CN117105673A - Aluminum nitride complex phase ceramic and preparation method thereof - Google Patents
Aluminum nitride complex phase ceramic and preparation method thereof Download PDFInfo
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- CN117105673A CN117105673A CN202311378997.XA CN202311378997A CN117105673A CN 117105673 A CN117105673 A CN 117105673A CN 202311378997 A CN202311378997 A CN 202311378997A CN 117105673 A CN117105673 A CN 117105673A
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- aluminum nitride
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 127
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical group O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 17
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 13
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- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
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- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
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- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- Ceramic Products (AREA)
Abstract
The invention discloses an aluminum nitride complex phase ceramic and a preparation method thereof. The preparation method comprises the following steps: dissolving polyvinyl butyral in absolute ethyl alcohol and dropwise adding a dispersing agent to obtain a solvent A; uniformly mixing aluminum nitride powder, sintering aid powder and silicon dioxide powder to obtain solute B; adding the solvent A and the solute B into a ball milling medium for ball milling to obtain ceramic slurry C; drying and crushing the ceramic slurry C, and then secondarily grinding to obtain complex-phase powder D; pressing and molding the complex phase powder D to obtain a ceramic blank E; discharging glue from the ceramic blank E under the air atmosphere for degreasing to obtain a ceramic biscuit F; and sintering the ceramic biscuit F in a nitrogen atmosphere to obtain the aluminum nitride complex phase ceramic. The invention can solve the problem that the existing aluminum nitride ceramics cannot have both low dielectric loss and high dielectric constant.
Description
Technical Field
The invention relates to the technical field of aluminum nitride complex phase ceramics. In particular to aluminum nitride complex phase ceramic and a preparation method thereof.
Background
Aluminum nitride (AlN) is used as an important functional material, has the advantages of bandwidth inhibition, low dielectric constant and the like, and has wide application in blue light and ultraviolet light luminescence and preparation of high-temperature and high-frequency high-power device materials; meanwhile, the material has the characteristic of spontaneous polarization, has good ferroelectric property and dielectric property, and is an ideal large-scale integrated circuit substrate and packaging material.
For AlN, its application as a dielectric material to electronic devices remains deficient, oxygen impurities in aluminum nitride deteriorate thermal conductivity, and dissipation factor is extremely large; meanwhile, alN has better room temperature performance, but the range of stable working temperature is narrower, and the application of the packaging material device is limited to a certain extent. AlN has a small dielectric loss and a low dielectric constant, and can be used as an excellent capacitor material if the dielectric constant can be increased. AlN powder is high in price, and Al-N bonds have high covalent bond components and small in self-diffusion coefficient, so that sintering densification is difficult and commercial production of the AlN powder is limited.
The aluminum nitride ceramic is non-toxic, corrosion-resistant, high in heat conductivity, low in thermal expansion coefficient, low in dielectric loss, low in dielectric constant, excellent in thermal shock resistance, mechanical performance and the like. Sialon (Sialon) is a solid solution formed by four elements of Si, al, O and N, sialon ceramics has the characteristics of wear resistance, corrosion resistance, small friction coefficient and the like, and has an operating temperature of more than 1000 ℃, and is widely applied to the fields of microwave electronics, optoelectronics, sensors, biotechnology, aerospace and the like due to its excellent performance. Accordingly, the AlN ceramic material with high heat conduction and SiO with high dielectric constant real part and low dielectric loss characteristic 2 And the medium components are compounded, and the ceramic material with excellent performance is finally obtained by combining the high-temperature characteristics of Sialon ceramic.
The preparation methods of Sialon complex phase ceramics at present mainly comprise a reaction sintering method, a hot-press sintering method and a spark plasma sintering methodAnd hot isostatic pressing sintering, etc., and the methods have the defects of complicated process, high production cost, long preparation period, lower strength, etc., thereby limiting the industrial production and application thereof. Such as reaction sintering, relies mainly on the solid phase (Si 3 N 4 、Al 2 O 3 AlN), liquid phase (Y) 2 O 3 、Al 2 O 3 ) And the gas phase to react with each other to obtain ceramic body. However, the ceramic prepared by the process has higher porosity and poor mechanical property, and the quality of the sintered integral sample is lower due to lack of a forming process; the hot-press sintering method is mainly characterized in that raw material powder is uniformly mixed according to stoichiometric proportion, and sintering is carried out at high temperature and high pressure, and the problems of powder agglomeration, local segregation during sintering and the like often exist due to the strong and difficult control of the solid phase reaction of the raw materials at high temperature and high pressure, and the purity is lower although the density is high; the spark plasma sintering method is a rapid sintering technology in which raw material powder is filled into a graphite mold, sintering activity is improved by a specific power supply, and cooling is completed after electric activation. And the hot isostatic pressing sintering is carried out by a sintering technology under the combined action of high-temperature and high-pressure gas, so that the preparation parameters are more, the process is complex and the cost is too high.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide the aluminum nitride composite ceramic and the preparation method thereof, wherein the method directly synthesizes Sialon phase in situ, effectively reduces sintering temperature, shortens preparation period, can obviously improve the structure and mechanical property of AlN-Sialon composite ceramic, and can solve the problem that the existing aluminum nitride ceramic cannot have both low dielectric loss and high dielectric constant. The method has the characteristics of simple process, low cost, environmental friendliness and mass production.
In order to solve the technical problems, the invention provides the following technical scheme:
an aluminum nitride complex phase ceramic has an AlN phase, a Y-Al-O phase and a Si-Al-O-N phase.
The chemical formula of the aluminum nitride complex phase ceramic Si-Al-O-N phase is Si 1.1 Al 7.9 O 1.9 N 8.1 。
A preparation method of aluminum nitride complex phase ceramic comprises the following steps:
step (1), dissolving polyvinyl butyral in absolute ethyl alcohol under the condition of heating in a water bath, dropwise adding castor oil and/or fish oil as a dispersing agent, and uniformly mixing to obtain a solvent A; the castor oil and the absolute ethyl alcohol have good solubility and good dispersibility, and have good dispersing effect as a dispersing agent; fish oils are more dispersible than castor oil, but various residues are typically present in fish oils;
Uniformly mixing aluminum nitride powder, sintering aid powder and silicon dioxide powder to obtain solute B;
adding the solvent A and the solute B into a ball milling tank, uniformly mixing, and performing ball milling by taking zirconia grinding balls as ball milling media to obtain ceramic slurry C;
step (4), transferring the ceramic slurry C into a vacuum drying oven for drying, crushing the block obtained after the drying is finished, and performing secondary grinding to obtain complex phase powder D;
pouring the complex phase powder D into a pressing die for pressing and forming to obtain a ceramic blank E;
step (6), placing the ceramic blank E in an alumina boat paved with boron nitride powder, and performing glue removal degreasing in an air atmosphere; obtaining a ceramic biscuit F;
and (7) filling aluminum nitride powder on the upper surface, the lower surface and the periphery of the ceramic biscuit F, sintering in a nitrogen atmosphere, and ending sintering to obtain the aluminum nitride composite ceramic.
