Composite material and preparation method thereof, and automobile glass

Abstract

The application belongs to the technical field of new materials, and discloses a composite material, a preparation method thereof and automobile glass, the composite material is a curved surface, and sequentially comprises a composite base, a glass plate and an organic back plate from bottom to top; wherein: the composite base comprises a plurality of transparent ceramics and a glass base, the plurality of transparent ceramics are spliced and laid in the interior of the glass base to form a structure of the glass filled with the segmented transparent ceramics; the glass is used as the base, the plurality of transparent ceramics are used as the filling body, the composite base structure of the glass filled with the segmented transparent ceramics is formed, the composite base structure is combined with the glass plate and the organic back plate, the composite material with high safety, light weight and large size (1000mm*1800mm) of the curved surface transparent ceramic filled glass is obtained, and the light transmittance of 64.2-81.2% and the bending strength of 168.4-213.7MPa are achieved.

Description

Technical Field

[0001] This invention belongs to the field of new materials technology, specifically relating to a composite material and its preparation method, and automotive glass. Background Technology

[0002] Currently, automotive safety glass is generally multi-layered composite glass. To achieve better protective performance, the number of layers usually needs to be increased, which leads to an increase in the glass's weight and a decrease in optical performance. Moreover, this type of composite glass is prone to crack propagation after being subjected to external impact, thus affecting its impact resistance.

[0003] Transparent ceramics possess high hardness, high strength, and good light transmittance, making them highly promising for applications in the field of transparent protection. Compared to traditional multi-layered protective composite glass, using transparent ceramics can achieve a weight reduction of approximately 50%, a thinning of approximately 40%, and improved impact resistance. However, due to limitations in the manufacturing process of transparent ceramics, obtaining large-sized transparent ceramics is quite difficult, especially the fabrication of curved transparent ceramics larger than 200mm × 200mm (length × width), which currently remains a technological gap, limiting the further application of transparent ceramics. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention proposes a composite material and its preparation method, wherein the composite material has good light transmittance and impact resistance, and is suitable for use in large-size curved transparent automotive glass.

[0005] To solve the above-mentioned technical problems, the first aspect of the present invention provides a composite material, wherein the composite material is curved and comprises, from bottom to top, a composite matrix, a glass plate and an organic backing plate; the composite matrix comprises multiple transparent ceramic pieces and a glass matrix, wherein the multiple transparent ceramic pieces are spliced ​​and laid inside the glass matrix to form a structure in which segmented transparent ceramic pieces are filled with glass.

[0006] This invention uses glass as the matrix and multiple pieces of transparent ceramic as fillers to form a composite matrix structure of segmented transparent ceramic-filled glass. This structure is then combined with a glass plate and an organic backing plate to obtain a composite material of large-size curved transparent ceramic-filled glass with high safety and lightweight properties.

[0007] Specifically, transparent ceramics possess high hardness and strength, significantly improving impact resistance compared to ordinary glass. By using segmented transparent ceramics spliced ​​together and then filling the glass, cracks from impact damage will not affect adjacent transparent ceramic blocks, effectively preventing widespread crack propagation and thus enhancing the composite material's resistance to repeated impacts. Furthermore, the impact on visibility is reduced, ensuring vehicle safety. Simultaneously, compared to traditional multi-layered composite glass, using high-strength transparent ceramics as the glass reinforcement phase can reduce the overall weight of the composite material while maintaining the same protective effect, improving vehicle maneuverability. Moreover, by controlling the refractive index and coefficient of thermal expansion of the transparent ceramics and glass matrix, and improving the matching accuracy between them, large-size curved transparent ceramic-filled glass composites with excellent optical properties can be obtained, broadening the application range of transparent ceramics.

[0008] In some embodiments of the present invention, the transparent ceramic is selected from any one of AlON transparent ceramic, YAG transparent ceramic, and MgAl2O4 transparent ceramic.

[0009] In some embodiments of the present invention, the light transmittance of the transparent ceramic is >80%.

[0010] In some embodiments of the present invention, the shape of the transparent ceramic is selected from any one of an equilateral triangle, a regular quadrilateral, a regular pentagon, and a regular hexagon.

[0011] In some embodiments of the present invention, the transparent ceramic has a side length of 50-150 mm and a thickness of 4-8 mm.

