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CN118978390B - Ceramic material for multilayer ceramic substrate and preparation method thereof - Google Patents

Ceramic material for multilayer ceramic substrate and preparation method thereof Download PDF

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CN118978390B
CN118978390B CN202411474199.1A CN202411474199A CN118978390B CN 118978390 B CN118978390 B CN 118978390B CN 202411474199 A CN202411474199 A CN 202411474199A CN 118978390 B CN118978390 B CN 118978390B
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organic carbon
short fiber
ceramic material
aluminum oxide
cerium oxide
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CN118978390A (en
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金华江
高珊
杜刘赓
田建强
陈新桥
史冰冰
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Hebei Dingci Electronic Technology Co ltd
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Hebei Dingci Electronic Technology Co ltd
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Abstract

本发明涉及陶瓷技术领域，更具体地，涉及多层陶瓷基板用陶瓷材料及其制备方法。所述多层陶瓷基板用陶瓷材料，原料包括氧化铝、氧化铈/氧化铝短纤维/有机碳复合物和烧结助剂；所述烧结助剂包括硅酸锂/透辉石凝胶和羟乙基纤维素改性钨酸钇。本发明解决了陶瓷材料中的氧化铝与导体材料的附着力差，无法满足高温钎焊要求问题，同时本发明所提供的陶瓷材料具有较低的介电常数和介电损耗角正切，具有较高的抗弯强度，满足高密度多层射频SiP集成基板和数字SiP集成基板的要求。The present invention relates to the field of ceramic technology, and more specifically, to a ceramic material for a multilayer ceramic substrate and a preparation method thereof. The ceramic material for the multilayer ceramic substrate comprises raw materials including alumina, cerium oxide/alumina short fiber/organic carbon composite and a sintering aid; the sintering aid comprises lithium silicate/diopside gel and yttrium tungstate modified by hydroxyethyl cellulose. The present invention solves the problem that the alumina in the ceramic material has poor adhesion to the conductor material and cannot meet the requirements of high-temperature brazing. At the same time, the ceramic material provided by the present invention has a lower dielectric constant and dielectric loss tangent, and has a higher bending strength, meeting the requirements of a high-density multilayer RF SiP integrated substrate and a digital SiP integrated substrate.

Description

Ceramic material for multilayer ceramic substrate and preparation method thereof
Technical Field
The invention relates to the technical field of ceramics, in particular to a ceramic material for a multilayer ceramic substrate and a preparation method thereof.
Background
With the rapid development of large-scale integrated circuits, consumers have more stringent requirements on miniaturization, integration and reliability of electronic devices. The heat dissipation performance of the electronic component plays an important role in the normal operation of the equipment, and the ceramic substrate has excellent electrical insulation, high heat conductivity, low thermal expansion coefficient and good chemical stability, so that the ceramic substrate is widely applied to the electronic component.
In order to further improve the packaging integration level and miniaturization of electronic components, a high-temperature multilayer cofired ceramic (HTCC) (High Temperature co-FIRED CERAMIC) technology is developed, high-temperature conductor slurry is combined with a casting sheet for application in a printing and filling mode according to the circuit design requirement, and finally, the high-temperature conductor slurry is integrally formed through multilayer lamination.
The ceramic powder mainly comprises aluminum oxide, aluminum nitride, boron nitride and the like, the aluminum nitride has excellent performance, but the price is high, the boron nitride is difficult to process due to high hardness, and the aluminum oxide has high cost performance and has excellent application prospect in HTCC products.
The Chinese patent with publication number of CN109437863A discloses a high-strength HTCC ceramic material and a preparation method thereof, wherein the high-strength HTCC ceramic material comprises, by weight, 60% -90% of micron-sized alumina, 0.1% -30% of submicron-sized alumina, 3% -5% of kaolin, 3% -5% of talcum powder, 1% -3% of chromium oxide, 1% -3% of molybdenum oxide and 0.1% -1% of yttrium oxide. According to the technical scheme, the porosity of the ceramic material is reduced and the compactness and the bending strength of the ceramic material are improved through the introduction of submicron alumina. The Chinese patent with the publication number of CN116332627A discloses a low-thermal expansion coefficient high-temperature cofiring ceramic material, which comprises, by weight, 70% -90% of micron-sized alumina, 1% -20% of submicron-sized alumina, 3% -5% of cordierite, 3% -5% of beta-eucryptite, 1% -3% of chromium trioxide, 1% -3% of molybdenum trioxide and 0.1% -1% of yttrium oxide, and a plurality of casting aids.
