CN113429200B - Medium low-loss low-temperature co-fired ceramic material and preparation method thereof - Google Patents

Medium low-loss low-temperature co-fired ceramic material and preparation method thereof Download PDF

Info

Publication number
CN113429200B
CN113429200B CN202110820476.XA CN202110820476A CN113429200B CN 113429200 B CN113429200 B CN 113429200B CN 202110820476 A CN202110820476 A CN 202110820476A CN 113429200 B CN113429200 B CN 113429200B
Authority
CN
China
Prior art keywords
low
temperature
ceramic material
parts
fired
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.)
Active
Application number
CN202110820476.XA
Other languages
Chinese (zh)
Other versions
CN113429200A (en
Inventor
宋锡滨
刘振锋
闫鑫升
艾辽东
奚洪亮
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.)
Shandong Sinocera Functional Material Co Ltd
Original Assignee
Shandong Sinocera Functional Material 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 Shandong Sinocera Functional Material Co Ltd filed Critical Shandong Sinocera Functional Material Co Ltd
Priority to CN202110820476.XA priority Critical patent/CN113429200B/en
Publication of CN113429200A publication Critical patent/CN113429200A/en
Application granted granted Critical
Publication of CN113429200B publication Critical patent/CN113429200B/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
    • C04B35/465—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 based on alkaline earth metal titanates
    • C04B35/468—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 based on alkaline earth metal titanates based on barium titanates
    • C04B35/4686—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 based on alkaline earth metal titanates based on barium titanates based on phases other than BaTiO3 perovskite phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445—Magnesium silicates, e.g. forsterite
    • 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
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
    • C04B2235/365—Borosilicate glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

Ba 2 Ti 9 O 20 The low-temperature co-fired glass ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation: ba 2 Ti 9 O 20 55‑70wt％；Mg 2 SiO 4 10-20 wt%; 10-25wt% of low-melting-point glass powder; the low-melting-point glass powder comprises the following components in parts by weight: 40-48 parts of ZnO; b is 2 O 3 20-30 parts by weight; SiO2 2 10-20 parts by weight; al (Al) 2 O 3 10-15 parts by weight; 0-7 parts of BaO; li 2 0-5 parts of O. The low-temperature co-fired glass ceramic material has near-zero temperature coefficient of resonant frequency and less than 2 multiplied by 10 of loss tangent value ‑3 The dielectric constant is about 20, and the use requirement of a sub6GHz microwave device is met; and the sintering temperature is low.

Description

Medium low-loss low-temperature co-fired ceramic material and preparation method thereof
Technical Field
The invention belongs to the technical field of low-temperature co-fired ceramic materials, and particularly relates to a ceramic material with high density, moderate dielectric constant, higher quality factor and lower resonant frequency coefficient and a preparation method thereof. The method can be used for manufacturing components such as dielectric filters, duplexers, baluns and the like in the field of electronic communication.
Background
In recent years, with the rapid development of emerging communication technologies such as 5G and the like and high-density packaging technologies, the development of devices towards structure miniaturization, higher integration density, faster transmission rate and the like is promoted, and the low-temperature co-fired ceramic technology is an important basis for realizing the development. Meanwhile, materials capable of being sintered at low temperature for manufacturing components have become a hot spot in the research field of materials at home and abroad in recent years.
Through decades of development, the mainstream low-temperature co-fired ceramic material system at present is mainly divided into two types, namely microcrystalline glass and glass ceramic composite material. The glass ceramic composite material system mainly comprises low-melting-point glass and a ceramic material, wherein the glass mainly plays a role in reducing dielectric constant and sintering temperature, and the ceramic phase is used as a base material.
In general, ceramic materials can be classified into three main groups according to the magnitude of dielectric constant: a low dielectric constant ceramic comprising A1 2 O 3 、MgTiO 3 、Mg 2 SiO 4 Etc.; medium dielectric constant ceramics, including BaO-TiO 2 System, complex perovskites, and the like; high dielectric constant ceramics, including TiO 2 、CaTiO 3 And the like.
Ba 2 Ti 9 O 20 The microwave material has a dielectric constant of 39-40 and a high quality factor, but the sintering temperature is too high (1350-. To Ba 2 Ti 9 O 20 The addition of the low-softening-point glass into the microwave material can effectively reduce the sintering temperature, but the addition of the glass can improve the dielectric loss and the temperature coefficient of the resonant frequency of a material system, thereby limiting the use.
Therefore, how to effectively reduce the temperature coefficient of the resonant frequency of the material system, and further develop a Ba with the temperature coefficient of the resonant frequency close to zero, low sintering temperature, proper dielectric constant, low dielectric loss and convenient realization of industrial production 2 Ti 9 O 20 The low-temperature co-fired ceramic material has positive significance.
Disclosure of Invention
Therefore, the present invention provides a Ba 2 Ti 9 O 20 The low-temperature co-fired ceramic material has a dielectric constant of about 20 and good low-temperature sintering performance, and is suitable for application in the fields of microwave dielectric filters, duplexers, baluns and the like.
The second technical problem to be solved by the present invention is to provide the above-mentioned Ba 2 Ti 9 O 20 A preparation method and application of a base low-temperature co-fired ceramic material.
