CN114394828A - Electronic ceramic material with medium dielectric constant and preparation method thereof - Google Patents

Electronic ceramic material with medium dielectric constant and preparation method thereof Download PDF

Info

Publication number
CN114394828A
CN114394828A CN202210019481.5A CN202210019481A CN114394828A CN 114394828 A CN114394828 A CN 114394828A CN 202210019481 A CN202210019481 A CN 202210019481A CN 114394828 A CN114394828 A CN 114394828A
Authority
CN
China
Prior art keywords
ceramic material
electronic ceramic
dielectric
medium
composite powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210019481.5A
Other languages
Chinese (zh)
Other versions
CN114394828B (en
Inventor
方豪杰
贺亦文
张晓云
曾雄
张斗
黄荣厦
龙莹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Meicheng Ceramic Technology Co ltd
Original Assignee
Hunan Meicheng Ceramic Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Meicheng Ceramic Technology Co ltd filed Critical Hunan Meicheng Ceramic Technology Co ltd
Priority to CN202210019481.5A priority Critical patent/CN114394828B/en
Publication of CN114394828A publication Critical patent/CN114394828A/en
Application granted granted Critical
Publication of CN114394828B publication Critical patent/CN114394828B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C04B35/46—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 titanium oxides or titanates
    • C04B35/462—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 titanium oxides or titanates based on titanates
    • 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
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • 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
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • 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
    • C04B2235/3215—Barium oxides 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium 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
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445—Fluoride containing anions, e.g. fluosilicate
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (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

The invention relates to the field of electronic ceramic materials, in particular to an electronic ceramic material with a medium dielectric constant and a preparation method thereof, wherein the electronic ceramic material consists of a main crystal phase, a sintering aid and composite powder; the main crystal phase is BaSm2Ti4O12(ii) a The sintering aid is CuTa2O6、Eu2O3And fluoride; the composite powder is porous Al2O3Adsorption of nano SnO2And nano CeO2The dielectric constant of the electronic ceramic material prepared by the invention is between 45.20 and 45.37, the electronic ceramic material has high stability, small dielectric loss, high quality factor, infinite temperature coefficient of resonant frequency close to zero, small drift degree and capability of ensuring stable workAnd the qualitative performance can be satisfied, and the requirement for the construction of a 5G communication base station can be met.

