Laminated sintering method, setter plate and method for preparing the setter plate

Abstract

The present invention discloses a laminated sintering method and a support plate and a method for preparing the support plate. In the laminated sintering method, green blanks are stacked in a direction perpendicular to the plane of the support plate, the green blank closest to the support plate is in direct contact with the support plate, and anti-sticking powder is arranged between adjacent green blanks; the support plate includes a support plate body and an aluminum-silicon composite oxide film layer arranged on the surface of the support plate body, and the aluminum-silicon composite oxide film layer is formed by aluminum-silicon oxide particles in which aluminum oxide coats silicon oxide. In the laminated sintering method described in the present invention, the support plate is in direct contact with the green blank, and the aluminum-silicon composite oxide film layer is formed by stacking a large number of silicon oxide particles, and there are pores between the particles, so that the sintering atmosphere of the ceramic substrate can effectively flow in the sintering furnace during sintering to ensure the uniformity of the atmosphere in the furnace; most of the aluminum-based silicon oxide film is an amorphous structure with a smooth surface, so that the ceramic substrate can shrink and deform smoothly during sintering.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic materials, in particular to a laminated sintering method, a setter plate and a method for preparing the setter plate. Background Art

[0002] In the production process of ceramic substrates, the sintering process is a key step in determining the quality of the substrate. In the traditional sintering method, the flaky ceramic blanks are stacked together in multiple layers before being placed in a sintering furnace for high-temperature sintering. The blanks are sintered into porcelain to form ceramic sheets. The multi-layer ceramic sheets are easy to stick to each other and are difficult to open. Even after opening, there are traces of adhesion on the surface, which seriously affects the ceramic production efficiency and product quality. In order to prevent the ceramic sheets from sticking to each other after sintering, an isolation powder can be sprinkled between the ceramic blanks before sintering. However, the existing method of using isolating powder has a problem, that is, during the sintering process, when multiple layers (such as 8 or 12 layers) are stacked, the bottom green body that directly contacts the setter plate will be uneven after sintering because the setter plate is a porous ceramic substrate with a rough surface. Even if a layer of isolating powder is placed on the setter plate, the ceramic green body shrinks by about 20% during sintering, while the setter plate and the isolating powder will not shrink, that is, the ceramic green body moves relative to the setter plate, and the ceramic green body softens at 800-1200℃, while the hardness of alumina isolating powder is very high, and the softened ceramic green body will be scratched by the hard isolating powder when it shrinks and moves. These surface depressions, protrusions and scratches seriously affect the yield of the target ceramic sheet. Summary of the invention

[0003] The object of the present invention is to solve the above problems and to provide a laminated sintering method, a setter plate and a method for preparing the setter plate.

[0004] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0005] In the first aspect, the present invention provides a laminated sintering method for sintering a ceramic substrate; the laminated sintering method comprises the steps of: stacking green blanks in a direction perpendicular to the plane of a supporting plate, the green blanks closest to the supporting plate are in direct contact with the supporting plate, and anti-sticking powder is arranged between adjacent green blanks; the supporting plate comprises a supporting plate main body and an aluminum-silicon composite oxide film layer arranged on the surface of the supporting plate main body, the aluminum-silicon composite oxide film layer is formed by aluminum-silicon oxide particles coated with silicon oxide by aluminum oxide.

[0006] Optionally, the method for preparing the setter plate comprises the steps of:

[0007] S1, depositing a phenolic resin layer on the surface of the support plate body; then spraying a hydrolyzed organosilicon monomer on the surface of the phenolic resin layer, so that the hydrolyzed organosilicon monomer and the phenolic resin in a partial area of ​​the phenolic resin layer undergo a cross-linking reaction to form an organosilicon-modified phenolic resin;

[0008] S2, at a temperature of 85-95°C, aluminum salt is deposited on the surface of the organosilicon-modified phenolic resin layer obtained in step S1, and the aluminum salt reacts with part of the unreacted phenolic resin to form an aluminoxane film on the surface of the organosilicon-modified phenolic resin to obtain an intermediate; then, the intermediate is heat-treated in an inert atmosphere to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; the deposition thickness of the aluminum-silicon composite oxide film layer on the surface of the support plate body is between 0.8-1.2 mm.