In order to solve the above technical problems, the present invention provides a Ba 2 Ti 9 O 20 The low-temperature co-fired glass ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba 2 Ti 9 O 20 55-70wt％；
Mg 2 SiO 4 10-20wt％；
10-25wt% of low-melting-point glass powder.
The low-melting-point glass powder comprises the following components in parts by weight:
Figure BDA0003171816650000021
Figure BDA0003171816650000031
wherein, when preparing the glass powder, ZnO and SiO are introduced in the form of corresponding oxides 2 And Al 2 O 3 Introduction of B in the form of boric acid 2 O 3 BaO in the form of barium carbonate and Li in the form of lithium carbonate 2 O。
The invention also discloses a preparation method of the low-temperature co-fired glass ceramic material, which comprises the following steps:
(1) weighing Ba according to the formula amount 2 Ti 9 O 20 、Mg 2 SiO 4 Mixing the mixture with low-melting-point glass powder to obtain a mixture, and then grinding the mixture to a required particle size to obtain a mixed material;
(2) and (2) drying and sieving the mixed material obtained in the step (1) to obtain the low-temperature co-fired glass ceramic material.
Wherein, in the step (1), water and a dispersing agent are added into the mixture for ball milling, and then sand milling is carried out to further reduce the particle size.
Wherein, in the step (1):
controlling the mass ratio of the mixture to water to be 1: 1.5-2;
the addition amount of the dispersant accounts for 0.2 to 1.0wt percent of the amount of the mixture;
in the ball milling step, the solid content of the material is controlled to be 35-45%;
in the sanding step, the specific surface area of the mixed material is controlled to be 2-6m 2 /g；
Wherein, in the step (2), the drying is spray drying.
In the step (2), the spray granulation step is carried out by using a spray dryer, the inlet temperature is controlled to be 250 +/-5 ℃, the outlet temperature is controlled to be 120 +/-5 ℃, and the rotation speed of an atomizer is 10800 +/-50 r/min.
The preparation method of the low-temperature co-fired glass ceramic material further comprises the following steps: prior to step (1) one or more of the following steps (i), (ii) and (iii) are performed:
(i) obtaining Ba 2 Ti 9 O 20 A step (2);
(ii) obtaining Mg 2 SiO 4 A step (2);
(iii) and obtaining the low-melting-point glass powder.
Wherein said step (i) comprises solid phase synthesis of said Ba 2 Ti 9 O 20 The method specifically comprises the following steps: taking BaTiO according to stoichiometric ratio 3 And TiO 2 Mixing to obtain a mixture; adding water and a dispersing agent to perform ball milling, premixing and dispersing, and performing sanding and redispersion treatment; then spray drying the dispersed material, calcining the dried powder at 1200 +/-10 ℃ for 4h, ball-milling the calcined powder, then performing sand milling dispersion treatment, and finally spray drying the dispersed slurry to obtain the required Ba 2 Ti 9 O 20 A material.
Specifically, the solid phase synthesis of Ba 2 Ti 9 O 20 In the steps of (A): the BaTiO 3 And TiO 2 The stoichiometric ratio of (a) to (b) is 2: 7; controlling the mixture withThe mass ratio of water is 1: 1-1.5; the addition amount of the dispersant accounts for 0.2 to 2.0 weight percent of the amount of the mixture; the dispersant is an ammonium salt dispersant; the granularity D50 of the sanded material is controlled to be 0.5-1 mu m, and the moisture content of the material is controlled in the spray drying step<0.5％。
Wherein said step (ii) comprises solid phase synthesis of said Mg 2 SiO 4 The method specifically comprises the following steps: weighing Mg (OH) according to a stoichiometric ratio 2 、SiO 2 Mixing to obtain a mixture; adding water and a dispersing agent for ball milling dispersion, and sanding and redispersing; then spray drying the dispersed material, calcining the dried powder at the temperature of 900-1000 ℃, keeping the temperature for 2-4h, ball-milling the calcined powder, sanding and redispersing the calcined powder, and finally spray drying the dispersed material to obtain the required Mg 2 SiO 4 。
Specifically, the Mg 2 SiO 4 The preparation steps of (A): the Mg (OH) 2 :SiO 2 The stoichiometric ratio of (a) to (b) is 2: 1; controlling the mass ratio of the mixture to water to be 1: 0.5-1.5; the addition amount of the dispersant accounts for 1.0 to 1.5 weight percent of the amount of the mixture; the dispersant comprises an ammonium salt dispersant; the granularity D50 of the sanded material is controlled to be 0.4-1 mu m, and the moisture content of the material is controlled in the spray drying step<0.5％。
Wherein step (iii) comprises: weighing ZnO and B with certain mass 2 O 3 、SiO 2 、Al 2 O 3 、BaO、Li 2 And O, uniformly mixing, melting, water quenching, crushing and drying to obtain the required low-melting-point glass powder.
The invention provides a low-temperature co-fired glass ceramic slurry, which comprises the low-temperature co-fired glass ceramic material and an organic auxiliary agent.
The invention also provides a preparation method of the low-temperature co-fired glass ceramic slurry, which comprises the steps of adding the organic auxiliary agent into the low-temperature co-fired glass ceramic material and uniformly mixing.
