WO2013091560A1 - Procédé de fabrication d'un matériau céramique diélectrique pour micro-ondes - Google Patents

Procédé de fabrication d'un matériau céramique diélectrique pour micro-ondes Download PDF

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Publication number
WO2013091560A1
WO2013091560A1 PCT/CN2012/087041 CN2012087041W WO2013091560A1 WO 2013091560 A1 WO2013091560 A1 WO 2013091560A1 CN 2012087041 W CN2012087041 W CN 2012087041W WO 2013091560 A1 WO2013091560 A1 WO 2013091560A1
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Prior art keywords
powder
oxide
mol
microwave dielectric
ceramic material
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PCT/CN2012/087041
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English (en)
Chinese (zh)
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赵可沦
陈明
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深圳市大富科技股份有限公司
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Priority claimed from CN201110435610.0A external-priority patent/CN103172366B/zh
Priority claimed from CN201110435609.8A external-priority patent/CN103172365B/zh
Application filed by 深圳市大富科技股份有限公司 filed Critical 深圳市大富科技股份有限公司
Publication of WO2013091560A1 publication Critical patent/WO2013091560A1/fr

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Definitions

  • the invention relates to the technical field of ceramic materials, in particular to a method for preparing a microwave dielectric ceramic material.
  • Microwave dielectric ceramic is a ceramic material suitable for the dielectric constant and high quality factor of the microwave frequency band. It functions as dielectric isolation, dielectric waveguide and dielectric resonance in the microwave circuit. It can be used to fabricate microwave tubes and tube lines.
  • the microwave hybrid integrated circuit is constructed to greatly reduce the quality and volume of devices such as microwave dielectric resonators.
  • This conventional preparation method mainly has the following drawbacks:
  • the powder has a poor reactivity during high-temperature sintering, requires a high sintering temperature (at least 1450 degrees Celsius or more) and a long sintering time, resulting in extremely high production energy consumption;
  • the ceramic powder prepared by the reaction has a large particle size, a wide particle size distribution, and a large number of heterophases, which affects the purity of the main crystal phase of the CTNA and makes it difficult to achieve complete densification of the sintering, that is, it is difficult to obtain a dielectric ceramic material having stable and excellent microwave dielectric properties.
  • the adverse effect of the "lattice defect effect" of the Ca element during the sintering process on the microwave performance of the product is neglected.
  • the technical problem to be solved by the present invention is to provide a method for preparing a microwave dielectric ceramic material, which can reduce the sintering temperature, shorten the sintering time and inhibit the "lattice defect effect" caused by the volatile element Ca in the process of preparing the microwave dielectric ceramic material.
  • a technical solution adopted by the present invention is: Providing a method for preparing a microwave dielectric ceramic material, comprising: mixing a carbonate powder, an alumina, a cerium oxide, and a mixed powder of titanium dioxide with barium carbonate or calcium oxide; The machine is uniformly mixed to form powder particles; the powder particles are subjected to the first high-energy ball milling to knead the powder particles to form a refined powder; the refined powder is subjected to high-temperature calcination in a closed container. Forming a precursor powder; the precursor powder is subjected to a second high-energy ball milling to further uniformly refine the precursor powder to form a ceramic powder.
  • the method further comprises: spray granulation, adding a polyvinyl alcohol aqueous solution having a concentration of 5% and a mass percentage of 5% to 10% to the ceramic powder, and forming the ceramic powder into a spherical flow.
  • Spray granulation adding a polyvinyl alcohol aqueous solution having a concentration of 5% and a mass percentage of 5% to 10% to the ceramic powder, and forming the ceramic powder into a spherical flow.
  • sexual powder particles after the second high-energy ball milling step, the method further comprises: spray granulation, adding a polyvinyl alcohol aqueous solution having a concentration of 5% and a mass percentage of 5% to 10% to the ceramic powder, and forming the ceramic powder into a spherical flow.
  • the method further comprises: press molding, and the spherical particles having spherical fluidity are formed into a ceramic green compact of a desired shape.
  • the press forming step further comprises: sintering, continuously sintering the ceramic compact to form a ceramic blank, wherein the highest sintering temperature is 1200-1500 degrees Celsius, and the holding time is 3-6 hours.
  • the ceramic green compact when the mixed powder is calcium carbonate, aluminum oxide, cerium oxide, titanium dioxide and barium carbonate, the ceramic green compact is placed in a sealed crucible for continuous sintering, and the carbonic acid 4 bow and titanium oxide are preliminarily placed in the sealed crucible.
  • the sintering step further comprises: machining and sample testing, surface treating the ceramic blank to obtain a ceramic sample, and measuring a dielectric property index of the ceramic sample.
  • the carbon powder 4, aluminum oxide, cerium oxide and the mixed powder of titanium dioxide and barium carbonate or calcium oxide are mechanically and uniformly mixed
  • the steps of forming the powder particles include: placing the mixed powder in a spherical tank, adding the dioxide The honing ball is used as a grinding medium, and anhydrous ethanol or deionized water is added as an organic solvent for mechanically mixing, and after the powder particles are formed, the organic solvent is removed and dried, wherein the powder, the grinding medium, and the organic solvent are mixed.
  • the weight ratio of the three is 1:3:3 and accounts for 60% ⁇ 80% of the volume of the spherical tank, and the mixing time is 1 ⁇ 3 hours.
  • the ball-to-batch ratio is 8:1 ⁇ 10:1
  • the ball milling time is 1 ⁇ 3 hours
  • the rotation speed is 600 ⁇ 800 rpm.
  • the fine powder size distribution after the first high-energy ball milling is in the range of 1 ⁇ 2 ⁇ m.
  • the closed container is resistant to high temperature
  • the calcination temperature is 900 to 1200 degrees Celsius
  • the holding time is 3 to 6 hours.
  • the ball to material ratio is 10:1 to 12:1, and the ball milling time is 1 to 3 hours.