[0009] Optionally, in step S1, the preparation method of the organosilicon-modified phenolic resin specifically includes the steps of: adding an organosilicon monomer to sodium hydroxide for hydrolysis to form a hydrolyzed organosilicon monomer; coating the phenolic resin on the surface of the supporting plate body; spraying the hydrolyzed organosilicon monomer on the phenolic resin, and heating it to 130-140°C, so that the organosilicon monomer undergoes a cross-linking reaction with the hydroxyl groups in the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin having a cross-linked structure; wherein the Si ion concentration in the formed hydrolyzed organosilicon monomer is 40wt% to 50%.

[0010] Optionally, the aluminum salt includes one or more of aluminum ethanolate, aluminum isobutoxide or aluminum butoxide.

[0011] Optionally, in step S2, the intermediate is heat-treated, specifically comprising the steps of: raising the temperature from 85-95°C to 130±2°C to allow part of the phenolic resin to undergo a cross-linking reaction to form a stable three-dimensional network structure; raising the temperature to 380±2°C to thermally decompose the organosilicon-modified phenolic resin to allow the silanol (Si-OH) to undergo a dehydration condensation reaction to form a silicon-oxygen bond (Si-0-Si), thereby forming a network structure of silicon oxide; raising the temperature to 600±2°C to form an aluminum-silicon composite oxide film layer on the surface of the supporting plate body, wherein the aluminum-silicon composite oxide is an aluminum-silicon oxide in which aluminum oxide is coated with silicon oxide.

[0012] Optionally, the organosilicon monomer includes alkoxysilane; the mass percentage of the organosilicon monomer in the organosilicon-modified phenolic resin is 18-22wt%.

[0013] Optionally, the anti-sticking powder includes target ceramic powder, carbon powder, adhesive and water; wherein the mass ratio of the carbon powder to the target powder is 10:3, the particle size of the target ceramic powder is 8-12 microns, and the particle size of the carbon powder is 1.5-5μm; and the adhesive includes sodium carboxymethyl cellulose.

[0014] Optionally, the method for preparing the anti-sticking powder includes the steps of: uniformly mixing aluminum oxide powder, a binder and water to obtain a spray solution; spraying the spray solution on the surface of the blank with a high-pressure spray gun to form a first film layer; spraying the carbon powder on the first film layer so that the carbon powder covers the first film layer.

[0015] In the second aspect, the present invention provides a support plate, which is used in the laminated sintering method as described above; the support plate includes a support plate body and an aluminum-silicon composite oxide film layer arranged on the surface of the support plate body, and the aluminum-silicon composite oxide film layer is formed by aluminum-silicon oxide particles coated with silicon oxide.

[0016] In a third aspect, the present invention provides a method for preparing a setter plate, which is used to prepare the setter plate as described above.

[0017] The beneficial effects produced by the present invention include at least:

[0018] In the laminated sintering method described in the present invention, a support plate coated with an aluminum-silicon composite oxide film layer on the surface is directly in contact with the green blank. The aluminum-silicon composite oxide film layer is formed by stacking a large number of silicon oxide particles, and there are pores between the particles, so that the sintering atmosphere of the ceramic substrate can effectively flow in the sintering furnace during sintering to ensure the uniformity of the atmosphere in the furnace; most of the aluminum-based silicon oxide film is an amorphous structure with a smooth surface, so that the ceramic substrate can shrink and deform smoothly during sintering. DETAILED DESCRIPTION

[0019] In order to facilitate the understanding of the present invention, the preferred embodiments of the present invention are provided below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described in the present invention. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0020] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0021] In the present invention, descriptions such as “first”, “second”, etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features.

[0022] It should be noted that, unless otherwise specified, the raw materials used in the present invention can be sourced from suppliers known in the art, or can be prepared by known methods.

[0023] In a first aspect, the present invention provides a laminated sintering method for sintering a ceramic substrate; the laminated sintering method comprises the following steps: stacking green blanks in a direction perpendicular to the plane of a support plate, wherein the green blanks closest to the support plate are in direct contact with the support plate, and anti-sticking powder is arranged between adjacent green blanks; the support plate comprises a support plate body and an aluminum-silicon composite oxide film layer arranged on the surface of the support plate body, wherein the aluminum-silicon composite oxide film layer is formed by aluminum-silicon oxide particles in which aluminum oxide covers silicon oxide; the number of stacked layers of the green blanks on the support plate is at least 3; the preparation method of the support plate comprises the following steps:

[0024] S1, depositing a phenolic resin layer on the surface of the support plate body; then spraying a hydrolyzed silicone monomer on the surface of the phenolic resin layer, so that the hydrolyzed silicone monomer and the phenolic resin in a partial area of ​​the phenolic resin layer undergo a cross-linking reaction to form a silicone-modified phenolic resin, that is, after the silicone monomer and the phenolic resin in a partial area of ​​the phenolic resin layer undergo a cross-linking reaction, a film layer including both the phenolic resin and the silicone-modified phenolic resin is formed on the surface of the support plate body; when depositing the phenolic resin layer on the surface of the support plate body, adding a solvent such as methanol, ethanol, acetone, etc. to the phenolic resin and stirring evenly to adjust the viscosity to 500-2000mPa·s.

[0025] S2, at a temperature of 85-95°C, aluminum salt is deposited on the surface of the organosilicon-modified phenolic resin layer obtained in step S1, and the aluminum salt reacts with part of the unreacted phenolic resin to form an aluminoxane film on the surface of the organosilicon-modified phenolic resin to obtain an intermediate; then, the intermediate is heat-treated in an inert atmosphere to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; the aluminum-silicon composite oxide film layer is deposited at a thickness of 0.8-1.2 mm on the surface of the support plate body. In an inert atmosphere, the cracking process of the phenolic resin will not be affected by oxygen, thereby avoiding oxidation reactions; at the same time, the cross-linking reaction can be fully carried out to ensure the formation and stability of the cross-linking structure.

[0026] In step S1, the coating thickness of the phenolic resin layer, the coating thickness of the hydrolyzed organosilicon monomer on the phenolic resin layer, and the coating thickness of the aluminum salt on the organosilicon-modified phenolic resin can be specifically defined according to actual requirements such as the surface area of ​​the main body of the support plate. The thickness of the organosilicon-modified phenolic resin layer coated on the surface of the main body of the support plate is at least 10 μm. For example, in some embodiments, a phenolic resin layer with a coating thickness of 100 μm is coated on the surface of the main body of the support plate; an organosilicon monomer containing 5% sodium hydroxide is sprayed on the phenolic resin layer, and the coating thickness of the hydrolyzed organosilicon monomer is 20 μm; and then an aluminum salt is deposited, and the coating thickness of the aluminum salt is 50 μm. According to this thickness, the aluminum-silicon composite oxide film layer finally formed on the surface of the main body of the support plate has a thickness of 100-120 μm.

[0027] In step S2, the aluminum salt is coated at a temperature of 85-95°C. The silicone-modified phenolic resin may undergo thermal degradation or performance degradation at high temperatures. The temperature range of 85-95°C is relatively low, which can effectively avoid thermal damage to the resin substrate and ensure that its physical and chemical properties remain stable. Moreover, at this temperature, the aluminum salt and the unreacted phenolic resin can react more stably, better controlling the growth uniformity of the aluminoxane film and helping to form a dense and uniform film.

[0028] S3, post-treatment: heat-treating the aluminum-silicon composite oxide film layer in step S2 at a temperature below 350-380° C., so that the aluminum-silicon composite oxide film layer remains in an amorphous state.

[0029] Optionally, the stacked sintering method further includes step S4: doping hydrogen into the aluminum-silicon composite oxide film layer treated in step S3 by plasma doping; to stabilize the amorphous structure and reduce defects; by using plasma to generate a large number of hydrogen free radicals, these free radicals can be better integrated into the film, reduce defects, and enhance the stability of the amorphous structure. The content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%.

[0030] Step S4 specifically includes the steps of: using a plasma doping device, during the plasma doping process, the plasma doping device is set to the following conditions: the vacuum degree of the reaction chamber is less than 10 -6Torr, reaction chamber pressure: 1Torr, gas introduced is argon, hydrogen and silane; at a frequency of 13.56MHz and a power of 300W, ignition generates plasma, the ignition time is about 1 minute, until stable plasma is formed; the plasma injection temperature is maintained at 200°C, the deposition time is 2-5 minutes, and it is naturally cooled to room temperature. Among them, the flow rate of hydrogen is 50sccm, the flow rate of silane is 10sccm, and the flow rate of argon is 50sccm. Argon is used as a protective atmosphere, and the protective atmosphere is used to stabilize the plasma.