The invention also provides a green ceramic tape which is prepared by tape casting the low-temperature co-fired glass ceramic slurry.
The invention also provides a low-temperature co-fired ceramic material, which comprises the sintered low-temperature co-fired glass ceramic material; or comprises sintering the low-temperature co-fired glass ceramic slurry; or comprises sintered green tape as described above.
The invention also provides the application of the low-temperature co-fired glass ceramic material, the low-temperature co-fired glass ceramic slurry and the green ceramic tape in preparing ceramic devices.
The invention also provides a ceramic device, which comprises the sintered low-temperature co-fired glass ceramic material; or comprises the sintered low-temperature co-fired glass ceramic slurry; or comprises sintered green tape as described above.
The ceramic device comprises a microwave dielectric filter, a duplexer, a balun and the like.
The invention also provides a preparation method of the ceramic device, which comprises the steps of carrying out compression molding on the low-temperature co-fired ceramic material to obtain a blank body and carrying out heat preservation sintering on the blank body at the temperature of 850-900 ℃.
The invention has the following beneficial technical effects:
ba of the invention 2 Ti 9 O 20 Based on a low temperature co-fired ceramic material with Ba 2 Ti 9 O 20 、Mg 2 SiO 4 And low-melting point glass as raw materials. Wherein:
(1)Ba 2 Ti 9 O 20 as a base material, the dielectric constant is 39-40, the quality factor is more than 8000(4GHz), and the temperature coefficient of resonance frequency is +2 ppm/DEG C;
(2) the addition of the low-melting-point glass powder can effectively reduce the sintering temperature of the material and influence the dielectric property of the material, so that the Ba 2 Ti 9 O 20 The sintering temperature of the base low-temperature co-fired ceramic material can be reduced from 1350-1400 ℃ to 850-900 ℃, so that the low-temperature sintering performance of the material is greatly improved, and the industrial production is facilitated;
(3) mg2SiO4 is a material with olivine structure formed by linking Si-O tetrahedra and Mg-O tetrahedra through a common vertex, pyramid-like framework, wherein the Si-O bond is composed of 55% covalent bond and 45% ionic bond, the high content of covalent bond makes Mg2SiO4 have low dielectric constant (6.8) and low dielectric loss, and the temperature coefficient of resonance frequency τ f is about-68 ppm/DEG C. Therefore, the addition of the negative temperature coefficient Mg2SiO4 material helps to move the resonant frequency temperature coefficient of the material in the negative direction and gradually approaches zero. Meanwhile, the Mg2SiO4 has low raw material cost and simple synthesis process, and is suitable for industrial production.
Ba of the invention 2 Ti 9 O 20 The base low-temperature co-fired ceramic material has good stability along with temperature change and lower material loss tangent value (the material loss tangent value is less than 2 multiplied by 10) -3 ) The dielectric constant is about 20, and the use requirement of a sub6GHz microwave device is met; and the sintering temperature of the material is reduced from 1350-1400 ℃ to 850-900 ℃, and the low-temperature sintering performance is greatly improved.
Brief description of the drawings
FIG. 1 is an SEM image of the powder of a low-temperature co-fired ceramic material obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The present example describes Ba 2 Ti 9 O 20 The low-temperature co-fired ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba2Ti9O20 55wt％；
Mg2SiO4 20wt％；
25wt% of low-melting-point glass powder;
the low-melting-point glass powder comprises the following components in parts by weight:
Figure BDA0003171816650000071
the present example describes Ba 2 Ti 9 O 20 The preparation method of the base low-temperature co-fired ceramic material comprises the following steps:
(1) weighing BaTiO with corresponding weight according to the selected mass content ratio 3 、TiO 2 Adding water (material: water is 1: 1.2) and an ammonium acrylate dispersant (accounting for 0.7 wt% of the powder amount), uniformly mixing, premixing for 3 hours by using a ball mill, and then dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) to obtain uniformly dispersed slurry;
(2) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calciner at 1200 ℃, and keeping the temperature for 4 hours to obtain Ba 2 Ti 9 O 20 And is ready for use;
the chemical equation for this reaction is: 2BaTiO3+7TiO2 → Ba2Ti9O20
(3) Weighing Mg (OH) with corresponding weight according to the selected mass ratio 2 、SiO 2 Adding water (material: water is 1: 1.2) and an ammonium acrylate dispersant (accounting for 1 wt% of the powder amount), uniformly mixing, premixing for 3 hours by using a ball mill, and further dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) after ball milling to obtain uniformly dispersed slurry;
(4) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calcining furnace at 950 ℃, and keeping the temperature for 3 hours to obtain Mg 2 SiO 4 And is ready for use;
the reaction equation is: mg (OH)2+ SiO2 → Mg2SiO4+2H2O
(5) Taking the ZnO and the SiO according to the selected mass content ratio 2 、BaO、B 2 O 3 、Li 2 O、Al 2 O 3 Corresponding raw materials, in which ZnO, SiO are introduced in the form of corresponding oxides 2 And Al 2 O 3 Introduction of B in the form of boric acid 2 O 3 BaO is introduced in the form of barium carbonate, in order toIntroduction of Li in the form of lithium carbonate 2 O, uniformly mixing the raw materials, carrying out melting treatment at 1400 ℃, cooling the melted glass, crushing the glass by using a roll mill, grinding the glass by using a dry ball mill and a jet mill, and obtaining the required low-melting-point glass powder for later use, wherein the particle size of the ground glass powder is less than 2 microns;
and (3) taking the glass powder with the selected content and the main burning block in the steps (2) and (4), adding water (material: water is 1: 0.4) and an ammonium acrylate dispersant (accounting for 0.8 wt% of the mixed material), uniformly mixing, performing premixing dispersion by using a ball mill, and performing redispersion on the slurry after primary dispersion by using a horizontal sand mill to obtain the mixed slurry after sand grinding. Then spray drying with a spray dryer at inlet temperature of 250 + -5 deg.C and outlet temperature of 120 + -5 deg.C, and sieving the spray dried powder with 80 mesh sieve to obtain the desired Ba 2 Ti 9 O 20 A low-temperature co-fired ceramic material.
