WO2019113973A1 - Dielectric ceramic material and preparation method therefor - Google Patents

Dielectric ceramic material and preparation method therefor Download PDF

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WO2019113973A1
WO2019113973A1 PCT/CN2017/116617 CN2017116617W WO2019113973A1 WO 2019113973 A1 WO2019113973 A1 WO 2019113973A1 CN 2017116617 W CN2017116617 W CN 2017116617W WO 2019113973 A1 WO2019113973 A1 WO 2019113973A1
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ceramic material
dielectric ceramic
analytically pure
powder
sintering
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PCT/CN2017/116617
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French (fr)
Chinese (zh)
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袁亮亮
陆正武
曾俊
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深圳市大富科技股份有限公司
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Priority to PCT/CN2017/116617 priority Critical patent/WO2019113973A1/en
Priority to CN201780034792.6A priority patent/CN109415266B/en
Publication of WO2019113973A1 publication Critical patent/WO2019113973A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the invention belongs to the technical field of ceramic materials, and in particular relates to a dielectric ceramic material and a preparation method thereof.
  • Alumina dielectric ceramic is a new type of electronic functional ceramic used as a medium in microwave and frequency band circuits. It has high physical strength (refractive strength >300MPa), low dielectric constant ( ⁇ r value ⁇ 9), low loss (quality). Factor Q value>100000), frequency temperature coefficient ⁇ f value is small, so it can be made into chip antenna, radar substrate, resonator support and other components, widely used in mobile communication, military radar, satellite positioning navigation system and other technologies. field. However, the sintering temperature of the ceramic material is usually higher than 1700 ° C, and the Q value of the quality factor is generally not high due to the micro defects generated in the sintering process, thereby restricting the more popular promotion and application of the alumina dielectric ceramic in the communication industry. .
  • conventional alumina dielectric ceramics are mainly prepared by solid phase synthesis, and a large amount of low-melting glass phase is added to reduce the sintering temperature.
  • the inventors of the present application found that by adding a large amount of low-melting glass phase, the dielectric properties of the alumina dielectric ceramic material are impaired, and the Q value of the alumina dielectric ceramic quality factor is lowered.
  • the technical problem mainly solved by the present invention is to provide a dielectric ceramic material and a preparation method thereof, which can obtain a dielectric ceramic material with high density and high quality factor while reducing the sintering temperature.
  • a technical solution adopted by the present invention is to provide a method for preparing a dielectric ceramic material, the method comprising:
  • a ball milling medium, deionized water and a dispersing agent are added to the starting material of the analytically pure alumina and the sintering aid having an alpha crystal phase having a purity of 99.9% or more, and mechanically mixed in a planetary ball mill, and dried after mixing. Processing, obtaining a mixed powder, wherein the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1 to 1.3, the ball milling time is 4 hours, and the diameter range of the ball milling medium a diameter of 2 to 3 mm, the mass percentage of the dispersant in the dielectric ceramic material is from three thousandths to six thousandths;
  • the mixed powder is placed in a nano-scale circulating sander for sanding and dispersing treatment to obtain a ceramic powder;
  • the ceramic powder is subjected to heat sintering to obtain the dielectric ceramic material.
  • the sintering aid is at least one selected from the group consisting of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide.
  • the molar ratio of the analytical pure alumina to each of the sintering aids contained in the dielectric ceramic material is 1:x, and the value of x ranges from 0.01 to 0.1.
  • the dielectric ceramic material has a dielectric constant ⁇ r of 9.7 to 9.8 and a quality factor Q of 150,000 to 290000 GHz.
  • the ceramic powder has a sintering temperature of 1350 to 1500 ° C and a holding time of 2 to 8 hours.
  • the mixed powder after ball milling by a planetary ball mill has a particle size of 800 nm or more.
  • the method further comprises:
  • Spray granulation to form the ceramic powder into powder particles having spherical fluidity Spray granulation to form the ceramic powder into powder particles having spherical fluidity.
  • the powder particles obtained by the spray granulation have a size distribution of 200 to 250 mesh.
  • the method further comprises:
  • Dry compression molding to form the spherical fluid powder particles into a ceramic green compact of a desired shape.
  • the method further comprises:
  • the dielectric properties of the obtained dielectric ceramic material were tested using a network analyzer, wherein the test frequency was 9 to 10 GHz.
  • the ceramic powder obtained by the sanding dispersion treatment has a particle size distribution in the range of 50 to 100 nm.
  • another technical solution adopted by the present invention is to provide a dielectric ceramic material comprising an analytically pure alumina of ⁇ phase and a sintering aid, and the molecular formula of Al 2 O 3 —xMO Wherein MO represents a sintering aid, and x has a value in the range of 0.01 to 0.1.
  • the dielectric ceramic material has a grain size distribution ranging from 50 to 100 nanometers.
  • the sintering aid is at least one selected from the group consisting of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide.
  • the dielectric ceramic material has a dielectric constant ⁇ r of 9.7 to 9.8 and a quality factor Q of 150,000 to 290000 GHz.
  • the invention has the beneficial effects that, in the preparation method of the dielectric ceramic material provided by the prior art, since the ceramic powder is a powder with high microscopic uniformity obtained after the nano-scale ultrafine grinding treatment, That is, the ceramic powder is finer and the particle size distribution is uniform, so that the growth of the crystal grains is uniform, the grain size is uniform, the grain arrangement is dense, and the crystal grains, the grain boundaries and the combination therebetween are all in the nanometer order, and finally the obtained material.
  • High quality factor Q high compactness, high physical strength, microscopic defects The probability of trapping is greatly reduced.
  • the ceramic powder that has been refined into smaller particles has a smaller surface activation energy, and the temperature at the time of heating and sintering is also lowered, and at the same time, the industrial system of the material system can be effectively reduced. Energy consumption and production costs.
  • 1 is an SEM image of an embodiment of a dielectric ceramic material provided by the present invention
  • FIG. 2 is a schematic flow chart of an embodiment of a method for preparing a dielectric ceramic material of the present invention.
  • Figure 1 is an SEM image of an embodiment of a dielectric ceramic material provided by the present invention.
  • a dielectric ceramic material according to an embodiment of the present invention wherein the dielectric ceramic material may be, but not limited to, a millimeter wave dielectric ceramic material, and the dielectric ceramic material includes an analytically pure alumina having an alpha crystal phase having a purity of 99.9% or more and a sintering aid.
  • the dielectric ceramic material is a composite material of an analytically pure alumina and a sintering aid containing an ⁇ crystal phase having a purity of 99.9% or more.
  • the dielectric ceramic material has a grain size distribution in the range of 50 to 100 nanometers, for example, 50 nanometers, 75 nanometers, or 100 nanometers.
  • the dielectric ceramic material is prepared by at least high-temperature calcination of the ceramic powder, and the ceramic powder is obtained by a sand-dispersion treatment of a nano-scale circulating sander, so that the ceramic powder has a particle size distribution ranging from 50 to 100 nm. Internal, and has a high degree of dispersion.
  • High-efficiency centrifugal separation systems for nano-scale circulating sanders are commonly used in wet grinding and dispersion processes, especially for obtaining powders with high dispersibility and nanometer size.
  • the high-efficiency centrifugal separation system can use a minimum diameter of 30 ⁇ m to 300 ⁇ m.
  • the grinding media is subjected to continuous grinding to grind the raw material into nano-powders having a uniform particle size, a high degree of dispersion, and a particle size diameter of less than 200 nm.
  • the analytically pure alumina and the sintering aid are contained in an alpha phase having a purity of 99.9% or more.
  • the mixed material is also mechanically mixed before being subjected to the scrub dispersion treatment of the nano-scale circulating sander.
  • a ball milling medium, deionized water, and a dispersing agent are added to the starting material of the analytically pure alumina and the sintering aid having an alpha crystal phase having a purity of 99.9% or more, and mechanically mixed in a planetary ball mill. Drying is carried out to obtain a mixed powder in which the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1 to 1.3, for example, 1:4:1.1, 1:4:1.2 or 1:4: 1.3, etc., the ball milling time is 4 hours, and the diameter of the ball milling medium ranges from 2 to 3 mm in diameter, for example, 2 mm, 2.5 mm or 3 mm.
  • the mixed powder obtained by ball milling usually has a particle size of 800 nm or more.
  • the ball-milled mixed powder is placed in a nano-scale circulating sander for sanding and dispersion treatment, and a ceramic powder having a high dispersibility and a particle size distribution in the range of 50 to 100 nm can be obtained. Since the ceramic powder is a high-micro-uniformity powder obtained after nano-scale ultra-fine grinding treatment, that is, the ceramic powder is fine and the particle size distribution is uniform, so that the crystal grains are uniformly distributed, the crystal grain size is uniform, and the crystal is uniform.
  • the grain arrangement is dense and the grain, the grain boundary and the combination between them are in the nanometer order, so that the material quality factor Q obtained at the end is higher, the compactness is higher, the physical strength is high, and the probability of microscopic defects is greatly reduced.
  • the refined ceramic powder has a small particle size, and the activated surface activation energy is low, so that the temperature during heating and sintering is also lowered, and at the same time, the industrial energy consumption and production cost of the material system can be effectively reduced.