[0012] In some embodiments of the present invention, the glass matrix is ​​made by firing glass powder, and the chemical composition of the glass powder, by weight percentage, includes: La2O3 35-60%, SiO2 16-35%, B2O3 5-15%, Al2O3 3-10%, ZrO2 0-5%, MgO 0-8%, CaO 0-12%, Y2O3 1-8%, CeO2 0-3%, Li2O 0-8%, K2O 0-5%.

[0013] Specifically, the raw material composition of the glass powder is closely related to the selection of the transparent ceramic. The refractive index and coefficient of thermal expansion of both must be highly matched to ensure the light transmittance and impact resistance of the composite matrix. This invention employs a high-content La2O3-SiO2-Al2O3 glass system to increase the refractive index of the glass powder and match it with the transparent ceramic. Simultaneously, La2O3 and Al2O3 can form a glass network structure, improving the mechanical strength and stability of the glass powder.

[0014] In some embodiments of the present invention, when the transparent ceramic is YAG transparent ceramic, the chemical composition of the glass powder, by weight percentage, includes: La2O3 45-60%, SiO2 16-25%, B2O3 10-15%, Al2O3 5-10%, ZrO2 3-5%, Y2O3 3-8%, CeO2 1-3%, and Li2O 0-8%.

[0015] In some embodiments of the present invention, when the transparent ceramic is MgAl2O4 transparent ceramic, the chemical composition of the glass powder, by weight percentage, includes: La2O3 35-45%, SiO2 25-35%, B2O3 5-10%, Al2O3 3-10%, ZrO2 0-5%, MgO 3-8%, CaO 8-12%, Y2O3 1-3%, K2O 1-5%.

[0016] In some embodiments of the present invention, the difference between the refractive index of the glass substrate and the refractive index of the transparent ceramic is 0.003-0.03.

[0017] In some embodiments of the present invention, the difference between the coefficient of thermal expansion of the glass substrate and the coefficient of thermal expansion of the transparent ceramic is (0.1-0.3) × 10⁻¹⁰. -6 / ℃.

[0018] In some embodiments of the present invention, the glass plate may be made of conventional transparent glass, including but not limited to alkali silicate glass, titanate glass, aluminosilicate glass, lanthanum silicate glass, germanium silicate glass, lead-containing glass, bismuth borate glass, etc.

[0019] In some embodiments of the present invention, the number of glass plates is ≥1; preferably 1-3 layers.

[0020] In some embodiments of the present invention, the thickness of a single layer of the glass plate is 5-10 mm.

[0021] In some embodiments of the present invention, the light transmittance of the glass plate is >90%.

[0022] In some embodiments of the present invention, the adjacent transparent ceramics are separated by a glass sheet, the glass sheet having the same chemical composition as the glass powder, which serves to fix and control the gap.

[0023] In some embodiments of the present invention, the layers of the composite matrix, the glass plate, and the organic backing plate are laminated together by means of a film comprising a polyurethane material.

[0024] In some embodiments of the present invention, the thickness of the film is 0.38-1.35 mm.

[0025] In some embodiments of the present invention, the light transmittance of the film is >90%.

[0026] In some embodiments of the present invention, the organic backing plate is made of polycarbonate material, and the organic backing plate can prevent glass fragments from splashing.

[0027] In some embodiments of the present invention, the thickness of the organic backsheet is 2-5 mm.

[0028] In some embodiments of the present invention, the light transmittance of the organic backsheet is >90%.

[0029] In some embodiments of the present invention, the maximum dimensions of the composite material are length × width = 1000mm × 1800mm.

[0030] A second aspect of the present invention provides a method for preparing the above-mentioned composite material, comprising the following steps:

[0031] The powder used to prepare transparent ceramics is pressed into shape, and then sintered, annealed, cut, ground, and polished to obtain transparent ceramic blocks.

[0032] The raw materials for preparing glass powder are mixed, melted, poured into water for quenching, and then ground to obtain glass powder.

[0033] The glass powder, transparent ceramic block and glass powder are sequentially laid in the molding mold so that the glass powder completely covers the transparent ceramic block. After compaction, it is fired and annealed to obtain a composite matrix of transparent ceramic filled with glass in sections.

[0034] The composite material is obtained by heat-bending the composite matrix, glass plate and organic backing plate, or by heat-bending the glass plate and organic backing plate and then stacking the composite matrix, glass plate and organic backing plate in sequence.

[0035] In some embodiments of the present invention, when the transparent ceramic powder is pressed, it is first pressed using a dry pressing process with a pressure of 15-30 MPa and a holding time of 2-10 min; then it is pressed using cold isostatic pressing with a pressure of 180-220 MPa and a holding time of 5-10 min.