  • the speed is 800 ⁇ 1000 rev / min.
  • the ball to material ratio is 10:1 to 12:1, and the ball milling time is 1 to 3 hours.
  • the speed is 600 ⁇ 1000 rev / min.
  • the ceramic powder after the second high-energy ball milling has a particle size of less than 1 ⁇ m.
  • the mixed powder when the mixed powder is calcium carbonate, aluminum oxide, cerium oxide, titanium oxide, and cerium carbonate, the mixed powder is formulated according to the chemical formula (1- ⁇ ) [ & 1- ⁇ 8 ⁇ ] ⁇ 0 3 — x [Nd 1-z Re z A10 3 ] such that the molar percentages x, y and z thereof respectively satisfy 0.28 mol% ⁇ x ⁇ 0.48 mol%, 0.01 mol% ⁇ y ⁇ 0.25 mol%, and 0.1 mol% ⁇ z ⁇ 0.5 mol%, wherein, carbonic acid
  • the purity of calcium, barium carbonate and alumina is more than 99.5%, and the purity of titanium dioxide and barium oxide is not less than 99.9%.
  • the formula of the mixed powder is such that x and y are respectively satisfied according to the chemical formula (lx) Ca 1+ yTi0 3 — x[NdA10 3 ] 0.28 mol% ⁇ x ⁇ 0.48 mol% and 0.05 mol% ⁇ y ⁇ 0.5 mol% (y optional calcium carbonate or calcium oxide;), Among them, the purity of carbonic acid 4 bow, calcium oxide and aluminum oxide is more than 99.5%, and the purity of titanium dioxide and cerium oxide is not less than 99.9%.
  • a modifying additive and a sintering aid are further added.
  • the modifying additive is one or more of CaO, SrO, Ti0 2 , ZnO, A1 2 0 3 , Nb 2 0 5 and Ta 2 0 5
  • the sintering aid is Bi 2 0 3 , B 2 0 3
  • CuO, V 2 0 5 and BaO is one or more of CuO, V 2 0 5 and BaO.
  • the mixed powder is calcium carbonate, aluminum oxide, cerium oxide, titanium dioxide and cerium carbonate
  • a modified dopant is further added, and the modified dopant is oxidized by the rare earth element.
  • the rare earth element is one or more of 4, B, ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , 4L, ⁇ , ⁇ and ⁇ .
  • the formulation of microwave dielectric ceramic materials is in accordance with the chemical formula
  • the molar percentages x, y, and z satisfy 0.28 mol% ⁇ x ⁇ 0.48 mol%, 0.01 mol% ⁇ y ⁇ 0.25 mol%, and 0.1 mol% ⁇ z ⁇ 0.5 mol%, respectively, wherein the mass percentage of the modified additive is carbonic acid 1% to 4% of the total amount of calcium, barium carbonate, alumina, cerium oxide and titanium dioxide, and the mass percentage of sintering aid is 0.1% to 1% of the total amount of carbonic acid 4 bow, strontium carbonate, alumina, cerium oxide and titanium dioxide. .
  • the formula of the microwave dielectric ceramic material is such that x and y satisfy 0.28 mol% ⁇ x ⁇ 0.48 mol% and 0.05 mol% ⁇ y ⁇ 0.5 mol%, respectively, according to the chemical formula (lx) Ca 1+ yTi0 3 — x [NdA10 3 ] ( y optional calcium carbonate or calcium oxide), wherein the mass percentage of the modified additive is 1% to 4% of the total amount of carbonic acid 4, calcium oxide, aluminum oxide, cerium oxide and titanium dioxide, and the mass percentage of the sintering aid is carbonic acid 4%, 1% to 1% of the total amount of bow, calcium oxide, aluminum oxide, cerium oxide and titanium dioxide.
  • the preparation method of the microwave dielectric ceramic material of the present invention can suppress the "lattice defect effect" of the volatile element Ca by adding cesium carbonate or calcium oxide to the raw material on the basis of two high-energy ball milling.
  • the sintering temperature is greatly reduced and the sintering time is shortened, and high densification is achieved, which reduces production cost and technical difficulty.
  • FIG. 1 is a schematic flow chart of a method for preparing a microwave dielectric ceramic material according to an embodiment of the present invention
  • FIG. 2 is a schematic view of a method for preparing a microwave dielectric ceramic material according to an embodiment of the present invention, using a conventional solid phase reaction synthesis method combined with high energy ball milling technology
  • FIG. 3 is a microwave dielectric ceramic sample prepared by a conventional solid phase reaction synthesis method combined with a high energy ball milling technique in a method for preparing a microwave dielectric ceramic material according to an embodiment of the present invention.
  • FIG. 5 is a schematic diagram of a method for preparing a microwave dielectric ceramic material according to another embodiment of the present invention, using a conventional mechanical mixing + solid phase reaction method (a) and a solid phase reaction method + high energy ball milling combined with an A element replacement step (Sr). Scanning electron microscopy (SEM) images of microwave dielectric ceramic samples prepared by 2+ instead of Ca 2+ ) and sintering atmosphere control process (b).
  • a method for preparing a microwave dielectric ceramic material comprising: Step S 101 , mechanically uniformly mixing calcium carbonate, aluminum oxide, cerium oxide and titanium oxide with a mixed powder of barium carbonate or calcium oxide; , forming powder particles.
  • the mixed powder contains at least carbonic acid carbonate, aluminum oxide, cerium oxide and titanium oxide.
  • the present embodiment further adds cerium carbonate or calcium oxide to the mixed powder.
  • the mixed powder is carbonic acid, calcium oxide, aluminum oxide, cerium oxide and titanium dioxide
  • the mixed powder is placed in a spherical tank, the zirconia grinding ball is added as a grinding medium, and anhydrous ethanol or deionized water is added as an organic solvent.