And (3) wafer pressing the sieved low-temperature co-fired ceramic material powder by using a tablet press, and carrying out heat preservation sintering on the pressed wafer at 900 ℃ for 4h for carrying out microwave dielectric property test.
FIG. 1 shows an SEM image of a low-temperature co-fired ceramic material powder obtained in example 1, in which various components are uniformly distributed.
Example 2
The present example describes Ba 2 Ti 9 O 20 The low-temperature co-fired ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba2Ti9O20 60wt％；
Mg2SiO4 15wt％；
25wt% of low-melting-point glass powder;
the low-melting-point glass powder comprises the following components in parts by weight:
Figure BDA0003171816650000091
ba of this example 2 Ti 9 O 20 The preparation method of the base low-temperature co-fired ceramic material comprises the following steps:
(1) weighing BaTiO with corresponding weight according to the selected mass content ratio 3 、TiO 2 Adding water (material: water is 1: 1.1) and an ammonium acrylate dispersant (accounting for 0.5 wt% of the powder amount), uniformly mixing, premixing for 3h by using a ball mill, and then dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) to obtain uniformly dispersed slurry;
(2) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calciner at 1190 ℃, and preserving the temperature for 4 hours to obtain Ba 2 Ti 9 O 20 And is ready for use;
the chemical equation for this reaction is: 2BaTiO3+7TiO2 → Ba2Ti9O20
(3) Weighing Mg (OH) with corresponding weight according to the selected mass ratio 2 、SiO 2 Adding water (material: water is 1: 1.1) and an ammonium acrylate dispersant (accounting for 0.8 wt% of the powder amount), uniformly mixing, premixing for 3h by using a ball mill, and further dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) after ball milling to obtain uniformly dispersed slurry;
(4) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calcining furnace at 950 ℃, and keeping the temperature for 3 hours to obtain Mg 2 SiO 4 And is ready for use;
the reaction equation is: mg (OH)2+ SiO2 → Mg2SiO4+2H2O
(5) Taking the ZnO and the SiO according to the selected mass content ratio 2 、BaO、B 2 O 3 、Li 2 O、Al 2 O 3 Corresponding raw materials, in which ZnO, SiO are introduced in the form of corresponding oxides 2 And Al 2 O 3 Introduction of B in the form of boric acid 2 O 3 BaO in the form of barium carbonate and Li in the form of lithium carbonate 2 O, mixing the raw materials uniformly, carrying out melting treatment at 1400 ℃, cooling the molten glass, and carrying out rolling treatment by using a pair roller machineCrushing, grinding by using a dry ball mill and an air flow crusher after crushing, wherein the particle size after grinding is required to be less than 2 mu m, and obtaining the required low-melting-point glass powder for later use;
and (3) taking the glass powder with the selected content and the main burning block in the steps (2) and (4), adding water (material: water is 1: 0.5) and an ammonium acrylate dispersing agent (accounting for 0.8 wt% of the mixed material), uniformly mixing, premixing and dispersing by using a ball mill, and re-dispersing the slurry after primary dispersion by using a horizontal sand mill to obtain the mixed slurry after sand grinding. Then spray drying with a spray dryer at inlet temperature of 250 + -5 deg.C and outlet temperature of 120 + -5 deg.C, and sieving with 80 mesh sieve to obtain Ba powder 2 Ti 9 O 20 A low-temperature co-fired ceramic material.
And (3) wafer pressing the sieved low-temperature co-fired ceramic material powder by using a tablet press, and carrying out heat preservation sintering on the pressed wafer at 850 ℃ for 4h for carrying out microwave dielectric property test.