  • the dielectric ceramic material has a molecular formula of Al 2 O 3 —xMO, wherein MO represents a sintering aid, and the sintering aid is selected from at least one of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide.
  • the molar ratio of the pure alumina to each of the sintering aids contained in the material is 1:x, and the value of x ranges from 0.01 to 0.1, such as 0.01, 0.05 or 0.1.
  • the molecular ceramic material may have a molecular formula of Al 2 O. 3 —0.07 ⁇ SiO 2 —(1-y)ZnO—yMgO ⁇ , which means that the analytical pure alumina, analytically pure silica, analytically pure zinc oxide, and analytical pure magnesium oxide have a molar ratio of 1:0.07:0.07 (1).
  • the selected sintering aid comprises analytically pure silica and analytically pure Zinc oxide, when the value of y is greater than 0 and less than 1, the selected sintering aid is composed of analytically pure silica, analytically pure zinc oxide and analytically pure magnesium oxide.
  • the auxiliaries include analytically pure silica and analytically pure magnesium oxide.
  • the material type and content of the sintering aid can be adjusted according to requirements.
  • the ceramic powder can be effectively improved during the sintering process. Problems such as abnormal grain growth, such as avoiding the phenomenon that a plurality of crystal grains are agglomerated, thereby effectively improving the Q value of the material quality factor.
  • the sintering temperature of the material of the present embodiment is 1350 to 1500 ° C, for example, 1350 ° C, 1425 ° C or 1500 ° C; the dielectric constant ⁇ r is 9.7 to 9.8, for example, 9.7, 9.75, 9.8, etc.; the quality factor Q is 150,000. 290000 GHz, for example, 150,000 GHz, 200000 GHz, 290,000 GHz, and the like.
  • the present embodiment provides a dielectric ceramic material which is a composite material of analytically pure alumina and a sintering aid containing an ⁇ crystal phase having a purity of 99.9% or more.
  • a sintering aid to the analysis of pure alumina, problems such as abnormal growth of crystal grains in the sintering process can be effectively avoided, thereby effectively improving the Q value of the quality factor of the material.
  • FIG. 2 is a schematic flow chart of an embodiment of a method for preparing a dielectric ceramic material according to the present invention.
  • a method for preparing a dielectric ceramic material according to an embodiment of the present invention, the preparation method comprising:
  • Step S101 adding a ball milling medium, deionized water and a dispersing agent to the starting material of the analytically pure alumina and the sintering aid having an ⁇ crystal phase having a purity of 99.9% or more, and mechanically mixing in a planetary ball mill, and mixing is completed. Thereafter, drying treatment is carried out to obtain a mixed powder.
  • the molecular formula is Al 2 O 3 —xMO, wherein MO represents a sintering aid, and the sintering aid is selected from at least one of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide.
  • the molar ratio of alumina to each of the sintering aids contained in the material is 1:x, and the value of x ranges from 0.01 to 0.1, such as 0.01, 0.05 or 0.1.
  • the molecular ceramic material may have a molecular formula of Al 2 O. 3 —0.07 ⁇ SiO 2 —(1-y)ZnO—yMgO ⁇ , which means that the analytical pure alumina, analytically pure silica, analytically pure zinc oxide, and analytical pure magnesium oxide have a molar ratio of 1:0.07:0.07 (1).
  • the selected sintering aid comprises analytically pure silica and analytically pure Zinc oxide, when the value of y is greater than 0 and less than 1, the selected sintering aid is composed of analytically pure silica, analytically pure zinc oxide and analytically pure magnesium oxide.
  • the auxiliaries include analytically pure silica and analytically pure magnesium oxide.
  • the material type and content of the sintering aid can be adjusted according to requirements.
  • the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1 to 1.3, for example, 1:4:1.1, 1:4:1.2 or 1:4:1.3, etc.
  • the ball milling time is 4 hours.
  • the diameter of the ball milling medium ranges from 2 to 3 mm in diameter, for example 2 mm, 2.5 mm or 3 mm, etc.
  • the mass percentage of the dispersant in the material is from three thousandths to six thousandths, for example, three thousandths, one thousandths Five or six thousandths, etc.
  • the particle size of the mixed powder after ball milling by a planetary ball mill is greater than or equal to 800 nm.
  • step S102 the mixed powder is placed in a nano-scale circulating sander for sanding and dispersion treatment to obtain a ceramic powder.
  • the starting material is placed in a nano-scale circulating sander for sanding and dispersing treatment, a highly dispersible ceramic powder is obtained, and the particle size distribution of the ceramic powder is in the range of 50 to 100 nm, for example, 50 nm, 75 nm, 100 nm, etc. .
  • the ceramic powder is a high-micro-uniformity powder obtained after nano-scale ultra-fine grinding treatment, that is, the ceramic powder is fine and the particle size distribution is uniform, so that the crystal grains are uniformly distributed, the crystal grain size is uniform, and the crystal is uniform.
  • the grain arrangement is dense and the grain, the grain boundary and the combination between them are in the nanometer order, so that the material quality factor Q obtained at the end is higher, the compactness is higher, the physical strength is high, and the probability of microscopic defects is greatly reduced.
  • the refined ceramic powder has a small particle size, and the activated surface activation energy is low, so that the temperature during heating and sintering is also lowered, and at the same time, the industrial energy consumption and production cost of the material system can be effectively reduced.
  • step S103 the ceramic powder is heated and sintered to obtain a dielectric ceramic material.
  • the ceramic powder is placed in a muffle furnace for sintering, and the sintering temperature is 1350 to 1500 ° C, for example, 1350 ° C, 1425 ° C, 1500 ° C, etc., and the holding time is 2 to 8 hours, for example, 2 hours, 5 hours, After 8 hours, etc., a dielectric ceramic material was obtained.
  • the dielectric constant ⁇ r of the material is 9.7 to 9.8, for example, 9.7, 9.75, 9.8, etc.; the quality factor Q is 150,000 to 290000 GHz, for example, 150,000 GHz, 200,000 GHz, 290,000 GHz, and the like.
  • the dispersing agent volatilizes in a high temperature environment, that is, the formed dielectric ceramic material does not contain a dispersing agent.
  • the method before the step of subjecting the raw material of the analytically pure alumina and the sintering aid having an alpha crystal phase having a purity of 99.9% or more to the nano-scale circulating sander for the sanding dispersion treatment, the method further comprises:
  • the method before the step of heating and sintering the ceramic powder, the method further comprises:
  • Spray granulation to form the ceramic powder into powder particles having spherical fluidity Spray granulation to form the ceramic powder into powder particles having spherical fluidity.
  • polyvinyl alcohol having a mass percentage of 10% is added to the ceramic powder, and spray granulation is carried out to obtain powder particles having spherical fluidity.
  • the powder particles obtained by spray granulation have a size distribution of 200 to 250 mesh, for example, 200 mesh, 225 mesh or 250 mesh.
  • the method further comprises:
  • Dry pressing to form spherical powdery powder particles into a ceramic compact of a desired shape, wherein The pressure during dry pressing is in the range of 140 to 160 MPa, for example, 140 MPa, 150 MPa or 160 MPa.
  • the powder particles are dry-formed under a pressure of 150 MPa to obtain a green wafer having a diameter of 12 mm and a thickness of 6 mm.
  • the shape of the ceramic green compact depends on the shape and size of the mold, and can be adjusted accordingly according to requirements, which is not limited herein.
  • the method further comprises:
  • the dielectric properties of the obtained materials were tested using a network analyzer, wherein the test frequency was 9 to 10 GHz.
  • the material of the present embodiment was tested to have a dielectric constant ⁇ r of 9.7 to 9.8 and a quality factor Q of 150,000 to 290000 GHz.
  • the method for preparing a dielectric ceramic material includes: adding a ball milling medium, deionized water, and a dispersing agent to a starting material of an analytically pure alumina and a sintering aid having an ⁇ crystal phase having a purity of 99.9% or more, And mechanically mixing in a planetary ball mill, and after drying, drying treatment is performed to obtain a mixed powder, wherein the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1-1.3 a ball milling time of 4 hours, a diameter of the ball milling medium ranging from 2 to 3 mm, and a mass percentage of the dispersing agent in the dielectric ceramic material of from three thousandths to six thousandths; The powder is placed in a nano-scale circulating sander for sanding and dispersing treatment to obtain a ceramic powder; the ceramic powder is heated and sintered to obtain the dielectric ceramic material.
  • the ceramic powder is a high-micro-uniformity powder obtained after nano-scale ultra-fine grinding treatment, that is, the ceramic powder is fine and the particle size distribution is uniform, so that the crystal grains are uniformly distributed, the crystal grain size is uniform, and the crystal is uniform.
  • the grain arrangement is dense and the grain, the grain boundary and the combination between them are in the nanometer order, so that the material quality factor Q obtained at the end is higher, the compactness is higher, the physical strength is high, and the probability of microscopic defects is greatly reduced.
  • the refined ceramic powder has a small particle size, and the activated surface activation energy is low, so that the temperature during heating and sintering is also lowered, and at the same time, the industrial energy consumption and production cost of the material system can be effectively reduced.
  • the starting material of Example 1 is compounded according to the formula Al 2 O 3 —xMO, wherein MO represents one of B 2 O 3 , SiO 2 , MgO, ZnO, and the molar ratio of the analytical pure alumina to the sintering aid is 1: x, where x ranges from 0.01 to 0.1.