Description

Electronic ceramic material with medium dielectric constant and preparation method thereof
Technical Field
The invention relates to the field of electronic ceramic materials, in particular to an electronic ceramic material with a medium dielectric constant and a preparation method thereof.
Background
Electronic ceramics (electronic ceramics) refers to ceramics that can utilize electrical and magnetic properties in the electronics industry. The method is to finally obtain the ceramic with new functions by precisely controlling the surface, the crystal boundary and the size structure, is also an important component and an indispensable material basis of high and new technologies such as aerospace, new energy, new materials, microelectronics, laser, ocean engineering, bioengineering and the like at present, and is one of hot spots of current high-technology competition.
One of the keys to the development of 5G communication is the construction of communication base stations. The development of 5G communication puts forward the requirements of high integration level, high frequency, high speed, high temperature stability and ultra-low power consumption on novel microwave components. Electronic ceramic material (30) with medium dielectric constant<εr<70) Is an important material in the aspect of microwave components for communication base stations, and has higher requirements on the dielectric property of electronic ceramic materials.
In order to meet the requirements of electronic ceramic materials in the field of communication base station construction, it is important to prepare an electronic ceramic material with a medium dielectric constant.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above-mentioned drawbacks and needs of the prior art, the present invention provides a medium-dielectric-constant electronic ceramic material and a method for preparing the same.
The technical scheme adopted by the invention is as follows:
an electronic ceramic material with a medium dielectric constant is characterized by comprising a main crystal phase, a sintering aid and composite powder;
the main crystal phase is BaSm2Ti4O12；
The sintering aid is CuTa2O6、Eu2O3And fluoride;
the composite powder is porous Al2O3Adsorption of nano SnO2And nano CeO2。
Further, the fluoride is LF or MF2Or ReF3Wherein L is alkali metal, M is Ca or Mg, and Re is Y, La, Gd, Dy, Tm and Yb.
Furthermore, the addition amount of the sintering aid is 4-9% of the mass of the main crystal phase.
Further, the CuTa2O6、Eu2O3The mass ratio of the fluoride is 10-12: 3-5: 1.
further, the preparation method of the composite powder comprises the following steps:
SnCl4·5H2O、Ce(NO3)3·6H2Adding O into water, dropwise adding dilute HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al2O3Slowly dropwise adding ammonia water under ice bath, adjusting pH of the reaction solution to 8-10, removing ice bath, heating to 40-50 deg.C, stirring for 5-8h, filtering, washing solid with water until no Cl is formed-、NO3 -Then adding saturated ammonia water, stirring for 5-10h, filtering, washing with water and ethanol, vacuum drying at 60-80 ℃ for 6-10h, heating to 650-680 ℃ and roasting for 3-5 h.
Further, the porous Al2O3The particle diameter of (A) is 8-20 μm.
Further, the mass concentration of the dilute HCl is 1-2%, and the mass concentration of the ammonia water is 15-25%.
Further, the temperature rise rate during the calcination is 3-10 ℃/min.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio3、Sm2O3、TiO2Wet ball milling for 8-10h after mixing, pre-sintering for 2-5h at 1150 ℃ after drying and sieving, mixing with sintering aid and composite powder, wet ball milling for 15-20h, adding binder for granulation after drying and sieving, heating to 1280 ℃ after tabletting, and sintering for 4-6 h.
Further, the binder is a polyvinyl alcohol solution with the mass concentration of 10-15%.
The invention has the beneficial effects that:
the invention provides an electronic ceramic material with medium dielectric constant, the dielectric constant of the prepared electronic ceramic material is 45.20-45.37, and the main crystal phase of the electronic ceramic material is BaSm2Ti4O12，BaCO3-Sm2O3-TiO2The system is one of the main materials of wet medium dielectric constant microwave dielectric ceramic, but the system is easy to generate oxygen vacancy at high temperature to increase the dielectric loss, and if the temperature is not well controlled in the high-temperature firing process, the floating range of the dielectric constant is increased and the stability is poor, so the inventor adds CuTa2O6、Eu2O3Fluoride, can accelerate BaCO3-Sm2O3-TiO2The invention is an atomic transmission process when ceramic materials are fired, which promotes crystal grains to carry out mass transfer at a lower temperature, is beneficial to generating a liquid phase with a low melting point, promotes the growth, movement, diffusion, connection and uniform growth of the crystal grains, promotes sintering densification, ensures that the ceramic crystal grains are good in growth, high in density and few in pores, also reduces the fluctuation of sintering temperature