  • the machine is uniformly mixed, and after the powder particles are formed, the organic solvent is removed and dried, wherein the weight ratio of the mixed powder, the grinding medium and the organic solvent is 1:3:3 and accounts for 60% of the volume of the spherical tank. 80%, mixing time is 1 ⁇ 3 hours.
  • the formula of the mixed powder is such that JC and y satisfy 0.28 mol% ⁇ ⁇ 0.48 mol% and 0.05 mol% ⁇ y ⁇ 0.5 mol%, respectively, according to the chemical formula ( 1 - ) Ca 1+y Ti0 3 — [NdA10 3 ] (y Optional calcium carbonate or calcium oxide).
  • the purity of calcium carbonate, calcium oxide and aluminum oxide is more than 99.5%, and the purity of titanium dioxide and cerium oxide is not less than 99.9%. Since the raw material has 4 strontium carbonate and calcium oxide, the molar percentage of the volatile element Ca in the CTNA-based dielectric material is increased, and the "lattice defect effect" caused by the volatile element Ca can be suppressed.
  • the mixed powder is carbonic acid, cesium carbonate, aluminum oxide, cerium oxide, titanium dioxide
  • the mixed powder is placed in a spherical tank, the zirconia grinding ball is added as a grinding medium, and anhydrous ethanol or deionized water is added as an organic solvent.
  • the machine is uniformly mixed, and after the powder particles are formed, the organic solvent is removed and dried, wherein the weight ratio of the mixed powder, the grinding medium and the organic solvent is 1:3:3 and accounts for 60% of the volume of the spherical tank. 80%, mixing time is 1 ⁇ 3 hours.
  • the mixed powder is formulated according to the formula (1-x) [Ca 1-y Sr y ]Ti0 3 — [Nd 1-z Re z A10 3 ] such that the percentages JC, y and z thereof respectively satisfy 0.28 mol% ⁇ 0.48 mol%, 0.01 mol% ⁇ y ⁇ 0.25 mol% and 0.1 mol% ⁇ z ⁇ 0.5 mol%.
  • the purity of calcium carbonate, barium carbonate and alumina is more than 99.5%
  • the purity of titanium dioxide and barium oxide is not less than 99.9%. Since the addition of strontium carbonate to the raw material instead of a part of calcium carbonate, that is, replacing Ca 2+ with Sr 2+ , the "lattice defect effect" caused by the volatile element Ca can be effectively suppressed.
  • Step S102 the powder particles are subjected to a first high-energy ball milling to uniformly refine the powder particles to form a refined powder.
  • the first high-energy ball milling is performed using the zirconia grinding ball as a grinding medium for high-energy ball milling, so that the particle size distribution of the refined powder after the first high-energy ball milling is in the range of 1 ⁇ 2 ⁇ , effectively improving The reaction activity and contact area of the powder particles are achieved, thereby achieving the purpose of lowering the synthesis temperature of the calcination reaction, wherein the ball-to-batch ratio is 8:1 to 10:1, the ball milling time is 1 to 3 hours, and the rotation speed is 600 to 800 rpm. minute.
  • Step S103 the fine powder is subjected to high-temperature calcination in a closed container to form a precursor powder.
  • the first high-energy ball-milled powder is placed in a sealed high-temperature resistant crucible, and a high-purity main crystalline phase precursor powder is synthesized by a high temperature reaction.
  • the process parameters of the high-temperature calcination process are as follows: The closed vessel is resistant to high temperature, the calcination temperature is 900-1200 degrees Celsius, and the holding time is 3-6 hours.
  • Step S104 the precursor powder is subjected to a second high-energy ball milling to further uniformly refine the precursor powder to form a ceramic powder.
  • the zirconia grinding ball is used as a grinding medium for high energy ball milling, and further adding a modifying additive and a sintering aid for the second time. High energy ball mill.
  • the ceramic powder formed by the control has a particle size smaller than ⁇
  • the modified additive is one or more of CaO, SrO, Ti0 2 , ZnO, A1 2 0 3 , Nb 2 0 5 and Ta 2 0 5
  • the sintering aid is One or more of Bi 2 0 3 , B 2 0 3 , CuO, V 2 0 5 and BaO
  • the formulation of the microwave dielectric ceramic material is according to the chemical formula (l- ) Ca 1+ yTi0 3 _ [NdA10 3 ] JC and y respectively satisfy 0.28 mol% ⁇ ⁇ 0.48 mol% and 0.05 mol% ⁇ y ⁇ 0.5 mol% (y optional carbonic acid 4 bow or calcium oxide).
  • the mass percentage of the modified additive is 1% to 4% of the total amount of the carbonic acid 4 bow, calcium oxide, aluminum oxide, cerium oxide and titanium dioxide
  • the mass percentage of the sintering aid is carbonic acid 4 bow, calcium oxide, aluminum oxide, oxidation 0.1% to 1% of the total amount of cerium and titanium dioxide.
  • the ball-to-batch ratio is 10:1 ⁇ 12:1
  • the ball milling time is 1 ⁇ 3 hours
  • the rotation speed is 600 ⁇ 1000 rev/min.
  • the ceramic powder By adding a modification additive and a sintering aid, the ceramic powder can be further uniformly distributed, and the porosity between the ceramic powders can be reduced, and the sintering temperature and the microwave dielectric ceramic sintering can be reduced to some extent.
  • the zirconia grinding ball is used as a grinding medium for high energy ball milling, and further modified dopants, modified additives and sintering are added.
  • the additive is subjected to a second high energy ball milling.
  • the ceramic powder formed by the control has a particle size smaller than ⁇
  • the modified dopant is an oxide containing a rare earth element
  • the rare earth element is one of lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum and cerium.
  • the modifying additive is one or more of CaO, SrO, Ti0 2 , ZnO, A1 2 0 3 , Nb 2 0 5 and Ta 2 0 5
  • the sintering aid is Bi 2 0 3 , B 2 One or more of 0 3 , CuO, V 2 0 5, and BaO.
