed component obtained in the step S3, and uniformly stirring to obtain the glass wear-resistant coating material;

s4: after washing and drying the glass substrate, uniformly brushing the glass wear-resistant coating material on the surface of the glass substrate according to a dip-coating method, standing for 8 hours at 45 ℃, and then curing and reacting for 8 hours at 70 ℃ to form a wear-resistant coating with the thickness of 1 mm.

Example 3

S1: dissolving 0.25mol of zirconium tetrachloride in 500mL of deionized water to prepare ZrCl₄-ZrOCl₂Mixing the solution;

s2: to 500mL of ZrCl₄-ZrOCl₂Adding 500mL of ammonia water solution with the pH value of 12 into the mixed solution, and stirring until white flocculent precipitate is generated to obtain mother liquor;

s3: adding 1mol of nano alumina into the mother liquor obtained in the step S2, fully stirring the mixture until a uniform suspension is formed, transferring the suspension into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 6 hours, naturally cooling the mixture to room temperature, carrying out vacuum filtration, washing the mixture with deionized water and acetone, and carrying out vacuum filtration to obtain a wet sample;

s4: placing the obtained wet sample in a muffle furnace, and drying at 110 ℃ for 24h to obtain the nano ZrO₂/Al₂O₃A composite material.

The scheme also provides the nano ZrO of the embodiment₂/Al₂O₃The application of the composite material in the glass wear-resistant coating material comprises the following steps:

s1: to 100g of nano-ZrO₂/Al₂O₃100mL of gamma-glycidoxypropyltrimethoxysilane (KH-560) -absolute ethanol solution is dripped into the composite material, stirred for 3 hours, and then absolute ethanol is evaporated to dryness at 95 ℃ to obtain the treated nano ZrO₂/Al₂O₃A composite material; the mass fraction of the gamma-glycidoxypropyltrimethoxysilane in the gamma-glycidoxypropyltrimethoxysilane-absolute ethanol solution is 10 percent;

s2: 90g of the treated ZrO₂/Al₂O₃Adding the composite material and 45g of the friction reducer into 150g of benzyl alcohol diluent, stirring and dispersing, adding into 300g of the organic fluorine-silicon modified epoxy resin, and fully stirring to obtain a mixed component; the friction reducer is prepared from polytetrafluoroethylene superfine powder and heptadecafluorodecyltrimethoxysilane according to the weight ratio of 1: 0.8 by mass ratio;

s3: adding 300g of polyamide 650 curing agent into the mixed component obtained in S3, and uniformly stirring to obtain the glass wear-resistant coating material;

s4: after washing and drying the glass substrate, uniformly brushing the glass wear-resistant coating material on the surface of the glass substrate according to a dip-coating method, standing for 12h at 50 ℃, and then curing and reacting for 8h at 75 ℃ to form a wear-resistant coating with the thickness of 1 mm.

Comparative example 1 replacement of nano ZrO by nano alumina₂/Al₂O₃The composite material was applied in the same manner as in example 1.

Comparative example 2 is the same as example 1 except that in the application step S2, the epoxy resin E51 was used instead of the organofluorosilicone modified epoxy resin and no friction reducing agent was added.

The wear resistance of the wear-resistant coatings of examples 1-3 and comparative examples 1-2 was tested on a paint film abrader with a load of 5N and 400 cycles of abrasion, and the loss of wear was determined.

The friction performance of the coating is carried out on a high-temperature friction and wear tester, which is a ball-disk type contact, and the glass round substrates with the surface of phi 25 multiplied by 5mm in the examples 1-3 and the comparative examples 1-2 are respectively taken and fixed by a steel ball with the phi 6.35mm, and the load of 15N and the 125 speed/min are used^-1After circular motion at constant speed for 10min, the average wear scar width and the average friction factor were measured.