[0031] Optionally, in step S1, the preparation method of the organosilicon-modified phenolic resin specifically includes the steps of: adding an organosilicon monomer to sodium hydroxide for hydrolysis to activate the organosilicon molecules in the organosilicon monomer so that the organosilicon monomer can undergo a cross-linking reaction with the phenolic resin to form a hydrolyzed organosilicon monomer; applying the phenolic resin to the surface of the support plate body; spraying the hydrolyzed organosilicon monomer on the phenolic resin, heating it to 130-140° C. so that the organosilicon monomer undergoes a cross-linking reaction with the hydroxyl groups in the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin with a cross-linked structure; wherein the Si ion concentration in the formed hydrolyzed organosilicon monomer is 40wt% to 50wt%. wherein the organosilicon monomer is hydrolyzed by adding sodium hydroxide so that the reaction formula is (CH3)2SiCl2+2NaOH→(CH3)2Si(OH)2+2NaCl, and after the reaction, the concentration of the final solution can be adjusted by evaporating water or by adding more water.

[0032] Optionally, the aluminum salt includes one or more of aluminum ethoxide, aluminum isobutoxide or aluminum butoxide. Specifically, the aluminum salt includes trimethylaluminum.

[0033] Optionally, in step S2, the intermediate is heat treated, specifically including the steps of: raising the temperature from 85-95°C to 130±2°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; raising the temperature to 380±2°C to pyrolyze the organosilicon-modified phenolic resin, so that the silanol (Si-OH) undergoes a dehydration condensation reaction to form a silicon-oxygen bond (Si-0-Si), thereby forming a network structure of silicon oxide; raising the temperature to 600±2°C to form an aluminum-silicon composite oxide film layer on the surface of the support plate body, wherein the aluminum-silicon composite oxide is an aluminum-silicon oxide in which aluminum oxide is coated with silicon oxide. Aluminum oxide is formed on the surface of silicon oxide, and finally an aluminum-silicon composite oxide film layer is formed. Since silicon oxide itself has a strong tendency to be amorphous, the aluminum-silicon composite oxide obtained for this purpose also tends to be amorphous.

[0034] Optionally, the organosilicon monomer includes alkoxysilane; specifically, the organosilicon monomer is methyltrichlorosilane; the mass percentage of the organosilicon monomer in the organosilicon-modified phenolic resin is 18-22 wt %.

[0035] Optionally, the anti-sticking powder includes target ceramic powder, carbon powder, adhesive and water; wherein the mass ratio of the carbon powder to the target powder is 10:3, the particle size of the target ceramic powder is 8-12 microns, and the particle size of the carbon powder is 1.5-5μm; and the adhesive includes sodium carboxymethyl cellulose.

[0036] In some embodiments, the anti-sticking powder includes 78g of sodium carboxymethyl cellulose powder, 10000g of water and 330g of alumina powder. Optionally, the ceramic substrate is an alumina ceramic substrate, and the corresponding blank is an alumina ceramic blank; the target powder in the isolation powder is an alumina ceramic powder.

[0037] Optionally, the method for preparing the anti-sticking powder includes the steps of: uniformly mixing aluminum oxide powder, a binder and water to obtain a spray solution; spraying the spray solution on the surface of the blank with a high-pressure spray gun to form a first film layer; spraying the carbon powder on the first film layer so that the carbon powder covers the first film layer.

[0038] In the second aspect, the present invention provides a support plate, which is used in the laminated sintering method as described above; the support plate includes a support plate body and an aluminum-silicon composite oxide film layer arranged on the surface of the support plate body, and the aluminum-silicon composite oxide film layer is formed by aluminum-silicon oxide particles coated with silicon oxide.

[0039] In the third aspect, the present invention provides a method for preparing a support plate, which is used to prepare the support plate as described above. The support plate preparation method described in the present invention replaces the isolation powder in the prior art by forming an aluminum-silicon composite oxide film layer on the surface of the support plate body, sprays phenolic resin on the surface of the support plate body, and uses organic silicon to modify part of the phenolic resin to generate organic silicon-modified phenolic resin; then introduces an aluminum source, and generates an aluminoxane film through aluminum salt and hydroxyl groups in the phenolic resin that have not undergone cross-linking reaction; initially forms a structural framework of inner silicon and outer aluminum; then forms the aluminum-silicon composite oxide film layer on the surface of the support plate body by heat treatment, and the substructure layer of the film layer is composed of Si-0-Si random network ring structure. The aluminum-silicon composite oxide film layer is formed by stacking a large number of silicon oxide particles, and there are pores between the particles, so that the sintering atmosphere of the ceramic substrate can flow effectively in the sintering furnace during sintering to ensure the uniformity of the atmosphere in the furnace; most of the aluminum-based silicon oxide film is an amorphous structure with a smooth surface, so that the ceramic substrate can shrink and deform smoothly during sintering.