Example 3
The present example describes Ba 2 Ti 9 O 20 The low-temperature co-fired ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba2Ti9O20 65wt％；
Mg2SiO4 20wt％；
15 wt% of low-melting-point glass powder;
the low-melting-point glass powder comprises the following components in parts by weight:
Figure BDA0003171816650000111
the present example describes Ba 2 Ti 9 O 20 The preparation method of the base low-temperature co-fired ceramic material comprises the following steps:
(1) weighing BaTiO with corresponding weight according to the selected mass content ratio 3 、TiO 2 Adding water (material: water 1: 1.3) and ammonium acrylate dispersant (accounting for 0.8 wt% of the powder amount), mixing, and premixing by using a ball millMixing for 3h, and then dispersing by using a horizontal sand mill (grinding media adopt 0.65mm zirconium balls) to obtain uniformly dispersed slurry;
(2) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calcining furnace at 1210 ℃, and keeping the temperature for 4 hours to obtain Ba 2 Ti 9 O 20 And is ready for use;
the chemical equation for this reaction is: 2BaTiO3+7TiO2 → Ba2Ti9O20
(3) Weighing Mg (OH) with corresponding weight according to the selected mass ratio 2 、SiO 2 Adding water (material: water is 1: 1.2) and an ammonium acrylate dispersant (accounting for 1 wt% of the powder amount), uniformly mixing, premixing for 3 hours by using a ball mill, and further dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) after ball milling to obtain uniformly dispersed slurry;
(4) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calciner at 1000 ℃, and keeping the temperature for 3 hours to obtain Mg 2 SiO 4 And is ready for use;
the reaction equation is: mg (OH)2+ SiO2 → Mg2SiO4+2H2O
(5) Taking the ZnO and the SiO according to the selected mass content ratio 2 、BaO、B 2 O 3 、Li 2 O、Al 2 O 3 Corresponding raw materials, in which ZnO, SiO are introduced in the form of corresponding oxides 2 And Al 2 O 3 Introduction of B in the form of boric acid 2 O 3 BaO in the form of barium carbonate and Li in the form of lithium carbonate 2 O, uniformly mixing the raw materials, carrying out melting treatment at 1400 ℃, cooling the melted glass, crushing the glass by using a double-roller mill, and grinding the glass by using a dry ball mill and an air flow crusher, wherein the particle size of the ground glass is required to be less than 2 mu m, so as to obtain the required low-melting-point glass powder for later use;
taking the glass powder with the selected content and the main burning block obtained in the steps (2) and (4), and adding water (material: water is 1: 0.4) and an ammonium acrylate dispersant (accounting for the weight of the main burning block)0.8 wt% of the amount of the mixed material) and uniformly mixed, a ball mill is used for pre-mixing and dispersing, and the slurry after primary dispersion is re-dispersed by a horizontal sand mill to obtain the mixed slurry after sand milling. Then spray drying with a spray dryer at inlet temperature of 250 + -5 deg.C and outlet temperature of 120 + -5 deg.C, and sieving the spray dried powder with 80 mesh sieve to obtain the desired Ba 2 Ti 9 O 20 A low-temperature co-fired ceramic material.
And (3) wafer pressing the sieved low-temperature co-fired ceramic material powder by using a tablet press, and carrying out heat preservation sintering on the pressed wafer at 900 ℃ for 4h for carrying out microwave dielectric property test.
Example 4
The present example describes Ba 2 Ti 9 O 20 The low-temperature co-fired ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba2Ti9O20 70wt％；
Mg2SiO4 20wt％；
10 wt% of low-melting-point glass powder;
the low-melting-point glass powder comprises the following components in parts by weight:
Figure BDA0003171816650000121
Figure BDA0003171816650000131
ba of this example 2 Ti 9 O 20 The preparation method of the base low-temperature co-fired ceramic material comprises the following steps:
(1) weighing BaTiO with corresponding weight according to the selected mass content ratio 3 、TiO 2 Adding water (material: water is 1: 1.2) and an ammonium acrylate dispersant (accounting for 0.7 wt% of the powder amount), uniformly mixing, premixing for 3 hours by using a ball mill, and then dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) to obtain uniformly dispersed slurry;
(2) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calciner at 1200 ℃, and keeping the temperature for 4 hours to obtain Ba 2 Ti 9 O 20 And is ready for use;
the chemical equation for this reaction is: 2BaTiO3+7TiO2 → Ba2Ti9O20
(3) Weighing Mg (OH) with corresponding weight according to the selected mass ratio 2 、SiO 2 Adding water (material: water is 1: 1.2) and an ammonium acrylate dispersant (accounting for 1 wt% of the powder amount), uniformly mixing, premixing for 3 hours by using a ball mill, and further dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) after ball milling to obtain uniformly dispersed slurry;
(4) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calcining furnace at 950 ℃, and keeping the temperature for 3 hours to obtain Mg 2 SiO 4 And is ready for use;
the reaction equation is: mg (OH)2+ SiO2 → Mg2SiO4+2H2O
(5) Taking the ZnO and the SiO according to the selected mass content ratio 2 、BaO、B 2 O 3 、Li 2 O、Al 2 O 3 Corresponding raw materials, in which ZnO, SiO are introduced in the form of corresponding oxides 2 And Al 2 O 3 Introduction of B in the form of boric acid 2 O 3 BaO in the form of barium carbonate and Li in the form of lithium carbonate 2 O, uniformly mixing the raw materials, carrying out melting treatment at 1400 ℃, cooling the melted glass, crushing the glass by using a roll mill, grinding the glass by using a dry ball mill and a jet mill, and obtaining the required low-melting-point glass powder for later use, wherein the particle size of the ground glass powder is less than 2 microns;
taking the glass powder with the selected content and the main burning block in the steps (2) and (4), adding water (material: water is 1: 0.4) and an ammonium acrylate dispersant (accounting for 0.8 wt% of the mixed material), uniformly mixing, performing pre-mixing dispersion by using a ball mill, performing re-dispersion on the slurry after the initial dispersion by using a horizontal sand mill,and obtaining the mixed slurry after sanding. Then spray drying with a spray dryer at inlet temperature of 250 + -5 deg.C and outlet temperature of 120 + -5 deg.C, and sieving with 80 mesh sieve to obtain Ba powder 2 Ti 9 O 20 A low-temperature co-fired ceramic material.