and dielectric constant, improves the sintering performance, the composite powder consists of micron and nano particles, the micron and nano particles with high surface energy can occupy the lowest free energy position, the generated melt can pull the crystal grains together to minimize the free energy, promotes the ordered growth of the crystal grains, further improves the dielectric performance, the electronic ceramic materials prepared by the invention have the advantages of small dielectric loss, high quality factor, infinite resonant frequency temperature coefficient close to zero, small drift degree and capability of ensuring the working stability, and the method can be used for manufacturing microwave components and parts and meets the requirements of 5G communication base station construction.
Drawings
Fig. 1 is an SEM image of the medium-dielectric-constant electronic ceramic material prepared in example 1 of the present invention, and it can be seen that the inter-granular continuity is good, the density is high, and the number of pores is small.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase2Ti4O12From CuTa2O6、Eu2O3、YF3Sintering aid and porous Al of composition2O3Adsorption of nano SnO2And nano CeO2Composite powder;
wherein, the addition amount of the sintering aid is 6 percent of the mass of the main crystal phase.
CuTa2O6、Eu2O3The mass ratio of the fluoride is 10: 4: 1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1: 1 SnCl4·5H2O、Ce(NO3)3·6H2Adding O into water, dropwise adding 1.5% diluted HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm2O3Slowly dropwise adding ammonia water with the mass concentration of 18% under ice bath, adjusting the pH of the reaction solution to 9, removing the ice bath, heating to 45 ℃, stirring for 5h, filtering, washing the solid with water until no Cl exists-、NO3 -Then adding saturated ammonia water, stirring for 10h, filtering, washing with water and ethanol, vacuum drying at 80 ℃ for 6h, heating to 680 ℃ at the speed of 3 ℃/min, and roasting for 5 h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio3、Sm2O3、TiO2And performing wet ball milling for 10h after mixing, pre-sintering for 5h at 1050 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 20h, adding a polyvinyl alcohol solution with the mass concentration of 10% as a binder for granulation after drying and sieving, heating to 1240 ℃ after tabletting, and sintering for 6h to obtain the product with the density of 98.5%.
Example 2:
intermediate dielectric constant electronCeramic material consisting of a main crystal phase BaSm2Ti4O12From CuTa2O6、Eu2O3、YF3Sintering aid and porous Al of composition2O3Adsorption of nano SnO2And nano CeO2Composite powder;
wherein, the addition amount of the sintering aid is 4 percent of the mass of the main crystal phase.
CuTa2O6、Eu2O3The mass ratio of the fluoride is 10: 5: 1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1: 1 SnCl4·5H2O、Ce(NO3)3·6H2Adding O into water, dropwise adding 1% diluted HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm2O3Slowly dropwise adding ammonia water with the mass concentration of 15% under ice bath, adjusting the pH of the reaction solution to 10, removing the ice bath, heating to 50 ℃, stirring for 6h, filtering, washing the solid with water until no Cl exists-、NO3 -Adding saturated ammonia water, stirring for 10h, filtering, washing with water and ethanol, vacuum drying at 70 deg.C for 10h, heating to 680 deg.C at 5 deg.C/min, and calcining for 5 h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio3、Sm2O3、TiO2And performing wet ball milling for 10 hours after mixing, pre-sintering for 5 hours at 1100 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 18 hours, adding a polyvinyl alcohol solution with the mass concentration of 12% as a binder for granulation after drying and sieving, heating to 1280 ℃ after tabletting, and sintering for 5 hours, wherein the density is 98.3%.
Example 3:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase2Ti4O12From CuTa2O6、Eu2O3、YF3Sintering aid and porous Al of composition2O3Adsorption of nano SnO2And nano CeO2Composite powder;
wherein, the addition amount of the sintering aid is 4 percent of the mass of the main crystal phase.
CuTa2O6、Eu2O3The mass ratio of the fluoride is 10: 3: 1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1: 1 SnCl4·5H2O、Ce(NO3)3·6H2Adding O into water, dropwise adding 1% diluted HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm2O3Slowly dropwise adding ammonia water with the mass concentration of 15% under ice bath, adjusting the pH of the reaction solution to 8, removing the ice bath, heating to 40 ℃, stirring for 5h, filtering, washing the solid with water until no Cl exists-、NO3 -Then adding saturated ammonia water, stirring for 5h, filtering, washing with water and ethanol, vacuum drying at 60 ℃ for 6h, heating to 650 ℃ at the speed of 3 ℃/min, and roasting for 3 h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio3、Sm2O3、TiO2And performing wet ball milling for 8h after mixing, pre-sintering for 2h at 1000 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 15h, adding a polyvinyl alcohol solution with the mass concentration of 10% as a binder for granulation after drying and sieving, heating to 1200 ℃ after tabletting, and sintering for 4h to obtain the product with the density of 98.1%.