[0040] The method for preparing the setter plate comprises the steps of:

[0041] S1, depositing a phenolic resin layer on the surface of the support plate body; then spraying a hydrolyzed organosilicon monomer on the surface of the phenolic resin layer, so that the hydrolyzed organosilicon monomer and the phenolic resin in a partial area of ​​the phenolic resin layer undergo a cross-linking reaction to form an organosilicon-modified phenolic resin;

[0042] S2, at a temperature of 85-95° C., depositing aluminum salt on the surface of the organosilicon-modified phenolic resin layer obtained in step S1, wherein the aluminum salt reacts with a portion of the unreacted phenolic resin to form an aluminoxane film on the surface of the organosilicon-modified phenolic resin to obtain an intermediate; then, heat-treating the intermediate in an inert atmosphere to form an aluminum-silicon composite oxide film layer on the surface of the setter body; the aluminum-silicon composite oxide film layer deposited on the surface of the setter body has a thickness of 0.8-1.2 mm;

[0043] S3, post-treatment: heat-treating the aluminum-silicon composite oxide film layer in step S2 at a temperature below 350-380° C., so that the aluminum-silicon composite oxide film layer remains in an amorphous state;

[0044] S4: hydrogen is doped into the aluminum-silicon composite oxide film layer treated in step S3 by plasma doping; the content of the doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15 atm%.

[0045] Step S4 specifically includes the steps of: using a plasma doping device, during the plasma doping process, the plasma doping device is set to the following conditions: the vacuum degree of the reaction chamber is less than 10 -6 Torr, reaction chamber pressure: 1Torr, gas introduced is argon, hydrogen and silane; at a frequency of 13.56MHz and a power of 300W, ignition generates plasma, the ignition time is about 1 minute, until stable plasma is formed; the plasma injection temperature is maintained at 200°C, the deposition time is 2-5 minutes, and it is naturally cooled to room temperature. Among them, the flow rate of hydrogen is 50sccm, the flow rate of silane is 10sccm, and the flow rate of argon is 50sccm. Argon is used as a protective atmosphere, and the protective atmosphere is used to stabilize the plasma.

[0046] In step S1, the preparation method of the organosilicon-modified phenolic resin specifically includes the steps of: adding an organosilicon monomer to sodium hydroxide for hydrolysis to form a hydrolyzed organosilicon monomer; coating the phenolic resin on the surface of the support plate body; spraying the hydrolyzed organosilicon monomer on the phenolic resin, heating it to 130-140°C, so that the organosilicon monomer reacts with the hydroxyl groups in the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin with a cross-linked structure; wherein the Si ion concentration in the formed hydrolyzed organosilicon monomer is 40wt% to 50wt%.

[0047] The aluminum salt includes trimethylaluminum.

[0048] In step S2, the intermediate is heat treated, specifically including the steps of: raising the temperature from 85-95°C to 130±2°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; raising the temperature to 380±2°C to pyrolyze the organosilicon-modified phenolic resin, so that the silanol (Si-OH) undergoes a dehydration condensation reaction to form a silicon-oxygen bond (Si-0-Si), thereby forming a network structure of silicon oxide; raising the temperature to 600±2°C to form an aluminum-silicon composite oxide film layer on the surface of the support plate body, wherein the aluminum-silicon composite oxide is an aluminum-silicon oxide in which aluminum oxide is coated with silicon oxide. Aluminum oxide is formed on the surface of silicon oxide, and finally an aluminum-silicon composite oxide film layer is formed. Since silicon oxide itself has a strong tendency to be amorphous, the aluminum-silicon composite oxide obtained for this purpose also tends to be amorphous.

[0049] The organosilicon monomer is methyltrichlorosilane; the mass percentage of the organosilicon monomer in the organosilicon-modified phenolic resin is 18-22wt%.