And (3) wafer pressing the sieved low-temperature co-fired ceramic material powder by using a tablet press, and carrying out heat preservation sintering on the pressed wafer at 875 ℃ for 4h to carry out microwave dielectric property test.
Example 5
The present example describes Ba 2 Ti 9 O 20 The low-temperature co-fired ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba2Ti9O20 70wt％；
Mg2SiO4 10wt％；
20 wt% of low-melting-point glass powder;
the low-melting-point glass powder comprises the following components in parts by weight:
Figure BDA0003171816650000141
the present example describes Ba 2 Ti 9 O 20 The preparation method of the base low-temperature co-fired ceramic material comprises the following steps:
(1) weighing BaTiO with corresponding weight according to the selected mass content ratio 3 、TiO 2 Adding water (material: water is 1: 1.4) and an ammonium acrylate dispersant (accounting for 0.6 wt% of the powder amount), uniformly mixing, premixing for 3h by using a ball mill, and then dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) to obtain uniformly dispersed slurry;
(2) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calciner at 1200 ℃, and keeping the temperature for 4 hours to obtain Ba 2 Ti 9 O 20 And is ready for use;
the chemical equation for this reaction is: 2BaTiO3+7TiO2 → Ba2Ti9O20
(3) Weighing Mg (OH) with corresponding weight according to the selected mass ratio 2 、SiO 2 Adding water (material: water is 1: 1.1) and an ammonium acrylate dispersant (accounting for 1 wt% of the powder amount), uniformly mixing, premixing for 3 hours by using a ball mill, and further dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) after ball milling to obtain uniformly dispersed slurry;
(4) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calcining furnace at 950 ℃, and keeping the temperature for 3 hours to obtain Mg 2 SiO 4 And is ready for use;
the reaction equation is: mg (OH)2+ SiO2 → Mg2SiO4+2H2O
(5) Taking the ZnO and the SiO according to the selected mass content ratio 2 、BaO、B 2 O 3 、Li 2 O、Al 2 O 3 Corresponding raw materials, wherein ZnO and SiO are introduced in the form of corresponding oxides 2 And Al 2 O 3 Introduction of B in the form of boric acid 2 O 3 BaO in the form of barium carbonate and Li in the form of lithium carbonate 2 O, uniformly mixing the raw materials, carrying out melting treatment at 1400 ℃, cooling the melted glass, crushing the glass by using a roll mill, grinding the glass by using a dry ball mill and a jet mill, and obtaining the required low-melting-point glass powder for later use, wherein the particle size of the ground glass powder is less than 2 microns;
and (3) taking the glass powder with the selected content and the main burning block in the steps (2) and (4), adding water (material: water is 1: 0.4) and an ammonium acrylate dispersant (accounting for 0.8 wt% of the mixed material), uniformly mixing, performing premixing dispersion by using a ball mill, and performing redispersion on the slurry after primary dispersion by using a horizontal sand mill to obtain the mixed slurry after sand grinding. Then spray drying with a spray dryer at inlet temperature of 250 + -5 deg.C and outlet temperature of 120 + -5 deg.C, and sieving the spray dried powder with 80 mesh sieve to obtain the desired Ba 2 Ti 9 O 20 A low-temperature co-fired ceramic material.
And (3) wafer pressing the sieved low-temperature co-fired ceramic material powder by using a tablet press, and carrying out heat preservation sintering on the pressed wafer at 900 ℃ for 4h for carrying out microwave dielectric property test.
