Highly transparent ceramic material and method for its production

Abstract

The application relates to the technical field of piezoelectric light-transmitting functional ceramics, and discloses a high-light-transmitting ceramic material and a preparation method thereof, which comprises the following preparation steps: taking sodium carbonate, potassium carbonate, di-niobium pentoxide, di-antimony trioxide, di-samaria trioxide and zirconium dioxide powder raw materials, carrying out one-time ball milling and drying on the powder raw materials to obtain mixed powder; carrying out pre-sintering and secondary ball milling on the mixed powder, and then carrying out compression molding to form a compression tablet; sintering, polishing and obtaining a ceramic matrix; spraying a composite slurry to the surface of the ceramic matrix, carrying out heat treatment, and cooling to room temperature to obtain the high-light-transmitting ceramic material. The ternary co-doping of di-antimony trioxide, di-samaria trioxide and zirconium dioxide generates antimony-samaria-zirconium liquid phase in the ceramic material, fills and eliminates the pores of the ceramic material, and the prepared ceramic material has excellent optical transmittance, piezoelectric performance and mechanical strength.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of piezoelectric light-transmitting functional ceramics, in particular to a high-transmittance ceramic material and a preparation method thereof. BACKGROUND

[0002] The light-transmitting ceramic material is a general term of ceramic materials capable of transmitting visible light, has piezoelectricity and transparency, and can be used for manufacturing high-voltage electrodes, transparent sensors, transparent electronic devices and the like.

[0003] The light-transmitting piezoelectric ceramic is prepared through a powder sintering technology, and in the sintering process, pores, grain boundaries and micro-cracks are prone to appear in the light-transmitting ceramic material. SUMMARY

[0004] The application provides a high-transmittance ceramic material and a preparation method thereof, and solves the problems of pores, grain boundaries and micro-cracks in the light-transmitting piezoelectric ceramic.

[0005] The technical scheme of the application is as follows:

[0006] A preparation method of a high-transmittance ceramic material, comprising the following preparation steps:

[0007] S1. Sodium carbonate, potassium carbonate, niobium pentoxide, antimony trioxide, samarium trioxide and zirconium dioxide powder raw materials are taken, the powder raw materials are subjected to one-time ball milling and drying to obtain mixed powder;

[0008] S2. The mixed powder is pre-sintered and subjected to secondary ball milling, then is pressed into a tablet, the tablet is sintered and polished to obtain a ceramic matrix;

[0009] S3. The composite slurry is sprayed onto the surface of the ceramic matrix, and after heat treatment, the high-transmittance ceramic material is obtained after cooling to room temperature.

[0010] Further, in step S1, the mass ratio of sodium carbonate, potassium carbonate, niobium pentoxide, antimony trioxide, samarium trioxide and zirconium dioxide is (2.5-2.6):(3.2-3.4):(13.2-13.5):(0.6-0.8):(0.2-0.3):(0.1-0.2).

[0011] Further, in step S1, the drying temperature is 80-100℃, and the drying time is 20-24h.

[0012] Further, in step S1 and step S2, the ball milling is wet ball milling, which is carried out in a nylon tank, the ball milling medium is ethanol, the grinding ball is zirconium ball with a diameter of 8-10mm, the ball milling ball-to-material ratio is (1.4-1.6):1, and the ball milling rotation speed is 220-230r / min.

[0013] Further, in step S1 and step S2, the first ball milling time is 20-24h, and the second ball milling time is 10-12h.

[0014] Further, in step S2, the pre-burning temperature is 800-900℃, the pre-burning time is 4-6h, the pre-burning medium is nitrogen, and the nitrogen flow rate is 5-10L / min.

[0015] Further, in step S2, the pressure for the press forming is 150-250MPa.

[0016] Further, in step S2, the sintering temperature is 1150-1200℃, and the sintering time is 5-7h.

[0017] Further, in step S2, the polishing is carried out by using sandpaper and diamond sand to polish the ceramic substrate to a thickness of 0.5-0.6mm.

[0018] Further, in step S3, the heat treatment temperature is 800-900℃, and the heat treatment time is 25-35min.

[0019] Further, in step S3, the composite slurry is prepared by mixing silica-titania sol and silver paste at a mass ratio of 1:(5-10).

[0020] Further, in step S3, the spraying amount of the composite slurry is 50-60g / m 2 , and the spraying pressure is 0.3-0.5MPa.

[0021] Further, the silica-titania sol is prepared by mixing silica sol and titania sol at a mass ratio of 1:(0.8-1.2).

[0022] Further, the silica-titania sol is prepared by the following steps:

[0023] A1. tetraethyl orthosilicate is added to ethanol and deionized water, stirred at 55-65℃ for 1-2h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 2-3, and then stirred to obtain silica sol;

[0024] A2. Tetra-n-butyl titanate is added into ethanol and deionized water, stirred at 40-50 DEG C for 1-2h, cooled to room temperature, hydrochloric acid is added to adjust pH to 2-3, and after continuous stirring, titanium dioxide sol is obtained;

[0025] A3. The silica sol and the titanium dioxide sol are mixed in a mass ratio of 1:(0.8-1.2), stirred at 55-65 DEG C for 1-3h to form a transparent homogeneous sol, cooled to room temperature, and after continuous stirring, the silica-titanium dioxide sol is obtained.