  • the formulation of the material is such that the molar percentages JC, y and z thereof satisfy 0.28 mol% ⁇ 0.48 mol%, 0.01 mol% ⁇ y ⁇ 0.25 mol% and 0.1 mol%, respectively, according to the chemical formula (lj ⁇ CauS TiOs-j ⁇ NdnRezAlC ⁇ ).
  • the mass percentage of the modified additive is 1% to 4% of the total amount of carbonic acid 4 bow, strontium carbonate, alumina, cerium oxide and titanium dioxide, and the mass percentage of the sintering aid is carbonic acid 4 bow,
  • the total amount of barium carbonate, aluminum oxide, barium oxide and titanium dioxide is 0.1% to 1%, wherein the ball-to-batch ratio is 10:1 to 12:1, the ball milling time is 1 to 3 hours, and the rotation speed is 800 to 1000 rpm.
  • the firing temperature of the CTNA microwave dielectric ceramic can be effectively reduced, specifically, the high temperature calcination temperature is 900 to 1200 degrees Celsius; and the ceramic green compact sintering temperature is 1200 to 1500 In degrees Celsius, the ceramic powder can be further uniformly distributed, and the porosity between the ceramic powders can be reduced, so that the sintering temperature and the sintering densification of the microwave dielectric ceramic can be reduced to some extent.
  • the following steps may be further included as needed:
  • Spray granulation adding a polyvinyl alcohol aqueous solution having a concentration of 5% and a mass percentage of 5% to 10% to the ceramic powder, and forming the ceramic powder into powder particles having spherical fluidity so as to make the powder particles Has good fluidity.
  • the spherical particles having spherical fluidity are formed into a ceramic green compact of a desired shape.
  • the ceramic green compact is double-sided press-molded by a press in a manual or automatic filling manner, extruded by an extrusion forming process, or one injection by one injection molding technique.
  • the pressure of double-sided pressing is 80 ⁇ 120MPa.
  • the ceramic compact is continuously sintered to form a ceramic blank, wherein the highest sintering temperature is 1200-1500 degrees Celsius, and the holding time is 3-6 hours.
  • the ceramic green compact is placed in a closed high-temperature resistant alumina crucible for continuous sintering, and a solid phase reaction occurs at a high temperature to form a dense ceramic blank.
  • the mixed powder is calcium carbonate, aluminum oxide, cerium oxide, titanium oxide, and barium carbonate
  • a calcium carbonate and titanium oxide mixed powder or ceramic powder is previously placed in the sealed body as a mat powder to be sintered. Atmospheric control is performed, and a solid phase reaction occurs at a high temperature to form a dense ceramic blank.
  • ceramic blanks are surface treated to obtain ceramic samples, and the dielectric properties of ceramic samples are measured.
  • the ceramic blank can be surface-treated by grinding, polishing, etc. to obtain a ceramic sample of a desired size, and the dielectric properties of the ceramic sample are measured by a network analyzer: dielectric constant, temperature coefficient of resonance frequency T f and quality factor Q.
  • Step 1 Pre-sinter the cerium oxide powder at 800 °C for 3 hours before batching to remove moisture for drying; according to the chemical formula 0.72Ca 1+ . .lm . 1% TiO 3 _0.28NdAlO 3 4 ratio bow carbonate, calcium oxide, aluminum oxide, neodymium oxide and titania, zirconia balls were added as a mixed powder in the grinding media, adding ethanol as an organic or deionized water The solvent is placed in a spherical tank for mechanical mixing, and after the powder particles are formed, the organic solvent is removed for drying, and the ratio of the mixed powder, the grinding ball, and the solvent (weight) is 1:3:3 and the ball is occupied.
  • the tank volume is 60% ⁇ 80%, and the raw material mixing time is 3 hours.
  • the stoichiometric ratio of calcium carbonate and titanium dioxide is 0.72 mol%
  • the stoichiometric ratio of alumina and cerium oxide is 0.28 mol%
  • the stoichiometric ratio of calcium oxide is 0.1 mol% to increase Ca element. Percentage. It should be noted that the purity of the carbonate 4, calcium oxide and alumina powders is more than 99.5%, and the purity of the titanium dioxide and cerium oxide powders is not less than 99.9%.
  • Step 2 using the zirconia grinding ball as a grinding medium, drying the powder particles formed in the first step and performing the first high-energy ball milling to uniformly refine the powder particles to form a refined powder. Among them, the high-energy ball milling time is 2 hours, the ball-to-batch ratio is 8:1, and the rotation speed is 400 rpm.
  • Step 3 The refined powder formed in the second step is placed in a closed high temperature resistant crucible, and a precursor powder having a high purity main crystalline phase is synthesized by a high temperature calcination reaction.
  • the calcination temperature was 1000 ° C and the temperature retention time was 3 hours.
  • Step 4 using a zirconia grinding ball as a grinding medium, and subjecting the calcined precursor powder to a second high-energy ball milling to obtain a ceramic powder which is further uniformly refined.
  • the high-energy ball milling time is 1 hour
  • the ball-to-batch ratio is 10:1
  • the rotation speed is 1000 rpm.
  • Step 5 adding 10% by mass of a polyvinyl alcohol (PVA) aqueous solution (concentration: 5%) to the ceramic powder obtained in the fourth step, and using a drying tower or a granulator to form a spherical and fluid powder. Particles.
  • PVA polyvinyl alcohol
  • Step 6 Pressing the powder particles obtained in the fifth step into a ceramic compact of the desired shape by a press (manual or automatic filler) by double-sided pressing, the pressing pressure is 120 MPa; or obtaining the desired shape by one injection molding technique Ceramic compact.
  • Step 7 The ceramic green compact is placed in a sealed high temperature resistant alumina crucible for continuous sintering to form a ceramic blank.
  • the highest sintering temperature is 1350 degrees Celsius, and the holding time is 3 hours.