Example 6
Ba of this example 2 Ti 9 O 20 The low-temperature co-fired ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba2Ti9O20 60wt％；
Mg2SiO4 20wt％；
20 wt% of low-melting-point glass powder;
the low-melting-point glass powder comprises the following components in parts by weight:
Figure BDA0003171816650000161
the present example describes Ba 2 Ti 9 O 20 The preparation method of the base low-temperature co-fired ceramic material comprises the following steps:
(1) weighing BaTiO with corresponding weight according to the selected mass content ratio 3 、TiO 2 Adding water (material: water is 1: 1.3) and an ammonium acrylate dispersant (accounting for 0.8 wt% of the powder amount), uniformly mixing, premixing for 3h by using a ball mill, and then dispersing by using a horizontal sand mill (a grinding medium adopts 0.65mm zirconium balls) to obtain uniformly dispersed slurry;
(2) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calciner at 1190 ℃, and preserving the temperature for 4 hours to obtain Ba 2 Ti 9 O 20 And is ready for use;
the chemical equation for this reaction is: 2BaTiO3+7TiO2 → Ba2Ti9O20
(3) Weighing Mg (OH) with corresponding weight according to the selected mass ratio 2 、SiO 2 Adding water (material: water 1: 1.2) and ammonium acrylate dispersant (accounting for 1 wt% of the powder amount), mixing, premixing for 3h by using a ball mill, and after ball milling, using a horizontal sand mill (grinding medium adopts0.65mm zirconium balls) are further dispersed to obtain evenly dispersed slurry;
(4) drying the dispersed slurry by using a spray dryer until the water content is lower than 0.5%, calcining the dried powder by using a calcining furnace at 975 ℃, and keeping the temperature for 3 hours to obtain Mg 2 SiO 4 And is ready for use;
the reaction equation is: mg (OH)2+ SiO2 → Mg2SiO4+2H2O
(5) Taking the ZnO and the SiO according to the selected mass content ratio 2 、BaO、B 2 O 3 、Li 2 O、Al 2 O 3 Corresponding raw materials, in which ZnO, SiO are introduced in the form of corresponding oxides 2 And Al 2 O 3 Introduction of B in the form of boric acid 2 O 3 BaO in the form of barium carbonate and Li in the form of lithium carbonate 2 O, uniformly mixing the raw materials, carrying out melting treatment at 1400 ℃, cooling the melted glass, crushing the glass by using a roll mill, grinding the glass by using a dry ball mill and a jet mill, and obtaining the required low-melting-point glass powder for later use, wherein the particle size of the ground glass powder is less than 2 microns;
and (3) taking the glass powder with the selected content and the main burning block in the steps (2) and (4), adding water (material: water is 1: 0.4) and an ammonium acrylate dispersing agent (accounting for 0.8 wt% of the mixed material), uniformly mixing, premixing and dispersing by using a ball mill, and re-dispersing the slurry after primary dispersion by using a horizontal sand mill to obtain the mixed slurry after sand grinding. Then spray drying with a spray dryer at inlet temperature of 250 + -5 deg.C and outlet temperature of 120 + -5 deg.C, and sieving the spray dried powder with 80 mesh sieve to obtain the desired Ba 2 Ti 9 O 20 A low-temperature co-fired ceramic material.
And (3) wafer pressing the sieved low-temperature co-fired ceramic material powder by using a tablet press, and carrying out heat preservation sintering on the pressed wafer at 900 ℃ for 4h for carrying out microwave dielectric property test.
Comparative example 1-
The ceramic material of this comparative example was prepared using the same raw materials and method as in example 1 except that magnesium silicate was replaced with another negative temperature coefficient material, Li3AlB2O 6.
The low-temperature co-fired ceramic material in the comparative example 1 comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba2Ti9O20 55wt％；
Li3AlB2O6 20％；
25wt% of low-melting glass powder
The preparation method of the low-temperature co-fired ceramic material of comparative example 1 is the same as that of example 1, except that magnesium silicate is replaced by Li3AlB2O 6.
Sieving the low-temperature co-fired ceramic material powder obtained in the examples 1-6 and the comparative example 1, then using a tablet press to perform wafer pressing, and performing heat preservation sintering on the pressed wafer at 900 ℃ for 4h to perform microwave dielectric property test, wherein the test results are shown in Table 1.
Table 1 results of microwave dielectric property test of examples and comparative examples
Figure BDA0003171816650000181
From the data, the density of a Ba2Ti9O20+ glass + Mg2SiO4 material system sample is about 3.5-3.6, the shrinkage is about 12-13%, the dielectric constant is about 20, and the loss is less than 2 multiplied by 10 -3 The temperature coefficient of the resonance frequency is less than 1.
The sample of comparative example 1 prepared under the same conditions had a temperature coefficient of resonant frequency of 5.2, a dielectric constant of 18.7 and a dielectric loss of 3.73X 10 -3 It is shown that under the sintering condition of maintaining the temperature at 900 ℃ for 4 hours, the negative temperature coefficient material Li3AlB2O6 selected for the comparative sample cannot adjust the temperature coefficient of the material system to be nearly zero, and cannot be applied in practice.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. Ba 2 Ti 9 O 20 The low-temperature co-fired glass ceramic material comprises the following components in percentage by mass based on the total amount of raw materials for preparation:
Ba 2 Ti 9 O 20 55-70wt%;
Mg 2 SiO 4 10-20wt%；
10-25wt% of low-melting-point glass powder;
the low-melting-point glass powder comprises the following components in parts by weight:
40-48 parts of ZnO;
B 2 O 3 20-30 parts by weight;
SiO 2 10-20 parts by weight;
Al 2 O 3 10-15 parts by weight;
1-7 parts of BaO;
Li 2 and O1-5 parts by weight.
2. A method of preparing a low temperature co-fired glass ceramic material as claimed in claim 1, comprising the steps of:
(1) weighing Ba in a formula amount 2 Ti 9 O 20 、Mg 2 SiO 4 Mixing the mixture with low-melting-point glass powder to obtain a mixture, and then grinding the mixture to a required particle size to obtain a mixed material;
(2) and (2) drying and sieving the mixed material obtained in the step (1) to obtain the low-temperature co-fired glass ceramic material.
3. The method of claim 2, wherein the step (a)1) In the process, the specific surface area of the mixed material is controlled to be 2-6m 2 /g。
4. The method for preparing a low-temperature co-fired glass ceramic material according to claim 2, wherein in the step (2), the drying is spray drying.
5. A low-temperature co-fired glass ceramic paste comprising the low-temperature co-fired glass ceramic material according to claim 1 and an organic auxiliary agent.