However, both of the above solutions do not solve the problem that alumina is not easily well adhered to the conductive material due to its high chemical inertness, which results in difficulty in forming a firm bond of the conductive material (e.g., metal) on the ceramic surface during brazing.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the ceramic material for the multilayer ceramic substrate and the preparation method thereof, solves the problems that the adhesive force between alumina in the ceramic material and a conductor material is poor and the high-temperature brazing requirement cannot be met, and meanwhile, the ceramic material provided by the invention has lower dielectric constant and dielectric loss tangent, has higher bending strength and meets the requirements of a high-density multilayer radio frequency SiP integrated substrate and a digital SiP integrated substrate.
In order to achieve the above purpose, the present invention provides the following technical solutions:
The invention provides a ceramic material for a multilayer ceramic substrate, which comprises, by mass, (92-97% of aluminum oxide, 1-3% of a toughening agent and (2-5) of a sintering aid, wherein the toughening agent is a cerium oxide/aluminum oxide short fiber/organic carbon compound, the sintering aid comprises lithium silicate/diopside gel and hydroxyethylcellulose modified yttrium tungstate, and the mass ratio of the lithium silicate/diopside gel to the hydroxyethylcellulose modified yttrium tungstate is (1-3) and (2-4).
Alumina ceramics have poor toughness and in order to solve this problem, it is necessary to introduce a toughening agent. The alumina short fiber has larger length-diameter ratio, can theoretically improve the toughness of ceramic materials, however, the alumina short fiber forms a strong bonding interface with the ceramic matrix in the toughening matrix, is unfavorable for the debonding and pulling-out actions of the fiber, and can generate partial crystal phase change and secondary crystallization phenomena at a certain temperature in the high-temperature process, thereby influencing the toughening action of the fiber. In order to solve the problem, the inventor finds that when cerium oxide/aluminum oxide short fibers/organic carbon composite is adopted as a toughening agent, cerium oxide in the cerium oxide/aluminum oxide short fibers/organic carbon composite is dispersed in the aluminum oxide short fibers, and a carbon coating layer is formed on the surfaces of the aluminum oxide short fibers dispersed with cerium oxide, so that the fibers and fibers or ceramic groups are prevented from being sintered into a whole in the sintering process, the aluminum oxide short fibers can be interlocked, so that the fibers have bridging effect when local cracks are smaller, bear larger external stress, and meanwhile, granular cerium oxide is easier to separate out and is filled at the aluminum oxide grain boundary under the action of sintering pressure to serve as a crack resistance point to block crack propagation, thereby increasing the toughness of ceramic materials, and meanwhile, the inventor unexpectedly found that the cerium oxide/aluminum oxide short fibers/organic carbon composite also improves the dielectric property of the ceramic materials.
Besides reducing the sintering temperature of the ceramic material, the sintering aid can also be melted at high temperature to form glass-to-metal migration and promote the combination of the ceramic material and the conductor. The most common method for sintering the auxiliary agent mainly adopts a mode of ball milling and mixing with main phase ceramic powder, however, the mode needs to strictly control the particle size of the sintering auxiliary agent, the ball milling time is long, and the mixing effect is not ideal. The inventor finds that when the sintering aid comprises lithium silicate/diopside gel and hydroxyethyl cellulose modified yttrium tungstate in the experimental process, the sintering temperature can be effectively reduced, and meanwhile, the technical scheme solves the problem that the conductor adhesive force of the ceramic material can not meet the high-temperature brazing requirement when the ceramic material is used for a multilayer ceramic substrate. The inventors hypothesize that the cerium oxide/alumina short fiber/organic carbon composite is coated by the gel action and the polar group action of hydroxyethyl cellulose because of the lithium silicate/diopside gel and the hydroxyethyl cellulose modified yttrium tungstate, respectively, and the two are cooperated to change the interface action of the ceramic material, reduce the difference of thermal expansion coefficients between the ceramic material and the metal conductor, the glass phase flows into the metallized layer more easily during high-temperature brazing, and mechanically interlock the metal and the ceramic particles, thereby generating strong interface adhesion, and forming a compact composite metallized layer by filling pores.
Preferably, the mass ratio of the lithium silicate/diopside gel to the hydroxyethyl cellulose modified yttrium tungstate is 2:3.
Preferably, the alumina includes alpha-phase alumina A having a particle size of 0.3 to 0.8 μm, alpha-phase alumina B having a particle size of 30 to 80nm, and gamma-phase alumina C having a particle size of 30 to 80 nm.