[0026] Further, in the above reaction process, tetraethyl orthosilicate and tetra-n-butyl titanate are hydrolyzed to form silica sol and titanium dioxide sol respectively, and the silica sol and the titanium dioxide sol are combined by chemical bonds to form the silica-titanium dioxide sol with a cross-linked network structure.

[0027] Further, in step A1, the mass ratio of tetraethyl orthosilicate, ethanol and deionized water is (18-22):(35-45):(8-12).

[0028] Further, in step A2, the mass ratio of tetra-n-butyl titanate, ethanol and deionized water is (13-17):(30-40):(8-12).

[0029] A high-transmittance ceramic material prepared by the above method.

[0030] The present application has the following advantages:

[0031] (1) In the technical scheme of the present application, sodium carbonate, potassium carbonate and niobium pentoxide are used as the base body of the light-transmitting ceramic material, and antimony trioxide, samarium trioxide and zirconium dioxide are used as the solid solution phase, so that the ceramic material has excellent light-transmitting performance, and the antimony trioxide, samarium trioxide and zirconium dioxide effectively control the phase structure of the ceramic, so that the ceramic is in a pseudo-cubic phase structure in which tetragonal phase and cubic phase coexist, thereby significantly improving the optical transmittance, piezoelectric performance and mechanical strength of the ceramic material.

[0032] (2) In the technical scheme of the present application, samarium ions in the samarium trioxide can preferentially replace sodium ions in the A site to form samarium-sodium defects, compensate for oxygen vacancy charges, control the phase structure and optical performance, reduce visible light absorption, and make the ceramic material have a high transmittance; antimony ions in the antimony trioxide can replace niobium to induce the formation of a phase boundary and inhibit the formation of oxygen vacancies to avoid yellowing caused by the formation of oxygen vacancies; zirconium ions in the zirconium dioxide can also replace niobium and have the effect of refining the grains, thereby enhancing the mechanical strength of the ceramic material, and the zirconium dioxide can form a high-melting-point phase to hinder grain boundary migration, improve the compactness of the ceramic material, reduce the occurrence of pores, and improve the light transmittance.

[0033] In addition, the ternary co-doping of antimony trioxide, samarium trioxide and zirconium dioxide generates an antimony-samarium-zirconium liquid phase in the ceramic material, fills and eliminates the pores of the ceramic material, avoids the existence of pores to cause light scattering and reduces the light transmittance; and the antimony trioxide, samarium trioxide and zirconium dioxide are coated on the surface of the sodium carbonate, potassium carbonate and niobium pentoxide base material, inhibits the volatilization of potassium, sodium and niobium in the base material, improves the density of the ceramic material, and makes the prepared ceramic material have excellent optical transmittance, piezoelectric performance and mechanical strength.

[0034] (3) In the technical scheme of the present application, the silica-titania sol and the silver paste are mixed and sprayed on the surface of the ceramic substrate, and heat treatment is performed at 850 DEG C to form a transparent piezoelectric ceramic. The silver paste is sprayed on the surface of the ceramic substrate, which can form a dense conductive layer on the surface of the ceramic substrate, improve the piezoelectric performance, and the silver paste reacts with the ceramic substrate, which can eliminate the residual pores in the ceramic and improve the light transmittance.

[0035] The composite paste is coated on the surface of the ceramic substrate. On the one hand, the silica-titania sol and the silver paste form a gradient refractive index layer composed of a silica-titania sol layer and a silver layer on the surface of the ceramic substrate, which reduces the interface reflection and scattering loss and improves the light transmittance. On the other hand, the composite paste can penetrate into the cracks and pores on the surface of the ceramic substrate. After heat treatment at 850 DEG C, the silica-titania sol reacts with the ceramic substrate to form a silicate / titanate interface layer, which improves the peeling strength of the silver layer and avoids the peeling of the silver layer, which leads to the decrease of the light transmittance and piezoelectric performance of the light-transmitting ceramic.

[0036] The silica and titania penetrating into the ceramic substrate can generate silicate glass phase with the ceramic substrate, fill the grain boundary pores, and further improve the transmittance of the ceramic material and the density and mechanical properties. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0038] The raw materials used in the embodiments of the present application are shown below, and all the reagents used are analytical grade.

[0039] The purity of sodium carbonate, potassium carbonate, niobium pentoxide, antimony trioxide, samarium trioxide and zirconium dioxide is 99.99%.

[0040] The silver paste model is S-200G, purchased from Shenzhen Qian Dai Electronic Material Co., Ltd.