6. A green tape made by casting the low temperature co-fired glass ceramic slurry of claim 5.
7. A low temperature co-fired ceramic material comprising the low temperature co-fired glass ceramic material of claim 1 sintered; or comprising a sintered low temperature co-fired glass ceramic paste as claimed in claim 5; or comprising sintered green tape according to claim 6.
8. Use of the low-temperature co-fired glass ceramic material according to claim 1, the low-temperature co-fired glass ceramic paste according to claim 5, the green tape according to claim 6 for the production of ceramic devices.
9. A ceramic device comprising a sintered low temperature co-fired glass ceramic material of claim 1; or comprising a sintered low temperature co-fired glass ceramic paste as claimed in claim 5; or comprising sintered green tape according to claim 6.
10. The ceramic device of claim 9 wherein the ceramic device comprises a microwave dielectric filter, a duplexer, a balun.
CN202110820476.XA 2021-07-20 2021-07-20 Medium low-loss low-temperature co-fired ceramic material and preparation method thereof Active CN113429200B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110820476.XA CN113429200B (en) 2021-07-20 2021-07-20 Medium low-loss low-temperature co-fired ceramic material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110820476.XA CN113429200B (en) 2021-07-20 2021-07-20 Medium low-loss low-temperature co-fired ceramic material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113429200A CN113429200A (en) 2021-09-24
CN113429200B true CN113429200B (en) 2022-09-30

Family

ID=77761151

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110820476.XA Active CN113429200B (en) 2021-07-20 2021-07-20 Medium low-loss low-temperature co-fired ceramic material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113429200B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3680765B2 (en) * 2000-07-21 2005-08-10 株式会社村田製作所 Dielectric porcelain composition
CN1304327C (en) * 2005-06-22 2007-03-14 中国科学院上海硅酸盐研究所 Method for promoting insulation electrical resistivity of titanium containing microwave medium ceramic buring with copper
CN100429174C (en) * 2006-05-15 2008-10-29 中国科学院上海硅酸盐研究所 Method for preparing pure-phase barium-titanium series ceramic material
TWI531549B (en) * 2013-04-03 2016-05-01 Microwave dielectric glass ceramic compositions and their materials
CN106927792B (en) * 2015-12-30 2020-01-21 上海晶材新材料科技有限公司 Low-dielectric-constant low-loss near-zero-temperature-coefficient LTCC (Low temperature Co-fired ceramic) material and preparation method thereof
CN113061024B (en) * 2021-04-08 2022-08-26 山东国瓷功能材料股份有限公司 Low-temperature co-fired material and prepared green ceramic chip and device for overcurrent protection

Also Published As

Publication number Publication date
CN113429200A (en) 2021-09-24

Similar Documents

Publication Publication Date Title
CN102584233B (en) Medium and high dielectric constant low temperature co-fired ceramic material and preparation method thereof
CN112851344B (en) Microwave dielectric ceramic with medium dielectric constant and preparation method thereof
CN108516826B (en) Sn-containing intermediate microwave dielectric ceramic material and preparation method thereof
CN111170734B (en) Two-phase composite microwave dielectric ceramic material for filter and preparation method thereof
CN111592348A (en) Low-dielectric-constant microwave dielectric ceramic with excellent temperature stability and preparation method thereof
CN111116197B (en) Barium niobate system microwave dielectric ceramic material and preparation method and application thereof
CN107117967B (en) Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof
CN113336541B (en) Low-temperature co-fired glass ceramic material for duplex device and preparation method thereof
CN111138193B (en) Microwave dielectric ceramic material with medium dielectric constant and preparation method and application thereof
CN107555992A (en) A kind of microwave dielectric ceramic materials and preparation method thereof
CN113087507A (en) Low-dielectric magnesium silicate microwave dielectric ceramic material and preparation method thereof
CN111004030B (en) MgTiO (magnesium-titanium-oxide) powder3Microwave-based dielectric ceramic and preparation method thereof
CN111170733A (en) Low dielectric loss dielectric ceramic and preparation method thereof
CN113429200B (en) Medium low-loss low-temperature co-fired ceramic material and preparation method thereof
CN112321164B (en) Calcium borosilicate glass powder-based composite ceramic powder and preparation process thereof
CN105541319A (en) Microwave dielectric ceramic material with medium-high dielectric constant and preparation method thereof
CN115057695B (en) LTCC powder with high Q value and low dielectric constant, LTCC material, preparation method, raw porcelain belt, preparation method and application
CN115536377B (en) Black talc mineral microwave dielectric ceramic material and preparation method thereof
CN114804857B (en) Low-temperature co-fired ceramic material and preparation method thereof
CN111018524B (en) Low-loss trigonal tungstate-based microwave dielectric ceramic and preparation method thereof
CN111470778B (en) Calcium barium silicon aluminum glass-based low-dielectric low-temperature co-fired ceramic material and preparation method thereof
CN114671682A (en) Microwave dielectric ceramic material and preparation method thereof
CN113354412A (en) Temperature-stable low-temperature sintered microwave dielectric ceramic material and preparation method thereof
CN113248265A (en) Material for laminated high-frequency inductor and preparation method thereof
CN114804858B (en) Low-temperature co-fired ceramic material for filter 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