[0036] In some embodiments of the present invention, the sintering temperature of the transparent ceramic block is 1600-2000℃, and the holding time is 5-20h.

[0037] In some embodiments of the present invention, the annealing temperature of the transparent ceramic block is 1400-1500℃, and the holding time is 5-20h.

[0038] In some embodiments of the present invention, the annealing of the transparent ceramic block is carried out in an air atmosphere to eliminate oxygen vacancies.

[0039] In some embodiments of the present invention, after the transparent ceramic block is cut, the upper and lower surfaces and splicing surfaces are further polished and cleaned.

[0040] In some embodiments of the present invention, the melting temperature of the glass powder is 1000-1500℃, and the holding time is 20-40min.

[0041] In some embodiments of the present invention, the firing temperature regime of the composite matrix is ​​as follows: first, the temperature is raised to 1000-1500°C at a heating rate of 5-10°C / min and held for 20-40 minutes; then, it is rapidly cooled to room temperature at a cooling rate of 40-60°C / min. A suitable firing temperature ensures good bonding between the transparent ceramic and the glass powder, thereby improving the impact resistance of the composite material; simultaneously, a suitable cooling rate effectively prevents glass crystallization, thus ensuring the light transmittance and impact resistance of the composite material.

[0042] In some embodiments of the present invention, the annealing temperature of the composite matrix is ​​700-800℃, and the holding time is 2-3 hours.

[0043] In some embodiments of the present invention, the molding die is a planar die or a curved die. When the molding die is a planar die, the composite substrate, glass plate, and organic backing plate need to be bent by heat treatment; when the molding die is a curved die, the composite substrate is already curved, so only the glass plate and organic backing plate need to be bent by heat treatment.

[0044] In some embodiments of the present invention, the temperature of the bending treatment of the composite matrix and the glass plate is 500-700°C, and the holding time is 1-10h.

[0045] In some embodiments of the present invention, the temperature of the bending treatment of the organic backsheet is 110-150°C.

[0046] In some embodiments of the present invention, the lamination process is as follows: first, the composite matrix and the glass layer are laminated together, with a film placed between each layer, and the layers are initially bonded under vacuum conditions; then, pressure is applied to 6-10 bar, heated to 120-140°C, and held for 50-70 minutes to laminate; finally, it is laminated with the organic backing using the same method to obtain the composite material.

[0047] A third aspect of the present invention provides an automotive glass comprising the aforementioned composite material. The composite material of the present invention has good light transmittance and impact resistance, and can be fabricated into large-size curved surfaces, making it suitable for automotive safety glass.

[0048] Compared with the prior art, the above-described technical solution of the present invention has at least the following technical effects or advantages:

[0049] (1) The present invention uses glass as the matrix and multiple transparent ceramics as fillers to form a composite matrix structure of glass filled with segmented transparent ceramics. Then, it is combined with glass plate and organic backing plate to obtain a composite material of large-size (1000mm×1800mm) curved transparent ceramic filled glass with high safety and light weight, achieving a light transmittance of 64.2-81.2% and a bending strength of 168.4-213.7MPa.

[0050] (2) The composite material of the present invention uses transparent ceramics with high hardness and high strength, which greatly improves the impact resistance compared with traditional multilayer glass. By using segmented transparent ceramics spliced ​​together and then filling the glass, the cracks after impact will not affect the adjacent transparent ceramic blocks, thereby effectively avoiding the large-scale spread of cracks and improving the composite glass's resistance to multiple impacts; moreover, the field of vision is less affected after impact, which can ensure the driving safety of the vehicle.

[0051] (3) The composite material of the present invention uses high-strength transparent ceramic as the reinforcing phase of glass. Compared with traditional multilayer glass, it can reduce the total weight of composite glass under the same protective effect, thereby improving the vehicle's mobility performance.

[0052] (4) By controlling the refractive index and thermal expansion coefficient of the transparent ceramic and the glass matrix, the composite material of the present invention improves the matching accuracy between the two, obtains a large-size curved transparent ceramic-filled glass composite material with good optical performance, and broadens the application range of transparent ceramic. Attached Figure Description

[0053] Figure 1 This is a schematic diagram of the composite matrix laying in Embodiment 1 of the present invention;

[0054] Figure 2 This is a schematic diagram of the splicing of transparent ceramics according to Embodiment 1 of the present invention;

[0055] Figure 3 This is a schematic diagram of the composite matrix before the bending process in Embodiment 1 of the present invention;

[0056] Figure 4 This is a schematic diagram of the composite matrix after the bending process in Embodiment 1 of the present invention;

[0057] Figure 5 This is a schematic diagram of the composite matrix laying in Embodiment 2 of the present invention.