The invention can regulate and control the substitution of O for N and Al for Si, alN/SiO by changing the proportion of raw materials 2 When the raw material ratio is less than 10, part of AlN and SiO 2 Reaction to generate Al 2 O 3 And Si (Si) 3 N 4 Al ions more easily enter Si sites to form Si 1.1 Al 7.9 O 1.9 N 8.1 Phase, leadLattice distortion is generated, and the structure and the morphology of the lattice distortion are influenced; alN/SiO 2 When the raw material ratio is more than 10, all AlN and SiO 2 Reaction to generate Al 2 O 3 And Si (Si) 3 N 4 . Therefore, the raw material proportion can be changed according to specific application and property requirements so as to prepare the complex phase ceramics with different Sialon phase contents. Under the preparation process condition of the invention, al ions can enter Si position more easily to form Si 1.1 Al 7.9 O 1.9 N 8.1 And (3) phase, ion displacement polarization is generated, and the complex phase ceramic with good crystallinity, uniform crystal grains and high stability is obtained. The invention has the characteristics of low sintering temperature, energy consumption saving, uniform second phase distribution, excellent performance and the like.
In the preparation method of the aluminum nitride complex phase ceramic, in the step (1), the mass ratio of the polyvinyl butyral to the dispersing agent is (3-5) 1; the temperature of water bath heating is 40-50 ℃; the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1 (30-33), and the viscosity of the solvent A can be controlled within 1160-1984 mPa.s under the condition of the ratio. If the viscosity of the solvent A is too high, the glue discharging time needs to be prolonged to remove the organic matters in the later period, and if the organic matters are not removed sufficiently, carbon in the organic matters can serve as a reducing agent in the subsequent sintering process to deteriorate the sintering performance of the ceramic; if the viscosity of the solvent A is too high, the solvent A is easy to agglomerate after ball milling and drying, the local clustering phenomenon is obvious, the overall viscosity of the powder is uneven due to uneven dispersion of organic matters, and layering phenomenon exists during pressing; if the viscosity of the solvent A is too small, the powder after ball milling is difficult to form when being pressed into a block, and the problems of non-forming, broken edges and the like usually occur.
In the step (2), the sintering aid powder is yttrium oxide powder or is formed by mixing yttrium oxide powder and calcium carbonate powder according to the mass ratio of 2-4:1; the median grain diameter of the aluminum nitride powder is 1.2-1.5 mu m, and the specific surface area is 3-4 m 2 /g; the silicon dioxide powder and the sintering aid powder are both nanoscale powder; the mass ratio of the aluminum nitride powder to the silicon dioxide powder is (92-82): 2-18; the mass of the sintering aid powder is the sum of the mass of the aluminum nitride powder and the mass of the silicon dioxide powder(4-4.5) wt.%.
In the preparation method of the aluminum nitride composite ceramic, in the step (3), zirconia grinding balls are formed by mixing grinding balls with the diameter of 2mm and grinding balls with the diameter of 4mm according to the volume ratio of 2:1; or the zirconia grinding ball is formed by mixing a grinding ball with the diameter of 2mm, a grinding ball with the diameter of 3mm and a grinding ball with the diameter of 4mm according to the volume ratio of 1:1:1;
in the ball milling process, the volume ratio of the solvent A, the zirconia grinding ball and the solute B is always kept at 1.2:2:1, and the density of the solute B is 3.0-3.3 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Ball milling rotation speed is 200-400 rpm; the ball milling mode is as follows: and (3) carrying out unidirectional ball milling for 4 hours by adopting a planetary ball mill, or carrying out bidirectional ball milling by adopting a double-pendulum high-speed ball mill, carrying out forward ball milling for 30 minutes and reverse ball milling for 30 minutes, and carrying out alternating in sequence, wherein the total ball milling time is 5 hours. The ball milling conditions can lead the powder to be uniformly mixed and lead the powder to be continuously ground to a certain extent.
In the preparation method of the aluminum nitride composite ceramic, in the step (4), the drying temperature of the ceramic slurry C is 50-60 ℃ and the drying time is 4-5 min [ the ceramic slurry C is dried under the drying condition, but is in a block shape, is easy to take out and grind for the second time, and can be completely dried under the effect of the residual temperature in the process of taking out the block body, thereby effectively avoiding the problem that the ceramic slurry C is seriously agglomerated and is difficult to crush ], and the secondary grinding time is 0.1-0.5 h; grinding, and sieving with a 60-mesh sieve to obtain a screen lower product which is the complex phase powder D;
in the step (5), the conditions of the press molding are as follows: adopting dry pressing to form, wherein the dry pressing pressure is 4-6 MPa, and the pressure maintaining time is 1-2 min; or firstly, carrying out axial pressing at 4-6 MPa, maintaining the pressure for 2min, and then maintaining the pressure for 40min at 200MPa through cold isostatic pressing. The elastic post effect exists in dry pressing, so that the upper and lower density of the green body is uneven, and the phenomenon of edge warping exists after sintering; and cold isostatic pressing is carried out after dry pressing, so that the upper and lower densities of the blank body after dry pressing molding are uniform through high pressure and long-time pressure maintaining, the deformation after sintering is less, and the shrinkage is uniform.
In the preparation method of the aluminum nitride complex phase ceramic, in the step (6), the glue discharging and degreasing conditions are as follows: heating to 550-600 ℃ at a heating rate of 1 ℃/min, preserving heat for 1-2 h, and then cooling to room temperature along with a furnace; or, firstly heating to 250-280 ℃ at a heating rate of 1 ℃/min for 1h to decompose PVB organic matters, then heating to 300-320 ℃ at a heating rate of 1 ℃/min for 1h to volatilize the dispersed castor oil, finally heating to 550-600 ℃ at a heating rate of 1 ℃/min for 2h, and then cooling to room temperature along with a furnace;
In the step (7), the sintering conditions are as follows: raising the temperature to 1200-1300 ℃ at a heating rate of 5-10 ℃/min, raising the temperature to 1700-1750 ℃ at a heating rate of 3-5 ℃/min, and preserving the temperature for 3-4 h at 1700-1750 ℃; after the heat preservation is finished, firstly, cooling to 700-800 ℃ at a cooling rate of 5 ℃/min, and then cooling to room temperature along with a furnace; nitrogen is introduced in the whole sintering process, and the nitrogen flow is 0.5L/min.
