Oxide solid solution and preparation method thereof, coating material and coating

Abstract

The invention provides an oxide solid solution and a preparation method thereof, a coating material and a coating, the structural formula of the oxide solid solution is Ti1-xZrxO2, x is more than or equal to 0.01 and less than or equal to 0.08, and the oxide solid solution is of a rutile crystal structure. The oxide solid solution has both ultraviolet aging resistance and wear resistance, and when the oxide solid solution is added into an organic coating, the ultraviolet aging resistance and wear resistance of the coating can be improved at the same time. The solid solution is added into the organic coating as a single component and can be easily and uniformly mixed with the organic coating, and the problem of mixing difficulty caused by simultaneous addition of multiple components into the organic coating can be solved.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, specifically relating to an oxide solid solution and its preparation method, coating materials, and coatings. Background Technology

[0002] Organic coatings, such as polyurethane-based coatings, vinyl ester-based coatings, epoxy ester-based coatings, and unsaturated polyester-based coatings, are affected by factors such as light, heat, rain, and oxygen when used in natural climatic environments. This reduces their mechanical properties and corrosion resistance, shortening their service life. In particular, ultraviolet light can break the chemical bonds in the resin, causing cracks on the surface of the organic coating. Furthermore, due to the open outdoor environment, organic coatings are also easily scratched, especially in areas with frequent sandstorms, where weathering can cause defects in the organic coating, further shortening its service life.

[0003] Inorganic materials, such as zinc oxide and titanium oxide, possess high UV shielding properties and are chemically stable, easy to process, and non-toxic. To obtain coating materials with superior UV aging resistance and wear resistance, some researchers have added inorganic functional fillers to organic coatings. For example, Chinese patent application CN 116003993A adds sodium persulfate to polyurethane; Chinese patent application CN 113185662A adds layered bimetallic hydroxide to polyurethane; and Chinese patent application CN 117070140A adds nano-TiO2 to polyurethane. These methods of adding inorganic functional fillers to organic coatings all result in organic coatings with superior UV aging resistance. In addition, in order to obtain organic coatings with high wear resistance, some researchers have added wear-resistant phases to the organic coatings. For example, Chinese patent application CN112341798A adds flake TiO2 and sodalite to the organic coating; Chinese patent application CN110862677A adds modified nano ZrO2 and diatomaceous earth to the organic coating; and Chinese patent application CN102585684A adds mica or talc and TiO2 to the organic coating.

[0004] To simultaneously improve the UV aging resistance and abrasion resistance of organic coatings, it is necessary to add functional fillers that absorb or reflect ultraviolet rays, as well as a wear-resistant phase with high hardness. However, the simultaneous addition of multiple fillers greatly increases the difficulty of uniformly mixing the organic coating and the fillers. The inhomogeneity of the composition leads to a decrease in coating performance, which in turn affects the final coating performance. Summary of the Invention

[0005] To address the technical problems existing in the prior art, the present invention provides an oxide solid solution and its preparation method, coating material and coating. The oxide solid solution has both UV aging resistance and wear resistance properties, which can solve the mixing difficulty problem caused by adding multiple components to organic coatings at the same time.

[0006] This invention is achieved through the following technical solution: This invention provides an oxide solid solution, wherein the oxide solid solution has the structural formula Ti. 1－x Zr x O2, where 0.01≤ x ≤0.08, the oxide solid solution has a rutile crystal structure.

[0007] This invention provides a method for preparing the oxide solid solution, comprising the following steps: S1, mix TiO2 powder and ZrO2 powder to obtain a mixed powder; the TiO2 powder has a rutile crystal structure; S2, heat the mixed powder to 1400~1700℃, keep it at that temperature for 60~120 min, and pulverize the resulting product to obtain oxide solid solution powder.

[0008] Preferably, in S1, the ZrO2 powder has a monoclinic phase crystal structure.