  • Step 1 Pre-sinter the cerium oxide powder at 800 °C for 3 hours before batching to remove moisture for drying; according to the chemical formula 0.62Ca 1+ . .15m . 1% TiO 3 — 0.38 NdAlO 3 is blended with carbonic acid 4 bow, calcium oxide, aluminum oxide, cerium oxide and titanium dioxide, and a zirconia grinding ball is added as a grinding medium to the mixed powder.
  • the stoichiometric ratio of calcium carbonate and titanium dioxide is 0.62 mol%
  • the stoichiometric ratio of alumina and cerium oxide is 0.38 mol%
  • the stoichiometric ratio of calcium oxide is 0.15 mol% to increase
  • the percentage of Ca element It should be noted that the purity of the carbonated carbon, calcium oxide and alumina powders is greater than 99.5%, and the purity of the titanium dioxide and cerium oxide powders is not less than 99.9%.
  • Step 2 using the zirconia grinding ball as a grinding medium, drying the powder particles formed in the first step and performing the first high-energy ball milling to uniformly refine the powder particles to form a refined powder.
  • the high-energy ball milling time is 3 hours
  • the ball-to-batch ratio is 12:1
  • the rotation speed is 800 rpm.
  • Step 3 The refined powder formed in the second step is placed in a closed high temperature resistant crucible, and a precursor powder having a high purity main crystalline phase is synthesized by a high temperature calcination reaction.
  • the calcination temperature was 900 ° C and the temperature retention time was 5 hours.
  • Step 4 using a zirconia grinding ball as a grinding medium, and subjecting the calcined precursor powder to a second high-energy ball milling to obtain a ceramic powder which is further uniformly refined.
  • the high-energy ball milling time is 2 hours
  • the ball-to-batch ratio is 10:1
  • the rotation speed is 800 rpm.
  • Step 5 adding 10% by mass of a polyvinyl alcohol (PVA) aqueous solution (concentration: 5%) to the ceramic powder obtained in the fourth step, and using a spray drying tower or a granulator to form a spherical and fluid powder. Body particles.
  • PVA polyvinyl alcohol
  • Step 6 Pressing the powder particles obtained in the fifth step into a ceramic compact of the desired shape by a press (manual or automatic filler) by double-sided pressing, the pressing pressure is 120 MPa; or obtaining the desired shape by one injection molding technique Ceramic compact.
  • Step 7 The ceramic green compact is placed in a sealed high temperature resistant alumina crucible for continuous sintering to form a ceramic blank.
  • the highest sintering temperature is 1450 degrees Celsius, and the holding time is 4 hours.
  • Step 1 Pre-burn the cerium oxide raw powder at 800 ° C for 3 hours before batching to dry; according to the chemical formula 0.52Ca 1+ 25m .
  • 1% TiO 3 — 0.48NdAlO 3 is matched with carbonic acid 4 bow, calcium oxide, aluminum oxide, cerium oxide and titanium dioxide.
  • Tirconia grinding balls are added to the mixed powder as grinding media, and anhydrous ethanol or deionized water is added as organic
  • the solvent is placed in a spherical tank for mechanical mixing, and after the powder particles are formed, the organic solvent is removed for drying, and the ratio of the mixed powder, the grinding ball, and the solvent (weight) is 1:3:3 and the ball is occupied.
  • the tank volume is 60% ⁇ 80%, and the raw material mixing time is 3 hours.
  • the stoichiometric ratio of calcium carbonate and titanium dioxide is 0.52 mol%
  • the stoichiometric ratio of alumina and cerium oxide is 0.48 mol%
  • the stoichiometric ratio of calcium carbonate is 0.25 mol% to increase Ca element. Percentage. It should be noted that the purity of the carbonated carbon, calcium oxide and alumina powders is greater than 99.5%, and the purity of the titanium dioxide and cerium oxide powders is not less than 99.9%.
  • Step 2 using the zirconia grinding ball as a grinding medium, drying the powder particles formed in the first step and performing the first high-energy ball milling to uniformly refine the powder particles to form a refined powder.
  • the high-energy ball milling time is 3 hours
  • the ball-to-batch ratio is 10:1
  • the rotation speed is 600 rpm.
  • Step 3 The refined powder formed in the second step is placed in a closed high temperature resistant crucible, and a precursor powder having a high purity main crystalline phase is synthesized by a high temperature calcination reaction. Among them, the calcination temperature was 1150 ° C and the temperature retention time was 4 hours.
  • Step 4 using a zirconia grinding ball as a grinding medium, and subjecting the calcined precursor powder to a second high-energy ball milling to obtain a ceramic powder which is further uniformly refined.
  • the high-energy ball milling time is 2 hours
  • the ball-to-batch ratio is 8:1
  • the rotation speed is 1000 rpm.
  • Step 5 adding 10% by mass of a polyvinyl alcohol (PVA) aqueous solution (concentration: 5%) to the ceramic powder obtained in the fourth step, and using a spray drying tower or a granulator to form a spherical and fluid powder. Body particles.
  • Step 6. Pressing the powder particles obtained in the fifth step into a ceramic compact of the desired shape by a press (manual or automatic filler) by double-sided pressing, the pressing pressure is 120 MPa; or obtaining the desired shape by one injection molding technique Ceramic compact.
  • a press manual or automatic filler
  • Step 7 The ceramic green compact is placed in a sealed high temperature resistant alumina crucible for continuous sintering to form a ceramic blank.
  • the highest sintering temperature is 1250 degrees Celsius and the holding time is 6 hours.
  • a modified additive and a sintering aid are added in an appropriate amount, and the modified additive is one of CaO, SrO, Ti0 2 , ZnO, A1 2 0 3 , Nb 2 0 5 and Ta 2 0 5
  • the sintering aids are one or more of Bi 2 O 3 , B 2 0 3 , CuO, V 2 0 5 and BaO
  • the wave dielectric ceramic material is formulated according to the chemical formula 0.62Ca G+ i5m . 1% ) TiO 3 -0.38NdAlO 3 ) was blended.