In the preparation method of the aluminum nitride complex phase ceramic, in the step (1), the mass ratio of the polyvinyl butyral to the dispersing agent is 3:1; the temperature of water bath heating is 50 ℃ [ under the condition, the volatilization of absolute ethyl alcohol can be avoided, meanwhile, the polyvinyl butyral can be effectively dissolved, and the turbidity phenomenon of the solvent A is avoided ]; the dispersing agent is castor oil; the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1:30;
in the step (2), the sintering aid powder is yttrium oxide powder, the median particle diameter of the aluminum nitride powder is 1.248 mu m, and the specific surface area is 3898m 2 /kg; the silicon dioxide powder and the sintering aid powder are both nanoscale powder; the mass ratio of the aluminum nitride powder, the silicon dioxide powder and the yttrium oxide powder is 92:4:4; the particle size of the aluminum nitride powder influences the sintering temperature, and the density, strength and porosity of the aluminum nitride composite ceramic obtained by sintering. The coarser the aluminum nitride powder particles are, the higher the sintering temperature is needed, and the finer the particles are, the higher the sintering density is; coarse particles provide support during sintering, and generally have a slightly higher sintering strength than fine particles, but are also affected by factors such as density and sintering aids. In addition, if the aluminum nitride powder particles are too large, micro-pores are formed. The finer the aluminum nitride powder, the larger the specific surface area, the larger the sintering driving force of the powder, the faster the diffusion, and the more the diffusion path The smaller the reaction is, the more direct the reaction probability is, and the more favorable the sintering is. However, too small an amount of aluminum nitride powder may result in poor flowability. According to the invention, the median particle diameter of the aluminum nitride powder is controlled to be 1.248 mu m, and the binder polyvinyl butyral with a specific proportion is introduced, so that the powder can be pressed into a blank body with uniform upper and lower parts, and the blank body can obtain ideal density, strength and air pore structure after sintering.
In the step (3), the zirconia grinding ball is formed by mixing a grinding ball with the diameter of 2mm and a grinding ball with the diameter of 4mm according to the volume ratio of 2:1 [ the grinding ball with the diameter of 4mm is beneficial to grinding, and the grinding ball with the diameter of 2mm is beneficial to uniform mixing of powder; the ball milling in the proportion has better grinding effect, and the ceramic slurry C obtained by grinding has better uniformity; in the ball milling process, the volume ratio of the solvent A, the zirconia grinding balls and the solute B is always kept at 1.2:2:1, and the density of the solute B is 3.26g/cm 3 The solvent A and the grinding balls are excessively large in dosage, the formed raw materials are too thin, and the binder is easily present in a large amount in supernatant fluid during drying, so that the powder viscosity is uneven, and the compression molding effect is poor; if the consumption of the solvent A and the grinding balls is too small, the formed raw materials are too thick, the grinding balls are prevented from rotating during ball milling, the grinding and mixing of the powder are not facilitated, and the viscosity of the formed raw material powder is extremely uneven; adopting a planetary ball mill to perform unidirectional ball milling for 4 hours, wherein the ball milling rotating speed is 200rpm;
In the step (4), the drying temperature of the ceramic slurry C is 50 ℃ [ a plurality of drying temperatures are too high, the drying speed is too high, and the slurry is rapidly agglomerated due to the small absolute ethyl alcohol content in the solvent, so that the grinding balls are difficult to take out and peel. When the temperature is too low, the drying speed is low, caking is easy to occur in the area close to the wall of the ball milling tank, the central area is not dried yet, the drying time is 5min, and the secondary grinding time is 0.5h; grinding, and sieving with a 60-mesh sieve to obtain a screen lower product which is the complex phase powder D;
in the step (5), the dry pressure intensity is 4MPa, and the pressure maintaining time is 2min; when the dry pressure is too high, the obtained ceramic blank E has larger internal stress and shearing stress, when in sintering, the stress is released too quickly, so that the ceramic blank E is easy to bulge, delaminate, crack at corners and the like, when the powder is pressed and formed, air is difficult to be discharged in time, and closed pores are formed when in sintering; however, if the pressure intensity of a plurality of presses is too small, the blank body is poor in molding quality, the overall strength is low, the particles are not tightly contacted, and the sintering densification is low;
in the step (6), the glue discharging and degreasing conditions are as follows: heating to 600 ℃ at a heating rate of 1 ℃/min, preserving heat for 120min, and then cooling to room temperature along with a furnace; the temperature is raised at the heating rate of 1 ℃/min, so that organic matters can be slowly and uniformly removed from the blank; if the temperature rising speed is too high, the organic matters can not be completely discharged, or the holes can be formed too quickly. If the heat preservation temperature is lower than 600 ℃, the glue discharge is insufficient, and organic matters are decomposed at high temperature in the sintering process to deteriorate the ceramic performance, but if the heat preservation temperature is higher than 600 ℃, the glue discharge effect is poor on one hand, and on the other hand, the oxidation is easy to occur due to the overhigh temperature.
In the step (7), the sintering conditions are as follows: raising the temperature to 1200 ℃ at the heating rate of 10 ℃/min, raising the temperature to 1750 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 4 hours at 1750 ℃ so that the AlN complex phase ceramic basically does not react at 1200 ℃, and only the crystalline water in the blank body is removed and the internal stress is released when the AlN complex phase ceramic is heated, thereby playing a role of presintering; after 1200 ℃, the ceramic body gradually undergoes solid phase reaction, and the heating rate needs to be reduced, so that on one hand, the element diffusion is more thorough, and on the other hand, the grain size is controlled to a certain extent; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at a cooling rate of 5 ℃/min, then the temperature is reduced to room temperature (adopting a circulating water cooling system for cooling), if furnace-following cooling is adopted after the sintering at 1750 ℃, the cooling rate is too high, on one hand, the SiO is enabled to be formed 2 Forming an amorphous phase or glass phase, on the other hand, a blank with too high cooling speed is also easy to crack; meanwhile, the cooling rate is controlled at 5 ℃/min, so that the stabilization of a second phase in the ceramic is facilitated, and the phase transition is more complete; nitrogen is introduced in the whole sintering process, and the nitrogen flow is 0.5L/min.