[0009] Preferably, S1 specifically involves: wet ball milling TiO2 powder and ZrO2 powder, followed by drying to obtain a mixed powder.

[0010] Furthermore, the ball milling conditions are as follows: rotation speed of 50~200 rpm, time of 1~5 h, ball milling media of ethanol and / or water, and ball-to-material ratio of (6~10):1.

[0011] Preferably, in S2, the heating rate is 10~50℃ / min.

[0012] The present invention also provides a coating material comprising, by mass percentage, 80% to 90% organic coating and 10% to 20% modified oxide solid solution, wherein the modified oxide solid solution is obtained by modifying the oxide solid solution as described above with a silane coupling agent.

[0013] Preferably, the organic coating is a polyurethane coating, an epoxy resin coating, or an unsaturated polyester coating.

[0014] Preferably, the method includes: reacting the oxide solid solution with a silane coupling agent to obtain a modified oxide solid solution; and mixing the modified oxide solid solution with an organic coating to obtain a coating material.

[0015] The present invention provides a coating obtained by curing a coating material as described above.

[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention provides an oxide material composed of Ti, Zr, and O atoms. This oxide material is a single-phase Ti. 1－x Zr x The O2 solid solution possesses a rutile crystal structure. Introducing Zr into TiO2 improves its wear resistance without affecting its UV aging resistance. This oxide solid solution combines UV aging resistance and wear resistance; when added to organic coatings, it can simultaneously enhance both the coating's UV aging resistance and wear resistance. As a single component, the solid solution is easily and uniformly mixed with organic coatings, reducing the mixing difficulties associated with adding multiple components simultaneously.

[0017] This invention employs a ZrO2 solid solution method for TiO2, and by controlling the composition ratio of the two and the heat treatment process, prepares TiO2 with a rutile crystal structure. 1－x Zr x O2 solid solution powder. The ZrO2 component content selected in this invention is ≤ 0.01%. x With a ZrO2 content ≤0.08, a suitable ZrO2 content allows for complete solid dissolution in TiO2. During solid dissolution, Zr atoms replace Ti atoms in the crystal lattice without affecting the original TiO2 crystal structure. However, excessive ZrO2 content will form a second phase. Furthermore, this invention selects a suitable heat treatment temperature; temperatures that are too high or too low will prevent the synthesis of a single-phase Ti. 1－x Zr x O2 solid solution powder. Ti prepared according to this invention. 1－ x Zr x O2 solid solution powder has both UV aging resistance and wear resistance, which can solve the mixing difficulties caused by adding multiple components to organic coatings at the same time.

[0018] Furthermore, this invention employs ball milling to mix TiO2 powder and ZrO2 powder, and optimizes suitable ball milling conditions. When the ball milling speed is too high, the time is too long, or the ball-to-material ratio is too large, the milling media will be incorporated into the prepared ceramic powder, contaminating the product. Conversely, when the ball milling speed is too low, the time is too short, or the ball-to-material ratio is too small, the raw material powders will not mix uniformly, resulting in incomplete reaction of the prepared product and preventing the formation of a single-phase oxide. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 For Ti with different Zr contents 1－x Zr x X-ray diffraction pattern of O2 powder.

[0021] Figure 2 For Ti with different Zr contents 1－x Zr x UV-Vis absorption spectrum (a) and transmission spectrum (b) of O2 powder.

[0022] Figure 3 The surface morphology (a) and elemental surface scan analysis (b, c and d) of the oxide solid solution powder in Example 2 are shown.

[0023] Figure 4 The morphology of the composite epoxy resin coating after spraying and forming film in Example 3 is shown in the following figures: (a) substrate, (b) composite epoxy resin coating.

[0024] Figure 5 X-ray diffraction pattern of the powder in Comparative Example 2.

[0025] Figure 6 X-ray diffraction pattern of the powder in Comparative Example 3. Detailed Implementation

[0026] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0027] It should be noted that the process equipment or apparatus not specifically mentioned in the following embodiments are all conventional equipment or apparatus in the art.