  • the mass percentage of the modified additive is 1% to 4% of the total amount of the carbonic acid 4 bow, calcium oxide, aluminum oxide, cerium oxide and titanium dioxide, and the mass percentage of the sintering aid is carbonic acid 4 bow, calcium oxide, aluminum oxide, oxidation
  • the total amount of bismuth and titanium dioxide is 0.1% ⁇ 1%, and the same process parameters are used for sample trial production and testing, so that the above embodiments of the present invention are applied to specific environments for detailed description.
  • the basic performance indexes are shown in Table 3-4. Table 3 Dielectric properties of samples corresponding to different proportioning modified additives
  • the embodiment of the invention combines the high-energy ball milling technology on the basis of the traditional mechanical mixing and solid phase reaction method, and promotes the finening of the ceramic powder by the first high-energy ball milling, which not only effectively reduces the calcination temperature of the powder, but also ensures the reaction.
  • the synthesized ceramic powder main crystalline phase has high purity.
  • the powder particles are further densified to lay a good particle size basis for spray granulation, and the sintering temperature is lowered, and the molar percentage of the volatile element Ca is increased in the raw material, thereby suppressing the volatilization of Ca element during sintering.
  • the "lattice defect effect" ensures a high degree of densification of the fired ceramic.
  • FIG. 2 is a view showing a method for preparing a microwave dielectric ceramic material according to an embodiment of the present invention, using a conventional solid phase reaction synthesis method combined with high energy ball milling technology to obtain a refined powder obtained by the first high energy ball milling.
  • the abscissa of the particle size distribution map (a) is the particle size diameter, the unit is ⁇ , and the ordinate is the volume of the powder, and the unit is %. From the particle size distribution diagram (a), the preparation method of the microwave dielectric ceramic material using the present invention can be seen. After the first high-energy ball milling, the fine powder particle size is highly concentrated, the particle size is narrowed, and the diameter is generally less than 1 ⁇ m.
  • the X-ray diffraction (XRD) pattern (b) has an abscissa of 2 ⁇ in degrees and the ordinate is the count detected by the receiver in CPS. None is found from the X-ray diffraction (XRD) pattern (b).
  • the hetero peak, and thus its crystal structure (main crystal phase) is a single-phase orthogonal type perovskite structure.
  • FIG. 3 is a diagram showing a microwave dielectric ceramic sample prepared by a conventional solid phase reaction synthesis method combined with a high energy ball milling technique and using a conventional method for preparing a microwave dielectric ceramic material according to an embodiment of the present invention.
  • the microwave dielectric ceramic material prepared by the preparation method of the microwave dielectric ceramic material of the invention not only has no obvious local pores (pores), but also has a more uniform and dense distribution of the ceramic particles, effectively suppressing the "crystal”. Grid defect effect”.
  • a method for preparing a microwave dielectric ceramic material, the mixed powder is calcium carbonate, aluminum oxide, cerium oxide, titanium dioxide and cerium carbonate, the method comprising:
  • Step 1 Pre-burn the yttrium oxide powder at 800 °C for 3 hours before batching to remove moisture. Drying, and calcining the original titanium dioxide powder at 1280 ° C for 3 hours; according to the chemical formula 0.72 (Ca.. 9 Sr ai ) TiO 3 _0.28 NdAlO 3 ratio of carbonic acid 4 bow, strontium carbonate, alumina, cerium oxide and titanium dioxide Adding zirconia grinding balls as a grinding medium to the mixed powder, adding anhydrous ethanol or deionized water as an organic solvent, placing them in a spherical tank for mechanically mixing, and removing the organic solvent after forming the powder particles. The drying treatment is carried out, and the ratio of the mixed powder, the grinding ball, and the solvent (weight) is 1:3:3 and it accounts for 60% to 80% of the volume of the spherical tank, and the mixing time of the raw materials is 3 hours.
  • the stoichiometric ratio of calcium carbonate and titanium oxide was 0.72 mol%
  • the stoichiometric ratio of alumina and cerium oxide was 0.28 mol%
  • the stoichiometric ratio of cerium carbonate was 0.1 mol%.
  • the purity of the carbonic acid carbonate, strontium carbonate and alumina powders is more than 99.5%
  • the purity of the titanium dioxide and cerium oxide powders is not less than 99.9%.
  • Step 2 using the zirconia grinding ball as a grinding medium, drying the powder particles formed in the first step and performing the first high-energy ball milling to uniformly refine the powder particles to form a refined powder.
  • the high-energy ball milling time is 1 hour
  • the ball-to-batch ratio is 8:1
  • the rotation speed is 800 rpm.
  • Step 3 The refined powder formed in the second step is placed in a closed high temperature resistant crucible, and a precursor powder having a high purity main crystalline phase is synthesized by a high temperature calcination reaction. Among them, the calcination temperature was 1200 ° C and the temperature retention time was 3 hours.
  • Step 4 using a zirconia grinding ball as a grinding medium, and subjecting the calcined precursor powder to a second high-energy ball milling to obtain a ceramic powder which is further uniformly refined.
  • the high-energy ball milling time is 1 hour
  • the ball-to-batch ratio is 10:1
  • the rotation speed is 1000 rpm.
  • Step 5 adding 10% by mass of a polyvinyl alcohol (PVA) aqueous solution (concentration: 5%) to the ceramic powder obtained in the fourth step, and using a drying tower or a granulator to form a spherical and fluid powder. Particles.
  • PVA polyvinyl alcohol
  • Step 6 Using a press (manual or automatic packing) to press the powder particles obtained in the fifth step into a ceramic compact of the desired shape by a double-sided pressing, the pressing pressure is 120 MPa, and the extrusion molding process is used for extrusion or adopting A single injection molding technique produces a ceramic compact of the desired shape.