Preferably, the mass ratio of the alpha-phase alumina A, the alpha-phase alumina B and the gamma-phase alumina C is (10-30): (65-85): (0.5-1), and preferably 25:70:0.8.
Preferably, the ceria/alumina short fiber/organic carbon composite comprises a ceria/alumina short fiber/organic carbon composite a and a ceria/alumina short fiber/organic carbon composite B;
the preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon composite A comprises the following steps:
S1, adding 0.2-0.5 part by mass of cerium oxide, 3-5 parts by mass of alumina short fibers and 0.4-0.6 part by mass of 30-40wt% organic carbon into 8-10 parts by mass of ethanol, adding 0.5-1 part by mass of surfactant, ball-milling to obtain slurry A, sanding the slurry A to obtain slurry B, and spray-drying the slurry B to obtain powder A;
s2, pre-sintering the powder A, mixing the pre-sintered product with the rest organic carbon, adding 8-10 parts by mass of ethanol, ball-milling to obtain slurry C, spray-drying the slurry C to obtain powder B, and performing secondary sintering on the powder B to obtain the cerium oxide/aluminum oxide short fiber/organic carbon composite A;
The preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon composite B is different from the preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon source composite A only in that the powder A is directly sintered to obtain the cerium oxide/aluminum oxide short fiber/organic carbon composite B.
Preferably, the mass ratio of the cerium oxide/aluminum oxide short fiber/organic carbon composite A to the cerium oxide/aluminum oxide short fiber/organic carbon composite B is (5-7): (2-4), preferably 6:3.
The inventors have unexpectedly found during the experiment that when the ceria/alumina short fiber/organic carbon composite of the present invention includes the ceria/alumina short fiber/organic carbon composite a and the ceria/alumina short fiber/organic carbon composite B, the flexural strength of the ceramic material is significantly improved. The inventors hypothesize that the two-time sintering of the cerium oxide/aluminum oxide short fiber/organic carbon composite A forms a double-layer carbon coating layer on the surface of the cerium oxide/aluminum oxide short fiber, the one-time sintering of the cerium oxide/aluminum oxide short fiber/organic carbon composite B forms a single-layer carbon coating layer on the surface of the cerium oxide/aluminum oxide short fiber, the particle sizes and the structures of the two are different, the two particles and the structures can be mutually complemented when the two are mixed for use, and cracks are effectively deflected and crack tip stress is released through bridging, debonding or pulling out, and meanwhile, the formation of a compact structure of a ceramic material and the refinement of crystal grains are facilitated, so that the bending resistance of the ceramic material is improved.
Preferably, the rotational speed of the ball milling in the step S1 and the step S2 is 500-800rpm, and the ball milling time is 1-3h.
Preferably, the rotational speed of the sanding in the step S1 and the step S2 is 3000-5000rpm, and the sanding time is 2-4h.
Preferably, the outlet temperature of the spray drying in step S1 and step S2 is 100-120 ℃.
Preferably, the temperature of the pre-sintering in step S2 is 300-400 ℃ and the pre-sintering time is 3-4 hours.
Preferably, the temperature of the secondary sintering in the step S2 is 600-700 ℃, and the time of the secondary sintering is 6-8h.
Preferably, the organic carbon is glucose or sucrose.
Preferably, the surfactant is at least one selected from the group consisting of octylphenol polyoxyethylene ether, castor oil polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
Preferably, the particle size of the cerium oxide is 20-50nm.
Preferably, the alumina staple fiber is composed of 85-88% alpha-alumina and 12-15% silica.
Preferably, the alumina staple fibers have an average diameter of 4-7 μm.
The preparation method of the lithium silicate/diopside gel comprises the following steps of dissolving lithium hydroxide in water to obtain a lithium hydroxide solution, adding acidic silica sol into the lithium hydroxide solution, stirring for 20-30min at 20-25 ℃, heating to 50-60 ℃ and curing for 1-2h to obtain the lithium silicate sol, adding diopside powder into the lithium silicate sol, mixing uniformly, and adding a complexing agent to obtain the lithium silicate/diopside gel.
Preferably, the concentration of the lithium hydroxide solution is 0.5-1mol/L.
Preferably, the mass ratio of the acidic silica sol to the lithium hydroxide is (2-4): 1.
Preferably, the mass ratio of the lithium silicate sol to the diasporite powder to the complexing agent is (1-3) (0.5-1.5).
Preferably, the complexing agent is citric acid.
Preferably, the preparation method of the hydroxyethyl cellulose modified yttrium tungstate comprises the following steps of ball-milling and drying tin and indium doped yttrium tungstate and hydroxyethyl cellulose in water to obtain the hydroxyethyl cellulose modified yttrium tungstate.
Preferably, the mass of the yttrium tungstate, the hydroxyethyl cellulose and the water doped with tin and indium is 1 (1.5-2): 10-20.
Preferably, the ball milling speed is 500-800rpm, and the ball milling time is 6-10h.
Preferably, the preparation method of the tin and indium doped yttrium tungstate comprises the following steps of dissolving ammonium tungstate in water, adding hydrogen peroxide, stirring to obtain a solution A, adding yttrium carbonate, tin nitrate and indium nitrate into the solution A, heating and stirring to obtain gel, and drying and calcining the gel to obtain the tin and indium doped yttrium tungstate.
The inventor finds that when the hydroxyethyl cellulose is adopted to modify pure yttrium tungstate, the sintering effect is poor, and the dielectric property of the ceramic material is reduced, and when the hydroxyethyl cellulose is adopted to modify tin and indium doped yttrium tungstate, the dielectric property of the ceramic material is improved, and the bending strength of the ceramic material is improved. The inventors hypothesize that the low melting point of tin and indium can reduce the melting point of solid solution of a ceramic material system, reduce the viscosity of high-temperature liquid phase, generate enough liquid phase, improve the compactness of the ceramic material and the bending strength, and can reduce the mismatch of the thermal expansion coefficients of a generated phase and the ceramic material, so that microcracks are avoided in the cooling process of the ceramic material, and the dielectric property of the ceramic material is further improved.
The invention further finds in the experimental process that the comprehensive performance of the obtained ceramic material is optimal only when the mass ratio of the alumina to the toughening agent to the sintering aid is (92-97): 1-3): 2-5, and when a certain component exceeds the mass ratio, the dielectric constant, dielectric loss, toughness, bending resistance and adhesive force of the ceramic material are reduced.
Preferably, the mass ratio of the ammonium tungstate to the water to the hydrogen peroxide is (5-7): 15-18): 1.
Preferably, the mass ratio of the yttrium carbonate to the tin nitrate to the indium nitrate is (30-40): 1-2.
Preferably, the temperature of the heating and stirring is 50-60 ℃ and the time is 4-6h.
Preferably, the drying is carried out at a temperature of 80-100 ℃ for a time of 1-2 hours.
Preferably, the calcination is carried out at a temperature of 900-1000 ℃ for a time of 5-7 hours.
The invention provides a preparation method of a ceramic material for a multilayer ceramic substrate, which comprises the following steps of uniformly mixing alumina, a toughening agent and a sintering aid, and sintering at 1000-1200 ℃ for 1-3 hours to obtain the ceramic material.
Advantageous effects
1. When the cerium oxide/aluminum oxide short fiber/organic carbon compound is used as the toughening agent, cerium oxide in the cerium oxide/aluminum oxide short fiber/organic carbon compound is dispersed in the aluminum oxide short fiber, and a carbon coating layer is formed on the surface of the aluminum oxide short fiber dispersed with cerium oxide, so that the fibers and the fibers or ceramic groups are prevented from being sintered into a whole in the sintering process, the aluminum oxide short fibers can be interlocked, the fibers have a bridging effect when local cracks are smaller, bear larger external stress, and meanwhile, granular cerium oxide is easier to separate out under the action of sintering pressure, is filled at an aluminum oxide grain boundary and serves as a resistance point of cracks to block crack propagation, thereby increasing the toughness of the ceramic material, and meanwhile, the inventor unexpectedly discovers that the cerium oxide/aluminum oxide short fiber/organic carbon compound also improves the dielectric property of the ceramic material.
2. When the sintering aid comprises the lithium silicate/diopside gel and the hydroxyethyl cellulose modified yttrium tungstate, the sintering temperature can be effectively reduced, and meanwhile, the technical scheme is found to solve the problem that the conductor adhesive force of the ceramic material can not meet the high-temperature brazing requirement when the ceramic material is used for a multilayer ceramic substrate.
3. When the cerium oxide/aluminum oxide short fiber/organic carbon compound comprises the cerium oxide/aluminum oxide short fiber/organic carbon compound A and the cerium oxide/aluminum oxide short fiber/organic carbon compound B, the bending strength of the ceramic material is remarkably improved.
4. When the hydroxyethyl cellulose is adopted to modify tin and indium doped yttrium tungstate, the dielectric property of the ceramic material can be improved, and the bending strength of the ceramic material is improved.
5. The invention prevents the dielectric constant, dielectric loss, toughness, bending resistance and adhesive force of ceramic materials from being reduced when the mass ratio of alumina, toughening agent and sintering aid is (92-97): (1-3): (2-5).
Detailed Description
In order to better explain the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with examples in the embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
In the examples described below, unless otherwise specified, the methods of operation employed were conventional, the equipment employed was conventional, and the starting materials employed were commercially available.
The raw materials used in the examples and comparative examples of the present invention:
alpha-phase alumina A, alpha-phase alumina B and gamma-phase alumina C are all purchased from Zhengzhou green fleabane New Material technology Co., ltd;
octyl phenol polyoxyethylene ether, which is purchased from Jiangsu sea-An petrochemical plant, model number OP-4;
Cerium oxide, purchased from BoHuasi nanotechnology (Ningbo Co., ltd., model number Brofos-CeO 2 -35);
Alumina short fiber purchased from Shandong honing China fiber New Material Co., ltd, model 85;
acidic silica sol, which is purchased from Zhejiang Yuda chemical industry Co., ltd., model number of HS-2-20;
hydroxyethyl cellulose, purchased from the city of Feichong rain field chemical Co.
Example 1
The ceramic material for the multilayer ceramic substrate comprises raw materials of aluminum oxide, cerium oxide/aluminum oxide short fiber/organic carbon compound and sintering aid, wherein the sintering aid comprises lithium silicate/diopside gel and hydroxyethyl cellulose modified yttrium tungstate.
The mass ratio of the alumina to the toughening agent to the sintering aid is 94:2:4.
The mass ratio of the lithium silicate/diopside gel to the hydroxyethyl cellulose modified yttrium tungstate is 2:3.
The alumina comprises alpha-phase alumina A with the particle size of 0.4+/-0.1 mu m, alpha-phase alumina B with the particle size of 50nm and gamma-phase alumina C with the particle size of 50 nm.
The mass ratio of the alpha-phase alumina A to the alpha-phase alumina B to the gamma-phase alumina C is 25:70:0.8.
The cerium oxide/aluminum oxide short fiber/organic carbon composite comprises a cerium oxide/aluminum oxide short fiber/organic carbon composite A and a cerium oxide/aluminum oxide short fiber/organic carbon composite B, wherein the mass ratio of the cerium oxide/aluminum oxide short fiber/organic carbon composite A to the cerium oxide/aluminum oxide short fiber/organic carbon composite B is 6:3.
The preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon composite A comprises the following steps:
S1, adding 0.4 part by mass of cerium oxide, 4 parts by mass of alumina short fibers and 0.5 part by mass of 30wt% organic carbon into 10 parts by mass of ethanol, adding 0.8 part by mass of surfactant, ball-milling to obtain slurry A, sanding the slurry A to obtain slurry B, and spray-drying the slurry B to obtain powder A;
S2, pre-sintering the powder A, mixing the pre-sintered product with the rest organic carbon, adding 10 parts by mass of ethanol, ball-milling to obtain slurry C, spray-drying the slurry C to obtain powder B, and performing secondary sintering on the powder B to obtain the cerium oxide/aluminum oxide short fiber/organic carbon composite A;
The preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon composite B is different from the preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon source composite A only in that the powder A is directly sintered to obtain the cerium oxide/aluminum oxide short fiber/organic carbon composite B.
The rotational speed of the ball milling in the step S1 and the step S2 is 600rpm, and the ball milling time is 2 hours.
The rotational speed of the sanding in the step S1 and the step S2 is 4000rpm, and the sanding time is 3h.
The outlet temperature of the spray drying in step S1 and step S2 was 110 ℃.
The temperature of the pre-sintering in the step S2 is 350 ℃, and the pre-sintering time is 3.5h.
The temperature of the secondary sintering in the step S2 is 650 ℃, and the time of the secondary sintering is 7h.
The organic carbon is glucose.
The surfactant is octyl phenol polyoxyethylene ether.
The particle size of the cerium oxide was 35nm.
The alumina short fiber consists of 85-88% alpha-alumina and 12-15% silica.
The alumina short fibers have an average diameter of 4-7 μm.
The preparation method of the lithium silicate/diopside gel comprises the following steps of dissolving lithium hydroxide in water to obtain a lithium hydroxide solution, adding acidic silica sol into the lithium hydroxide solution, stirring for 25min at 25 ℃, heating to 60 ℃ and curing for 1.5h to obtain a lithium silicate sol, adding diopside powder into the lithium silicate sol, uniformly mixing, and adding a complexing agent to obtain the lithium silicate/diopside gel.
The concentration of the lithium hydroxide solution is 1mol/L.
The mass ratio of the acidic silica sol to the lithium hydroxide is 3:1.
The mass ratio of the lithium silicate sol to the brushite powder to the complexing agent is 3:1:1.
The complexing agent is citric acid.
The preparation method of the hydroxyethyl cellulose modified yttrium tungstate comprises the following steps of ball-milling and drying tin and indium doped yttrium tungstate and hydroxyethyl cellulose in water to obtain the hydroxyethyl cellulose modified yttrium tungstate.
The mass ratio of the yttrium tungstate doped with tin and indium, the hydroxyethyl cellulose and the water is 1:2:18.
The ball milling speed is 600rpm, and the ball milling time is 8 hours.
The preparation method of the tin and indium doped yttrium tungstate comprises the following steps of dissolving ammonium tungstate in water, adding hydrogen peroxide, stirring to obtain a solution A, adding yttrium carbonate, tin nitrate and indium nitrate into the solution A, heating and stirring to obtain gel, and drying and calcining the gel to obtain the tin and indium doped yttrium tungstate.
The mass ratio of the ammonium tungstate to the water to the hydrogen peroxide is 6:18:1.
The mass ratio of the yttrium carbonate to the tin nitrate to the indium nitrate is 35:1:2.
The temperature of the heating and stirring is 60 ℃ and the time is 5h.
The temperature of the drying was 90 ℃ for 1.5 hours.
The calcination temperature was 900 ℃ and the time was 6h.
The preparation method of the ceramic material for the multilayer ceramic substrate comprises the following steps of uniformly mixing alumina, a toughening agent and a sintering aid, and sintering for 2 hours at 1100 ℃ to obtain the ceramic material.
Example 2
The difference from example 1 is that the mass ratio of alumina, toughening agent and sintering aid is 92:3:5, the mass ratio of lithium silicate/diopside gel and hydroxyethylcellulose modified yttrium tungstate is 1:2, and the rest are the same.
Example 3
The difference from example 1 is that the mass ratio of alumina, toughening agent and sintering aid is 97:1:2, the mass ratio of lithium silicate/diopside gel and hydroxyethylcellulose modified yttrium tungstate is 3:4, and the rest are the same.
Comparative example 1
The difference from example 1 is that the mass ratio of alumina, toughening agent and sintering aid is 90:4:6, the remainder being the same.
Comparative example 2
The difference from example 1 is that the cerium oxide/aluminum oxide short fiber/organic carbon composite a is replaced with the aluminum oxide short fiber/organic carbon composite a, and the cerium oxide/aluminum oxide short fiber/organic carbon composite B is replaced with the aluminum oxide short fiber/organic carbon composite B, and the rest are the same.
The preparation method of the alumina short fiber/organic carbon composite A comprises the following steps:
S1, adding 4 parts by mass of alumina short fibers and 0.5 part by mass of 30wt% organic carbon into 10 parts by mass of ethanol, adding 0.8 part by mass of surfactant, ball-milling to obtain slurry A, sanding the slurry A to obtain slurry B, and spray-drying the slurry B to obtain powder A;
S2, pre-sintering the powder A, mixing the pre-sintered product with the rest organic carbon, adding 10 parts by mass of ethanol, ball-milling to obtain slurry C, spray-drying the slurry C to obtain powder B, and performing secondary sintering on the powder B to obtain the cerium oxide/aluminum oxide short fiber/organic carbon composite A;
The preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon composite B is different from the preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon source composite A only in that the powder A is directly sintered to obtain the cerium oxide/aluminum oxide short fiber/organic carbon composite B.
Comparative example 3
The difference from example 1 is that the cerium oxide/aluminum oxide short fiber/organic carbon composite a is replaced with an aluminum oxide short fiber/organic carbon composite B of the same quality, and the others are the same.
Comparative example 4
The difference from example 1 is that the cerium oxide/aluminum oxide short fiber/organic carbon composite B is replaced with an aluminum oxide short fiber/organic carbon composite a of the same quality, and the others are the same.
Comparative example 5
The difference from example 1 is that the hydroxyethylcellulose-modified yttrium tungstate is replaced by an equivalent mass of lithium silicate/diopside gel, all the others being identical.
Comparative example 6
The difference from example 1 is that the lithium silicate/diopside gel is replaced by an equal mass of hydroxyethylcellulose-modified yttrium tungstate, all the others being identical.
Comparative example 7
The difference from example 1 is that the hydroxyethyl cellulose modified tin and indium doped yttrium tungstate is replaced with the same quality of hydroxyethyl cellulose modified yttrium tungstate, the remainder being the same.
Performance test:
The ceramic materials of examples 1-3, comparative examples 1-7 were tested as follows:
1. flexural strength, tested according to GB/T6569-2006 standard, the results are shown in Table 1;
2. Fracture toughness is tested according to GB/T23806-2009 standard, and the results are shown in Table 1;
3. Dielectric constant and dielectric loss tangent values were measured according to GB/T5594.4-2015 standards, and the results are shown in Table 1;
4. Conductor adhesion-alumina-based HTCC ceramic was prepared by a tape casting method conventional in the art, in which a metal (tungsten) ink was printed on a membrane (membrane thickness 100 μm) using a screen printing technique, the number of lamination layers was 3, sintered for 3 hours at 1550 ℃ in a wet nitrogen-hydrogen atmosphere, nickel plated for 2 μm, gold plated for 2 μm, and then copper wires with a diameter of 0.5mm were welded on the ceramic at 800 ℃ and loaded at a rate of 1mm/min using a standard universal tester, and shear strength was tested, and the results are shown in table 1.
TABLE 1 results of Performance test of ceramic materials of examples 1-3, comparative examples 1-7
As can be seen from table 1:
The ceramic materials of the examples 1 and 2 have bending strength of 472MPa or more, fracture toughness of 9.6MPa.m 1/2 or more, dielectric constant of 6.3 or less, dielectric loss tangent of 0.002 or less, and conductor adhesion of 50MPa or more;
The ceramic material of example 3 had a flexural strength of 465MPa, a fracture toughness of 9.1 MPa.m 1/2, a dielectric constant of 6.5, a dielectric loss tangent of 0.007, and a conductor adhesion of 48MPa;
Comparative example 1 since the mass ratio of alumina, toughening agent and sintering aid is not in the range of (92-97): 1-3): 2-5, the ceramic material is reduced in flexural strength, fracture toughness, dielectric constant, dielectric loss tangent and conductor adhesion;
Comparative example 2 cerium oxide/aluminum oxide short fiber/organic carbon composite a was replaced with aluminum oxide short fiber/organic carbon composite a, cerium oxide/aluminum oxide short fiber/organic carbon composite B was replaced with aluminum oxide short fiber/organic carbon composite B, fracture toughness of ceramic materials was reduced to 6.8mpa·m 1/2, dielectric constant and dielectric loss tangent were 7.3 and 0.0034, respectively;
Comparative example 3 the cerium oxide/aluminum oxide short fiber/organic carbon composite a was replaced with the same mass of aluminum oxide short fiber/organic carbon composite B, comparative example 4 the cerium oxide/aluminum oxide short fiber/organic carbon composite B was replaced with the same mass of aluminum oxide short fiber/organic carbon composite a, the flexural strength of the ceramic material was reduced to 448MPa and 436MPa, respectively, and other properties were also reduced to different extents;
Comparative example 5 the substitution of hydroxyethyl cellulose modified yttrium tungstate with equivalent mass of lithium silicate/diopside gel, comparative example 6 the substitution of lithium silicate/diopside gel with equivalent mass of hydroxyethyl cellulose modified yttrium tungstate, the conductor adhesion of the ceramic material is reduced to 31 and 35MPa respectively, and other properties are also reduced to different degrees;
Comparative example 7 the hydroxyethyl cellulose modified tin and indium doped yttrium tungstate was replaced with the same quality of hydroxyethyl cellulose modified yttrium tungstate, the flexural strength of the ceramic material was reduced to 442MPa, the dielectric constant and dielectric loss tangent were 8.8 and 0.043, respectively, and other properties were also reduced to different extents.
The foregoing description of the embodiments of the present invention should not be construed as limiting the scope of the invention, but rather should be construed in view of the appended claims, or any equivalent manner of using the present invention, or any other suitable application, directly or indirectly, within the scope of the present invention.

Claims (7)

1. The ceramic material for the multilayer ceramic substrate is characterized by comprising, by mass, (92-97) of aluminum oxide, (1-3) of a toughening agent and (2-5) of a sintering aid, wherein the toughening agent is a cerium oxide/aluminum oxide short fiber/organic carbon compound, the sintering aid comprises lithium silicate/diopside gel and hydroxyethyl cellulose modified yttrium tungstate, and the mass ratio of the lithium silicate/diopside gel to the hydroxyethyl cellulose modified yttrium tungstate is (1-3) of (2-4);
The cerium oxide/aluminum oxide short fiber/organic carbon composite comprises cerium oxide/aluminum oxide short fiber/organic carbon composite A and cerium oxide/aluminum oxide short fiber/organic carbon composite B;
the preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon composite A comprises the following steps:
S1, adding 0.2-0.5 part by mass of cerium oxide, 3-5 parts by mass of alumina short fibers and 0.4-0.6 part by mass of 30-40wt% organic carbon into 8-10 parts by mass of ethanol, adding 0.5-1 part by mass of surfactant, ball-milling to obtain slurry A, sanding the slurry A to obtain slurry B, and spray-drying the slurry B to obtain powder A;
s2, pre-sintering the powder A, mixing the pre-sintered product with the rest organic carbon, adding 8-10 parts by mass of ethanol, ball-milling to obtain slurry C, spray-drying the slurry C to obtain powder B, and performing secondary sintering on the powder B to obtain the cerium oxide/aluminum oxide short fiber/organic carbon composite A;
The preparation method of the cerium oxide/aluminum oxide short fiber/organic carbon composite B and the cerium oxide/aluminum oxide short fiber/organic carbon source composite A is different in that the powder A is directly sintered to obtain the cerium oxide/aluminum oxide short fiber/organic carbon composite B;
The preparation method of the lithium silicate/diopside gel comprises the following steps of dissolving lithium hydroxide in water to obtain a lithium hydroxide solution, adding acidic silica sol into the lithium hydroxide solution, stirring for 20-30min at 20-25 ℃, heating to 50-60 ℃ and curing for 1-2h to obtain a lithium silicate sol;
The preparation method of the hydroxyethyl cellulose modified yttrium tungstate comprises the following steps of ball-milling and drying tin and indium doped yttrium tungstate and hydroxyethyl cellulose in water to obtain the hydroxyethyl cellulose modified yttrium tungstate.
2. The ceramic material for a multilayer ceramic substrate according to claim 1, wherein the alumina comprises an alpha-phase alumina A having a particle diameter of 0.3 to 0.8 μm, an alpha-phase alumina B having a particle diameter of 30 to 80nm, and a gamma-phase alumina C having a particle diameter of 30 to 80nm, and the mass ratio of the alpha-phase alumina A, the alpha-phase alumina B, and the gamma-phase alumina C is (10 to 30): (65 to 85): (0.5 to 1).
3. The ceramic material for a multilayer ceramic substrate according to claim 1, wherein the mass ratio of the lithium silicate sol to the diabody is (1-3): 0.5-1.5.
4. The ceramic material for a multilayer ceramic substrate according to claim 1, wherein the mass of tin and indium doped yttrium tungstate, hydroxyethyl cellulose, and water is 1 (1.5-2): 10-20.
5. The ceramic material for the multilayer ceramic substrate according to claim 4, wherein the preparation method of the tin and indium doped yttrium tungstate comprises the steps of dissolving ammonium tungstate in water, adding hydrogen peroxide, stirring to obtain a solution A, adding yttrium carbonate, tin nitrate and indium nitrate into the solution A, heating and stirring to obtain gel, and drying and calcining the gel to obtain the tin and indium doped yttrium tungstate.
6. The ceramic material for a multilayer ceramic substrate according to claim 5, wherein the mass ratio of yttrium carbonate, tin nitrate and indium nitrate is (30-40): 1-2.
7. The method for preparing the ceramic material for the multilayer ceramic substrate according to any one of claims 1 to 6, comprising the step of uniformly mixing alumina, a toughening agent and a sintering aid and then sintering at 1000 to 1200 ℃ for 1 to 3 hours to obtain the ceramic material.
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CN101774804A (en) * 2010-01-21 2010-07-14 上海大学 Low temperature microwave medium ceramic materials without glass phase additions
CN116329812A (en) * 2022-12-31 2023-06-27 浙江工业大学 A kind of preparation method of yttrium tungstate reinforced AgCuSnTi-based composite solder

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Publication number Priority date Publication date Assignee Title
CN101774804A (en) * 2010-01-21 2010-07-14 上海大学 Low temperature microwave medium ceramic materials without glass phase additions
CN116329812A (en) * 2022-12-31 2023-06-27 浙江工业大学 A kind of preparation method of yttrium tungstate reinforced AgCuSnTi-based composite solder

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