[0050] Embodiment 1: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 130°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin, wherein the mass percentage of the silicone monomer in the organosilicon-modified phenolic resin is 20wt%; wherein the viscosity of the sprayed phenolic resin is 500mPa·s, the molar concentration of the hydrolyzed silicone monomer is 50%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 1; at a temperature of 95°C, apply aluminum salt on the surface of the obtained organosilicon-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09g / mo l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 95°C to 130°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 380°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 600°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 2min.

[0051] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0052] Embodiment 2: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 135°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin, wherein the mass percentage of the silicone monomer in the organosilicon-modified phenolic resin is 18wt%; wherein the viscosity of the sprayed phenolic resin is 760mPa·s, the molar concentration of the hydrolyzed silicone monomer is 40%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 4 times; at a temperature of 85°C, apply aluminum salt on the surface of the obtained organosilicon-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09g / mo l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 85°C to 132°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 380°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 602°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 2.5min.

[0053] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0054] Embodiment 3: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 130°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin, wherein the mass percentage of the silicone monomer in the organosilicon-modified phenolic resin is 20wt%; wherein the viscosity of the sprayed phenolic resin is 900mPa·s, the molar concentration of the hydrolyzed silicone monomer is 45%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 3 times; at a temperature of 90°C, apply aluminum salt on the surface of the obtained organosilicon-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09g / mo l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 90°C to 130°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 378°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 598°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 3min.

[0055] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0056] Embodiment 4: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 140°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form silicone-modified phenolic resin; wherein the viscosity of the sprayed phenolic resin is 1200 mPa·s, the molar concentration of the hydrolyzed silicone monomer is 50%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 5 times; at a temperature of 95°C, apply aluminum salt on the surface of the obtained silicone-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09 g / mol l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 95°C to 130°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 380°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 600°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 2min.

[0057] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0058] Embodiment 5: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 140°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin; wherein the viscosity of the sprayed phenolic resin is 1600 mPa·s, the molar concentration of the hydrolyzed silicone monomer is 40%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 4 times; at a temperature of 95°C, apply aluminum salt on the surface of the obtained organosilicon-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09 g / mol l; Then, in an inert atmosphere, the intermediate is heat-treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 95°C to 130°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 382°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 600°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 2.5min.

[0059] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0060] Example 6: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 140°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin; wherein the viscosity of the sprayed phenolic resin is 2000mPa·s, the molar concentration of the hydrolyzed silicone monomer is 45%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 5 times; at a temperature of 95°C, apply aluminum salt on the surface of the obtained organosilicon-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09g / mo l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 95°C to 130°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 382°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 602°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 3min.

[0061] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0062] Example 7: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 138°C, and cross-link the hydrolyzed silicone monomer with the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin; wherein the viscosity of the sprayed phenolic resin is 1200 mPa·s, the molar concentration of the hydrolyzed silicone monomer is 50%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 5 times; at a temperature of 95°C, apply aluminum salt on the surface of the obtained organosilicon-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09 g / mol l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 95°C to 130°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 382°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 602°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 3min.

[0063] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0064] Embodiment 8: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 138°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form silicone-modified phenolic resin; wherein the viscosity of the sprayed phenolic resin is 1200 mPa·s, the molar concentration of the hydrolyzed silicone monomer is 50%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 6 times; at a temperature of 95°C, apply aluminum salt on the surface of the obtained silicone-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09 g / mol l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 95°C to 128°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 382°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 602°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 3.5min.

[0065] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0066] Example 9: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 130°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin; wherein the viscosity of the sprayed phenolic resin is 1200 mPa·s, the molar concentration of the hydrolyzed silicone monomer is 50%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 7 times; at a temperature of 95°C, apply aluminum salt on the surface of the obtained organosilicon-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09 g / mol l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is as follows: in an inert atmosphere, the temperature is raised from 95°C to 130°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 380°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 600°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 4min.