Example 4:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase2Ti4O12From CuTa2O6、Eu2O3、YF3Sintering aid and porous Al of composition2O3Adsorption of nano SnO2And nano CeO2Composite powder;
wherein, the addition amount of the sintering aid is 9 percent of the mass of the main crystal phase.
CuTa2O6、Eu2O3And the mass ratio of the fluoride is 12: 5: 1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1: 1 SnCl4·5H2O、Ce(NO3)3·6H2Adding O into water, dropwise adding diluted HCl with mass concentration of 2% while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm2O3Slowly dropwise adding 25% ammonia water under ice bath, adjusting pH of the reaction solution to 10, removing ice bath, heating to 50 deg.C, stirring for 8h, filtering, and washing the solid with water until no Cl is formed-、NO3 -Adding into saturated ammonia water, stirring for 10h, filtering, washing with water and ethanol, vacuum drying at 80 deg.C for 10h, heating to 680 deg.C at a speed of 10 deg.C/min, and calcining for 5 h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio3、Sm2O3、TiO2And performing wet ball milling for 10 hours after mixing, pre-burning for 5 hours at 1150 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 20 hours, adding a polyvinyl alcohol solution with the mass concentration of 15% as a binder for granulation after drying and sieving, heating to 1280 ℃ after tabletting, and sintering for 6 hours, wherein the density is 98.3%.
Example 5:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase2Ti4O12From CuTa2O6、Eu2O3、YF3Sintering aid and porous Al of composition2O3Adsorption of nano SnO2And nano CeO2Composite powder;
wherein, the addition amount of the sintering aid is 4 percent of the mass of the main crystal phase.
CuTa2O6、Eu2O3And the mass ratio of the fluoride is 12: 3: 1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1: 1 SnCl4·5H2O、Ce(NO3)3·6H2Adding O into water, dropwise adding diluted HCl with mass concentration of 2% while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm2O3Slowly dropwise adding ammonia water with the mass concentration of 15% under ice bath, adjusting the pH of the reaction solution to 10, removing the ice bath, heating to 40 ℃, stirring for 8h, filtering, washing the solid with water until no Cl exists-、NO3 -Then adding saturated ammonia water, stirring for 5h, filtering, washing with water and ethanol, vacuum drying at 80 ℃ for 6h, heating to 650 ℃ at the speed of 10 ℃/min, and roasting for 5 h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio3、Sm2O3、TiO2And performing wet ball milling for 8h after mixing, pre-sintering for 2h at 1150 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 20h, adding a polyvinyl alcohol solution with the mass concentration of 10% as a binder for granulation after drying and sieving, heating to 1280 ℃ after tabletting, and sintering for 4h, wherein the density is 97.9%.
Example 6:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase2Ti4O12From CuTa2O6、Eu2O3、YF3Sintering aid and porous Al of composition2O3Adsorption of nano SnO2And nano CeO2Composite powder;
wherein, the addition amount of the sintering aid is 9 percent of the mass of the main crystal phase.
CuTa2O6、Eu2O3The mass ratio of the fluoride is 10: 5: 1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1: 1 SnCl4·5H2O、Ce(NO3)3·6H2Adding O into water, dropwise adding 1% diluted HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm2O3Slowly adding 25% by mass of water solution dropwise under ice bathAmmonia water, adjusting the pH value of the reaction solution to 8, removing the ice bath, heating to 50 ℃, stirring for 5h, filtering, washing the solid with water until no Cl exists-、NO3 -Then adding saturated ammonia water, stirring for 10h, filtering, washing with water and ethanol, vacuum drying at 60 ℃ for 10h, heating to 680 ℃ at the speed of 3 ℃/min, and roasting for 3 h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio3、Sm2O3、TiO2And performing wet ball milling for 10h after mixing, pre-sintering for 5h at 1000 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 15h, adding a polyvinyl alcohol solution with the mass concentration of 15% as a binder for granulation after drying and sieving, heating to 1200 ℃ after tabletting, and sintering for 6h to obtain the product with the density of 98.3%.
Comparative example 1:
comparative example 1 is substantially the same as example 1 except that the compactness of 64.2% is not achieved without adding a sintering aid.
Comparative example 2:
comparative example 2 is substantially the same as example 1 except that CuTa is not added to the sintering aid2O6The compactness is 70.8 percent, and the use requirement cannot be met.
Comparative example 3:
comparative example 3 is substantially the same as example 1 except that Eu is not added to the sintering aid2O3The compactness is 76.1 percent, and the use requirement cannot be met.
Comparative example 4:
comparative example 4 is substantially the same as example 1 except that YF is not added to the sintering aid3The compactness is 82.6 percent, and the use requirement cannot be met.
Comparative example 5:
comparative example 5 is substantially the same as example 1 except that the compactness thereof is 95.3% without adding the composite powder.
Comparative example 6:
comparative example 6 is substantially the same as example 1 except that porous Al is used2O3Nano SnO2CeO, CeO nanoparticles2The mixture is added separately, and the compactness is 96.6 percent.
Comparative example 7:
comparative example 7 is substantially the same as example 1 except that the composite powder does not contain nano CeO2The compactness thereof is 96.9 percent.
Comparative example 8:
comparative example 8 is substantially the same as example 1 except that the composite powder does not contain nano SnO2The compactness thereof is 97.4%.
And (3) performance testing:
after the electronic ceramic materials prepared in examples 1 to 6 of the present invention and comparative examples 5 to 8 were double-side polished, dielectric properties thereof were measured using a Hakki vector network analyzer of angiont corporation, usa, and dielectric constants, dielectric losses, quality factors, and temperature coefficients of resonant frequency were measured using a TEo11 resonant mode, and the results are shown in table 1.
Table 1:
Figure BDA0003461856820000091
as can be seen from the above table 1, the dielectric constant of the electronic ceramic material prepared by the invention is 45.20-45.37, the electronic ceramic material has high stability, small dielectric loss, high quality factor, infinite resonant frequency temperature coefficient close to zero, small drift degree, and can ensure the working stability and meet the requirements of 5G communication base station construction.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. An electronic ceramic material with a medium dielectric constant is characterized by comprising a main crystal phase, a sintering aid and composite powder;
the main crystal phase is BaSm2Ti4O12；
The sintering aid is CuTa2O6、Eu2O3And fluoride;
the composite powder is porous Al2O3Adsorption of nano SnO2And nano CeO2。
2. A dielectric constant electron ceramic material according to claim 1 wherein said fluoride is LF, MF2Or ReF3Wherein L is alkali metal, M is Ca or Mg, and Re is Y, La, Gd, Dy, Tm and Yb.
3. A dielectric constant electronic ceramic material as claimed in claim 1, wherein said sintering aid is added in an amount of 4 to 9% by mass based on the mass of the main crystal phase.
4. A medium-dielectric-constant electronic ceramic material according to claim 1, wherein the CuTa2O6、Eu2O3The mass ratio of the fluoride is 10-12: 3-5: 1.
5. a dielectric constant electronic ceramic material as claimed in claim 1, wherein the composite powder is prepared by the following steps:
SnCl4·5H2O、Ce(NO3)3·6H2Adding O into water, dropwise adding dilute HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al2O3Slowly dropwise adding ammonia water under ice bath, adjusting pH of the reaction solution to 8-10, removing ice bath, heating to 40-50 deg.C, stirring for 5-8h, filtering, washing solid with water until no Cl is formed-、NO3 -Then adding saturated ammonia water, stirring for 5-10h, filtering, washing with water and ethanol, vacuum drying at 60-80 ℃ for 6-10h, heating to 650-680 ℃ and roasting for 3-5 h.
6. A medium-dielectric-constant electronic ceramic material according to claim 5, wherein the porous Al is2O3The particle diameter of (A) is 8-20 μm.
7. A medium-dielectric-constant electronic ceramic material as claimed in claim 5, wherein the dilute HCl has a mass concentration of 1-2% and the ammonia has a mass concentration of 15-25%.
8. A medium-dielectric-constant electronic ceramic material as claimed in claim 5, wherein the temperature rise rate at the time of firing is 3 to 10 ℃/min.
9. A process for the preparation of a medium-dielectric-constant electronic ceramic material according to any one of claims 1 to 8, characterized in that BaCO is weighed in stoichiometric proportions3、Sm2O3、TiO2Ball milling for 8-10h by a wet method after mixing, pre-burning for 2-5h at 1150 ℃ after drying and sieving, mixing with sintering aid and composite powder, ball milling for 15-20h by the wet method, adding binder for granulation after drying and sieving, heating to 1280 ℃ after tabletting, and sintering for 4-6 h.
10. The method of claim 9, wherein the binder is a polyvinyl alcohol solution with a mass concentration of 10-15%.
CN202210019481.5A 2022-01-10 2022-01-10 Electronic ceramic material with medium dielectric constant and preparation method thereof Active CN114394828B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210019481.5A CN114394828B (en) 2022-01-10 2022-01-10 Electronic ceramic material with medium dielectric constant and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210019481.5A CN114394828B (en) 2022-01-10 2022-01-10 Electronic ceramic material with medium dielectric constant and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114394828A true CN114394828A (en) 2022-04-26
CN114394828B CN114394828B (en) 2022-10-18