[0058] In the attached diagram: 101-flat mold, 201-glass powder A, 301-transparent ceramic A, 401-glass block A, 501-glass substrate, 102-curved mold, 202-glass powder B, 302-transparent ceramic B, 402-glass block B. Detailed Implementation

[0059] The present invention will now be described in detail with reference to embodiments to facilitate understanding of the invention by those skilled in the art. It is particularly important to note that the embodiments are merely illustrative of the invention and should not be construed as limiting the scope of protection of the invention. Non-essential improvements and adjustments made to the invention by those skilled in the art based on the above description should still fall within the scope of protection of the invention. Furthermore, all raw materials mentioned below, unless otherwise specified, are commercially available products; all process steps or preparation methods not mentioned in detail are process steps or preparation methods known to those skilled in the art.

[0060] Example 1

[0061] A method for preparing a segmented transparent ceramic-filled glass composite material includes the following steps:

[0062] (1) Preparation of transparent ceramics: YAG powder was placed in a mold and a pressure of 20 MPa was applied for 3 min. The molded sample was then subjected to cold isostatic pressing to improve the density of the green body. The pressure of cold isostatic pressing was 200 MPa and the holding time was 5 min. The cold isostatic pressing sample was placed in a vacuum sintering furnace for pressureless sintering at a temperature of 1780℃ for 10 h. The sintered YAG transparent ceramics were annealed in an air atmosphere to eliminate oxygen vacancies at a temperature of 1450℃ for 10 h. The obtained sample was then cut and the top, bottom, and joint surfaces were polished to obtain a regular hexagonal transparent ceramic block with a side length of 100 mm. Finally, the transparent ceramic block was ultrasonically cleaned with alcohol as a medium for 20 min to remove surface impurities, and transparent ceramic A was obtained.

[0063] (2) Preparation of glass powder: The measured raw material powders are mixed evenly. The chemical composition of the glass powder, by weight percentage, includes: La2O3 46%, SiO2 20%, B2O3 13%, Al2O3 7%, ZrO2 5%, Y2O3 4%, CeO2 1.5%, and Li2O 3.5%. The raw material powders are then placed in a muffle furnace and heated to 1500℃ and held for 30 minutes to make the powder molten. The molten glass is then poured into water and quenched to obtain glass fragments. After grinding and sieving, glass powder A is obtained.

[0064] (3) Splicing of transparent ceramics: such as Figure 1 As shown, first, a layer of glass powder A 201 with a thickness of 2mm is laid in the flat mold 101. The glass powder is compacted using a smooth press head, with a pressure of 3MPa applied and held for 5 minutes. Then, transparent ceramic A 301 is laid on top, in the following manner. Figure 2As shown, transparent ceramics are separated by glass blocks A401, which serve to fix and control the gaps. A 2mm layer of glass powder A201 is then laid on top of the transparent ceramics A301, ensuring the glass powder completely encapsulates the transparent ceramics A301. The powder is compacted using a smooth press head and held at 3MPa for 5 minutes. Finally, it is placed in a muffle furnace and heated to 1300℃ at a heating rate of 8℃ / min, held for 30 minutes, and then rapidly cooled to room temperature at a cooling rate of 50℃ / min. It is immediately placed in a muffle furnace at 700℃ for annealing, held for 2 hours, and then cooled to room temperature with the furnace, resulting in a composite matrix of segmented transparent ceramics A301 filled with glass matrix 501. Figure 3 As shown. The refractive index of glass substrate 501 is 1.817, and the refractive index of transparent ceramic A 301 is 1.820, with a difference of 0.003. The coefficient of thermal expansion of glass substrate 501 is 8 × 10⁻⁶. -6 At / ℃, the coefficient of thermal expansion of transparent ceramic A 301 is 7.8×10. -6 / ℃, the difference in their coefficients of thermal expansion is 0.2×10 -6 / ℃.

[0065] (4) Bending process: The composite substrate and three layers of glass are stacked on a bending mold, with the composite substrate placed as the first layer. A layer of silicon powder is sprayed on the surface between each layer to prevent adhesion. Then, the substrate is heated and softened in a furnace, allowing it to adhere tightly to the mold surface under its own weight. The heating temperature is 570℃, the heating rate is 5℃ / min, and the bending time is 10h. Then, the substrate is slowly cooled to 100℃ at a cooling rate of 5℃ / min and then cooled to room temperature in the furnace. The polycarbonate sheet is bent into shape and naturally adheres to the mold. The bending temperature is 130℃. A schematic diagram of the structure of the composite substrate obtained by the bending process is shown below. Figure 4 As shown.

[0066] (5) Lamination process: Lay the composite matrix / multilayer glass in sequence, with polyurethane film placed between each layer. Make a vacuum bag to remove air and allow the glass and film to bond initially. Then transfer it to an autoclave for pressurization and heating at 8 bar and 130°C for 60 min. Take out the laminated glass, attach the sealing tape to the side contours of the laminated glass and polycarbonate plate and fix it. Lay the glass using the same lamination method as the glass, with the temperature set at 120°C, the pressure at 8 bar and the holding time at 90 min. Cut off the excess film around the edges to prepare the segmented transparent ceramic-filled glass composite material (1000mm×1800mm) of this embodiment.

[0067] Example 2

[0068] A method for preparing a segmented transparent ceramic-filled glass composite material includes the following steps:

[0069] (1) Preparation of transparent ceramics: MgAl2O4 powder was placed in a mold and a pressure of 20 MPa was applied for 3 min. Then, the molded sample was subjected to cold isostatic pressing to improve the density of the green body. The pressure of cold isostatic pressing was 200 MPa and the holding time was 5 min. The cold isostatic pressing sample was placed in a vacuum sintering furnace for pressureless sintering at a temperature of 1500℃ for 2 h. The sintered MgAl2O4 transparent ceramics were annealed in air to eliminate oxygen vacancies at a temperature of 1450℃ for 10 h. The obtained sample was then cut and the top, bottom and joint surfaces were polished to obtain a regular hexagonal transparent ceramic block with a side length of 100 mm. Finally, the transparent ceramic block was ultrasonically cleaned with alcohol as a medium for 20 min to remove surface impurities, and transparent ceramic B was obtained.

[0070] (2) Preparation of glass powder: The measured raw material powders are mixed evenly. The chemical composition of the glass powder, by weight percentage, includes: La2O3 38%, SiO2 28%, B2O3 10%, MgO 6%, CaO 10%, Al2O3 4%, Y2O3 1%, K2O 3%. Then the raw material powders are placed in a muffle furnace and heated to 1500℃ and held for 30 minutes to make the powder molten. The molten glass is then poured into water and quenched to obtain glass fragments. After grinding and sieving, glass powder B is obtained.

[0071] (3) Splicing of transparent ceramics: such as Figure 5 As shown, a layer of glass powder B 202 with a thickness of 2 mm is first laid in the curved mold 102. The glass powder is compacted using a smooth press head, and a pressure of 3 MPa is applied and held for 5 minutes. Then, transparent ceramic B 302 is laid on top, with glass blocks B 402 separating the transparent ceramics. The glass blocks B 402 serve to fix and control the gaps. Next, a 2 mm layer of glass powder B 202 is laid on top of the transparent ceramic B 302, so that the glass powder B 202 completely covers the transparent ceramic 300. The powder is compacted using a smooth press head and held at a pressure of 3 MPa for 5 minutes. Finally, it is placed in a muffle furnace and heated to 1300℃ at a heating rate of 8℃ / min, and held for 30 minutes. It is then rapidly cooled to room temperature at a cooling rate of 50℃ / min and immediately placed in a muffle furnace at 700℃ for annealing. The holding time is 2 hours, and it is cooled to room temperature with the furnace to obtain a composite matrix of segmented transparent ceramic B 302 filled with glass matrix 502. The refractive index of the glass substrate 502 is 1.643, and the refractive index of the transparent ceramic B302 is 1.655, with a difference of 0.012 between the two. The coefficient of thermal expansion of the glass substrate 502 is 5.37 × 10⁻⁶. -6At / ℃, the coefficient of thermal expansion of transparent ceramic B 302 is 5.6×10. -6 / ℃, the difference in their coefficients of thermal expansion is 0.23×10 -6 / ℃.

[0072] (4) Bending process: Three layers of glass are stacked on a bending mold. A layer of silicon powder is sprayed on the surface between each layer to prevent sticking. Then, the glass is heated and softened in a furnace, and then adheres tightly to the surface of the mold by its own weight. The heating temperature is 570℃, the heating rate is 5℃ / min, and the bending time is 10h. Then, the temperature is slowly reduced to 100℃ at a cooling rate of 5℃ / min, and then cooled to room temperature in the furnace. The polycarbonate sheet is bent into shape and naturally adheres to the mold. The bending temperature is 130℃.

[0073] (5) Lamination process: Lay the composite matrix / multilayer glass in sequence, with polyurethane film placed between each layer. Make a vacuum bag to remove air and allow the glass and film to bond initially. Then transfer it to an autoclave for pressurization and heating at 8 bar and 130°C for 60 min. Take out the laminated glass, attach the sealing tape to the side contours of the laminated glass and polycarbonate plate and fix it. Lay the glass using the same lamination method as the glass, with the temperature set at 120°C, the pressure at 8 bar and the holding time at 90 min. Cut off the excess film around the edges to prepare the segmented transparent ceramic-filled glass composite material (1000mm×1800mm) of this embodiment.

[0074] Example 3

[0075] The only difference between Example 3 and Example 1 is the chemical composition of the glass powder. The glass powder in Example 3, by weight percentage, comprises: La₂O₃ 49.5%, SiO₂ 20%, B₂O₃ 13%, Al₂O₃ 7%, ZrO₂ 5%, Y₂O₃ 4%, and CeO₂ 1.5%. The refractive index of the prepared glass matrix is ​​1.797, and the coefficient of thermal expansion is 8.06 × 10⁻⁶. -6 / ℃; the difference in refractive index between it and transparent ceramic A301 is 0.023, and the difference in their coefficients of thermal expansion is 0.26×10. -6 / ℃.

[0076] Example 4

[0077] The only difference between Example 4 and Example 1 is the chemical composition of the glass powder. The chemical composition of the glass powder in Example 3, by weight percentage, includes: La₂O₃ 41.5%, SiO₂ 20%, B₂O₃ 13%, Al₂O₃ 7%, ZrO₂ 5%, Y₂O₃ 4%, CeO₂ 1.5%, and Li₂O 8%. The refractive index of the prepared glass matrix is ​​1.833, and the coefficient of thermal expansion is 7.98 × 10⁻⁶.-6 / ℃; the difference in refractive index between it and transparent ceramic A 301 is 0.013, and the difference in their coefficients of thermal expansion is 0.18×10. -6 / ℃.

[0078] Example 5

[0079] The only difference between Example 5 and Example 2 is the chemical composition of the glass powder. The chemical composition of the glass powder in Example 3, by weight percentage, includes: La₂O₃ 40%, SiO₂ 28%, B₂O₃ 10%, MgO 6%, CaO 10%, Al₂O₃ 4%, Y₂O₃ 1%, and K₂O 1%. The refractive index of the prepared glass matrix is ​​1.681, and the coefficient of thermal expansion is 5.73 × 10⁻⁶. -6 / ℃; the difference in refractive index between it and transparent ceramic B 302 is 0.026, and the difference in their coefficients of thermal expansion is 0.13×10. -6 / ℃.

[0080] Example 6

[0081] The only difference between Example 6 and Example 2 is the chemical composition of the glass powder. The chemical composition of the glass powder in Example 3, by weight percentage, includes: La₂O₃ 36%, SiO₂ 28%, B₂O₃ 10%, MgO 6%, CaO 10%, Al₂O₃ 4%, Y₂O₃ 1%, and K₂O 5%. The refractive index of the prepared glass matrix is ​​1.636, and the coefficient of thermal expansion is 5.79 × 10⁻⁶. -6 / ℃; the difference in refractive index between it and transparent ceramic B 302 is 0.019, and the difference in their coefficients of thermal expansion is 0.19×10. -6 / ℃.

[0082] Comparative Example 1

[0083] The only difference between Comparative Example 1 and Example 1 is the chemical composition of the glass powder. The glass powder in Comparative Example 1, by weight percentage, comprises: La₂O₃ 39.5%, SiO₂ 20%, B₂O₃ 13%, Al₂O₃ 7%, ZrO₂ 5%, Y₂O₃ 4%, CeO₂ 1.5%, and Li₂O 10%. The refractive index of the prepared glass matrix is ​​1.788, and the coefficient of thermal expansion is 8.13 × 10⁻⁶. -6 / ℃;

[0084] The difference in refractive index between it and transparent ceramic A301 is 0.083, and the difference in their coefficients of thermal expansion is 0.33 × 10⁻⁶. -6 / ℃.

[0085] Comparative Example 2

[0086] The only difference between Comparative Example 2 and Example 1 is the splicing temperature regime of the transparent ceramic. The splicing temperature regime of the transparent ceramic in Comparative Example 2 is as follows: the temperature is raised to 1300°C at a heating rate of 8°C / min and held for 30 min; it is then rapidly cooled to room temperature at a cooling rate of 30°C / min and immediately placed in a muffle furnace at 700°C for annealing. The holding time is 2 h, and the ceramic is cooled to room temperature with the furnace.

[0087] Comparative Example 3

[0088] The only difference between Comparative Example 3 and Example 2 is the chemical composition of the glass powder. The chemical composition of the glass powder in Comparative Example 3, by weight percentage, includes: La₂O₃ 33%, SiO₂ 28%, B₂O₃ 10%, MgO 6%, CaO 10%, Al₂O₃ 4%, Y₂O₃ 1%, and K₂O 8%. The refractive index of the prepared glass matrix is ​​1.637, and the coefficient of thermal expansion is 5.39 × 10⁻⁶. -6 / ℃; the difference in refractive index between it and transparent ceramic B 302 is 0.018, and the difference in their coefficients of thermal expansion is 0.21×10. -6 / ℃.

[0089] Comparative Example 4

[0090] The only difference between Comparative Example 4 and Example 2 is the splicing temperature regime of the transparent ceramic. The splicing temperature regime of the transparent ceramic in Comparative Example 4 is as follows: the temperature is raised to 900°C at a heating rate of 8°C / min and held for 30 min; it is then rapidly cooled to room temperature at a cooling rate of 50°C / min and immediately placed in a muffle furnace at 700°C for annealing. The holding time is 2 h, and the ceramic is then cooled to room temperature in the furnace.

[0091] Comparative Example 5

[0092] The only difference between Comparative Example 5 and Example 1 is the chemical composition of the glass powder. The glass powder in Comparative Example 5, by weight percentage, comprises: La₂O₃ 35%, SiO₂ 38.5%, B₂O₃ 13%, Al₂O₃ 3%, ZrO₂ 5%, Y₂O₃ 4%, and CeO₂ 1.5%. The refractive index of the prepared glass matrix is ​​1.772, and the coefficient of thermal expansion is 7.462 × 10⁻⁶. -6 / ℃; the difference in refractive index between it and transparent ceramic A 301 is 0.048, and the difference in their coefficients of thermal expansion is 0.338×10. -6 / ℃.

[0093] Performance testing

[0094] The transmittance and mechanical strength of the segmented transparent ceramic-filled glass composite material samples prepared in Examples 1-6 and Comparative Examples 1-5 were tested. The transmittance was tested at a wavelength of 1000 nm, and the bending strength refers to the bending strength at the joint of the sample. The results are shown in Table 1.

[0095] Table 1:

[0096]

[0097] As shown in Table 1, the block transparent ceramic-filled glass composite material samples prepared in Examples 1-6 have a light transmittance of 64.2-81.2% and a flexural strength of 168.4-213.7 MPa, all of which have good light transmittance and flexural strength and are suitable for large-size curved automotive glass.

[0098] Compared to Example 1, Comparative Example 1 shows that the increased Li2O content in the chemical composition of the glass powder reduces the stability of the glass, induces crystallization, thereby increasing the light scattering points and reducing the light transmittance; at the same time, the bending strength at the joint also decreases significantly due to the increase in residual stress.

[0099] Compared to Example 1, Comparative Example 2 showed that the slow cooling rate in the splicing temperature regime of the transparent ceramic led to glass crystallization, which greatly reduced the light transmittance and flexural strength of the sample.

[0100] Compared to Example 2, Comparative Example 3 shows that the increased K2O content in the chemical composition of the glass powder leads to the formation of tiny grains in the glass, thereby reducing the refractive index of the glass. At the same time, it also results in the generation of residual stress at the interface during the cooling process, and the bending strength is significantly reduced.

[0101] Compared to Example 2, Comparative Example 4 shows that due to the excessively low firing temperature in the splicing temperature regime of the transparent ceramic, the diffusion between glass powders is insufficient, resulting in pores in the molten glass powder, which leads to a significant decrease in both light transmittance and flexural strength.

[0102] Compared to Example 1, Comparative Example 5 showed a decrease in light transmittance because the content of La2O3 and Al2O3 in the glass powder was reduced, which failed to match the refractive index of the transparent ceramic. Furthermore, the absence of Li2O in the glass powder resulted in a higher melting temperature and viscosity, leading to a decrease in flexural strength.

[0103] For those skilled in the art, several simple deductions or substitutions can be made without departing from the inventive concept, without requiring creative effort. Therefore, any simple improvements made to this invention by those skilled in the art based on the disclosure of this invention should be within the scope of protection of this invention. The above embodiments are preferred embodiments of this invention, and all processes similar to this invention and equivalent changes should fall within the scope of protection of this invention.

Claims

1. A composite material, characterized by, The composite material is a curved surface, sequentially comprising a composite substrate, a glass plate and an organic back plate from bottom to top; the composite substrate comprises a plurality of transparent ceramics and a glass substrate, the plurality of transparent ceramics being spliced and laid in the interior of the glass substrate to form a structure of the glass filled with the transparent ceramics; The glass substrate is sintered from glass powder, and the glass powder comprises, in terms of percentage by weight, La2O3 35-60%, SiO2 16-35%, B2O3 5-15%, Al2O3 3-10%, ZrO2 0-5%, MgO 0-8%, CaO 0-12%, Y2O3 1-8%, CeO2 0-3%, Li2O 0-8%, and K2O 0-5%. the difference between the refractive index of the glass matrix and the refractive index of the transparent ceramic is 0.003 to 0.03, and the difference between the coefficient of thermal expansion of the glass matrix and the coefficient of thermal expansion of the transparent ceramic is (0.1 to 0.3) x 10 -6 / °C; The composite substrate is prepared by a preparation method comprising the following steps: The transparent ceramic powder is pressed into a shape, sintered, annealed, cut, polished and ground to obtain a transparent ceramic block; The raw materials for preparing the glass powder are mixed, melted, poured into water for quenching, and ground to obtain the glass powder; The glass powder, the transparent ceramic block and the glass powder are sequentially laid in a forming mold, so that the glass powder completely wraps the transparent ceramic block, and after compaction, sintering and annealing are performed to obtain the composite substrate of the glass filled with the transparent ceramics; The sintering temperature schedule of the composite substrate is: first, the temperature is raised to 1000-1500℃ at a rate of 5-10℃ / min, and then the temperature is cooled to room temperature at a rate of 40-60℃ / min.

2. The composite material of claim 1, wherein, The transparent ceramic is selected from any one of AlON transparent ceramic, YAG transparent ceramic and MgAl2O4 transparent ceramic; and / or the light transmittance of the transparent ceramic is >80%.

3. The composite material of claim 1, wherein, The number of layers of the glass plate is ≥1; and / or the light transmittance of the glass plate is >90%.

4. The composite material of claim 1, wherein, The layers of the composite substrate, the glass plate and the organic back plate are bonded by adhesive sheets, and the adhesive sheets comprise polyurethane material.

5. A method of producing a composite material, characterized by, The preparation method is used for preparing the composite material according to any one of claims 1-4, comprising the following steps: The transparent ceramic powder is pressed into a shape, sintered, annealed, cut, polished and ground to obtain a transparent ceramic block; The raw materials for preparing the glass powder are mixed, melted, poured into water for quenching, and ground to obtain the glass powder; The glass powder, the transparent ceramic block and the glass powder are sequentially laid in a forming mold, so that the glass powder completely wraps the transparent ceramic block, and after compaction, sintering and annealing are performed to obtain the composite substrate of the glass filled with the transparent ceramics; The composite substrate, the glass plate and the organic back plate are subjected to bending treatment, or the glass plate and the organic back plate are subjected to bending treatment, and then the composite substrate, the glass plate and the organic back plate are sequentially stacked and bonded to obtain the composite material.

6. The method of claim 5, wherein the step of applying the second layer of material is performed after the step of applying the first layer of material. The forming mold is a plane mold or a curved surface mold.

7. The method of claim 5, wherein the step of applying the second layer of material is performed after the step of applying the first layer of material. The sintering temperature schedule of the composite substrate is: first, the temperature is raised to 1000-1500℃ at a rate of 5-10℃ / min, and then the temperature is cooled to room temperature at a rate of 40-60℃ / min.

8. An automotive glass characterized by The composite material according to any one of claims 1-4.

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