  • Analytically pure alumina having a purity of 99.9% of the ⁇ crystal phase and a mixed material of analytically pure boron oxide, analytically pure silica, analytically pure magnesium oxide or analytically pure zinc oxide were respectively used as starting materials, and were obtained by the following process steps.
  • the polyurethane ball mill can be ball milled in a planetary ball mill for 4 hours;
  • step 3 transferring the ball-milled mixed powder in step 2 to a nano-scale circulating sand mill, and performing sanding dispersion treatment until a ceramic powder having a particle size ranging from 50 to 100 nm and having high dispersibility is obtained;
  • step 3 adding the ceramic powder after the sanding in step 3 to a polyvinyl alcohol having a mass percentage of 10% for spray granulation to obtain powder particles having a size ranging from 250 to 300 mesh;
  • the powder particles obtained in the step 4 are dry-formed, and a green wafer having a diameter of 12 mm and a thickness of 6 mm is obtained under a pressure of 150 MPa;
  • the green compact wafer in the step 5 is placed in a muffle furnace for sintering, the sintering temperature is 1400 to 1500 ° C, and the sintering holding time is 4 hours to obtain an alumina ceramic sample.
  • the dielectric properties of the alumina ceramic samples obtained above were tested using a network analyzer (Agilient 5071C) at a test frequency of 9.46 GHz and a Q factor of up to 194,000 GHz. See Table 1 for detailed results.
  • Example 2 The starting material of Example 2 was formulated according to the formula Al 2 O 3 —0.07 ⁇ SiO 2 —(1-y)ZnO—yMgO ⁇ , wherein pure alumina, analytically pure silica, analytically pure zinc oxide and analytical analysis were analyzed.
  • the molar ratio of pure magnesium oxide is 1:0.07:0.07 (1-y): 0.07y, wherein y ranges from 0 to 1.
  • a mixed material of analytically pure alumina, analytically pure silica and analytically pure magnesium oxide or/and analytically pure zinc oxide having a purity of 99.9% of ⁇ phase was used as a starting material, and was achieved by the following process steps.
  • the polyurethane ball mill can be ball milled in a planetary ball mill for 4 hours;
  • step 3 transferring the ball-milled mixed powder in step 2 to a nano-scale circulating sand mill, and performing sanding dispersion treatment until a ceramic powder having a particle size ranging from 50 to 100 nm and having high dispersibility is obtained;
  • step 3 adding the ceramic powder after the sanding in step 3 to a polyvinyl alcohol having a mass percentage of 10% for spray granulation to obtain powder particles having a size ranging from 250 to 300 mesh;
  • the powder particles obtained in the step 4 are dry-formed, and a green wafer having a diameter of 12 mm and a thickness of 6 mm is obtained under a pressure of 150 MPa;
  • the green compact wafer in the step 5 is placed in a muffle furnace for sintering, the sintering temperature is 1300 to 1450 ° C, and the sintering holding time is 6 hours to obtain an alumina ceramic sample.
  • the dielectric properties of the alumina ceramic samples obtained above were tested by a network analyzer (Agilient 5071C) at a test frequency of 9.53 GHz, a dielectric constant ⁇ r of 9.7, and a Q factor of up to 297000 GHz.
  • a network analyzer Agilient 5071C

Abstract

Disclosed are a dielectric ceramic material and a preparation method therefor. The method involves adding a ball milling medium, deionized water and a dispersing agent to a starting material made up of analytically pure α-alumina having a purity of 99. 9% or more and sintering auxiliaries, mechanically mixing same in a planetary ball mill, and drying same to obtain a mixed powder, wherein the mass ratio of the starting material to the ball milling medium to the deionized water is 1 : 4 : 1.1-1.3, the ball milling time is 4 hours, the range of the diameter of the ball milling medium is 2-3 mm, and the mass percentage content of the dispersing agent in the dielectric ceramic material is from three thousandths to six thousandths; placing the mixed powder in a nano-scale circulating sander for a sanding and dispersing treatment to obtain a ceramic powder; and heating and sintering the ceramic powder to obtain the dielectric ceramic material.

Description

一种介质陶瓷材料及其制备方法Medium ceramic material and preparation method thereof 【技术领域】[Technical Field]
本发明属于陶瓷材料技术领域，尤其涉及一种介质陶瓷材料及其制备方法。The invention belongs to the technical field of ceramic materials, and in particular relates to a dielectric ceramic material and a preparation method thereof.
【背景技术】【Background technique】
氧化铝介质陶瓷是一种在微波与频段电路中作为介质应用的新型电子功能陶瓷，其具有物理强度高(抗折强度＞300MPa)、介电常数低(εr值≈9)、损耗低(品质因素Q值>100000)、频率温度系数τf值小等特点，因此，可制成片式天线、雷达基板、谐振器支撑等元器件，广泛应用于移动通讯、军用雷达、卫星定位导航***等技术领域。然而，该陶瓷材料的烧结温度通常高于1700℃，由于在烧结过程中产生的微观缺陷导致其品质因素Q值普遍不高，从而制约了氧化铝介质陶瓷在通信行业中更普遍的推广和应用。Alumina dielectric ceramic is a new type of electronic functional ceramic used as a medium in microwave and frequency band circuits. It has high physical strength (refractive strength >300MPa), low dielectric constant (εr value ≈9), low loss (quality). Factor Q value>100000), frequency temperature coefficient τf value is small, so it can be made into chip antenna, radar substrate, resonator support and other components, widely used in mobile communication, military radar, satellite positioning navigation system and other technologies. field. However, the sintering temperature of the ceramic material is usually higher than 1700 ° C, and the Q value of the quality factor is generally not high due to the micro defects generated in the sintering process, thereby restricting the more popular promotion and application of the alumina dielectric ceramic in the communication industry. .
目前，常规氧化铝介质陶瓷主要采用固相合成法制备，通过添加大量的低熔点玻璃相以达到降低烧结温度。At present, conventional alumina dielectric ceramics are mainly prepared by solid phase synthesis, and a large amount of low-melting glass phase is added to reduce the sintering temperature.
本申请的发明人在长期的研发过程中，发现通过添加大量的低熔点玻璃相会损害氧化铝介质陶瓷材料的介电性能，使氧化铝介质陶瓷品质因素Q值降低。In the long-term development process, the inventors of the present application found that by adding a large amount of low-melting glass phase, the dielectric properties of the alumina dielectric ceramic material are impaired, and the Q value of the alumina dielectric ceramic quality factor is lowered.
【发明内容】[Summary of the Invention]
本发明主要解决的技术问题是提供一种介质陶瓷材料及其制备方法，能够在降低烧结温度的同时，获取高致密度、高品质因素的介质陶瓷材料。The technical problem mainly solved by the present invention is to provide a dielectric ceramic material and a preparation method thereof, which can obtain a dielectric ceramic material with high density and high quality factor while reducing the sintering temperature.
为解决上述技术问题，本发明采用的一个技术方案是：提供一种介质陶瓷材料的制备方法，所述方法包括：In order to solve the above technical problem, a technical solution adopted by the present invention is to provide a method for preparing a dielectric ceramic material, the method comprising:
在以纯度为99.9％以上的α晶相的分析纯氧化铝和烧结助剂的起始原料中加入球磨介质、去离子水以及分散剂，并在行星球磨机中进行机械混合，混合完毕后进行干燥处理，得到混合粉体，其中，所述起始原料、所述球磨介质以及所述去离子水的质量比为1:4:1.1～1.3，球磨时间为4小时，所述球磨介质的直径范围为直径2～3mm，所述分散剂在所述介质陶瓷材料中的质量百分比含量为千分之三至千分之六；A ball milling medium, deionized water and a dispersing agent are added to the starting material of the analytically pure alumina and the sintering aid having an alpha crystal phase having a purity of 99.9% or more, and mechanically mixed in a planetary ball mill, and dried after mixing. Processing, obtaining a mixed powder, wherein the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1 to 1.3, the ball milling time is 4 hours, and the diameter range of the ball milling medium a diameter of 2 to 3 mm, the mass percentage of the dispersant in the dielectric ceramic material is from three thousandths to six thousandths;
将所述混合粉体置于纳米级循环磨砂机中进行磨砂分散处理，得到陶瓷粉体；The mixed powder is placed in a nano-scale circulating sander for sanding and dispersing treatment to obtain a ceramic powder;
将所述陶瓷粉体进行加热烧结，进而获得所述介质陶瓷材料。 The ceramic powder is subjected to heat sintering to obtain the dielectric ceramic material.
其中，所述烧结助剂选自分析纯氧化硼、分析纯二氧化硅、分析纯氧化镁以及分析纯氧化锌中的至少一种。Wherein the sintering aid is at least one selected from the group consisting of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide.
其中，所述分析纯氧化铝与所述介质陶瓷材料中所含有的每一种烧结助剂的摩尔比为1：x，x的取值范围为0.01～0.1。Wherein, the molar ratio of the analytical pure alumina to each of the sintering aids contained in the dielectric ceramic material is 1:x, and the value of x ranges from 0.01 to 0.1.