  • Step 7 Place the ceramic compact into a sealed high temperature resistant alumina crucible for continuous sintering. Into a ceramic blank. Among them, the highest sintering temperature is 1450 degrees Celsius, and the holding time is 4 hours. In the present embodiment, a mixed powder of titanium carbonate and titanium oxide or a ceramic powder is placed in the sealed high-temperature resistant alumina crucible as a mat powder in advance to control the atmosphere during sintering, and a solid phase reaction occurs at a high temperature. A dense ceramic blank is produced.
  • a method for preparing a microwave dielectric ceramic material, the mixed powder is calcium carbonate, aluminum oxide, cerium oxide, titanium dioxide and cerium carbonate, the method comprising:
  • Step 1 Pre-sinter the cerium oxide powder at 800 °C for 3 hours before batching, remove the water for drying, and pre-burn the titanium dioxide raw powder at 1280 °C for 3 hours; according to the chemical formula 0.62 (Ca 0 . 8 Sr a2 ) TiO 3 _0.38NdAlO 3 4
  • TiO 3 _0.38NdAlO 3 4
  • carbonate, strontium carbonate, aluminum oxide, neodymium oxide and titania, zirconia balls were added as a mixed powder in the milling media was added deionized water or ethanol as the organic solvent , placed in a spherical tank for mechanical mixing, and after the formation of powder particles, the organic solvent is removed for drying, the ratio of mixed powder, grinding ball, solvent (weight) is 1:3:3 and it accounts for the spherical tank The volume is 60% ⁇ 80%, and the raw material mixing time is 2 hours.
  • the stoichiometric ratio of calcium carbonate and titanium oxide was 0.62 mol%
  • the stoichiometric ratio of alumina and cerium oxide was 0.38 mol%
  • the stoichiometric ratio of cerium carbonate was 0.2 mol%.
  • the purity of the carbonic acid carbonate, strontium carbonate and alumina powders is more than 99.5%
  • the purity of the titanium dioxide and cerium oxide powders is not less than 99.9%.
  • Step 2 using the zirconia grinding ball as a grinding medium, drying the powder particles formed in the first step and performing the first high-energy ball milling to uniformly refine the powder particles to form a refined powder.
  • the high-energy ball milling time is 2 hours
  • the ball-to-batch ratio is 12:1
  • the rotation speed is 800 rpm.
  • Step 3 The refined powder formed in the second step is placed in a closed high temperature resistant crucible, and a precursor powder having a high purity main crystalline phase is synthesized by a high temperature calcination reaction.
  • the calcination temperature is 900 degrees Celsius, The temperature is 10 hours.
  • Step 4 using a zirconia grinding ball as a grinding medium, and subjecting the calcined precursor powder to a second high-energy ball milling to obtain a ceramic powder which is further uniformly refined.
  • the high-energy ball milling time is 1 hour
  • the ball-to-batch ratio is 10:1
  • the rotation speed is 800 rpm.
  • Step 5 adding 10% by mass of a polyvinyl alcohol (PVA) aqueous solution (concentration: 5%) to the ceramic powder obtained in the fourth step, and using a spray drying tower or a granulator to form a spherical and fluid powder. Body particles.
  • PVA polyvinyl alcohol
  • Step 6 Using a press (manual or automatic packing) to press the powder particles obtained in the fifth step into a ceramic compact of the desired shape by a double-sided pressing, the pressing pressure is 120 MPa, and the extrusion molding process is used for extrusion or adopting A single injection molding technique produces a ceramic compact of the desired shape.
  • Step 7 The ceramic green compact is placed in a sealed high temperature resistant alumina crucible for continuous sintering to form a ceramic blank.
  • the highest sintering temperature is 1350 ° C and the holding time is 4 hours.
  • a mixed powder of titanium carbonate and titanium oxide or a ceramic powder is placed in the sealed high-temperature resistant alumina crucible as a mat powder in advance to control the atmosphere during sintering, and a solid phase reaction occurs at a high temperature.
  • a dense ceramic blank is produced.
  • a method for preparing a microwave dielectric ceramic material, the mixed powder is calcium carbonate, aluminum oxide, cerium oxide, titanium dioxide and cerium carbonate, the method comprising:
  • Step 1 Pre-sinter the yttrium oxide powder at 800 °C for 3 hours before batching, remove the moisture for drying, and pre-burn the original titanium dioxide powder at 1280 °C for 3 hours; according to the chemical formula 0.52 (Ca 0 . 75 Sr 0 .
  • TiO 3 _0.48NdAlO 3 4 hack ratio carbonate, strontium carbonate, aluminum oxide, neodymium oxide and titania, zirconia balls were added as a mixed powder in the grinding media, adding ethanol or deionized water as Organic solvent, placed in a spherical tank for mechanical mixing, and after forming powder particles, The organic solvent is dried, and the ratio of the mixed powder, the grinding ball, and the solvent (weight) is 1:3:3 and it accounts for 60% to 80% of the volume of the spherical tank, and the mixing time of the raw material is 3 hours.
  • the stoichiometric ratio of calcium carbonate and titanium oxide was 0.52 mol%
  • the stoichiometric ratio of alumina and cerium oxide was 0.48 mol%
  • the stoichiometric ratio of cerium carbonate was 0.25 mol%.
  • the purity of the carbonic acid carbonate, strontium carbonate and alumina powders is more than 99.5%
  • the purity of the titanium dioxide and cerium oxide powders is not less than 99.9%.
  • Step 2 using the zirconia grinding ball as a grinding medium, drying the powder particles formed in the first step and performing the first high-energy ball milling to uniformly refine the powder particles to form a refined powder.
  • the high-energy ball milling time is 3 hours
  • the ball-to-batch ratio is 10:1
  • the rotation speed is 600 rpm.
  • Step 3 The refined powder formed in the second step is placed in a closed high temperature resistant crucible, and a precursor powder having a high purity main crystalline phase is synthesized by a high temperature calcination reaction.
  • the calcination temperature was 1050 degrees Celsius and the temperature retention time was 6 hours.