In the preparation method of the aluminum nitride complex phase ceramic, in the step (1), the mass ratio of the polyvinyl butyral to the dispersing agent is 3:1; the temperature of water bath heating is 45 ℃; the dispersing agent is castor oil; the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1:33;
In the step (2), the sintering aid powder is formed by mixing yttrium oxide powder and calcium carbonate powder according to a mass ratio of 3:1 [ the main purpose of calcium carbonate is to reduce the co-melting temperature of yttrium oxide and form a liquid phase. Calcium carbonate reacts at high temperature to form calcium oxide and carbon dioxide, the calcium oxide is favorable for promoting yttrium oxide and aluminum oxide to form aluminate, promoting sintering densification, and calcium is introduced to form calcium sialon. Excessive amounts of calcium carbonate introduce excessive alkali metals and the dielectric properties are unstable. The calcium carbonate is too little to promote the sintering temperature to rise, the median particle diameter of the aluminum nitride powder is 1.31 mu m, and the specific surface area is 3771 m 2 /kg; the silicon dioxide powder and the sintering aid powder are both nanoscale powder; the mass ratio of the aluminum nitride powder, the silicon dioxide powder and the sintering aid powder is 82:18:4;
in the step (3), the zirconia grinding ball is formed by mixing a grinding ball with the diameter of 2mm, a grinding ball with the diameter of 3mm and a grinding ball with the diameter of 4mm according to the volume ratio of 1:1:1; in the ball milling process, the volume ratio of the solvent A, the zirconia grinding balls and the solute B is always kept at 1.2:2:1, and the density of the solute B is 3.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The ball milling rotating speed is 400rpm, a double-pendulum high-speed ball mill is adopted for bidirectional ball milling, the ball milling is carried out for 30min in the forward direction and 30min in the reverse direction, the ball milling is carried out alternately in sequence, and the total ball milling time is 5h;
In the step (4), the drying temperature of the ceramic slurry C is 50 ℃, the drying time is 5min, and the secondary grinding time is 0.5h; grinding, and sieving with a 60-mesh sieve to obtain a screen lower product which is the complex phase powder D;
in the step (5), the conditions of the press molding are as follows: firstly, carrying out axial pressing at 4MPa, maintaining the pressure for 2min, and then maintaining the pressure for 40min at 200MPa through cold isostatic pressing;
in the step (6), the glue discharging and degreasing conditions are as follows: firstly, heating to 250 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, then heating to 320 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, finally heating to 600 ℃ at a heating rate of 1 ℃/min, preserving heat for 2h, and then cooling to room temperature along with a furnace; the step heating degreasing can avoid pores of the sintered ceramic body caused by rapid decomposition of organic matters at high temperature, and the step heating is beneficial to element diffusion, a layer of film is derived on the surface of ceramic particles, the film fills tiny gaps on the surface of the particles, and simultaneously, tiny cracks and defects can be eliminated in the process of decomposition.
In the step (7), the sintering conditions are as follows: raising the temperature to 1200 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 1750 ℃ at a heating rate of 3 ℃/min, and preserving the temperature for 4h at 1750 ℃; after the heat preservation is finished, firstly, cooling to 800 ℃ at a cooling rate of 5 ℃/min, and then cooling to room temperature; nitrogen is introduced in the whole sintering process, and the nitrogen flow is 0.5L/min.
Miniaturization is the main stream direction of microwave radiators, such as microwave communication antennas of mobile phones and base stations, and the size of the radiators needs to be compressed as much as possible in design. The co-typing design simply relying on the antenna is limited by the 1/4 wavelength wave oscillator, and the purpose of reducing the size of the antenna cannot be achieved. The invention takes the binary composite of yttrium oxide and calcium carbonate as the sintering aid, which not only can effectively reduce the sintering temperature of the ceramic, but also can effectively eliminate oxygen impurities in AlN, thus preparing the dielectric ceramic with high dielectric constant real part and low dielectric loss performance; the invention maintains the junction problem of AlN, provides a composite thought of heat conduction and dielectric, and realizes the purposes of heat conduction and wave contraction (shortening the transmission wavelength of electromagnetic waves in a medium). The aluminum nitride complex phase ceramic prepared by the method is a high dielectric constant functional material, and the dielectric ceramic with high dielectric constant real part and low dielectric loss performance can play a unique role in microwave communication antennas of mobile phones and base stations.
The technical scheme of the invention has the following beneficial technical effects:
1. the invention adopts AlN and SiO with different proportions 2 The mixed powder is used as raw material, and Si is generated in situ by using the pressureless liquid phase technology 1.1 Al 7.9 O 1.9 N 8.1 AlN-Sialon complex phase ceramic prepared directly by phase, and Si is commonly adopted in the traditional method 3 N 4 、Al 2 O 3 、AlN、Y 2 O 3 Etc. 4 kinds of powder are mixed, and the invention can be obtained by only changing AlN and SiO 2 Raw material preparationSpecific control of Si 3 N 4 And Al 2 O 3 The preparation method has the advantages of simple operation, short production period, environmental protection, no pollution, high densification of products and the like.
2. The invention uses only AlN powder and SiO for the first time 2 In situ synthesis of Si from powder by solid phase reaction 1.1 Al 7.9 O 1.9 N 8.1 The phase is sintered by using the pressureless liquid phase for the first time to prepare the complex phase ceramic containing AlN and Sialon two phases, and compared with the existing preparation method, the sintering temperature is effectively reduced, and the process is simple.
3. According to the invention, the proportion of the raw materials can be changed to regulate and control the substitution of O for N and Al for Si, so that the AlN-Sialon complex phase ceramic is formed. And according to the medium theory of composite materials, alN and SiO with high dielectric constant real part and low dielectric loss characteristic 2 The medium components are compounded to generate Sialon phase in situ and combine the high temperature characteristics, so that different application requirements can be met, and the industrial production and application of the Sialon phase are enhanced.
4. According to the invention, a one-step mixing method is adopted, so that the solute and the solvent can be uniformly mixed, when the viscosity of the solvent A is 1160-1984 mPa.s, the volume ratio of the solvent to the solute is 1.2:1, the formability is good, the drying time is short, the glue discharging process is simple, the ceramic green body can be sintered in one step, compared with the traditional preparation method, the steps such as presintering are not needed, and the preparation period is greatly shortened while the process is simple.
5. The invention uses AlN as a main matrix, and introduces a dielectric component (SiO 2 ) According to the equivalent electromagnetic medium theory, the composition and interface structure of the complex phase ceramic are designed to generate a second phase of Si-Al-O-N, so that the problem of deterioration of oxygen impurities on AlN ceramic performance can be effectively eliminated, the path of phonon propagation is shortened, and the process of replacing Al with Si is beneficial to ion displacement polarization, thereby greatly regulating and controlling the dielectric property of the material and enabling the material to be a novel energy storage material. Therefore, the invention further expands the application field of the AlN material, and utilizes the high heat conduction and low dielectric property of the AlN materialThe performance, introduce the complex phase composition, the high-efficient preparation "double-effect" pottery, and while preparing the complex phase pottery, reduced the cost of the raw materials powder, offer value for actual production and processing.