[0028] It should be noted that the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or apparatus that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to these processes, methods, products, or apparatuses. Furthermore, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not intended to limit the order of the method steps or define the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0029] This invention provides an oxide solid solution composed of Ti, Zr, and O atoms, with the molecular formula Ti 1－x Zr x O2, where 0.01≤ x ≤0.08, with a single-phase rutile crystal structure.

[0030] The method for preparing the oxide solid solution of the present invention includes the following steps: S1, mix TiO2 powder and ZrO2 powder to obtain a mixed powder; the TiO2 powder has a rutile crystal structure; S2, the mixed powder is heated to 1400~1700℃ at a heating rate of 10~50℃ / min and held for 60~120 min. After the heat treatment, it is cooled to room temperature at a cooling rate of 10~30℃ / min to obtain a loose porous solid solution ceramic. This porous ceramic is crushed and pulverized to obtain oxide solid solution powder.

[0031] This invention uses a mixture of TiO2 powder and ZrO2 powder. TiO2 has a rutile crystal structure and exhibits excellent resistance to UV aging, but its wear resistance is insufficient. ZrO2, on the other hand, has excellent wear resistance. By dissolving ZrO2 into TiO2 without altering its rutile structure, the wear resistance of TiO2 can be improved while maintaining its UV aging resistance. Zr and Ti have similar particle sizes. By controlling the ratio of their components and the high-temperature heat treatment parameters, Ti with a rutile crystal structure can be prepared. 1－x Zr x O2 single-phase oxide solid solution powder material has both UV aging resistance and wear resistance.

[0032] The technical challenge of this invention lies in how to dissolve ZrO2 in TiO2 to generate Ti 1－x Zr x The O2 solid solution does not alter the crystal structure of TiO2 and does not generate a second phase. Firstly, the ZrO2 component content selected in this invention is ≤ 0.01%. xA suitable ZrO2 content (≤0.08) allows for complete solid dissolution in TiO2. During solid dissolution, Zr atoms replace Ti atoms in the crystal lattice without affecting the original TiO2 crystal structure. However, excessive ZrO2 content will lead to the formation of a second phase. Furthermore, the heat treatment conditions are crucial in this invention. If the heat treatment conditions deviate from the description in this invention, a single-phase Ti cannot be synthesized. 1－x Zr x O2 solid solution powder.

[0033] To ensure uniform mixing of TiO2 powder and ZrO2 powder, this invention employs wet ball milling. The ball milling conditions are: rotation speed of 50-200 rpm, time of 1-5 h, ball milling media of ethanol and / or water, and ball-to-powder ratio of (6-10):1. Excessive ball milling speed, time, or ball-to-powder ratio may lead to the incorporation of the prepared ceramic powder into the ball milling media, contaminating the product. Conversely, excessively low ball milling speed, short time, or small ball-to-powder ratio may result in uneven mixing of the raw material powders, incomplete reaction of the prepared product, and failure to generate a single-phase oxide.

[0034] As a preferred embodiment, the TiO2 powder of the present invention has a purity of ≥99% and a particle size of micrometers.

[0035] As a preferred embodiment, the ZrO2 powder of the present invention has a purity of ≥99%, a particle size of micrometers, and a monoclinic crystal structure.

[0036] To obtain refined oxide solid solution powder, this invention ball-mills the loose, porous solid solution ceramic. The ball-milling conditions are: a rotation speed of 200-300 rpm, a time of 3-5 h, ethanol and / or water as the milling medium, and a ball-to-powder ratio of 6-10:1. When the ball-milling speed is too high, the time is too long, or the ball-to-powder ratio is too large, the milling medium will be incorporated into the prepared powder, contaminating the product. Conversely, when the ball-milling speed is too low, the time is too short, or the ball-to-powder ratio is too small, the crushed oxide powder particles will be coarse, which is detrimental to subsequent mixing with coatings and to coating performance.

[0037] This invention also provides an anti-UV aging and wear-resistant coating material, which uses the Ti prepared above. 1－x Zr x After O2 solid solution powder is surface modified with KH-550, the resulting modified Ti 1－x Zr x O2 solid solution powder is added to organic coatings and mixed evenly to obtain an anti-UV aging and wear-resistant coating material, thereby improving the coating's anti-UV aging and wear-resistant properties.

[0038] In this invention, the organic coating is a polyurethane coating, an epoxy resin coating, or an unsaturated polyester coating.

[0039] In this invention, modified Ti1－x Zr x The mixing conditions for O2 solid solution powder and organic coating are: mixing speed 100~400 rpm, time 1~4 h.

[0040] Example 1: TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.99:0.01. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. The ball milling medium was ethanol, the rotation speed was 50 rpm, the ball milling time was 5 h, and the ball-to-powder ratio was 6:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0041] The mixed powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1700℃ and held for 60 min at a heating rate of 50℃ / min. Then, it was cooled to room temperature at a rate of 30℃ / min. The product was then removed and crushed. It was then ball-milled into powder in a ball mill for 3 h. The ball milling medium was ethanol, the rotation speed was 300 rpm, and the ball-to-powder ratio was 6:1. After drying at 40℃, the oxide solid solution powder was obtained.

[0042] The oxide solid solution powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide solid solution powder. The modified oxide solid solution powder was then mixed with epoxy resin coating at a mass ratio of 10%:90% at 400 rpm for 1 hour to obtain the epoxy resin composite coating.

[0043] The epoxy resin coating used in this embodiment is WU132, and the ratio of resin to curing agent is 4.7:1.

[0044] Example 2: TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.92:0.08. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. Water was used as the ball milling medium, the rotation speed was 200 rpm, the ball milling time was 1 h, and the ball-to-powder ratio was 10:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0045] The mixed powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1400℃ and held for 120 min at a heating rate of 10℃ / min. Then, it was cooled to room temperature at a rate of 10℃ / min. The product was then crushed and ball-milled into powder in a ball mill for 5 h. The ball milling medium was ethanol, the rotation speed was 200 rpm, and the ball-to-powder ratio was 10:1. After drying at 40℃, the oxide solid solution powder was obtained.

[0046] The oxide solid solution powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide solid solution powder. The modified oxide solid solution powder was then mixed with epoxy resin coating at a mass ratio of 20%:80% at 100 rpm for 4 hours to obtain the epoxy resin composite coating.

[0047] The epoxy resin coating used in this embodiment is WU132, and the ratio of resin to curing agent is 4.7:1.

[0048] Example 3: TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.96:0.04. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. The ball milling medium was ethanol, the rotation speed was 150 rpm, the ball milling time was 3 h, and the ball-to-powder ratio was 8:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0049] The mixed powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1600℃ and held for 80 min at a heating rate of 30℃ / min. Then, it was cooled to room temperature at a rate of 20℃ / min. The product was then removed and crushed. It was then ball-milled into powder in a ball mill for 2 h. The ball milling medium was ethanol, the rotation speed was 200 rpm, and the ball-to-powder ratio was 8:1. After drying at 40℃, the oxide solid solution powder was obtained.

[0050] The oxide solid solution powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide solid solution powder. The modified oxide solid solution powder was then mixed with epoxy resin coating at a mass ratio of 10%:90% at 300 rpm for 3 hours to obtain the epoxy resin composite coating.

[0051] The epoxy resin coating used in this embodiment is WU132, and the ratio of resin to curing agent is 4.7:1.