[0067] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0068] Embodiment 10: Preparation of a support plate: spray phenolic resin on the surface of the support plate body to form a phenolic resin layer; then spray hydrolyzed silicone monomer on the surface of the phenolic resin layer, heat to 130°C, and the hydrolyzed silicone monomer cross-links with the phenolic resin in a partial area of ​​the phenolic resin layer to form silicone-modified phenolic resin; wherein the viscosity of the sprayed phenolic resin is 1200 mPa·s, the molar concentration of the hydrolyzed silicone monomer is 50%, and the number of times the hydrolyzed silicone monomer is applied to the surface of the phenolic resin layer is 8 times; at a temperature of 95°C, apply aluminum salt on the surface of the obtained silicone-modified phenolic resin layer to obtain an intermediate; the aluminum salt is trimethylaluminum (TMA), and the molar amount of TMA is 72.09 g / mol l; Then, in an inert atmosphere, the intermediate is heat treated to form an aluminum-silicon composite oxide film layer on the surface of the support plate body; wherein the heat treatment process of the intermediate is: in an inert atmosphere, the temperature is raised from 95°C to 130°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; the temperature is raised to 380°C, and the organosilicon-modified phenolic resin is pyrolyzed to form a silicon-oxygen bond (Si-0-Si); the temperature is raised to 600°C to form an aluminum-silicon composite oxide film layer. Post-treatment: heat-treating the formed aluminum-silicon composite oxide film layer at a temperature below 350-380°C to keep the aluminum-silicon composite oxide film layer in an amorphous state; hydrogen is doped into the aluminum-silicon composite oxide film layer after post-treatment by plasma doping; the content of doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15atm%, and the time is 4.5min.

[0069] The ceramic substrate is sintered by using the firing plate obtained by the preparation method described in Example 1; the ceramic substrate is an alumina ceramic substrate. Specifically, the steps include: stacking the alumina ceramic substrate blanks on the firing plate, the blanks closest to the firing plate are in direct contact with the silicon-aluminum composite oxide film layer; and the above-mentioned isolation powder is arranged between two adjacent blanks.

[0070] Comparative Example 1: During the sintering of the ceramic substrate in Comparative Example 1, anti-sticking powder was provided between the surface of the setter plate and the green body.

[0071] Comparative Example 2: Compared with Example 8, the difference of Comparative Example 2 is that there is no plasma doping step.

[0072] Comparative Example 3: Compared with Example 8, the difference of Comparative Example 3 is that the hydrolyzed silicone monomer is not applied on the phenolic resin layer.

[0073] Comparative Example 4: Compared with Example 8, the difference of Comparative Example 4 is that no aluminum source is coated on the organosilicon-modified phenolic resin layer.

[0074] Table 1. Statistical table of the yield of ceramic substrates obtained by sintering using the setter plates provided in Examples 1 to 10 and Comparative Examples 1 to 4.

[0075] Yield / % Example 1 96.55 Example 2 94.34 Example 3 96.48 Example 4 95.68 Example 5 94.47 Example 6 96.65 Example 7 99.53 Example 8 99.82 Example 9 97.73 Example 10 96.15 Comparative Example 1 68.57 Comparative Example 2 85.47 Comparative Example 3 82.65 Comparative Example 4 75.84

[0076] Test example: The firing plates provided in Examples 1 to 10 and Comparative Examples 1 to 4 are applied to the sintering process of the ceramic substrate; the process conditions during the sintering process are the same, and the number of stacked layers of the green blanks is also the same. The yield rate of the ceramic substrate obtained after sintering is statistically analyzed based on the fact that the substrate surface is free of defects, protrusions, scratches and other undesirable phenomena. The yield rate statistics described in the present invention refer to the yield rate statistics of the three layers of ceramic substrates closest to the firing plate. The statistical results are shown in Table 1 below. It can be seen from Table 1 that after the firing plate prepared by the technical solution of the present invention is applied to the sintering process of the ceramic substrate, the yield rate of the production of the ceramic substrate is improved.