The test results are shown in the following table:

	example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						Loss on abrasion/mg	11	8	6.5	20	16
Average wear scar width/mm	1.08	1.01	0.94	2.10	1.82
						Average friction factor	0.50	0.47	0.46	0.55	0.57

The test results of the example 1 and the comparative example 1 in the table are compared, and it is known that the abrasion weight loss of the wear-resistant coating of the comparative example 1 without surface nano-zirconia modification is 20mg, the abrasion weight loss of the wear-resistant coating of the example 1 is reduced to 11mg, the abrasion weight loss is only 45% of that of the composite wear-resistant coating of the comparative example 1, and the wear resistance is obviously improved. This shows that the interfacial state between the composite particles and the matrix in example 1 is better than that of the wear-resistant alumina powder coating not coated with nano-zirconia in comparative example 1, because ZrO in example 1₂/Al₂O₃The binding force between the composite material particles and the matrix interface is higher, when the composite material is worn under a load condition, the probability that the alumina powder falls off from the surface of the composite material to become loose abrasive is reduced, the abrasion degree of the abrasive generated in the abrasion process is reduced, and the abrasion loss is relatively reduced, so that the ZrO in the embodiment 1 is relatively reduced₂/Al₂O₃The abrasion resistance of the composite coating is improved by about 50% compared with that of the comparative example 1.

Examples 1-3 preparation of Al from zirconium tetrachloride by hydrothermal method₂O₃The zirconia nano particles are grown on the surface of the powder in situ, and the nano ZrO is directly prepared by one step₂/Al₂O₃The composite particles are not required to be calcined at high temperature, energy is saved, carbon is low, and the method is simple, convenient and easy to operate; meanwhile, as the nano ZrO₂Has high toughness and excellent chemical stability, and can be used for treating nano Al₂O₃Surface modification of Al₂O₃The fracture toughness and acid and alkali resistance of the powder are obviously improved; compared with the traditional physical mixing method or physical doping method, the nano ZrO prepared by the method₂Can be stably bonded or adhered to Al₂O₃Increasing the nano-ZrO on the surface of the powder₂/Al₂O₃The composite stability of (1).

Examples 1 to 3 Nano ZrO prepared₂/Al₂O₃The composite material is used as a reinforcement in a glass wear-resistant coating material, so that wear resistance is enhanced, and the wear resistance and mechanical strength of the composite wear-resistant coating are further improved.

Examples 1-3 nanometer ZrO₂/Al₂O₃When the composite material is applied to the glass wear-resistant coating, the nano ZrO is coupled by using the silane coupling agent containing amino or epoxy₂/Al₂O₃The surface of the composite material is modified, and the nano ZrO is treated under the action of a polyamide 650 curing agent₂/Al₂O₃The composite material utilizes amino or epoxy group and nano ZrO on the surface₂Surface hydroxyl (hydrothermal method can synthesize nano ZrO)₂A large number of active hydroxyl groups on the surface) and the organic fluorine-silicon modified epoxy resin to generate cross-linking reaction, thereby further leading the nano ZrO to be₂/Al₂O₃The composite material is stably grafted in epoxy resin molecules, so that nano ZrO is formed₂/Al₂O₃The composite material is stably embedded into the three-dimensional network structure of the wear-resistant coating material, and the ZrO content is remarkably improved₂/Al₂O₃The interface bonding strength of the composite material and the organic fluorine-silicon modified epoxy resin matrix.

In the embodiments 1-3, benzyl alcohol is used as a diluent, and a rigid benzene ring structure is grafted into an organic fluorine-silicon modified epoxy resin molecular chain by utilizing the ring-opening addition of hydroxyl and epoxy, so that the mechanical property, the mechanical property and the wear-resistant strength of the glass wear-resistant coating material are further improved.

In the embodiments 1-3, the self-lubricating property of the glass wear-resistant coating is further improved by using the friction reducer prepared from the polytetrafluoroethylene superfine powder and the fluorine-containing silane, the friction factor is reduced, and the effects of reducing friction and resisting wear are further achieved; in addition, the antifriction agent also has the functions of improving the hydrophobic and oleophobic properties of the wear-resistant coating and ensuring certain self-cleaning property of the coating.

While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.