[0052] Example 4: TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.96:0.04. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. The ball milling medium was ethanol, the rotation speed was 150 rpm, the ball milling time was 3 h, and the ball-to-powder ratio was 8:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0053] The mixed powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1600℃ and held for 80 min at a heating rate of 30℃ / min. Then, it was cooled to room temperature at a rate of 20℃ / min. The product was then removed and crushed. It was then ball-milled into powder in a ball mill for 2 h. The ball milling medium was ethanol, the rotation speed was 200 rpm, and the ball-to-powder ratio was 8:1. After drying at 40℃, the oxide solid solution powder was obtained.

[0054] The oxide solid solution powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide solid solution powder. The modified oxide solid solution powder was then mixed with a polyurethane coating at a mass ratio of 10%:90% at 300 rpm for 3 hours to obtain the polyurethane composite coating.

[0055] The polyurethane coating used in this embodiment is FU360, and the ratio of resin to curing agent is 5:1.

[0056] Example 5: Compared with Example 3, only the ratio of modified oxide solid solution powder to epoxy resin coating was changed. TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.96:0.04. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. The ball milling medium was ethanol, the rotation speed was 150 rpm, the ball milling time was 3 h, and the ball-to-powder ratio was 8:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0057] The mixed powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1600℃ and held for 80 min at a heating rate of 30℃ / min. Then, it was cooled to room temperature at a rate of 20℃ / min. The product was then removed and crushed. It was then ball-milled into powder in a ball mill for 2 h. The ball milling medium was ethanol, the rotation speed was 200 rpm, and the ball-to-powder ratio was 8:1. After drying at 40℃, the oxide solid solution powder was obtained.

[0058] The oxide solid solution powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide solid solution powder. The modified oxide solid solution powder was then mixed with epoxy resin coating at a mass ratio of 15%:85% at 300 rpm for 3 hours to obtain the epoxy resin composite coating.

[0059] The epoxy resin coating used in this embodiment is WU132, and the ratio of resin to curing agent is 4.7:1.

[0060] Example 6: Compared with Example 3, only the ratio of modified oxide solid solution powder to epoxy resin coating was changed. TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.96:0.04. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. The ball milling medium was ethanol, the rotation speed was 150 rpm, the ball milling time was 3 h, and the ball-to-powder ratio was 8:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0061] The mixed powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1600℃ and held for 80 min at a heating rate of 30℃ / min. Then, it was cooled to room temperature at a rate of 20℃ / min. The product was then removed and crushed. It was then ball-milled into powder in a ball mill for 2 h. The ball milling medium was ethanol, the rotation speed was 200 rpm, and the ball-to-powder ratio was 8:1. After drying at 40℃, the oxide solid solution powder was obtained.

[0062] The oxide solid solution powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide solid solution powder. The modified oxide solid solution powder was then mixed with epoxy resin coating at a mass ratio of 20%:80% at 300 rpm for 3 hours to obtain the epoxy resin composite coating.

[0063] The epoxy resin coating used in this embodiment is WU132, and the ratio of resin to curing agent is 4.7:1.

[0064] Comparative Example 1: TiO2 powder was ball-milled in a planetary ball mill. The particle size of the TiO2 powder was 2~3μm, the purity was ≥99%, and it had a rutile crystal structure. The ball milling medium was ethanol, the rotation speed was 150 rpm, the ball milling time was 3 h, and the ball-to-powder ratio was 8:1. After ball milling, the powder was taken out and dried at 40℃, and then sieved to obtain TiO2 powder.

[0065] TiO2 powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1600℃ and held for 80 min at a heating rate of 30℃ / min. Then, it was cooled to room temperature at a rate of 20℃ / min. The product was then removed, crushed, and ball-milled into powder in a ball mill for 2 h. The ball milling medium was ethanol, the rotation speed was 200 rpm, and the ball-to-powder ratio was 8:1. After drying at 40℃, oxide powder was obtained.

[0066] The oxide powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide powder. The modified oxide powder was then mixed with epoxy resin coating at a mass ratio of 10%:90% at 300 rpm for 3 hours to obtain the epoxy resin composite coating.

[0067] The epoxy resin coating used in this embodiment is WU132, and the ratio of resin to curing agent is 4.7:1.

[0068] Comparative Example 2: Compared with Example 3, only the molar ratio of TiO2 powder and ZrO2 powder was changed. TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.10:0.90. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. The ball milling medium was ethanol, the rotation speed was 150 rpm, the ball milling time was 3 h, and the ball-to-powder ratio was 8:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0069] The mixed powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1600℃ and held for 80 min at a heating rate of 30℃ / min. Then, it was cooled to room temperature at a rate of 20℃ / min. The product was then removed and crushed. It was then ball-milled into powder in a ball mill for 2 h. The ball milling medium was ethanol, the rotation speed was 200 rpm, and the ball-to-powder ratio was 8:1. After drying at 40℃, the oxide solid solution powder was obtained. The oxide solid solution powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide solid solution powder. The modified oxide solid solution powder was then mixed with epoxy resin coating at a mass ratio of 10%:90% at 300 rpm for 3 hours to obtain the epoxy resin composite coating.

[0070] The epoxy resin coating used in this comparative example is WU132, and the ratio of resin to curing agent is 4.7:1.

[0071] Comparative Example 3: Compared with Example 3, only the processing temperature was changed. TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.96:0.04. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. The ball milling medium was ethanol, the rotation speed was 150 rpm, the ball milling time was 3 h, and the ball-to-powder ratio was 8:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0072] The mixed powder was placed in a muffle furnace for high-temperature heat treatment. The atmosphere in the muffle furnace was air. The temperature was raised to 1200℃ and held for 80 min at a heating rate of 30℃ / min. Then, it was cooled to room temperature at a rate of 20℃ / min. The product was then removed and crushed. It was then ball-milled into powder in a ball mill for 2 h. The ball milling medium was ethanol, the rotation speed was 200 rpm, and the ball-to-powder ratio was 8:1. After drying at 40℃, the oxide solid solution powder was obtained.

[0073] The oxide solid solution powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20, respectively. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was collected and dried in an oven at 40°C for 24 hours to obtain the modified oxide solid solution powder. The modified oxide solid solution powder was then mixed with epoxy resin coating at a mass ratio of 10%:90% at 300 rpm for 3 hours to obtain the epoxy resin composite coating.

[0074] The epoxy resin coating used in this comparative example is WU132, and the ratio of resin to curing agent is 4.7:1.

[0075] Comparative Example 4: TiO2 powder and ZrO2 powder were added separately TiO2 powder and ZrO2 powder were mixed in a planetary ball mill at a molar ratio of 0.96:0.04. The TiO2 powder had a particle size of 2-3 μm, a purity of ≥99%, and a rutile crystal structure. The ZrO2 powder had a particle size of 2 μm, a purity of ≥99%, and a monoclinic crystal structure. The ball milling medium was ethanol, the rotation speed was 150 rpm, the ball milling time was 3 h, and the ball-to-powder ratio was 8:1. After ball milling, the powder was removed, dried at 40℃, and sieved to obtain the mixed powder.

[0076] The mixed powder and KH-550 were added to anhydrous ethanol at a weight ratio of 1:1 and 1:20. The pH was adjusted to 6 with glacial acetic acid, and the mixture was stirred at 80°C for 6 hours. The mixture was then washed three times with anhydrous ethanol and water. After centrifugation, the solid powder was removed and dried in an oven at 40°C for 24 hours to obtain the modified mixed powder.

[0077] The modified mixed powder and epoxy resin coating were mixed at a mass ratio of 10%:90% for 3 hours at a speed of 300 rpm to obtain the epoxy resin composite coating.

[0078] The epoxy resin coating used in this comparative example is WU132, and the ratio of resin to curing agent is 4.7:1.

[0079] Elemental analysis revealed that the atomic ratio of Ti, Zr, and O in the oxide solid solution powder prepared in Example 1 of this invention was 0.2475:0.0025:0.5, forming a (Ti... 0.99 Zr 0.01 O2 solid solution. Elemental analysis showed that the atomic ratio of Ti, Zr, and O in the oxide solid solution powder prepared in Example 2 of this invention was 0.23:0.02:0.5, forming (Ti... 0.92 Zr 0.08 O2 solid solution. Elemental analysis showed that the atomic ratio of Ti, Zr, and O in the oxide solid solution powder prepared in Example 3 of this invention was 0.24:0.01:0.5, forming (Ti... 0.96 Zr 0.04 O2 solid solution.

[0080] like Figure 1 The image shows the XRD patterns of the oxide solid solution powders prepared in Examples 1-3 of this invention and the oxide powder prepared in Comparative Example 1. Figure 1 As can be seen, the oxide solid solution powders prepared in Examples 1-3 of this invention all have a single phase and a rutile crystal structure. Compared with the crystal structure of the product in Comparative Example 1, the crystal structure of the oxide solid solution powders prepared in Examples 1-3 of this invention has not changed. This indicates that the present invention selects an appropriate ZrO2 content, allowing ZrO2 to completely dissolve in TiO2. During solid solution, Zr atoms replace Ti atoms in the crystal lattice, without affecting the original TiO2 crystal structure and without generating a second phase. Therefore, the introduction of ZrO2 will not adversely affect the UV aging resistance of TiO2. Figure 5 The XRD pattern of the oxide solid solution powder obtained in Comparative Example 2 shows that the oxide solid solution powder is composed of two phases, ZrO2 and (Zr,Ti)O2, indicating that excessive ZrO2 content will form a second phase. Figure 6 The XRD pattern of the solid solution powder obtained in Comparative Example 3 shows that the solid solution powder consists of two phases, TiO2 and (Ti,Zr)O2, indicating that the heat treatment temperature was too low to form a single-phase Ti. 1－x Zr x O2 solid solution powder.

[0081] like Figure 2 The image shows the UV-Vis absorption spectra of the oxide solid solution powders prepared in Examples 1-3 of this invention and the oxide powder prepared in Comparative Example 1. From... Figure 2 It can be seen that in the ultraviolet light range of 210–400 nm, the oxide solid solution powders prepared in Examples 1–3 of this invention exhibit strong absorption performance and very low ultraviolet light transmittance.

[0082] The surface morphology of the oxide solid solution powder prepared in Example 2 of this invention is as follows: Figure 3 As shown, the oxide solid solution powder has a particle size of less than 30 μm, and the three elements Zr, Ti and O are evenly distributed.

[0083] The epoxy resin composite coating obtained in Example 3 of this invention was sprayed onto a glass fiber reinforced epoxy resin composite material substrate, and the macroscopic morphology after curing was as follows: Figure 4 As shown.

[0084] The coatings prepared in Examples 1-8 and Comparative Examples 1-5 were subjected to UV aging and abrasion resistance tests, and the test results are shown in Table 1. The UV aging test involved applying the coating to the substrate surface and then subjecting it to UV aging under the following conditions: UVA -340 nm, 1000 h. The tensile strength before and after UV aging was then compared, with the tensile strength retention rate calculated as: tensile strength after UV aging / tensile strength before UV aging. The abrasion resistance test was conducted according to GB1768, under the following conditions: 500 g / 500 r.

[0085] Table 1. Test results of UV aging resistance and abrasion resistance

[0086] Table 1 shows that the coatings corresponding to the coatings in Examples 1-6 of the present invention retain a tensile strength of more than 90% after 1000 hours of UV aging, indicating that the coatings prepared in the examples of the present invention have high UV aging resistance.

[0087] Furthermore, it can be seen that, compared with TiO2 without Zr in Comparative Example 1, the Ti of the present invention... 1－x Zr x The addition of O2 solid solution to organic coatings significantly improves the wear resistance of the corresponding coatings without affecting their UV aging resistance. Furthermore, the use of Ti in this invention… 1－x Zr x When O2 solid solution powder is mixed with coating, the UV aging resistance of the corresponding coating is slightly improved.

[0088] Comparing the UV aging resistance and abrasion resistance of the coatings in Example 3 and Comparative Example 2, it can be seen that when the amount of ZrO2 powder added is too high, although the abrasion resistance of the coating is relatively good, the UV aging resistance is greatly reduced, failing to meet the usage requirements. Comparing the UV aging resistance and abrasion resistance of the coatings in Example 3 and Comparative Example 3, it can be seen that the UV aging resistance and abrasion resistance of the coating in Comparative Example 3 are both lower than those in Example 3. Figure 6 It can be seen that this is due to the formation of a second phase in the solid solution powder obtained in Comparative Example 3.

[0089] Comparing the UV aging resistance and abrasion resistance of the coatings in Example 3 and Comparative Example 4, it can be seen that compared with adding TiO2 powder and ZrO2 powder to organic coatings, using TiO2 powder... 1－x Zr x The coatings formed by adding O2 solid solution to organic coatings exhibit improved UV aging resistance and abrasion resistance. This is because Ti... 1－x Zr x O2 solid solution is easy to mix evenly with organic coatings, but when TiO2 powder and ZrO2 powder are added to organic coatings separately, uneven mixing will occur, which will affect the final performance.

[0090] Comparing the UV aging resistance and abrasion resistance of the coatings in Example 3 with those in Examples 5-6, it can be seen that with the improvement of Ti... 1－x Zr x With the increase of O2 solid solution powder addition, the wear resistance of the coating is continuously improved, while the UV aging resistance does not change significantly.

Claims

1. An oxide solid solution, characterized in that, The oxide solid solution has the structural formula Ti. 1－x Zr x O2, where 0.01≤ x ≤0.08, the oxide solid solution has a rutile crystal structure.

2. The method for preparing the oxide solid solution according to claim 1, characterized in that, Includes the following steps: S1, mix TiO2 powder and ZrO2 powder to obtain a mixed powder; the TiO2 powder has a rutile crystal structure; S2, heat the mixed powder to 1400~1700℃, keep it at that temperature for 60~120 min, and then pulverize the resulting product to obtain oxide solid solution powder.

3. The method for preparing the oxide solid solution according to claim 2, characterized in that, In S1, the ZrO2 powder has a monoclinic phase crystal structure.

4. The method for preparing the oxide solid solution according to claim 2, characterized in that, S1 specifically involves wet ball milling TiO2 powder and ZrO2 powder, followed by drying to obtain a mixed powder.

5. The method for preparing the oxide solid solution according to claim 4, characterized in that, The ball milling conditions are as follows: rotation speed of 50~200 rpm, time of 1~5 h, ball milling media of ethanol and / or water, and ball-to-material ratio of (6~10):

1.

6. The method for preparing the oxide solid solution according to claim 2, characterized in that, In S2, the heating rate is 10~50℃ / min.

7. A coating material, characterized in that, The product comprises, by weight percentage, 80% to 90% organic coating and 10% to 20% modified oxide solid solution, wherein the modified oxide solid solution is obtained by modifying the oxide solid solution of claim 1 with a silane coupling agent.

8. The coating material according to claim 7, characterized in that, The organic coating is a polyurethane coating, an epoxy resin coating, or an unsaturated polyester coating.

9. The method for preparing the coating material according to claim 7, characterized in that, include: The oxide solid solution is reacted with a silane coupling agent to obtain a modified oxide solid solution; The modified oxide solid solution is mixed with an organic coating to obtain a coating material.

10. A coating, characterized in that, It is obtained by curing the coating material as described in claim 7.

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