[0077] The technical features of the above embodiments may be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0078] The above embodiments only express the preferred implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A laminated sintering method, characterized in that: Used for sintering ceramic substrates; the stacking sintering method comprises the steps of: stacking green blanks in a direction perpendicular to the plane of a setter plate, wherein the green blanks closest to the setter plate are in direct contact with the setter plate, and anti-sticking powder is arranged between adjacent green blanks; the setter plate comprises a setter plate body and an aluminum-silicon composite oxide film layer arranged on the surface of the setter plate body, wherein the aluminum-silicon composite oxide film layer is formed by aluminum-silicon oxide particles in which aluminum oxide covers silicon oxide; the preparation method of the setter plate comprises the steps of: S1, depositing a phenolic resin layer on the surface of the support plate body; then spraying a hydrolyzed organosilicon monomer on the surface of the phenolic resin layer, so that the hydrolyzed organosilicon monomer and the phenolic resin in a partial area of ​​the phenolic resin layer undergo a cross-linking reaction to form an organosilicon-modified phenolic resin; S2, at a temperature of 85-95° C., depositing aluminum salt on the surface of the organosilicon-modified phenolic resin layer obtained in step S1, wherein the aluminum salt reacts with a portion of the unreacted phenolic resin to form an aluminoxane film on the surface of the organosilicon-modified phenolic resin to obtain an intermediate; then, heat-treating the intermediate in an inert atmosphere to form an aluminum-silicon composite oxide film layer on the surface of the setter body; the aluminum-silicon composite oxide film layer deposited on the surface of the setter body has a thickness of 0.8-1.2 mm; S3, post-treatment: heat-treating the aluminum-silicon composite oxide film layer in step S2 at a temperature below 350-380° C., so that the aluminum-silicon composite oxide film layer remains in an amorphous state.

2. The laminated sintering method according to claim 1, characterized in that: The stacked sintering method further comprises step S4: doping hydrogen into the aluminum-silicon composite oxide film layer processed in step S3 by plasma doping; the content of the doped hydrogen in the aluminum-silicon composite oxide film layer is 10-15 atm%.

3. The laminated sintering method according to claim 2, characterized in that: In step S1, the preparation method of the organosilicon-modified phenolic resin specifically includes the steps of: adding an organosilicon monomer to sodium hydroxide for hydrolysis to form a hydrolyzed organosilicon monomer; coating the phenolic resin on the surface of the support plate body; spraying the hydrolyzed organosilicon monomer on the phenolic resin, heating it to 130-140°C, so that the organosilicon monomer reacts with the hydroxyl groups in the phenolic resin in a partial area of ​​the phenolic resin layer to form an organosilicon-modified phenolic resin with a cross-linked structure; wherein the Si ion concentration in the formed hydrolyzed organosilicon monomer is 40wt% to 50wt%.

4. The laminated sintering method according to claim 2, characterized in that: The aluminum salt includes one or more of aluminum ethoxide, aluminum isobutoxide or aluminum butoxide.

5. The laminated sintering method according to claim 1, characterized in that: In step S2, the intermediate is heat-treated, specifically comprising the steps of: raising the temperature from 85-95°C to 130±2°C, so that part of the phenolic resin undergoes a cross-linking reaction to form a stable three-dimensional network structure; raising the temperature to 380±2°C to thermally decompose the organosilicon-modified phenolic resin, so that the silanol (Si-OH) undergoes a dehydration condensation reaction to form a silicon-oxygen bond (Si-0-Si), thereby forming a network structure of silicon oxide; raising the temperature to 600±2°C to form an aluminum-silicon composite oxide film layer on the surface of the supporting plate body, wherein the aluminum-silicon composite oxide is an aluminum-silicon oxide in which aluminum oxide is coated with silicon oxide.

6. The laminated sintering method according to claim 3, characterized in that: The organosilicon monomer comprises alkoxysilane; the mass percentage of the organosilicon monomer in the organosilicon-modified phenolic resin is 18-22 wt %.

7. The laminated sintering method according to claim 1, characterized in that: The anti-sticking powder comprises target ceramic powder, carbon powder, adhesive and water; wherein the mass ratio of the carbon powder to the target powder is 10:3, the particle size of the target ceramic powder is 8-12 microns, and the particle size of the carbon powder is 1.5-5 μm; and the adhesive comprises sodium carboxymethyl cellulose.

8. The laminated sintering method according to claim 7, characterized in that: The preparation method of the anti-sticking powder comprises the following steps: uniformly mixing aluminum oxide powder, a binder and water to obtain a spray solution; spraying the spray solution on the surface of the blank with a high-pressure spray gun to form a first film layer; and spraying the carbon powder on the first film layer so that the carbon powder covers the first film layer.

9. A setter plate, characterized in that: The support plate is used in the laminated sintering method as described in any one of claims 1 to 8; the support plate includes a support plate body and an aluminum-silicon composite oxide film layer arranged on the surface of the support plate body, and the aluminum-silicon composite oxide film layer is formed by aluminum-silicon oxide particles coated with silicon oxide.

10. A method for preparing a setter plate, characterized in that: Used to prepare the setter plate as claimed in claim 9.