其中，所述介质陶瓷材料的介电常数εr值为9.7～9.8，品质因数Q值为150000～290000GHz。The dielectric ceramic material has a dielectric constant ε r of 9.7 to 9.8 and a quality factor Q of 150,000 to 290000 GHz.
其中，所述陶瓷粉体的烧结温度为1350～1500℃，保温时间为2～8小时。Wherein, the ceramic powder has a sintering temperature of 1350 to 1500 ° C and a holding time of 2 to 8 hours.
其中，经行星球磨机球磨后的所述混合粉体的粒度大于等于800nm。Wherein, the mixed powder after ball milling by a planetary ball mill has a particle size of 800 nm or more.
其中，所述将所述陶瓷粉体进行加热烧结的步骤之前，所述方法还包括：Wherein, before the step of heating and sintering the ceramic powder, the method further comprises:
喷雾造粒，以将所述陶瓷粉体制成具球状流动性的粉体颗粒。Spray granulation to form the ceramic powder into powder particles having spherical fluidity.
其中，所述喷雾造粒得到的所述粉体颗粒的尺寸分布在200～250目。Wherein, the powder particles obtained by the spray granulation have a size distribution of 200 to 250 mesh.
其中，所述喷雾造粒的步骤之后，所述方法还包括：Wherein, after the step of spray granulation, the method further comprises:
干压成型，以将所述具球状流动性的粉体颗粒制成所需形状的陶瓷压坯。Dry compression molding to form the spherical fluid powder particles into a ceramic green compact of a desired shape.
其中，所述将所述陶瓷粉体进行加热烧结的步骤之后，所述方法还包括：Wherein, after the step of heating and sintering the ceramic powder, the method further comprises:
利用网络分析仪测试所得到的所述介质陶瓷材料的介电性能，其中，测试频率为9～10GHz。The dielectric properties of the obtained dielectric ceramic material were tested using a network analyzer, wherein the test frequency was 9 to 10 GHz.
其中，进行磨砂分散处理得到的所述陶瓷粉体的粒度分布在50～100纳米范围。The ceramic powder obtained by the sanding dispersion treatment has a particle size distribution in the range of 50 to 100 nm.
为解决上述技术问题，本发明采用的另一个技术方案是：提供一种介质陶瓷材料，所述介质陶瓷材料包含α晶相的分析纯氧化铝和烧结助剂，其分子式Al2O3—xMO，其中MO表示烧结助剂，x的取值范围为0.01～0.1。In order to solve the above technical problem, another technical solution adopted by the present invention is to provide a dielectric ceramic material comprising an analytically pure alumina of α phase and a sintering aid, and the molecular formula of Al 2 O 3 —xMO Wherein MO represents a sintering aid, and x has a value in the range of 0.01 to 0.1.
其中，所述介质陶瓷材料的晶粒粒度分布在50～100纳米范围。Wherein, the dielectric ceramic material has a grain size distribution ranging from 50 to 100 nanometers.
其中，所述烧结助剂选自分析纯氧化硼、分析纯二氧化硅、分析纯氧化镁以及分析纯氧化锌中的至少一种。Wherein the sintering aid is at least one selected from the group consisting of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide.
其中，所述介质陶瓷材料的介电常数εr值为9.7～9.8，品质因数Q值为150000～290000GHz。The dielectric ceramic material has a dielectric constant ε r of 9.7 to 9.8 and a quality factor Q of 150,000 to 290000 GHz.
本发明的有益效果是：区别于现有技术的情况，提供的介质陶瓷材料的制备方法中，由于陶瓷粉体是经过纳米级的超细研磨处理后所得到的高微观均匀性的粉体，即陶瓷粉体较细且粒度分布均匀，使得生长的晶粒分布均匀、晶粒大小均匀、晶粒排列密集和晶粒、晶界以及它们之间的结合都处于纳米级，从而最后获取的材料品质因数Q值较高，致密性较高，物理强度高，出现微观缺 陷的几率大大降低，另外，被细化成的陶瓷粉体粒径较小，被激活的表面活化能较低，从而在加热烧结时的温度也降低，同时，还能有效降低该材料体系的工业能耗和成产成本。The invention has the beneficial effects that, in the preparation method of the dielectric ceramic material provided by the prior art, since the ceramic powder is a powder with high microscopic uniformity obtained after the nano-scale ultrafine grinding treatment, That is, the ceramic powder is finer and the particle size distribution is uniform, so that the growth of the crystal grains is uniform, the grain size is uniform, the grain arrangement is dense, and the crystal grains, the grain boundaries and the combination therebetween are all in the nanometer order, and finally the obtained material. High quality factor Q, high compactness, high physical strength, microscopic defects The probability of trapping is greatly reduced. In addition, the ceramic powder that has been refined into smaller particles has a smaller surface activation energy, and the temperature at the time of heating and sintering is also lowered, and at the same time, the industrial system of the material system can be effectively reduced. Energy consumption and production costs.
【附图说明】[Description of the Drawings]
图1是本发明提供的介质陶瓷材料一实施方式的SEM图；1 is an SEM image of an embodiment of a dielectric ceramic material provided by the present invention;
图2是本发明介质陶瓷材料的制备方法一实施方式的流程示意图。2 is a schematic flow chart of an embodiment of a method for preparing a dielectric ceramic material of the present invention.
【具体实施方式】【Detailed ways】
下面将结合本发明实施方式中的附图，对本发明实施方式中的技术方案进行清楚、完整地描述，显然，所描述的实施方式仅仅是本发明一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，均属于本发明保护的范围。The technical solutions in the embodiments of the present invention are clearly and completely described in the following with reference to the accompanying drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
参见图1，图1是本发明提供的介质陶瓷材料一实施方式的SEM图。本发明一实施方式提供的介质陶瓷材料，其中该介质陶瓷材料可为但不限于为毫米波介质陶瓷材料，介质陶瓷材料包括纯度99.9％以上的α晶相的分析纯氧化铝和烧结助剂。Referring to Figure 1, Figure 1 is an SEM image of an embodiment of a dielectric ceramic material provided by the present invention. A dielectric ceramic material according to an embodiment of the present invention, wherein the dielectric ceramic material may be, but not limited to, a millimeter wave dielectric ceramic material, and the dielectric ceramic material includes an analytically pure alumina having an alpha crystal phase having a purity of 99.9% or more and a sintering aid.
可以理解，介质陶瓷材料是含有纯度99.9％以上的α晶相的分析纯氧化铝和烧结助剂的混合材料复合而成。It can be understood that the dielectric ceramic material is a composite material of an analytically pure alumina and a sintering aid containing an α crystal phase having a purity of 99.9% or more.
其中，介质陶瓷材料的晶粒粒度分布在50～100纳米范围，例如50纳米、75纳米或100纳米等。The dielectric ceramic material has a grain size distribution in the range of 50 to 100 nanometers, for example, 50 nanometers, 75 nanometers, or 100 nanometers.
本实施方式中，介质陶瓷材料由陶瓷粉体至少经高温煅烧制成，该陶瓷粉体经纳米级循环磨砂机的磨砂分散处理获得的，从而使得该陶瓷粉体粒度分布在50～100纳米范围内，且具有较高的分散性。In this embodiment, the dielectric ceramic material is prepared by at least high-temperature calcination of the ceramic powder, and the ceramic powder is obtained by a sand-dispersion treatment of a nano-scale circulating sander, so that the ceramic powder has a particle size distribution ranging from 50 to 100 nm. Internal, and has a high degree of dispersion.
纳米级循环砂磨机的高效离心分离***通常用于湿法研磨、分散工艺，尤其用于获取分散性高、粒度处于纳米级的粉体，该高效离心分离***可以使用最小直径为30μm～300μm的研磨介质进行连续研磨，以将原料研磨成粒度均匀、分散程度高且粒度直径小于200纳米的纳米粉体。High-efficiency centrifugal separation systems for nano-scale circulating sanders are commonly used in wet grinding and dispersion processes, especially for obtaining powders with high dispersibility and nanometer size. The high-efficiency centrifugal separation system can use a minimum diameter of 30μm to 300μm. The grinding media is subjected to continuous grinding to grind the raw material into nano-powders having a uniform particle size, a high degree of dispersion, and a particle size diameter of less than 200 nm.
在一实施方式中，含有纯度99.9％以上的α晶相的分析纯氧化铝和烧结助剂 的混合材料经纳米级循环磨砂机的磨砂分散处理前，还将该混合材料进行机械混合。In one embodiment, the analytically pure alumina and the sintering aid are contained in an alpha phase having a purity of 99.9% or more. The mixed material is also mechanically mixed before being subjected to the scrub dispersion treatment of the nano-scale circulating sander.
具体的，在以纯度99.9％以上的α晶相的分析纯氧化铝和烧结助剂的起始原料中加入球磨介质、去离子水以及分散剂，并在行星球磨机中进行机械混合，混合完毕后进行干燥处理，得到混合粉体，其中起始原料、球磨介质以及去离子水的质量比为1:4:1.1～1.3，例如，1:4:1.1、1:4:1.2或1:4:1.3等，球磨时间为4小时，球磨介质的直径范围为直径2～3mm，例如2mm、2.5mm或3mm等。Specifically, a ball milling medium, deionized water, and a dispersing agent are added to the starting material of the analytically pure alumina and the sintering aid having an alpha crystal phase having a purity of 99.9% or more, and mechanically mixed in a planetary ball mill. Drying is carried out to obtain a mixed powder in which the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1 to 1.3, for example, 1:4:1.1, 1:4:1.2 or 1:4: 1.3, etc., the ball milling time is 4 hours, and the diameter of the ball milling medium ranges from 2 to 3 mm in diameter, for example, 2 mm, 2.5 mm or 3 mm.
可以理解，行星球磨机虽然能够将起始原料混合的很均匀，通常经球磨后所获取的混合粉体粒度大于等于800纳米。本实施方式中，将球磨后的混合粉体置于纳米级循环磨砂机中进行磨砂分散处理，可以获得高分散性、粒度分布在50～100纳米范围内的陶瓷粉体。由于陶瓷粉体是经过纳米级的超细研磨处理后所得到的高微观均匀性的粉体，即陶瓷粉体较细且粒度分布均匀，使得生长的晶粒分布均匀、晶粒大小均匀、晶粒排列密集和晶粒、晶界以及它们之间的结合都处于纳米级，从而最后获取的材料品质因数Q值较高，致密性较高，物理强度高，出现微观缺陷的几率大大降低，另外，被细化成的陶瓷粉体粒径较小，被激活的表面活化能较低，从而在加热烧结时的温度也降低，同时，还能有效降低该材料体系的工业能耗和成产成本。It can be understood that although the planetary ball mill can mix the starting materials very uniformly, the mixed powder obtained by ball milling usually has a particle size of 800 nm or more. In the present embodiment, the ball-milled mixed powder is placed in a nano-scale circulating sander for sanding and dispersion treatment, and a ceramic powder having a high dispersibility and a particle size distribution in the range of 50 to 100 nm can be obtained. Since the ceramic powder is a high-micro-uniformity powder obtained after nano-scale ultra-fine grinding treatment, that is, the ceramic powder is fine and the particle size distribution is uniform, so that the crystal grains are uniformly distributed, the crystal grain size is uniform, and the crystal is uniform. The grain arrangement is dense and the grain, the grain boundary and the combination between them are in the nanometer order, so that the material quality factor Q obtained at the end is higher, the compactness is higher, the physical strength is high, and the probability of microscopic defects is greatly reduced. The refined ceramic powder has a small particle size, and the activated surface activation energy is low, so that the temperature during heating and sintering is also lowered, and at the same time, the industrial energy consumption and production cost of the material system can be effectively reduced.
介质陶瓷材料的分子式为Al2O3—xMO，其中，MO表示烧结助剂，烧结助剂选自分析纯氧化硼、分析纯二氧化硅、分析纯氧化镁以及分析纯氧化锌中的至少一种，分析纯氧化铝与材料中所含有的每一种烧结助剂的摩尔比为1：x，x的取值范围为0.01～0.1，例如0.01、0.05或0.1等。The dielectric ceramic material has a molecular formula of Al 2 O 3 —xMO, wherein MO represents a sintering aid, and the sintering aid is selected from at least one of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide. The molar ratio of the pure alumina to each of the sintering aids contained in the material is 1:x, and the value of x ranges from 0.01 to 0.1, such as 0.01, 0.05 or 0.1.
在一实施方式中，材料的起始原料中含有的烧结助剂包括分析纯二氧化硅以及分析纯氧化镁、分析纯氧化锌中的至少一种时，介质陶瓷材料的分子式可以为Al2O3—0.07{SiO2—(1-y)ZnO—yMgO}，即表示分析纯氧化铝、分析纯二氧化硅、分析纯氧化锌、分析纯氧化镁的摩尔比为1:0.07:0.07(1-y)：0.07y，其中y的取值范围为0～1，例如0、0.5或1等，即当y取值为0时，所选的烧结助剂包括分析纯二氧化硅和分析纯氧化锌，当y取值大于0且小于1时，所选的烧结助剂为包括分析纯二氧化硅、分析纯氧化锌以及分析纯氧化镁，当y取值为1时，所选的烧结助剂为包括分析纯二氧化硅以及分析纯氧化镁。In one embodiment, when the sintering aid contained in the starting material of the material comprises at least one of analytical pure silica and analytically pure magnesium oxide and analytically pure zinc oxide, the molecular ceramic material may have a molecular formula of Al 2 O. 3 —0.07{SiO 2 —(1-y)ZnO—yMgO}, which means that the analytical pure alumina, analytically pure silica, analytically pure zinc oxide, and analytical pure magnesium oxide have a molar ratio of 1:0.07:0.07 (1). -y): 0.07y, where y ranges from 0 to 1, such as 0, 0.5 or 1, etc., that is, when y is 0, the selected sintering aid comprises analytically pure silica and analytically pure Zinc oxide, when the value of y is greater than 0 and less than 1, the selected sintering aid is composed of analytically pure silica, analytically pure zinc oxide and analytically pure magnesium oxide. When y is taken as 1, the selected sintering is performed. The auxiliaries include analytically pure silica and analytically pure magnesium oxide.
可以理解，烧结助剂的材料种类以及含量可根据需求进行调整。It can be understood that the material type and content of the sintering aid can be adjusted according to requirements.
可以理解，通过添加烧结助剂，可以有效改善陶瓷粉体在烧结过程中出现 晶粒异常长大等问题，如，避免出现多个晶粒成团状等现象，从而有效提高材料的品质因素Q值。It can be understood that by adding a sintering aid, the ceramic powder can be effectively improved during the sintering process. Problems such as abnormal grain growth, such as avoiding the phenomenon that a plurality of crystal grains are agglomerated, thereby effectively improving the Q value of the material quality factor.
本实施方式的材料的烧结温度为1350～1500℃，例如1350℃、1425℃或1500℃等；介电常数εr值为9.7～9.8，例如9.7、9.75、9.8等；品质因数Q值为150000～290000GHz，例如150000GHz、200000GHz、290000GHz等。The sintering temperature of the material of the present embodiment is 1350 to 1500 ° C, for example, 1350 ° C, 1425 ° C or 1500 ° C; the dielectric constant ε r is 9.7 to 9.8, for example, 9.7, 9.75, 9.8, etc.; the quality factor Q is 150,000. 290000 GHz, for example, 150,000 GHz, 200000 GHz, 290,000 GHz, and the like.
区别于现有技术，本实施方式提供一种介质陶瓷材料，该介质陶瓷材料是含有纯度99.9％以上的α晶相的分析纯氧化铝和烧结助剂的混合材料复合而成。本实施方式通过在分析纯氧化铝中添加烧结助剂，可以有效避免陶瓷粉体在烧结过程中出现晶粒异常长大等问题，从而有效提高材料的品质因素Q值。Different from the prior art, the present embodiment provides a dielectric ceramic material which is a composite material of analytically pure alumina and a sintering aid containing an α crystal phase having a purity of 99.9% or more. In the present embodiment, by adding a sintering aid to the analysis of pure alumina, problems such as abnormal growth of crystal grains in the sintering process can be effectively avoided, thereby effectively improving the Q value of the quality factor of the material.
请参阅图2，图2是本发明介质陶瓷材料的制备方法一实施方式的流程示意图。本发明提供的一实施方式的介质陶瓷材料的制备方法，该制备方法包括：Please refer to FIG. 2. FIG. 2 is a schematic flow chart of an embodiment of a method for preparing a dielectric ceramic material according to the present invention. A method for preparing a dielectric ceramic material according to an embodiment of the present invention, the preparation method comprising:
步骤S101，在以纯度为99.9％以上的α晶相的分析纯氧化铝和烧结助剂的起始原料中加入球磨介质、去离子水以及分散剂，并在行星球磨机中进行机械混合，混合完毕后进行干燥处理，得到混合粉体。Step S101, adding a ball milling medium, deionized water and a dispersing agent to the starting material of the analytically pure alumina and the sintering aid having an α crystal phase having a purity of 99.9% or more, and mechanically mixing in a planetary ball mill, and mixing is completed. Thereafter, drying treatment is carried out to obtain a mixed powder.
分子式为Al2O3—xMO，其中，MO表示烧结助剂，烧结助剂选自分析纯氧化硼、分析纯二氧化硅、分析纯氧化镁以及分析纯氧化锌中的至少一种，分析纯氧化铝与材料中所含有的每一种烧结助剂的摩尔比为1：x，x的取值范围为0.01～0.1例如0.01、0.05或0.1等。The molecular formula is Al 2 O 3 —xMO, wherein MO represents a sintering aid, and the sintering aid is selected from at least one of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide. The molar ratio of alumina to each of the sintering aids contained in the material is 1:x, and the value of x ranges from 0.01 to 0.1, such as 0.01, 0.05 or 0.1.
在一实施方式中，材料的起始原料中含有的烧结助剂包括分析纯二氧化硅以及分析纯氧化镁、分析纯氧化锌中的至少一种时，介质陶瓷材料的分子式可以为Al2O3—0.07{SiO2—(1-y)ZnO—yMgO}，即表示分析纯氧化铝、分析纯二氧化硅、分析纯氧化锌、分析纯氧化镁的摩尔比为1:0.07:0.07(1-y)：0.07y，其中y的取值范围为0～1，例如0、0.5或1等，即当y取值为0时，所选的烧结助剂包括分析纯二氧化硅和分析纯氧化锌，当y取值大于0且小于1时，所选的烧结助剂为包括分析纯二氧化硅、分析纯氧化锌以及分析纯氧化镁，当y取值为1时，所选的烧结助剂为包括分析纯二氧化硅以及分析纯氧化镁。In one embodiment, when the sintering aid contained in the starting material of the material comprises at least one of analytical pure silica and analytically pure magnesium oxide and analytically pure zinc oxide, the molecular ceramic material may have a molecular formula of Al 2 O. 3 —0.07{SiO 2 —(1-y)ZnO—yMgO}, which means that the analytical pure alumina, analytically pure silica, analytically pure zinc oxide, and analytical pure magnesium oxide have a molar ratio of 1:0.07:0.07 (1). -y): 0.07y, where y ranges from 0 to 1, such as 0, 0.5 or 1, etc., that is, when y is 0, the selected sintering aid comprises analytically pure silica and analytically pure Zinc oxide, when the value of y is greater than 0 and less than 1, the selected sintering aid is composed of analytically pure silica, analytically pure zinc oxide and analytically pure magnesium oxide. When y is taken as 1, the selected sintering is performed. The auxiliaries include analytically pure silica and analytically pure magnesium oxide.
可以理解，烧结助剂的材料种类以及含量可根据需求进行调整。It can be understood that the material type and content of the sintering aid can be adjusted according to requirements.
其中，起始原料、球磨介质以及去离子水的质量比为1:4:1.1～1.3，例如，1:4:1.1、1:4:1.2或1:4:1.3等，球磨时间为4小时，球磨介质的直径范围为直径2～3mm，例如2mm、2.5mm或3mm等，分散剂在材料中的质量百分比含量为千分之三至千分之六，例如千分之三、千分之五或千分之六等。 Wherein, the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1 to 1.3, for example, 1:4:1.1, 1:4:1.2 or 1:4:1.3, etc., and the ball milling time is 4 hours. The diameter of the ball milling medium ranges from 2 to 3 mm in diameter, for example 2 mm, 2.5 mm or 3 mm, etc., and the mass percentage of the dispersant in the material is from three thousandths to six thousandths, for example, three thousandths, one thousandths Five or six thousandths, etc.
其中，经行星球磨机球磨后的混合粉体的粒度大于等于800nm。Among them, the particle size of the mixed powder after ball milling by a planetary ball mill is greater than or equal to 800 nm.
步骤S102，将混合粉体置于纳米级循环磨砂机中进行磨砂分散处理，得到陶瓷粉体。In step S102, the mixed powder is placed in a nano-scale circulating sander for sanding and dispersion treatment to obtain a ceramic powder.
起始原料置于纳米级循环磨砂机中进行磨砂分散处理后，获得高分散性陶瓷粉体，且陶瓷粉体的粒度分布在50～100纳米范围内，例如50纳米、75纳米、100纳米等。由于陶瓷粉体是经过纳米级的超细研磨处理后所得到的高微观均匀性的粉体，即陶瓷粉体较细且粒度分布均匀，使得生长的晶粒分布均匀、晶粒大小均匀、晶粒排列密集和晶粒、晶界以及它们之间的结合都处于纳米级，从而最后获取的材料品质因数Q值较高，致密性较高，物理强度高，出现微观缺陷的几率大大降低，另外，被细化成的陶瓷粉体粒径较小，被激活的表面活化能较低，从而在加热烧结时的温度也降低，同时，还能有效降低该材料体系的工业能耗和成产成本。After the starting material is placed in a nano-scale circulating sander for sanding and dispersing treatment, a highly dispersible ceramic powder is obtained, and the particle size distribution of the ceramic powder is in the range of 50 to 100 nm, for example, 50 nm, 75 nm, 100 nm, etc. . Since the ceramic powder is a high-micro-uniformity powder obtained after nano-scale ultra-fine grinding treatment, that is, the ceramic powder is fine and the particle size distribution is uniform, so that the crystal grains are uniformly distributed, the crystal grain size is uniform, and the crystal is uniform. The grain arrangement is dense and the grain, the grain boundary and the combination between them are in the nanometer order, so that the material quality factor Q obtained at the end is higher, the compactness is higher, the physical strength is high, and the probability of microscopic defects is greatly reduced. The refined ceramic powder has a small particle size, and the activated surface activation energy is low, so that the temperature during heating and sintering is also lowered, and at the same time, the industrial energy consumption and production cost of the material system can be effectively reduced.
步骤S103，将陶瓷粉体进行加热烧结，进而获得介质陶瓷材料。In step S103, the ceramic powder is heated and sintered to obtain a dielectric ceramic material.
具体的，将陶瓷粉体置于马弗炉中进行烧结，烧结温度为1350～1500℃，例如1350℃、1425℃、1500℃等，保温时间为2～8小时，例如2小时、5小时、8小时等，进而得到介质陶瓷材料。Specifically, the ceramic powder is placed in a muffle furnace for sintering, and the sintering temperature is 1350 to 1500 ° C, for example, 1350 ° C, 1425 ° C, 1500 ° C, etc., and the holding time is 2 to 8 hours, for example, 2 hours, 5 hours, After 8 hours, etc., a dielectric ceramic material was obtained.
其中，材料的介电常数εr值为9.7～9.8，例如9.7、9.75、9.8等；品质因数Q值为150000～290000GHz，例如150000GHz、200000GHz、290000GHz等。The dielectric constant ε r of the material is 9.7 to 9.8, for example, 9.7, 9.75, 9.8, etc.; the quality factor Q is 150,000 to 290000 GHz, for example, 150,000 GHz, 200,000 GHz, 290,000 GHz, and the like.
可以理解，在加热烧结的过程中，分散剂在高温的环境下挥发，即所形成的介质陶瓷材料不含分散剂。It can be understood that during the heating and sintering process, the dispersing agent volatilizes in a high temperature environment, that is, the formed dielectric ceramic material does not contain a dispersing agent.
在一实施方式中，将以纯度为99.9％以上的α晶相的分析纯氧化铝和烧结助剂的起始原料置于纳米级循环磨砂机中进行磨砂分散处理的步骤之前，方法还包括：In one embodiment, before the step of subjecting the raw material of the analytically pure alumina and the sintering aid having an alpha crystal phase having a purity of 99.9% or more to the nano-scale circulating sander for the sanding dispersion treatment, the method further comprises:
在一实施方式中，将陶瓷粉体进行加热烧结的步骤之前，方法还包括：In one embodiment, before the step of heating and sintering the ceramic powder, the method further comprises:
喷雾造粒，以将陶瓷粉体制成具球状流动性的粉体颗粒。Spray granulation to form the ceramic powder into powder particles having spherical fluidity.
具体的，在陶瓷粉体中添加质量百分比含量为10％的聚乙烯醇，进行喷雾造粒，得到具球状流动性的粉体颗粒。Specifically, polyvinyl alcohol having a mass percentage of 10% is added to the ceramic powder, and spray granulation is carried out to obtain powder particles having spherical fluidity.
其中，喷雾造粒得到的粉体颗粒的尺寸分布在200～250目，例如200目、225目或250目等。Among them, the powder particles obtained by spray granulation have a size distribution of 200 to 250 mesh, for example, 200 mesh, 225 mesh or 250 mesh.
在一实施方式中，喷雾造粒的步骤之后，方法还包括：In one embodiment, after the step of spray granulation, the method further comprises:
干压成型，以将具球状流动性的粉体颗粒制成所需形状的陶瓷压坯，其中 干压成型时的压强范围为140～160Mpa，例如140Mpa、150Mpa或160Mpa。Dry pressing to form spherical powdery powder particles into a ceramic compact of a desired shape, wherein The pressure during dry pressing is in the range of 140 to 160 MPa, for example, 140 MPa, 150 MPa or 160 MPa.
在一具体应用中，将粉体颗粒置于150Mpa的压强下干压成型，得到直径为12mm、厚度为6mm的生坯小圆片。In a specific application, the powder particles are dry-formed under a pressure of 150 MPa to obtain a green wafer having a diameter of 12 mm and a thickness of 6 mm.
可以理解，陶瓷压坯的形状取决于模具的形状大小，可以根据需求进行相应的调整，在此不作限定。It can be understood that the shape of the ceramic green compact depends on the shape and size of the mold, and can be adjusted accordingly according to requirements, which is not limited herein.
在一实施方式中，将陶瓷粉体进行加热烧结的步骤之后，方法还包括：In one embodiment, after the step of heating and sintering the ceramic powder, the method further comprises:
利用网络分析仪测试所得到的材料的介电性能，其中，测试频率为9～10GHz。The dielectric properties of the obtained materials were tested using a network analyzer, wherein the test frequency was 9 to 10 GHz.
本实施方式的材料经测试得到介电常数εr值为9.7～9.8，品质因数Q值为150000～290000GHz。The material of the present embodiment was tested to have a dielectric constant ε r of 9.7 to 9.8 and a quality factor Q of 150,000 to 290000 GHz.
本实施方式提供的介质陶瓷材料的制备方法，包括：在以纯度为99.9％以上的α晶相的分析纯氧化铝和烧结助剂的起始原料中加入球磨介质、去离子水以及分散剂，并在行星球磨机中进行机械混合，混合完毕后进行干燥处理，得到混合粉体，其中，所述起始原料、所述球磨介质以及所述去离子水的质量比为1:4:1.1～1.3，球磨时间为4小时，所述球磨介质的直径范围为直径2～3mm，所述分散剂在所述介质陶瓷材料中的质量百分比含量为千分之三至千分之六；将所述混合粉体置于纳米级循环磨砂机中进行磨砂分散处理，得到陶瓷粉体；将所述陶瓷粉体进行加热烧结，进而获得所述介质陶瓷材料。由于陶瓷粉体是经过纳米级的超细研磨处理后所得到的高微观均匀性的粉体，即陶瓷粉体较细且粒度分布均匀，使得生长的晶粒分布均匀、晶粒大小均匀、晶粒排列密集和晶粒、晶界以及它们之间的结合都处于纳米级，从而最后获取的材料品质因数Q值较高，致密性较高，物理强度高，出现微观缺陷的几率大大降低，另外，被细化成的陶瓷粉体粒径较小，被激活的表面活化能较低，从而在加热烧结时的温度也降低，同时，还能有效降低该材料体系的工业能耗和成产成本。The method for preparing a dielectric ceramic material provided by the embodiment includes: adding a ball milling medium, deionized water, and a dispersing agent to a starting material of an analytically pure alumina and a sintering aid having an α crystal phase having a purity of 99.9% or more, And mechanically mixing in a planetary ball mill, and after drying, drying treatment is performed to obtain a mixed powder, wherein the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1-1.3 a ball milling time of 4 hours, a diameter of the ball milling medium ranging from 2 to 3 mm, and a mass percentage of the dispersing agent in the dielectric ceramic material of from three thousandths to six thousandths; The powder is placed in a nano-scale circulating sander for sanding and dispersing treatment to obtain a ceramic powder; the ceramic powder is heated and sintered to obtain the dielectric ceramic material. Since the ceramic powder is a high-micro-uniformity powder obtained after nano-scale ultra-fine grinding treatment, that is, the ceramic powder is fine and the particle size distribution is uniform, so that the crystal grains are uniformly distributed, the crystal grain size is uniform, and the crystal is uniform. The grain arrangement is dense and the grain, the grain boundary and the combination between them are in the nanometer order, so that the material quality factor Q obtained at the end is higher, the compactness is higher, the physical strength is high, and the probability of microscopic defects is greatly reduced. The refined ceramic powder has a small particle size, and the activated surface activation energy is low, so that the temperature during heating and sintering is also lowered, and at the same time, the industrial energy consumption and production cost of the material system can be effectively reduced.
下面通过具体实施方式对本发明做进一步说明：The present invention is further described below by way of specific embodiments:
实施例1Example 1
实施例1的起始原料按分子式Al2O3—xMO进行配比，其中MO代表B2O3、SiO2、MgO、ZnO中的一种，分析纯氧化铝与烧结助剂的摩尔比为1：x，其中x的取值范围为0.01～0.1。将纯度99.9％的α晶相的分析纯氧化铝分别与分析纯氧 化硼、分析纯二氧化硅、分析纯氧化镁或分析纯氧化锌的混合材料作为起始原料，并通过以下工艺步骤实现。The starting material of Example 1 is compounded according to the formula Al 2 O 3 —xMO, wherein MO represents one of B 2 O 3 , SiO 2 , MgO, ZnO, and the molar ratio of the analytical pure alumina to the sintering aid is 1: x, where x ranges from 0.01 to 0.1. Analytically pure alumina having a purity of 99.9% of the α crystal phase and a mixed material of analytically pure boron oxide, analytically pure silica, analytically pure magnesium oxide or analytically pure zinc oxide were respectively used as starting materials, and were obtained by the following process steps.
1)以纯度99.9％的α晶相的分析纯氧化铝分别与分析纯氧化硼、分析纯二氧化硅、分析纯氧化镁或分析纯氧化锌的混合材料为起始原料，将上述起始原料按一定摩尔比例称取并置于聚氨酯球磨罐中，加入一定量的氧化锆磨介(直径为2～3mm)，去离子水、分散剂(多聚羧酸氨盐)。其中加入的起始原料、球磨介质和去离子水的质量比为1:4:1.2；1) Analytically pure alumina having an α phase with a purity of 99.9% and a mixed material of analytically pure boron oxide, analytically pure silica, analytically pure magnesium oxide or analytically pure zinc oxide as starting materials, and the above starting materials Weighed in a certain molar ratio and placed in a polyurethane ball mill jar, adding a certain amount of zirconia grinding media (2 to 3 mm in diameter), deionized water, dispersant (polycarboxylate ammonia salt). The mass ratio of the starting material, the ball milling medium and the deionized water added therein is 1:4:1.2;
2)将聚氨酯球磨罐放入行星球磨机中球磨4小时；2) The polyurethane ball mill can be ball milled in a planetary ball mill for 4 hours;
3)将步骤2中球磨后的混合粉体转移到纳米级循环砂磨机中，进行砂磨分散处理，直至获得粒度范围为50～100纳米、高分散性的陶瓷粉体；3) transferring the ball-milled mixed powder in step 2 to a nano-scale circulating sand mill, and performing sanding dispersion treatment until a ceramic powder having a particle size ranging from 50 to 100 nm and having high dispersibility is obtained;
4)将步骤3中砂磨后的陶瓷粉体加入质量百分比含量为10％的聚乙烯醇以进行喷雾造粒，获得尺寸范围为250～300目的粉体颗粒；4) adding the ceramic powder after the sanding in step 3 to a polyvinyl alcohol having a mass percentage of 10% for spray granulation to obtain powder particles having a size ranging from 250 to 300 mesh;
5)将步骤4中获得的粉体颗粒进行干压成型，在150MPa的压强下得到直径为12mm，厚度为6mm的生坯小圆片；5) The powder particles obtained in the step 4 are dry-formed, and a green wafer having a diameter of 12 mm and a thickness of 6 mm is obtained under a pressure of 150 MPa;
6)将步骤5中的生坯小圆片放在马弗炉进行烧结，烧結温度为1400～1500℃，烧结保温时间为4小时，得到氧化铝陶瓷样品。6) The green compact wafer in the step 5 is placed in a muffle furnace for sintering, the sintering temperature is 1400 to 1500 ° C, and the sintering holding time is 4 hours to obtain an alumina ceramic sample.
利用网络分析仪(Agilient5071C)测试上述获得的氧化铝陶瓷样品的介电性能，测试频率为9.46GHz，品质因数Q值高达194000GHz，详细结果参数请查看表一。The dielectric properties of the alumina ceramic samples obtained above were tested using a network analyzer (Agilient 5071C) at a test frequency of 9.46 GHz and a Q factor of up to 194,000 GHz. See Table 1 for detailed results.
表一：Table I:
Figure PCTCN2017116617-appb-000001
Figure PCTCN2017116617-appb-000001
Figure PCTCN2017116617-appb-000002
Figure PCTCN2017116617-appb-000002
Figure PCTCN2017116617-appb-000003
Figure PCTCN2017116617-appb-000003
实施例2Example 2
实施例2的起始原料按分子式Al2O3—0.07{SiO2—(1-y)ZnO—yMgO}进行配比，其中分析纯氧化铝、分析纯二氧化硅、分析纯氧化锌与分析纯氧化镁的摩尔比为1:0.07:0.07(1-y)：0.07y，其中，y的取值范围为0～1。将纯度99.9％的α晶相的分析纯氧化铝、分析纯二氧化硅与分析纯氧化镁或/和分析纯氧化锌的混合材料作为起始原料，并通过以下工艺步骤实现。The starting material of Example 2 was formulated according to the formula Al 2 O 3 —0.07 {SiO 2 —(1-y)ZnO—yMgO}, wherein pure alumina, analytically pure silica, analytically pure zinc oxide and analytical analysis were analyzed. The molar ratio of pure magnesium oxide is 1:0.07:0.07 (1-y): 0.07y, wherein y ranges from 0 to 1. A mixed material of analytically pure alumina, analytically pure silica and analytically pure magnesium oxide or/and analytically pure zinc oxide having a purity of 99.9% of α phase was used as a starting material, and was achieved by the following process steps.
1)以纯度99.9％的α晶相的分析纯氧化铝、分析纯二氧化硅与分析纯氧化镁或/和分析纯氧化锌的混合材料作为起始原料，将上述起始原料按一定摩尔比例称取并置于聚氨酯球磨罐中，加入一定量的氧化锆磨介(直径为2～3mm)，去离子水、分散剂(多聚羧酸氨盐)。其中加入的起始原料、球磨介质和去离子水的质量比为1:4:1.2；1) Analytically pure alumina, analytically pure silica and analytically pure magnesium oxide or/and analytically pure zinc oxide as a starting material with a purity of 99.9% of the α crystal phase, and the above starting materials are in a certain molar ratio. Weigh and place in a polyurethane ball mill jar, add a certain amount of zirconia grinding media (2 to 3 mm in diameter), deionized water, dispersant (polycarboxylate ammonia salt). The mass ratio of the starting material, the ball milling medium and the deionized water added therein is 1:4:1.2;
2)将聚氨酯球磨罐放入行星球磨机中球磨4小时；2) The polyurethane ball mill can be ball milled in a planetary ball mill for 4 hours;
3)将步骤2中球磨后的混合粉体转移到纳米级循环砂磨机中，进行砂磨分散处理，直至获得粒度范围为50～100纳米、高分散性的陶瓷粉体；3) transferring the ball-milled mixed powder in step 2 to a nano-scale circulating sand mill, and performing sanding dispersion treatment until a ceramic powder having a particle size ranging from 50 to 100 nm and having high dispersibility is obtained;
4)将步骤3中砂磨后的陶瓷粉体加入质量百分比含量为10％的聚乙烯醇以进行喷雾造粒，获得尺寸范围为250～300目的粉体颗粒；4) adding the ceramic powder after the sanding in step 3 to a polyvinyl alcohol having a mass percentage of 10% for spray granulation to obtain powder particles having a size ranging from 250 to 300 mesh;
5)将步骤4中获得的粉体颗粒进行干压成型，在150MPa的压强下得到直径为12mm，厚度为6mm的生坯小圆片； 5) The powder particles obtained in the step 4 are dry-formed, and a green wafer having a diameter of 12 mm and a thickness of 6 mm is obtained under a pressure of 150 MPa;
6)将步骤5中的生坯小圆片放在马弗炉进行烧结，烧結温度为1300～1450℃，烧结保温时间为6小时，得到氧化铝陶瓷样品。6) The green compact wafer in the step 5 is placed in a muffle furnace for sintering, the sintering temperature is 1300 to 1450 ° C, and the sintering holding time is 6 hours to obtain an alumina ceramic sample.
利用网络分析仪(Agilient5071C)测试上述获得的氧化铝陶瓷样品的介电性能，测试频率为9.53GHz，介电常数εr值为9.7，品质因数Q值最高为297000GHz，详细结果参数请查看表二。The dielectric properties of the alumina ceramic samples obtained above were tested by a network analyzer (Agilient 5071C) at a test frequency of 9.53 GHz, a dielectric constant ε r of 9.7, and a Q factor of up to 297000 GHz. For detailed parameter results, see Table 2 .
表二Table II
Figure PCTCN2017116617-appb-000004
Figure PCTCN2017116617-appb-000004
以上所述仅为本发明的实施方式，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围。 The above is only the embodiment of the present invention, and is not intended to limit the scope of the invention, and the equivalent structure or equivalent process transformations made by the description of the invention and the drawings are directly or indirectly applied to other related technologies. The fields are all included in the scope of patent protection of the present invention.

Claims (15)

  1. 一种介质陶瓷材料的制备方法，其特征在于，所述方法包括：A method for preparing a dielectric ceramic material, the method comprising:
    在以纯度为99.9％以上的α晶相的分析纯氧化铝和烧结助剂的起始原料中加入球磨介质、去离子水以及分散剂，并在行星球磨机中进行机械混合，混合完毕后进行干燥处理，得到混合粉体，其中，所述起始原料、所述球磨介质以及所述去离子水的质量比为1:4:1.1～1.3，球磨时间为4小时，所述球磨介质的直径范围为直径2～3mm，所述分散剂在所述介质陶瓷材料中的质量百分比含量为千分之三至千分之六；A ball milling medium, deionized water and a dispersing agent are added to the starting material of the analytically pure alumina and the sintering aid having an alpha crystal phase having a purity of 99.9% or more, and mechanically mixed in a planetary ball mill, and dried after mixing. Processing, obtaining a mixed powder, wherein the mass ratio of the starting material, the ball milling medium and the deionized water is 1:4:1.1 to 1.3, the ball milling time is 4 hours, and the diameter range of the ball milling medium a diameter of 2 to 3 mm, the mass percentage of the dispersant in the dielectric ceramic material is from three thousandths to six thousandths;
    将所述混合粉体置于纳米级循环磨砂机中进行磨砂分散处理，得到陶瓷粉体；The mixed powder is placed in a nano-scale circulating sander for sanding and dispersing treatment to obtain a ceramic powder;
    将所述陶瓷粉体进行加热烧结，进而获得所述介质陶瓷材料。The ceramic powder is subjected to heat sintering to obtain the dielectric ceramic material.
  2. 根据权利要求1所述的制备方法，其特征在于，所述烧结助剂选自分析纯氧化硼、分析纯二氧化硅、分析纯氧化镁以及分析纯氧化锌中的至少一种。The preparation method according to claim 1, wherein the sintering aid is at least one selected from the group consisting of analytical pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide.
  3. 根据权利要求1所述的制备方法，其特征在于，所述α晶相的分析纯氧化铝与所述介质陶瓷材料中所含有的每一种烧结助剂的摩尔比为1：x，x的取值范围为0.01～0.1。The preparation method according to claim 1, wherein a molar ratio of the analytically pure alumina of the α crystal phase to each of the sintering aids contained in the dielectric ceramic material is 1:x, x The value ranges from 0.01 to 0.1.
  4. 根据权利要求1所述的制备方法，其特征在于，所述介质陶瓷材料的介电常数εr值为9.7～9.8，品质因数Q值为150000～290000GHz。The preparation method according to claim 1, wherein the dielectric ceramic material has a dielectric constant ε r of 9.7 to 9.8 and a quality factor Q of 150,000 to 290000 GHz.
  5. 根据权利要求1所述的制备方法，其特征在于，所述陶瓷粉体的烧结温度为1350～1500℃，保温时间为2～8小时。The preparation method according to claim 1, wherein the ceramic powder has a sintering temperature of 1350 to 1500 ° C and a holding time of 2 to 8 hours.
  6. 根据权利要求1所述的制备方法，其特征在于，经行星球磨机球磨后的所述混合粉体的粒度大于等于800nm。The preparation method according to claim 1, wherein the mixed powder after ball milling by a planetary ball mill has a particle size of 800 nm or more.
  7. 根据权利要求1所述的制备方法，其特征在于，所述将所述陶瓷粉体进行加热烧结的步骤之前，所述方法还包括：The method according to claim 1, wherein before the step of heating and sintering the ceramic powder, the method further comprises:
    喷雾造粒，以将所述陶瓷粉体制成具球状流动性的粉体颗粒。Spray granulation to form the ceramic powder into powder particles having spherical fluidity.
  8. 根据权利要求7所述的制备方法，其特征在于，所述喷雾造粒得到的所述粉体颗粒的尺寸分布在200～250目。The method according to claim 7, wherein the powder particles obtained by the spray granulation have a size distribution of 200 to 250 mesh.
  9. 根据权利要求7所述的制备方法，其特征在于，所述喷雾造粒的步骤之后，所述方法还包括：The method according to claim 7, wherein after the step of spray granulation, the method further comprises:
    干压成型，以将所述具球状流动性的粉体颗粒制成所需形状的陶瓷压坯。 Dry compression molding to form the spherical fluid powder particles into a ceramic green compact of a desired shape.
  10. 根据权利要求1所述的制备方法，其特征在于，所述将所述陶瓷粉体进行加热烧结的步骤之后，所述方法还包括：The method according to claim 1, wherein after the step of heating and sintering the ceramic powder, the method further comprises:
    利用网络分析仪测试所得到的所述介质陶瓷材料的介电性能，其中，测试频率为9～10GHz。The dielectric properties of the obtained dielectric ceramic material were tested using a network analyzer, wherein the test frequency was 9 to 10 GHz.
  11. 根据权利要求1所述的制备方法，其特征在于，进行磨砂分散处理得到的所述陶瓷粉体的粒度分布在50～100纳米范围。The preparation method according to claim 1, wherein the ceramic powder obtained by the sanding dispersion treatment has a particle size distribution in the range of 50 to 100 nm.
  12. 一种介质陶瓷材料，其特征在于，所述介质陶瓷材料包含α晶相的分析纯氧化铝和烧结助剂，其分子式为Al2O3—xMO，其中MO表示烧结助剂，x的取值范围为0.01～0.1。A dielectric ceramic material, characterized in that the dielectric ceramic material comprises an analytical pure alumina of α phase and a sintering aid, and the molecular formula is Al 2 O 3 —xMO, wherein MO represents a sintering aid, and the value of x The range is from 0.01 to 0.1.
  13. 根据权利要求12所述的介质陶瓷材料，其特征在于，所述介质陶瓷材料的晶粒粒度分布在50～100纳米范围。The dielectric ceramic material according to claim 12, wherein the dielectric ceramic material has a grain size distribution in the range of 50 to 100 nm.
  14. 根据权利要求12所述的介质陶瓷材料，其特征在于，所述烧结助剂选自分析纯氧化硼、分析纯二氧化硅、分析纯氧化镁以及分析纯氧化锌中的至少一种。The dielectric ceramic material according to claim 12, wherein the sintering aid is at least one selected from the group consisting of analytically pure boron oxide, analytically pure silica, analytically pure magnesium oxide, and analytically pure zinc oxide.
  15. 根据权利要求12所述的介质陶瓷材料，其特征在于，所述介质陶瓷材料的介电常数εr值为9.7～9.8，品质因数Q值为150000～290000GHz。 The dielectric ceramic material according to claim 12, wherein the dielectric ceramic material has a dielectric constant ε r of 9.7 to 9.8 and a quality factor Q of 150,000 to 290000 GHz.
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