Drawings
FIG. 1 XRD diffraction patterns of standard diffraction patterns of aluminum nitride complex phase ceramics prepared in examples 1-3 of the present invention;
FIG. 2 is an XRD diffraction pattern refinement of the standard diffraction pattern of the aluminum nitride complex phase ceramic prepared in example 1 of the present invention;
FIG. 3 is a graph showing the volume density and apparent porosity of the aluminum nitride composite ceramic prepared in examples 1-3 of the present invention;
FIG. 4 is a graph showing the microhardness statistics of the aluminum nitride complex phase ceramics prepared in examples 1-3 of the present invention;
FIG. 5 is a statistical chart of flexural strength and impact toughness of aluminum nitride composite phase ceramics prepared in examples 1-3 of the present invention;
FIG. 6 is a scanning electron microscope image of the aluminum nitride complex phase ceramic prepared in example 2 of the present invention;
FIG. 7 is a photograph of the aluminum nitride complex phase ceramic prepared in example 2 of the present invention;
FIG. 8 is a scanning electron microscope image of the aluminum nitride complex phase ceramic prepared in example 4 of the present invention;
FIG. 9 XRD diffraction patterns of standard diffraction patterns of aluminum nitride composite ceramics prepared in examples 4-6 and other examples of the invention;
FIG. 10 is a graph showing the volume density and apparent porosity of aluminum nitride composite ceramic prepared in examples 4-6 and other examples of the present invention;
FIG. 11 is a graph showing the dielectric constant statistics of aluminum nitride complex phase ceramics prepared in examples 4-6 and other examples according to the present invention;
FIG. 12 is a graph showing the average dielectric constant of aluminum nitride complex phase ceramics prepared in examples 4-6 and other examples according to the present invention;
FIG. 13 is a graph showing the dielectric loss statistics of aluminum nitride complex phase ceramics prepared in examples 4-6 and other examples according to the present invention;
FIG. 14 is a graph showing the minimum dielectric loss statistics of aluminum nitride complex phase ceramics prepared in examples 4-6 and other examples according to the present invention;
FIG. 15 is a photograph of the aluminum nitride complex phase ceramic prepared in example 4 of the present invention;
FIG. 16 is a graph showing the microhardness statistics of the aluminum nitride complex phase ceramics prepared in examples 4 to 6 of the present invention;
FIG. 17 is a graph showing the flexural strength and impact toughness statistics of the aluminum nitride composite ceramics prepared in examples 4-6 of the present invention.
Detailed Description
Example 1
The preparation method of the aluminum nitride composite ceramic comprises the following steps:
step (1), dissolving polyvinyl butyral in absolute ethyl alcohol under the water bath heating condition of 50 ℃, dropwise adding castor oil as a dispersing agent, and uniformly mixing to obtain a solvent A; the mass ratio of the polyvinyl butyral to the dispersant is 3:1, and the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1:30; the viscosity of the finally obtained solvent A was 1160 mPa.s;
uniformly mixing aluminum nitride powder, yttrium oxide powder and silicon dioxide powder according to the mass ratio of 90:4:6 to obtain solute B; white powder having a median particle diameter D50 of 1.248 μm and a specific surface area of 3898m 2 /kg; the silicon dioxide powder and the yttrium oxide powder are both nanoscale white powder;
adding a solvent A and a solute B into a ball milling tank (the ball milling tank is made of nylon (PA)) for uniform mixing, preparing a mixed slurry which is not layered and not agglomerated, and then performing ball milling in a planetary ball mill by taking zirconia grinding balls as ball milling media to obtain ceramic slurry C; the zirconia grinding ball is formed by mixing a grinding ball with the diameter of 2mm and a grinding ball with the diameter of 4mm according to the volume ratio of 2:1; in the ball milling process, the volume ratio of the solvent A, the zirconia grinding balls and the solute B is always kept at 1.2:2:1, and the density of the solute B is 3.26g/cm 3 [ can guarantee the powder of solute B to be sufficiently wetted ]; adopting a planetary ball mill to perform unidirectional ball milling for 4 hours, wherein the ball milling rotating speed is 200rpm;
transferring the ceramic slurry C into a vacuum drying oven, drying for 5min at 50 ℃, crushing the block obtained after the drying is finished, performing secondary grinding for 0.5h in an agate mortar, and sieving the ground block with a 60-mesh sieve to obtain a complex phase powder D;
step (5), pouring the complex phase powder D into a stainless steel pressing die [ stainless steel die size ]φIn 12.7 mm, the height of the die wall is controlled to be flush with the powder filling surface, the powder filling surface is scraped off, compression molding is carried out, the axial pressure intensity is 4MPa during dry compression, and the pressure maintaining time is 2min; obtaining a qualified ceramic blank E without steps and cracks on the surface;
step (6), placing the ceramic blank E in an alumina boat paved with boron nitride powder, and performing glue removal degreasing in an air atmosphere; obtaining a ceramic biscuit F; the glue discharging degreasing conditions are as follows: in the air atmosphere, the temperature is raised to 600 ℃ at a heating rate of 1 ℃/min, and the temperature is kept for 120min, so that polyvinyl butyral (PVB) and castor oil are fully decomposed and volatilized, and then the polyvinyl butyral and the castor oil are cooled to room temperature along with a furnace;
and (7) filling aluminum nitride powder on the upper surface, the lower surface and the periphery of the ceramic biscuit F [ to prevent pollution of carbon atmosphere in the sintering process ], and sintering under nitrogen atmosphere, wherein the sintering conditions are as follows: raising the temperature to 1200 ℃ at a heating rate of 10 ℃/min, then raising the temperature to 1750 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 4h at 1750 ℃; after the heat preservation is finished, firstly, cooling to 800 ℃ at a cooling rate of 5 ℃/min, and then, cooling to room temperature in the auxiliary cooling of a cold water circulation system; introducing nitrogen in the whole sintering process, wherein the nitrogen flow is 0.5L/min; and (5) after the sintering is finished, obtaining white and turquoise distributed aluminum nitride complex phase ceramic.
The method for testing microhardness, bending strength and impact toughness in the embodiment of the invention is the same, and will not be described in detail later. Microhardness test: the samples were pretreated before measurement, the ceramic samples were cut into 6×6×8 mm rectangular parallelepiped samples by a machining method, the surfaces thereof were subjected to grinding and polishing treatment, and at the time of the test, the samples were subjected to pressure maintaining for 15.5 kgf load for 15 s, and the vickers hardness of each sample was measured 10 times and then averaged.
Flexural Strength test: the measurement is carried out by using a microcomputer control electronic universal tester WDW-30, and the three-point bending method is used for the measurement; processing the sample into a rod-shaped sample to be measured of 3 mm multiplied by 4 mm multiplied by 35 mm, polishing the surface of the sample to be measured, and polishing the lengthChamfering the square sample to be measured by (0.12 mm +/-0.05 mm) x (45+/-5 °; the tester parameters at the time of testing were determined to be span 30 mm, and the cross-sectional area of the test sample was 12 mm 2 The test was performed at a loading rate of 0.5 mm/min under air room temperature conditions.
Impact toughness: the impact toughness sample size was 4X 6X 50mm, the impact energy was 7.5J, the impact velocity was 3.8m/s, the pre-roll angle was 160℃and the sample span was 40mm.
According to detection, alN doped SiO prepared in the embodiment 2 The AlN-Sialon complex phase ceramic of (2) has an AlN phase, a Y-Al-O phase and Si 1.1 Al 7.9 O 1.9 N 8.1 Phase three phase composition, and XRD test data are consistent with calculation data; the volume density of Sialon complex phase ceramic is 3.23529 g/cm 3 Near the theoretical density of AlN 3.26 g/cm 3 The apparent pores are 2.85714 percent, the microhardness is 1088.4 HK, the bending strength is 379 MPa, and the impact toughness is 45.16702J/cm 2 。
Example 2
This embodiment differs from embodiment 1 only in that: the aluminum nitride powder, the yttrium oxide powder and the silicon dioxide powder are uniformly mixed according to the mass ratio of 92:4:4. The process parameters in the other preparation steps were the same as in example 1, and the raw materials used were the same as in example 1.
According to detection, alN doped SiO prepared in the embodiment 2 The AlN-Sialon complex phase ceramic has an AlN phase, a Y-Al-O phase and a small amount of Si 1.1 Al 7.9 O 1.9 N 8.1 Phase three-phase composition; the volume density of Sialon complex phase ceramic is 3.41176 g/cm 3 The apparent pores are 2.94118 percent, the microhardness is 1132.8 HK, the bending strength is 355 MPa, and the impact toughness is 67.23591J/cm 2 。
Example 3
This embodiment differs from embodiment 1 only in that: the aluminum nitride powder, the yttrium oxide powder and the silicon dioxide powder are uniformly mixed according to the mass ratio of 94:4:2. The process parameters in the other preparation steps were the same as in example 1, and the raw materials used were the same as in example 1.
AlN doped prepared in this example was detectedHetero SiO 2 The AlN-Sialon complex phase ceramic has an AlN phase, a Y-Al-O phase and a small amount of Si 1.1 Al 7.9 O 1.9 N 8.1 Phase three-phase composition; the volume density of Sialon complex phase ceramic is 3.52941 g/cm 3 The apparent pores are 2.85714 percent, the microhardness is 1117.5 HK, the bending strength is 330 MPa, and the impact toughness is 48.62772J/cm 2 。
Example 4
The preparation method of the aluminum nitride composite ceramic comprises the following steps:
step (1), dissolving polyvinyl butyral in absolute ethyl alcohol under the water bath heating condition of 45 ℃, dropwise adding castor oil as a dispersing agent, and uniformly mixing to obtain a solvent A; the mass ratio of the polyvinyl butyral to the dispersant is 3:1, and the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1:33; the viscosity of the finally obtained solvent A was 1984 mPas;
uniformly mixing aluminum nitride powder, sintering aid powder and silicon dioxide powder according to the mass ratio of 92:4:8 to obtain solute B; the sintering aid powder is formed by mixing yttrium oxide powder and calcium carbonate powder according to the mass ratio of 3:1; white powder having a median particle diameter D50 of 1.310 μm and a specific surface area of 3771m 2 /kg; the silicon dioxide powder and the sintering aid powder are both nanoscale white powder;
Adding a solvent A and a solute B into a ball milling tank (the ball milling tank is made of nylon (PA)) for uniform mixing, preparing a mixed slurry which is not layered and not agglomerated, and then performing ball milling in a planetary ball mill by taking zirconia grinding balls as ball milling media to obtain ceramic slurry C; the zirconia grinding ball is formed by mixing a grinding ball with the diameter of 2mm, a grinding ball with the diameter of 3mm and a grinding ball with the diameter of 4mm according to the volume ratio of 1:1:1; in the ball milling process, the volume ratio of the solvent A, the zirconia grinding balls and the solute B is always kept at 1.2:2:1, and the density of the solute B is 3.0g/cm 3 [ can guarantee the powder of solute B to be sufficiently wetted ]; the ball milling rotating speed is 400rpm, a double-pendulum high-speed ball mill is adopted for bidirectional ball milling, the ball milling is carried out for 30min in the forward direction and 30min in the reverse direction, the ball milling is carried out alternately in sequence, and the total ball milling time is 5h;
transferring the ceramic slurry C into a vacuum drying oven, drying for 5min at 50 ℃, crushing the block obtained after the drying is finished, performing secondary grinding for 0.5h in an agate mortar, and sieving the ground block with a 60-mesh sieve to obtain a complex phase powder D;
step (5), pouring the complex phase powder D into a stainless steel pressing die [ stainless steel die size ] φIn 12.7 mm ], the die wall height is controlled to be flush with the powder filling surface, the powder filling surface is scraped off, compression molding is carried out, the axial pressure is 4MPa during dry pressing, the dwell time is 2min, and then the pressure is maintained for 40min by cold isostatic pressing at 200 MPa; obtaining a qualified ceramic blank E without steps and cracks on the surface;
step (6), placing the ceramic blank E in an alumina boat paved with boron nitride powder, and performing glue removal degreasing in an air atmosphere; obtaining a ceramic biscuit F; the glue discharging degreasing conditions are as follows: under the air atmosphere, firstly heating to 250 ℃ at a heating rate of 1 ℃/min for heat preservation for 1h, then heating to 320 ℃ at a heating rate of 1 ℃/min for heat preservation for 1h, finally heating to 600 ℃ at a heating rate of 1 ℃/min for heat preservation for 2h, and then cooling to room temperature along with a furnace;
filling aluminum nitride powder (BN ceramic sheets are placed on a graphite boat, a proper amount of BN powder is filled in gaps between the graphite boat and the BN ceramic sheets, ceramic briquettes E are placed on the graphite boat, another BN ceramic sheet is placed on the graphite boat, and finally all gaps are filled with the BN powder) on the upper surface and the lower surface of the ceramic biscuit F so as to prevent pollution of carbon atmosphere in the sintering process; placing a graphite boat in a carbon tube furnace for sintering under the nitrogen atmosphere, wherein the sintering conditions are as follows: raising the temperature to 1200 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 1750 ℃ at a heating rate of 3 ℃/min, and preserving the temperature for 4h at 1750 ℃; after the heat preservation is finished, firstly, cooling to 800 ℃ at a cooling rate of 5 ℃/min, and then, cooling to room temperature in the auxiliary cooling of a cold water circulation system; introducing nitrogen in the whole sintering process, wherein the nitrogen flow is 0.5L/min; and (5) after the sintering is finished, obtaining white and turquoise distributed aluminum nitride complex phase ceramic.
In the embodiment of the invention, when the dielectric constant and dielectric loss are tested, aglient4396B and Aglient16453A are selected and combined in the frequency range of 1MHz-1GHz, and a parallel flat plate method is utilizedAnd (5) measuring. The sample size is the diameterφ>10mm, thickness h<3mm。
Through detection, the high-dielectric constant low-loss aluminum nitride-based complex phase ceramic prepared by the embodiment is composed of three phases of an AlN phase, a Y-Al-O phase and a Sialon phase, and XRD test data are identical with standard PDF card data; the volume density of the complex phase ceramic is 3.22747 g/cm 3 The pore-forming layer has a pore size of 5.8% and relative dielectric constants of 13.494, 13.015, 12.428, 11.411 and 9.777 at 0-200, 200-400, 400-600, 600-800 and 800-1000 MHz, respectively; dielectric loss minima are 0.000271, 0.01232, 0.03489, 0.05416 and 0.07934 at 0-200, 200-400, 400-600, 600-800 and 800-1000 MHz, respectively. The microhardness reaches 1058.5HK, the bending strength is 261MPa, and the impact toughness is 64.17228J/cm 2 。
Example 5
This embodiment differs from embodiment 4 only in that: uniformly mixing aluminum nitride powder, sintering aid powder and silicon dioxide powder according to the mass ratio of 86:4:14 to obtain solute B; the process parameters in the other preparation steps were the same as in example 4, and the raw materials used were the same as in example 4.
Through inspection, the high-dielectric constant low-loss aluminum nitride-based composite ceramic prepared by the embodiment is composed of three phases of AlN phase, Y-Al-O phase and Sialon phase, and XRD test data are identical with standard PDF card data; the volume density of the complex phase ceramic is 3.02372 g/cm 3 The pore-forming layer has a pore size of 5.6% and relative dielectric constants of 17.719, 14.681, 13.764, 12.567 and 10.774 at 0-200, 200-400, 400-600, 600-800 and 800-1000 MHz, respectively; dielectric loss minima are 0.15379, 0.07295, 0.03095, 0.00132 and 0.01286 at 0-200, 200-400, 400-600, 600-800 and 800-1000 MHz, respectively. Microhardness up to 889.0HK, bending strength up to 158MPa and impact toughness up to 59.68838J/cm 2 。
Example 6
This embodiment differs from embodiment 4 only in that: uniformly mixing aluminum nitride powder, sintering aid powder and silicon dioxide powder according to the mass ratio of 82:4:18 to obtain solute B; the process parameters in the other preparation steps were the same as in example 4, and the raw materials used were the same as in example 4.
Through inspection, the high-dielectric constant low-loss aluminum nitride-based composite ceramic prepared by the embodiment is composed of three phases of AlN phase, Y-Al-O phase and Sialon phase, and XRD test data are identical with standard PDF card data; the volume density of the complex phase ceramic is 3.05118 g/cm 3 The pore-forming is 1.6%, and the relative dielectric constants are 19.453, 14.939, 13.781, 12.451 and 10.575 respectively at 0-200, 200-400, 400-600, 600-800 and 800-1000 MHz; dielectric loss minima are 0.27443, 0.15955, 0.09525, 0.04079 and 0.000447 at 0-200, 200-400, 400-600, 600-800 and 800-1000 MHz, respectively. Microhardness up to 645.8HK, bending strength up to 149MPa and impact toughness up to 58.63665J/cm 2 。
In other embodiments, the preparation process of example 4 is used to prepare aluminum nitride composite ceramic by changing the mass ratio of aluminum nitride powder, sintering aid powder and silicon dioxide powder to be 90:4:10, 88:4:12 and 84:4:16 respectively.
The aluminum nitride composite phase ceramic prepared by the process of examples 4 to 6, after replacing the sintering aid with yttrium oxide and calcium carbonate in a mass ratio of 3:1, had a reduced mechanical properties, but had a relatively increased dielectric constant and a relatively reduced dielectric loss, as compared with examples 1 to 3, because of the SiO 2 An increase in the mass ratio to AlN, alN and SiO 2 The reaction is aggravated, the content of the generated Sialon phase is increased, and the Sialon phase is in a lath shape or a strip shape, so that the continuity of a matrix can be influenced under the condition of staggered distribution, and the mechanical property of the Sialon phase can be reduced; in addition, when SiO 2 When the mass ratio of AlN is increased, the generated strip Sialon phase interface has poor bonding property with an AlN matrix interface, and the strip Sialon phase interface is often used as a crack source when bearing load so as to influence the mechanical property. And due to SiO 2 Is a good point medium, has good dielectric strength, can bear higher voltage, and is SiO 2 There is some movable ion charges, which can effectively induce negative charges and accelerate the polarization of ions during the test, thus, in SiO 2 The dielectric property of the ceramic is improved when the mass ratio of the ceramic to AlN is increased, and the ceramic is sintered with AlNRedundant SiO after reaction 2 The glass phase can be formed in the sintering process and is reserved in the grain boundary, so that the effect of properly filling the air holes can be achieved, and the improvement of the density is facilitated.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While the obvious variations or modifications which are extended therefrom remain within the scope of the claims of this patent application.
Claims (10)
1. An aluminum nitride composite phase ceramic, characterized by having an AlN phase, a Y-Al-O phase and a Si-Al-O-N phase.
2. The aluminum nitride complex phase ceramic according to claim 1, wherein the Si-Al-O-N phase has the chemical formula Si 1.1 Al 7.9 O 1.9 N 8.1 。
3. The preparation method of the aluminum nitride complex phase ceramic is characterized by comprising the following steps:
step (1), dissolving polyvinyl butyral in absolute ethyl alcohol under the condition of heating in a water bath, dropwise adding castor oil and/or fish oil as a dispersing agent, and uniformly mixing to obtain a solvent A;
uniformly mixing aluminum nitride powder, sintering aid powder and silicon dioxide powder to obtain solute B;
adding the solvent A and the solute B into a ball milling tank, uniformly mixing, and performing ball milling by taking zirconia grinding balls as ball milling media to obtain ceramic slurry C;
step (4), transferring the ceramic slurry C into a vacuum drying oven for drying, crushing the block obtained after the drying is finished, and performing secondary grinding to obtain complex phase powder D;
pouring the complex phase powder D into a pressing die for pressing and forming to obtain a ceramic blank E;
step (6), placing the ceramic blank E in an alumina boat paved with boron nitride powder, and performing glue removal degreasing in an air atmosphere; obtaining a ceramic biscuit F;
And (7) filling aluminum nitride powder on the upper surface, the lower surface and the periphery of the ceramic biscuit F, sintering in a nitrogen atmosphere, and ending the sintering to obtain the aluminum nitride composite ceramic according to claim 1.
4. The method for producing an aluminum nitride composite ceramic according to claim 3, wherein in the step (1), the mass ratio of the polyvinyl butyral to the dispersant is (3 to 5): 1; the temperature of water bath heating is 40-50 ℃; the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1 (30-33).
5. The method for producing aluminum nitride composite ceramic according to claim 3, wherein in the step (2), the sintering aid powder is yttria powder or the sintering aid powder is formed by mixing yttria powder and calcium carbonate powder in a mass ratio of 2 to 4:1; the median grain diameter of the aluminum nitride powder is 1.2-1.5 mu m, and the specific surface area is 3-4 m 2 /g; the silicon dioxide powder and the sintering aid powder are both nanoscale powder; the mass ratio of the aluminum nitride powder to the silicon dioxide powder is (92-82): 2-18; the mass of the sintering aid powder is (4 to 4.5) wt.% of the sum of the mass of the aluminum nitride powder and the mass of the silicon dioxide powder.
6. The method for producing aluminum nitride composite ceramic according to claim 3, wherein in the step (3), zirconia grinding balls are mixed by grinding balls with a diameter of 2mm and grinding balls with a diameter of 4mm in a volume ratio of 2:1; or the zirconia grinding ball is formed by mixing a grinding ball with the diameter of 2mm, a grinding ball with the diameter of 3mm and a grinding ball with the diameter of 4mm according to the volume ratio of 1:1:1;
in the ball milling process, the volume ratio of the solvent A, the zirconia grinding ball and the solute B is always kept at 1.2:2:1, and the density of the solute B is 3.0-3.3 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Ball milling rotation speed is 200-400 rpm; the ball milling mode is as follows: and (3) carrying out unidirectional ball milling for 4 hours by adopting a planetary ball mill, or carrying out bidirectional ball milling by adopting a double-pendulum high-speed ball mill, carrying out forward ball milling for 30 minutes and reverse ball milling for 30 minutes, and carrying out alternating in sequence, wherein the total ball milling time is 5 hours.
7. The method for producing aluminum nitride composite ceramic according to claim 3, wherein in the step (4), the drying temperature of the ceramic slurry C is 50 to 60 ℃, the drying time is 4 to 5 minutes, and the secondary grinding time is 0.1 to 0.5 hours; grinding, and sieving with a 60-mesh sieve to obtain a screen lower product which is the complex phase powder D;
in the step (5), the conditions of the press molding are as follows: adopting dry pressing to form, wherein the dry pressing pressure is 4-6 MPa, and the pressure maintaining time is 1-2 min; or firstly, carrying out axial pressing at 4-6 MPa, maintaining the pressure for 2min, and then maintaining the pressure for 40min at 200MPa through cold isostatic pressing.
8. The method for preparing aluminum nitride composite ceramic according to claim 3, wherein in the step (6), the conditions of discharging the gel and degreasing are as follows: heating to 550-600 ℃ at a heating rate of 1 ℃/min, preserving heat for 1-2 h, and then cooling to room temperature along with a furnace; or, firstly heating to 250-280 ℃ at a heating rate of 1 ℃/min for heat preservation for 1h, then heating to 300-320 ℃ at a heating rate of 1 ℃/min for heat preservation for 1h, finally heating to 600 ℃ at a heating rate of 1 ℃/min for heat preservation for 2h, and then cooling to room temperature along with a furnace;
in the step (7), the sintering conditions are as follows: raising the temperature to 1200-1300 ℃ at a heating rate of 5-10 ℃/min, raising the temperature to 1700-1750 ℃ at a heating rate of 3-5 ℃/min, and preserving the temperature for 3-4 h at 1700-1750 ℃; after the heat preservation is finished, firstly, cooling to 700-800 ℃ at a cooling rate of 5 ℃/min, and then cooling to room temperature; nitrogen is introduced in the whole sintering process, and the nitrogen flow is 0.5L/min.
9. The method for producing aluminum nitride composite ceramic according to claim 3, wherein in the step (1), the mass ratio of polyvinyl butyral to dispersant is 3:1; the temperature of water bath heating is 50 ℃; the dispersing agent is castor oil; the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1:30;
In the step (2), the sintering aid powder is yttrium oxide powder, the median particle diameter of the aluminum nitride powder is 1.248 mu m, and the specific surface area is 3898m 2 /kg; the silicon dioxide powder and the sintering aid powder are both nanoscale powder; the mass ratio of the aluminum nitride powder, the silicon dioxide powder and the yttrium oxide powder is 92:4:4;
in the step (3), the zirconia grinding ball is formed by mixing a grinding ball with the diameter of 2mm and a grinding ball with the diameter of 4mm according to the volume ratio of 2:1; in the ball milling process, the volume ratio of the solvent A, the zirconia grinding balls and the solute B is always kept at 1.2:2:1, and the density of the solute B is 3.26g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Adopting a planetary ball mill to perform unidirectional ball milling for 4 hours, wherein the ball milling rotating speed is 200rpm;
in the step (4), the drying temperature of the ceramic slurry C is 50 ℃, the drying time is 5min, and the secondary grinding time is 0.5h; grinding, and sieving with a 60-mesh sieve to obtain a screen lower product which is the complex phase powder D;
in the step (5), the dry pressure intensity is 4MPa, and the pressure maintaining time is 2min;
in the step (6), the glue discharging and degreasing conditions are as follows: heating to 600 ℃ at a heating rate of 1 ℃/min, preserving heat for 120min, and then cooling to room temperature along with a furnace;
in the step (7), the sintering conditions are as follows: raising the temperature to 1200 ℃ at a heating rate of 10 ℃/min, then raising the temperature to 1750 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 4h at 1750 ℃; after the heat preservation is finished, firstly, cooling to 800 ℃ at a cooling rate of 5 ℃/min, and then cooling to room temperature; nitrogen is introduced in the whole sintering process, and the nitrogen flow is 0.5L/min.
10. The method for producing aluminum nitride composite ceramic according to claim 3, wherein in the step (1), the mass ratio of polyvinyl butyral to the dispersant is 3:1; the temperature of water bath heating is 45 ℃; the dispersing agent is castor oil; the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1:33;
in the step (2), the sintering aid powder is formed by mixing yttrium oxide powder and calcium carbonate powder according to the mass ratio of 3:1, and nitriding the mixtureThe median particle diameter of the aluminum powder was 1.31. Mu.m, and the specific surface area was 3771 and 3771 m 2 /kg; the silicon dioxide powder and the sintering aid powder are both nanoscale powder; the mass ratio of the aluminum nitride powder, the silicon dioxide powder and the sintering aid powder is 82:18:4;
in the step (3), the zirconia grinding ball is formed by mixing a grinding ball with the diameter of 2mm, a grinding ball with the diameter of 3mm and a grinding ball with the diameter of 4mm according to the volume ratio of 1:1:1; in the ball milling process, the volume ratio of the solvent A, the zirconia grinding balls and the solute B is always kept at 1.2:2:1, and the density of the solute B is 3.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The ball milling rotating speed is 400rpm, a double-pendulum high-speed ball mill is adopted for bidirectional ball milling, the ball milling is carried out for 30min in the forward direction and 30min in the reverse direction, the ball milling is carried out alternately in sequence, and the total ball milling time is 5h;
In the step (4), the drying temperature of the ceramic slurry C is 50 ℃, the drying time is 5min, and the secondary grinding time is 0.5h; grinding, and sieving with a 60-mesh sieve to obtain a screen lower product which is the complex phase powder D;
in the step (5), the conditions of the press molding are as follows: firstly, carrying out axial pressing at 4MPa, maintaining the pressure for 2min, and then maintaining the pressure for 40min at 200MPa through cold isostatic pressing;
in the step (6), the glue discharging and degreasing conditions are as follows: firstly, heating to 250 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, then heating to 320 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, finally heating to 600 ℃ at a heating rate of 1 ℃/min, preserving heat for 2h, and finally cooling to room temperature along with a furnace;
in the step (7), the sintering conditions are as follows: raising the temperature to 1200 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 1750 ℃ at a heating rate of 3 ℃/min, and preserving the temperature for 4h at 1750 ℃; after the heat preservation is finished, firstly, cooling to 800 ℃ at a cooling rate of 5 ℃/min, and then cooling to room temperature; nitrogen is introduced in the whole sintering process, and the nitrogen flow is 0.5L/min.
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