  • Step 4 using a zirconia grinding ball as a grinding medium, and subjecting the calcined precursor powder to a second high-energy ball milling to obtain a ceramic powder which is further uniformly refined.
  • the high-energy ball milling time is 1 hour
  • the ball-to-batch ratio is 8:1
  • the rotation speed is 1000 rpm.
  • Step 5 adding 10% by mass of a polyvinyl alcohol (PVA) aqueous solution (concentration: 5%) to the ceramic powder obtained in the fourth step, and using a spray drying tower or a granulator to form a spherical and fluid powder. Body particles.
  • PVA polyvinyl alcohol
  • Step 6 Using a press (manual or automatic filler) to press the powder particles obtained in the fifth step into a ceramic compact of the desired shape by a double press, the pressing pressure is 100 MPa, and the extrusion molding process is used for extrusion or adopting A single injection molding technique produces a ceramic compact of the desired shape.
  • a press manual or automatic filler
  • Step 7 The ceramic green compact is placed in a sealed high temperature resistant alumina crucible for continuous sintering to form a ceramic blank.
  • the maximum sintering temperature is 1200 ° C and the holding time is 6 hours.
  • a mixed powder of titanium carbonate and titanium oxide or a ceramic powder is placed in the sealed high-temperature resistant alumina crucible as a mat powder in advance to control the atmosphere during sintering, and a solid phase reaction occurs at a high temperature.
  • a dense ceramic blank is produced.
  • Step 8 The fired ceramic blank is taken out and subjected to surface treatment such as grinding and polishing to obtain a ceramic sample of a desired size for testing. Then, the dielectric performance indicators measured by the network analyzer are: ⁇ Qx household 42300 (test frequency is 1.1GHz).
  • a modified dopant, a modification additive and a sintering aid are added in an appropriate amount
  • the modified dopant is an oxide containing a rare earth element
  • the rare earth elements are lanthanum, cerium, lanthanum, cerium, One or more of cerium, lanthanum, 4L, lanthanum, cerium, and lanthanum
  • the modifying additive is one of CaO, SrO, Ti0 2 , ZnO, A1 2 0 3 , Nb 2 0 5 , and Ta 2 0 5 or more
  • the sintering aid is a Bi 2 0 3, B 2 0 3, CuO, V 2 0 5 and one or more of BaO
  • the material formulation of microwave dielectric ceramics according to the chemical formula 0.72Ca 0.
  • the mass percentage of the modified additive is 1% to 4% of the total amount of calcium carbonate, barium carbonate, aluminum oxide, barium oxide and titanium dioxide
  • the mass percentage of the sintering aid is calcium carbonate, barium carbonate, aluminum oxide, barium oxide and
  • the total amount of titanium dioxide is 0.1% ⁇ 1%, and the same process parameters are used for sample trial production and testing, so that the above embodiments of the present invention are applied to specific environments for detailed description.
  • the basic performance indexes are shown in Table 6-8. Table 6 Dielectric properties of doped samples modified with different ratios of rare earth elements
  • the embodiment of the invention combines high energy ball milling technology on the basis of traditional mechanical mixing and solid phase reaction methods
  • the ceramic powder is densified, which not only effectively reduces the calcination temperature of the powder, but also ensures the high purity of the main crystal phase of the ceramic powder synthesized by the reaction.
  • the powder particles are further densified, which lays a good grain foundation for spray granulation, and reduces the sintering temperature.
  • FIG. 4 illustrates a method for preparing a microwave dielectric ceramic material according to another embodiment of the present invention, which is subjected to conventional mechanical mixing (12 hours) (a) and first high energy ball milling (2 hours) ( b) Scanning electron microscopy (SEM) image of the prepared powder particles.
  • Fig. (b) shows no significant block (sheet) as compared with the powder particles after high energy ball milling of Fig. (a), and the particle size is more uniform.
  • FIG. 5 illustrates a method for preparing a microwave dielectric ceramic material according to another embodiment of the present invention, which is respectively combined with a conventional mechanical mixing + solid phase reaction method (a) and a solid phase reaction method + high energy ball milling.
  • the microwave dielectric ceramic material prepared by the preparation method of the microwave dielectric ceramic material of the present invention has not only obvious cracks and local pores (pores), but also the ceramic particles are more uniform and dense, and effectively inhibited.
  • the "lattice defect effect" caused by the volatile element Ca is not only obvious cracks and local pores (pores), but also the ceramic particles are more uniform and dense, and effectively inhibited.
  • the microwave dielectric ceramic material preparation method of the present invention adds cesium carbonate to the raw material on the basis of two high-energy ball milling, replaces part of the Ca element with the Sr element, and controls the atmosphere during sintering, or increases the volatile element Ca.
  • the molar percentage in the raw material suppresses the "lattice defect effect" of the volatile element Ca, greatly reduces the sintering temperature and shortens the sintering time, and achieves high densification, thereby reducing production cost and technical difficulty.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un matériau céramique diélectrique pour micro-ondes, comprenant : le mélange mécanique et uniforme de poudres mixtes de carbonate de calcium, d'oxyde d'aluminium, d'oxyde de néodyme, de dioxyde de titane et de carbonate de strontium ou d'oxyde de calcium pour former des particules de poudre ; un premier broyage à boulets des particules de poudre sous haute énergie pour raffiner uniformément les particules de poudre pour former des poudres raffinées ; la calcination des poudres raffinées sous haute température dans un récipient fermé pour former des poudres de précurseur ; un deuxième broyage à boulets des poudres de précurseur sous haute énergie pour raffiner plus uniformément les poudres de précurseur en vue de former les poudres céramiques. Le présent procédé abaisse la température de frittage et réduit la durée du frittage, inhibant ainsi "l'effet de défaut réticulaire cristallin".
PCT/CN2012/087041 2011-12-22 2012-12-20 Procédé de fabrication d'un matériau céramique diélectrique pour micro-ondes WO2013091560A1 (fr)

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