[0041] Example 1

[0042] A method for preparing a high-transmittance ceramic material, comprising the following preparation steps:

[0043] S1. Taking 2.5 g of sodium carbonate, 3.2 g of potassium carbonate, 13.2 g of niobium pentoxide, 0.6 g of antimony trioxide, 0.2 g of samarium trioxide, and 0.1 g of zirconium dioxide powder raw materials, and then performing one-time ball milling on the powder raw materials for 20 h, drying at 80°C for 20 h, and obtaining a mixed powder;

[0044] S2. Placing the mixed powder in a nitrogen atmosphere at 800°C for 4 h of pre-sintering, and then performing secondary ball milling for 10 h, controlling the pressing forming pressure to be 150 MPa, forming a tablet through pressing forming, placing the tablet in a sintering temperature of 1150°C for 5 h of sintering, and polishing to obtain a ceramic substrate;

[0045] S3. Controlling the spraying amount of the composite slurry to be 50 g / m 2 , spraying the composite slurry to the surface of the ceramic substrate, and then performing heat treatment at 800°C for 25 min, and cooling to room temperature to obtain a high-transmittance ceramic material.

[0046] In steps S1 and S2, the ball milling is wet ball milling, the ball milling is performed in a nylon tank, the ball milling medium is ethanol, the grinding balls are zirconium balls with a diameter of 9 mm, the ball milling ball-to-material ratio is 1.4:1, and the ball milling rotation speed is 220 r / min;

[0047] In step S2, the polishing is performed using 1500-mesh sandpaper and 1500-mesh diamond sandpaper until the ceramic substrate has a thickness of 0.55 mm;

[0048] In step S3, the composite slurry is obtained by mixing silica-titania sol and silver paste at a mass ratio of 1:5;

[0049] The silica-titania sol is prepared by the following steps:

[0050] A1. Adding tetraethyl orthosilicate to ethanol and deionized water, stirring at 55°C for 1 h, cooling to room temperature, adding hydrochloric acid to adjust the pH to 2, and continuing to stir for 24 h to obtain silica sol; the mass ratio of tetraethyl orthosilicate, ethanol, and deionized water is 18:35:8;

[0051] A2. Adding tetrabutyl titanate to ethanol and deionized water, stirring at 40°C for 1 h, cooling to room temperature, adding hydrochloric acid to adjust the pH to 2, and continuing to stir for 24 h to obtain titania sol; the mass ratio of tetrabutyl titanate, ethanol, and deionized water is 13:30:8;

[0052] A3. The silica sol and the titanium dioxide sol are mixed in a mass ratio of 1:0.8, stirred at 55℃ for 1h to form a transparent homogeneous sol, cooled to room temperature, and continuously stirred for 24h to obtain a silica-titanium dioxide sol.

[0053] Example 2

[0054] A method for preparing a high-transmittance ceramic material, comprising the following preparation steps:

[0055] S1. 2.55g of sodium carbonate, 3.25g of potassium carbonate, 13.35g of niobium pentoxide, 0.72g of antimony trioxide, 0.25g of samarium trioxide, and 0.15g of zirconium dioxide powder raw materials are taken, the powder raw materials are subjected to one-time ball milling for 22h, dried at 90℃ for 22h, and then mixed powders are obtained;

[0056] S2. The mixed powders are pre-sintered at 850℃ for 5h in a nitrogen atmosphere with a nitrogen flow rate of 8L / min, then subjected to secondary ball milling for 11h, the pressure for press forming is controlled to be 200MPa, the press piece is formed by press forming, and the press piece is sintered at a sintering temperature of 1170℃ for 6h, then polished to obtain a ceramic substrate;

[0057] S3. The spraying amount of the composite slurry is controlled to be 55g / m 2 , the spraying pressure is 0.4MPa, the composite slurry is sprayed onto the surface of the ceramic substrate, and the high-transmittance ceramic material is obtained after heat treatment at 850℃ for 30min and cooling to room temperature.

[0058] In step S1 and step S2, the ball milling is wet ball milling, the ball milling is carried out in a nylon tank, the ball milling medium is ethanol, the grinding balls are zirconium balls with a diameter of 9mm, the ball milling ball-to-material ratio is 1.5:1, and the ball milling rotation speed is 225r / min;

[0059] In step S2, the polishing is carried out using 1500-mesh sandpaper and 1500-mesh diamond sandpaper until the thickness of the ceramic substrate is 0.55mm;

[0060] In step S3, the composite slurry is obtained by mixing silica-titanium dioxide sol and silver paste in a mass ratio of 1:8;

[0061] The silica-titanium dioxide sol is prepared by the following steps:

[0062] A1. Tetraethyl orthosilicate is added to ethanol and deionized water, stirred at 60℃ for 1.5h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 2.5, and continuously stirred for 24h to obtain a silica sol; the mass ratio of tetraethyl orthosilicate, ethanol and deionized water is 20:40:10;

[0063] A2. Tetra-butyl titanate was added into ethanol and deionized water, stirred at 45℃ for 1.5h, cooled to room temperature, hydrochloric acid was added to adjust the pH to 2.5, and continued to stir for 24h to obtain a titanium dioxide sol; the mass ratio of tetra-butyl titanate, ethanol and deionized water was 15:35:10;

[0064] A3. The silica sol and the titanium dioxide sol were mixed in a mass ratio of 1:1, stirred at 60℃ for 2h to form a transparent homogeneous sol, cooled to room temperature, and continued to stir for 24h to obtain a silica-titanium dioxide sol.

[0065] Example 3

[0066] A preparation method of a high-transmittance ceramic material, comprising the following preparation steps:

[0067] S1. 2.6g of sodium carbonate, 3.4g of potassium carbonate, 13.5g of niobium pentoxide, 0.8g of antimony trioxide, 0.3g of samarium trioxide, and 0.2g of zirconium dioxide powder raw materials were taken, the powder raw materials were subjected to one-time ball milling for 24h, dried at 100℃ for 24h, and then mixed powder was obtained;

[0068] S2. The mixed powder was pre-sintered at 900℃ for 6h, the pre-sintering medium was nitrogen, the nitrogen flow rate was 10L / min, then the mixed powder was subjected to secondary ball milling for 12h, the pressing forming pressure was controlled to be 250MPa, the mixed powder was formed into a tablet by pressing forming, the tablet was sintered at a sintering temperature of 1200℃ for 7h, and then polished to obtain a ceramic substrate;

[0069] S3. The spraying amount of the composite slurry was controlled to be 60g / m 2 , the spraying pressure was 0.5MPa, the composite slurry was sprayed onto the surface of the ceramic substrate, and the ceramic substrate was heat-treated at 900℃ for 35min, and then cooled to room temperature to obtain a high-transmittance ceramic material.

[0070] In steps S1 and S2, the ball milling is wet ball milling, the ball milling is carried out in a nylon tank, the ball milling medium is ethanol, the grinding balls are zirconium balls with a diameter of 9mm, the ball milling ball-to-material ratio is 1.6:1, and the ball milling rotation speed is 230r / min;

[0071] In step S2, the polishing is carried out by using 1500-mesh sandpaper and 1500-mesh diamond sandpaper to polish the ceramic substrate to a thickness of 0.55mm;

[0072] In step S3, the composite slurry is obtained by mixing silica-titanium dioxide sol and silver paste in a mass ratio of 1:10;

[0073] The silica-titanium dioxide sol is prepared by the following steps:

[0074] A1. Tetraethyl orthosilicate was added into ethanol and deionized water, stirred at 65℃ for 2h, cooled to room temperature, hydrochloric acid was added to adjust the pH to 3, and stirred for 24h to obtain a silica sol; the mass ratio of tetraethyl orthosilicate, ethanol and deionized water was 22:45:12;

[0075] A2. Tetraethyl orthotitanate was added into ethanol and deionized water, stirred at 50℃ for 2h, cooled to room temperature, hydrochloric acid was added to adjust the pH to 3, and stirred for 24h to obtain a titanium dioxide sol; the mass ratio of tetraethyl orthotitanate, ethanol and deionized water was 17:40:12;

[0076] A3. The silica sol and the titanium dioxide sol were mixed in a mass ratio of 1:1.2, stirred at 65℃ for 3h to form a transparent homogeneous sol, cooled to room temperature, and stirred for 24h to obtain a silica-titanium dioxide sol.

[0077] Comparative Example 1

[0078] A method for preparing a high-transparency ceramic material, comprising the following preparation steps:

[0079] S1. 2.6g of sodium carbonate, 3.4g of potassium carbonate, 13.5g of niobium pentoxide, 1.1g of samarium trioxide, and 0.2g of zirconium dioxide powder raw materials were taken, the powder raw materials were subjected to one-time ball milling for 24h, dried at 100℃ for 24h, and then mixed powders were obtained;

[0080] S2. The mixed powders were pre-sintered at 900℃ for 6h, the pre-sintering medium was nitrogen, the nitrogen flow rate was 10L / min, then the mixed powders were subjected to secondary ball milling for 12h, the pressing forming pressure was controlled to be 250MPa, the mixed powders were formed into a tablet by pressing forming, the tablet was sintered at a sintering temperature of 1200℃ for 7h, and then polished to obtain a ceramic substrate;

[0081] S3. The spraying amount of the composite slurry was controlled to be 60g / m 2 , the spraying pressure was 0.5MPa, the composite slurry was sprayed onto the surface of the ceramic substrate, and the ceramic substrate was heat-treated at 900℃ for 35min, and then cooled to room temperature to obtain a high-transparency ceramic material.

[0082] In steps S1 and S2, the ball milling is wet ball milling, the ball milling is carried out in a nylon tank, the ball milling medium is ethanol, the grinding balls are zirconium balls with a diameter of 9mm, the ball-to-material ratio is 1.6:1, and the ball milling speed is 230r / min;

[0083] In step S2, the polishing is carried out using 1500-mesh sandpaper and 1500-mesh diamond sandpaper until the thickness of the ceramic substrate is 0.55mm;

[0084] In step S3, the composite slurry is obtained by mixing the silica-titanium dioxide sol and the silver paste in a mass ratio of 1:10.

[0085] The silica-titania sol is prepared by the following steps:

[0086] A1. Tetraethyl orthosilicate is added into ethanol and deionized water, stirred at 65℃ for 2h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 3, and stirring is continued for 24h to obtain a silica sol; the mass ratio of tetraethyl orthosilicate, ethanol and deionized water is 22:45:12;

[0087] A2. Tetra-n-butyl titanate is added into ethanol and deionized water, stirred at 50℃ for 2h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 3, and stirring is continued for 24h to obtain a titania sol; the mass ratio of tetra-n-butyl titanate, ethanol and deionized water is 17:40:12;

[0088] A3. The silica sol and the titania sol are mixed according to a mass ratio of 1:1.2, stirred at 65℃ for 3h to form a transparent homogeneous sol, cooled to room temperature, and stirring is continued for 24h to obtain a silica-titania sol.

[0089] Comparative Example 2

[0090] A preparation method of a high-transmittance ceramic material, comprising the following preparation steps:

[0091] S1. 2.6g of sodium carbonate, 3.4g of potassium carbonate, 13.5g of niobium pentoxide, 0.8g of antimony trioxide, and 0.5g of zirconium dioxide powder raw materials are taken, the powder raw materials are subjected to one-time ball milling for 24h, dried at 100℃ for 24h, and then mixed powders are obtained;

[0092] S2. The mixed powders are placed in a nitrogen atmosphere at 900℃ for 6h of pre-sintering, then subjected to secondary ball milling for 12h, the pressing forming pressure is controlled to be 250MPa, the pressing forming is performed to form a pressing tablet, the pressing tablet is placed in a sintering temperature of 1200℃ for 7h of sintering, and then polished to obtain a ceramic substrate;

[0093] S3. The spraying amount of the composite slurry is controlled to be 60g / m 2 , the spraying pressure is 0.5MPa, the composite slurry is sprayed on the surface of the ceramic substrate, and then the ceramic substrate is subjected to heat treatment at 900℃ for 35min, and then cooled to room temperature to obtain a high-transmittance ceramic material.

[0094] In steps S1 and S2, the ball milling is wet ball milling, the ball milling is performed in a nylon tank, the ball milling medium is ethanol, the grinding balls are zirconium balls with a diameter of 9mm, the ball-to-material ratio is 1.6:1, and the ball milling speed is 230r / min;

[0095] In step S2, polishing is performed using 1500 mesh sandpaper and 1500 mesh diamond polishing to a ceramic substrate thickness of 0.55 mm;

[0096] In step S3, the composite slurry is mixed from silica-titania sol and silver paste at a mass ratio of 1:10;

[0097] The silica-titania sol is prepared by the following steps:

[0098] A1. Tetraethyl orthosilicate is added to ethanol and deionized water, stirred at 65°C for 2h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 3, and stirring is continued for 24h to obtain silica sol; the mass ratio of tetraethyl orthosilicate, ethanol and deionized water is 22:45:12;

[0099] A2. Tetrabutyl titanate is added to ethanol and deionized water, stirred at 50°C for 2h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 3, and stirring is continued for 24h to obtain titania sol; the mass ratio of tetrabutyl titanate, ethanol and deionized water is 17:40:12;

[0100] A3. The silica sol and titania sol are mixed at a mass ratio of 1:1.2, stirred at 65°C for 3h to form a transparent homogeneous sol, cooled to room temperature, and stirred for 24h to obtain the silica-titania sol.

[0101] Comparative Example 3

[0102] A method for preparing a high-transparency ceramic material, comprising the following preparation steps:

[0103] S1. Take 2.6g of sodium carbonate, 3.4g of potassium carbonate, 13.5g of niobium pentoxide, 1g of antimony trioxide, and 0.3g of samarium trioxide powder raw materials, and then perform one-step ball milling for 24h, dry at 100°C for 24h, and obtain a mixed powder;

[0104] S2. The mixed powder is pre-fired at 900°C for 6h, the pre-firing medium is nitrogen, the nitrogen flow rate is 10L / min, then the second ball milling is performed for 12h, the pressing forming pressure is controlled to be 250MPa, the pressing forming is performed to form a tablet, the tablet is sintered at a sintering temperature of 1200°C for 7h, and then polished to obtain a ceramic substrate;

[0105] S3. The spraying amount of the composite slurry is controlled to be 60g / m 2 , the spraying pressure is 0.5MPa, the composite slurry is sprayed onto the surface of the ceramic substrate, and then the composite slurry is heat-treated at 900°C for 35min, and then cooled to room temperature to obtain a high-transparency ceramic material.

[0106] In step S1 and step S2, the ball milling is wet ball milling, which is carried out in a nylon tank, the ball milling medium is ethanol, the grinding ball is a zirconium ball with a diameter of 9mm, the ball milling ball-to-material ratio is 1.6:1, and the ball milling rotation speed is 230r / min;

[0107] In step S2, the polishing is carried out by using 1500-mesh sandpaper and 1500-mesh diamond sand until the ceramic substrate has a thickness of 0.55mm;

[0108] In step S3, the composite slurry is prepared by mixing silica-titania sol and silver paste at a mass ratio of 1:10;

[0109] The silica-titania sol is prepared by the following steps:

[0110] A1. Tetraethyl orthosilicate is added to ethanol and deionized water, stirred at 65℃ for 2h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 3, and stirring is continued for 24h to obtain silica sol; the mass ratio of tetraethyl orthosilicate, ethanol and deionized water is 22:45:12;

[0111] A2. Tetrabutyl titanate is added to ethanol and deionized water, stirred at 50℃ for 2h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 3, and stirring is continued for 24h to obtain titania sol; the mass ratio of tetrabutyl titanate, ethanol and deionized water is 17:40:12;

[0112] A3. The silica sol and the titania sol are mixed at a mass ratio of 1:1.2, stirred at 65℃ for 3h to form a transparent homogeneous sol, cooled to room temperature, and stirred for 24h to obtain the silica-titania sol.

[0113] Comparative Example 4

[0114] A preparation method of a high-transparency ceramic material, comprising the following preparation steps:

[0115] S1. 2.6g of sodium carbonate, 3.4g of potassium carbonate, 13.5g of niobium pentoxide, 0.8g of antimony trioxide, 0.3g of samarium trioxide, and 0.2g of zirconium dioxide powder raw materials are taken, the powder raw materials are subjected to one-time ball milling for 24h, dried at 100℃ for 24h, and then mixed powder is obtained;

[0116] S2. The mixed powder is placed at 900℃ for pre-sintering for 6h, the pre-sintering medium is nitrogen, the nitrogen flow rate is 10L / min, then the mixed powder is subjected to secondary ball milling for 12h, the pressing forming pressure is controlled to be 250MPa, the mixed powder is formed into a tablet by pressing forming, the tablet is placed at a sintering temperature of 1200℃ for sintering for 7h, and then the tablet is polished to obtain a ceramic substrate;

[0117] S3. The spraying amount of the composite slurry is controlled to be 60g / m 2, the spraying pressure is 0.5 MPa, the composite slurry is sprayed to the surface of the ceramic matrix, heat treatment is carried out at 900 DEG C for 35 min, and then the ceramic material with high light transmittance is obtained after cooling to room temperature.

[0118] In step S1 and step S2, the ball milling is wet ball milling, the ball milling is carried out in a nylon tank, the ball milling medium is ethanol, the grinding ball is a zirconium ball with a diameter of 9 mm, the ball milling ball-to-material ratio is 1.6:1, and the ball milling rotation speed is 230 r / min.

[0119] In step S2, the polishing is carried out by using 1500-mesh sandpaper and 1500-mesh diamond sand until the ceramic matrix has a thickness of 0.55 mm.

[0120] In step S3, the composite slurry is obtained by mixing silica sol and silver paste at a mass ratio of 1:10.

[0121] The silica sol is prepared by the following steps:

[0122] The tetraethyl orthosilicate is added into ethanol and deionized water, stirring is carried out at 65 DEG C for 2 h, cooling is carried out to room temperature, hydrochloric acid is added to adjust the pH to 3, and then stirring is carried out for 24 h, so that the silica sol is obtained; the mass ratio of the tetraethyl orthosilicate, the ethanol and the deionized water is 22:45:12.

[0123] Comparative example 5

[0124] A preparation method of a ceramic material with high light transmittance comprises the following preparation steps:

[0125] S1. 2.6 g of sodium carbonate, 3.4 g of potassium carbonate, 13.5 g of niobium pentoxide, 0.8 g of antimony trioxide, 0.3 g of samarium trioxide and 0.2 g of zirconium dioxide powder raw materials are taken, the powder raw materials are subjected to one-time ball milling for 24 h, dried at 100 DEG C for 24 h, and then mixed powder is obtained;

[0126] S2. The mixed powder is placed at 900 DEG C for pre-sintering for 6 h, the pre-sintering medium is nitrogen, the nitrogen flow rate is 10 L / min, then the mixed powder is subjected to secondary ball milling for 12 h, the pressing forming pressure is controlled to be 250 MPa, the tablet is formed by pressing forming, the tablet is placed at a sintering temperature of 1200 DEG C for sintering for 7 h, and then polishing is carried out, so that the ceramic matrix is obtained.

[0127] S3. The spraying amount of the composite slurry is controlled to be 60 g / m 2 , the spraying pressure is 0.5 MPa, the composite slurry is sprayed to the surface of the ceramic matrix, heat treatment is carried out at 900 DEG C for 35 min, and then the ceramic material with high light transmittance is obtained after cooling to room temperature.

[0128] In step S1 and step S2, the ball milling is wet ball milling, which is carried out in a nylon tank, the ball milling medium is ethanol, the grinding ball is a zirconium ball with a diameter of 9 mm, the ball milling ball-to-material ratio is 1.6:1, and the ball milling rotation speed is 230 r / min;

[0129] In step S2, the polishing is carried out by using 1500-mesh sandpaper and 1500-mesh diamond sand until the ceramic substrate has a thickness of 0.55 mm.

[0130] In step S3, the composite slurry is prepared by mixing titanium dioxide sol and silver paste at a mass ratio of 1:10.

[0131] The titanium dioxide sol is prepared by the following steps:

[0132] Tetrabutyl titanate is added into ethanol and deionized water, stirred at 50℃ for 2 h, cooled to room temperature, hydrochloric acid is added to adjust the pH to 3, and then stirred for 24 h to obtain the titanium dioxide sol; the mass ratio of tetrabutyl titanate, ethanol and deionized water is 17:40:12.

[0133] Comparative Example 6

[0134] A preparation method of a high-transmittance ceramic material includes the following preparation steps:

[0135] S1. 2.6 g of sodium carbonate, 3.4 g of potassium carbonate, 13.5 g of niobium pentoxide, 0.8 g of antimony trioxide, 0.3 g of samarium trioxide, and 0.2 g of zirconium dioxide powder raw materials are taken, the powder raw materials are once ball-milled for 24 h, dried at 100℃ for 24 h, and then mixed powder is obtained;

[0136] S2. The mixed powder is pre-fired at 900℃ for 6 h, the pre-firing medium is nitrogen, the nitrogen flow rate is 10 L / min, then the mixed powder is secondarily ball-milled for 12 h, the pressing forming pressure is controlled to be 250 MPa, the mixed powder is pressed and formed into a tablet, the tablet is sintered at a sintering temperature of 1200℃ for 7 h, and then polished to obtain a ceramic substrate;

[0137] S3. The silver paste spraying amount is controlled to be 60 g / m 2 , the silver paste is sprayed onto the surface of the ceramic substrate, the silver paste is heat-treated at 900℃ for 35 min, and then cooled to room temperature to obtain a high-transmittance ceramic material.

[0138] In step S1 and step S2, the ball milling is wet ball milling, which is carried out in a nylon tank, the ball milling medium is ethanol, the grinding ball is a zirconium ball with a diameter of 9 mm, the ball milling ball-to-material ratio is 1.6:1, and the ball milling rotation speed is 230 r / min;

[0139] In step S2, the polishing is carried out by using 1500-mesh sandpaper and 1500-mesh diamond sand until the ceramic substrate has a thickness of 0.55 mm.

[0140] The high light transmittance ceramic materials prepared in Examples 1-3 and Comparative Examples 1-6 were subjected to performance testing.

[0141] Vickers hardness test: the Vickers hardness of the high light transmittance ceramic materials prepared above was tested by using a hardness tester and indentation method, and the test conditions were: diamond indenter, force 10 kg, and test pressure time 15 s.

[0142] Bending strength test: the bending strength of the high light transmittance ceramic materials prepared above was determined by three-point bending method on an Instron-5569 type universal testing machine.

[0143] Density test: the density of the high light transmittance ceramic materials prepared above was measured by using Archimedes drainage method, and the experimental instrument was a TG328A type photoelectric analytical balance with an accuracy of one ten-thousandth of a gram.

[0144] Light transmittance test: the light transmittance of the high light transmittance ceramic materials prepared above was tested by using a 77C-1 type intelligent porcelain body light transmittance instrument (purchased from Xiangtan Instrument and Meter Co., Ltd.), and the thickness of the high light transmittance ceramic material was 1 mm, and the test light wave band was 800 nm.

[0145] Piezoelectric property test: the piezoelectric constant (25℃, pC / N) of the high light transmittance ceramic materials prepared above was measured by using a quasi-static d 33 / d 31 test instrument (model ZJ-3A, Institute of Acoustics, Chinese Academy of Sciences).

[0146] The test results are shown in Table 1 below.

[0147] Table 1 Performance testing of high light transmittance ceramic materials prepared in Examples 1-3 and Comparative Examples 1-6

[0148] Item Vickers hardness / MPa Bending strength / MPa Density g / cm 3 ]] Transmittance / % Piezoelectric constant (25°C, pC / N) Example 1 25.6 460.2 4.85 82.3 453 Example 2 26.1 461.7 4.91 83.7 455 Example 3 24.8 459.5 4.78 81.6 450 Comparative Example 1 14.1 342.1 2.23 50.4 373 Comparative Example 2 15.6 341.6 2.35 45.8 381 Comparative Example 3 12.1 330.9 2.15 51.4 383 Comparative Example 4 18.9 400.1 3.11 63.5 412 Comparative Example 5 18.2 402.6 3.15 64.7 418 Comparative Example 6 16.2 385.9 2.95 55.6 405

[0149] As can be seen from the data in Table 1, the high light transmittance ceramic materials prepared in Examples 1-3 have high light transmittance, mechanical properties and piezoelectric properties.

[0150] The high light transmittance ceramic materials prepared by replacing the antimony trioxide with samarium trioxide in Comparative Example 1, replacing the samarium trioxide with zirconium dioxide in Comparative Example 2, and replacing the zirconium dioxide with antimony trioxide in Comparative Example 3 have decreased piezoelectric properties and light transmittance, which proves that the antimony trioxide, samarium trioxide and zirconium dioxide effectively regulate the phase structure of the ceramic, so that the ceramic is in a pseudo-cubic phase structure in which the tetragonal phase and cubic phase coexist, and the optical transmittance, piezoelectric properties and mechanical strength of the ceramic material are significantly improved.

[0151] The composite slurry prepared by replacing the titanium dioxide sol with silica sol in Comparative Example 4 and replacing the silica sol with titanium dioxide sol in Comparative Example 5 is sprayed onto the surface of the ceramic substrate, and the high-transmittance ceramic material prepared therefrom has a decreased piezoelectric property and transmittance, proving that the silica sol and the titanium dioxide sol that penetrate into the ceramic substrate can form a silicate glass phase with the ceramic substrate, fill the grain boundary pores, and thus improve the transmittance of the ceramic material and increase the density and mechanical properties.

[0152] The silver paste is sprayed onto the surface of the ceramic substrate in Comparative Example 6, and the high-transmittance ceramic material prepared therefrom has a decreased piezoelectric property and transmittance, proving that the silica-titanium dioxide sol and the silver paste form a gradient refractive index layer composed of a silica-titanium dioxide sol layer and a silver layer on the surface of the ceramic substrate, reduce the interface reflection and scattering loss, improve the transmittance, and avoid the silver layer from falling off, which leads to a decrease in the transmittance and piezoelectric property of the light-transmitting ceramic.

[0153] In the description of the specification, the description of the terms "one embodiment", "an example", "a specific example", and the like means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials, or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0154] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, as long as they do not deviate from the invention or exceed the scope defined by the present claims, which shall be within the protection scope of the present application.

Claims

1. A method for preparing a high-transmittance ceramic material, characterized in that, The preparation steps include the following: S1. Take sodium carbonate, potassium carbonate, niobium pentoxide, antimony trioxide, samarium trioxide and zirconium dioxide powder raw materials, and ball mill and dry the powder raw materials once to obtain a mixed powder; S2. The mixed powder is pre-fired and ball-milled twice, then pressed into a sheet, which is then sintered and polished to obtain a ceramic matrix. S3. Spray the composite slurry onto the surface of the ceramic substrate, heat treat it, and then cool it to room temperature to obtain a high-transmittance ceramic material; The composite slurry is made by mixing silica-titanium dioxide sol and silver paste in a mass ratio of 1:(5-10); The silica-titanium dioxide sol is prepared by mixing silica sol and titanium dioxide sol in a mass ratio of 1:(0.8-1.2). The silica-titanium dioxide sol is prepared by the following steps: A1. Add tetraethyl orthosilicate to ethanol and deionized water, stir at 55-65℃ for 1-2 hours, cool to room temperature, add hydrochloric acid to adjust the pH to 2-3, and continue stirring to obtain silica sol. A2. Add tetrabutyl titanate to ethanol and deionized water, stir at 40-50℃ for 1-2 hours, cool to room temperature, add hydrochloric acid to adjust the pH to 2-3, and continue stirring to obtain titanium dioxide sol. A3. Mix silica sol and titanium dioxide sol at a mass ratio of 1:(0.8-1.2), stir at 55-65℃ for 1-3 hours to form a transparent homogeneous sol, cool to room temperature, and continue stirring to obtain silica-titanium dioxide sol.

2. The method for preparing a high-transmittance ceramic material according to claim 1, characterized in that, In step S1, the mass ratio of sodium carbonate, potassium carbonate, niobium pentoxide, antimony trioxide, samarium trioxide, and zirconium dioxide is (2.5-2.6):(3.2-3.4):(13.2-13.5):(0.6-0.8):(0.2-0.3):(0.1-0.2).

3. The method for preparing a high-transmittance ceramic material according to claim 1, characterized in that, In step S1, the drying temperature is 80-100℃ and the drying time is 20-24h.

4. The method for preparing a high-transmittance ceramic material according to claim 1, characterized in that, In steps S1 and S2, the ball milling is wet ball milling, which is carried out in a nylon tank. The ball milling medium is ethanol, the grinding balls are zirconium balls with a diameter of 8-10 mm, the ball-to-material ratio is (1.4-1.6):1, and the ball milling speed is 220-230 r / min. The ball milling time for the first ball milling is 20-24 hours; the ball milling time for the second ball milling is 10-12 hours.

5. The method for preparing a high-transmittance ceramic material according to claim 1, characterized in that, In step S2, the pre-firing temperature is 800-900℃, the pre-firing time is 4-6h, the pre-firing medium is nitrogen, and the nitrogen flow rate is 5-10L / min.

6. The method for preparing a high-transmittance ceramic material according to claim 1, characterized in that, In step S2, the pressing pressure is 150-250 MPa; In step S2, the sintering temperature is 1150-1200℃ and the sintering time is 5-7h.

7. The method for preparing a high-transmittance ceramic material according to claim 1, characterized in that, In step S3, the heat treatment temperature is 800-900℃ and the heat treatment time is 25-35min.

8. A high-transmittance ceramic material prepared by the preparation method of the high-transmittance ceramic material according to any one of claims 1-7.