Family

ID=81228254

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210019481.5A Active CN114394828B (en) 2022-01-10 2022-01-10 Electronic ceramic material with medium dielectric constant and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114394828B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08157216A (en) * 1994-12-01 1996-06-18 Chichibu Onoda Cement Corp Production of barium oxide-titanium oxide-rate earth metal oxide dielectric material
CN102757219A (en) * 2012-07-31 2012-10-31 嘉兴佳利电子股份有限公司 Two-phase compound microwave medium ceramic material and preparation method thereof
CN110015894A (en) * 2019-05-06 2019-07-16 广州光鼎科技集团有限公司 The bismuth-sodium titanate base ceramics and its preparation method and application of dielectric stable under a kind of high temperature
CN110256088A (en) * 2019-06-14 2019-09-20 山东格仑特电动科技有限公司 A kind of microwave-medium ceramics composite sintering agent and preparation method thereof
CN110483035A (en) * 2019-09-24 2019-11-22 福建省德化福杰陶瓷有限公司 A kind of microwave dielectric ceramic materials and its preparation method and application, a kind of filter ceramic material
CN111943664A (en) * 2020-07-29 2020-11-17 无锡鑫圣慧龙纳米陶瓷技术有限公司 Barium samarium titanium series microwave dielectric ceramic with low sintering temperature and preparation method thereof
CN113493345A (en) * 2021-06-30 2021-10-12 清华大学 Samarium-doped bismuth ferrite-barium titanate ceramic film and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08157216A (en) * 1994-12-01 1996-06-18 Chichibu Onoda Cement Corp Production of barium oxide-titanium oxide-rate earth metal oxide dielectric material
CN102757219A (en) * 2012-07-31 2012-10-31 嘉兴佳利电子股份有限公司 Two-phase compound microwave medium ceramic material and preparation method thereof
CN110015894A (en) * 2019-05-06 2019-07-16 广州光鼎科技集团有限公司 The bismuth-sodium titanate base ceramics and its preparation method and application of dielectric stable under a kind of high temperature
CN110256088A (en) * 2019-06-14 2019-09-20 山东格仑特电动科技有限公司 A kind of microwave-medium ceramics composite sintering agent and preparation method thereof
CN110483035A (en) * 2019-09-24 2019-11-22 福建省德化福杰陶瓷有限公司 A kind of microwave dielectric ceramic materials and its preparation method and application, a kind of filter ceramic material
CN111943664A (en) * 2020-07-29 2020-11-17 无锡鑫圣慧龙纳米陶瓷技术有限公司 Barium samarium titanium series microwave dielectric ceramic with low sintering temperature and preparation method thereof
CN113493345A (en) * 2021-06-30 2021-10-12 清华大学 Samarium-doped bismuth ferrite-barium titanate ceramic film and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李斌等: "B_2O_3对BaO-Sm_2O_3-TiO_2微波介质陶瓷性能的影响", 《材料科学与工艺》 *

Also Published As

Publication number Publication date
CN114394828B (en) 2022-10-18

Similar Documents

Publication Publication Date Title
CN108358632B (en) Ultralow-temperature sintered high-Q x f-value microwave dielectric material and preparation method thereof
WO1992012929A2 (en) Beneficiated lanthanum chromite for low temperature firing
CN111087235B (en) Method for preparing YAG transparent ceramic by adopting yttrium/auxiliary agent/aluminum triple core-shell structure powder
CN103172364B (en) Preparation method of microwave dielectric ceramic material
CN115536390B (en) Transparent dielectric energy storage ceramic material and preparation method and application thereof
CN108358633B (en) Low-temperature sintered Ca5Mn4-xMgxV6O24Microwave dielectric material and preparation method thereof
CN102049514B (en) Powder for aluminum oxide ceramics nano metallized paste and preparation method thereof
CN110818405A (en) Microwave dielectric ceramic, preparation method thereof and 5G base station
CN113372115A (en) Preparation of tantalate (Y/Al/RE) by centrifugal spray granulation method3TaO7Method for preparing hollow sphere powder
CN116854472B (en) Microwave dielectric material and preparation method thereof
CN114394828B (en) Electronic ceramic material with medium dielectric constant and preparation method thereof
CN116283251B (en) Alumina ceramic and preparation method and application thereof
CN114349504B (en) Doped perovskite relay electronic ceramic material and preparation method thereof
CN106278192A (en) A kind of multi-phase microwave dielectric ceramic with Fructus Jujubae cake model structure and preparation method thereof
CN112898022B (en) Ultralow temperature sintered microwave dielectric material Ca2V2O7-H3BO3And method for preparing the same
CN112979306B (en) Method for preparing ferroelectric energy storage ceramic
JP2009067619A (en) Zirconium tungstate-silicon oxide composite sintered compact, method of manufacturing the composite sintered compact and formed body provided with composite sintered compact
CN112830780B (en) Regulating agent, LTCC microwave dielectric material and preparation method thereof
CN110357628B (en) Ca5Mg4-xCox(VO4)6Low-temperature sintering microwave ceramic material and preparation method thereof
CN114149261A (en) Lead hafnate antiferroelectric ceramic material and preparation method thereof
TWI461385B (en) Low Temperature Co - firing Microwave Dielectric Ceramics and Its Preparation
Ma et al. Improving the Dielectric Properties of the‎ Ba (Zr0. 1Ti0. 9) O3-based Ceramics by Adding‎ a Li2O–SiO2 Sintering Agent Step by Step‎
CN116217213B (en) Preparation method of silicon-based microwave dielectric ceramic with ultralow dielectric constant
CN110734286B (en) Iron-based garnet ceramic material, preparation and application thereof
CN116789448B (en) Medium-temperature sintering high-Q-value microwave dielectric material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant