CN106904968B - Niobium-based composite microwave dielectric ceramic material and preparation method thereof - Google Patents

Niobium-based composite microwave dielectric ceramic material and preparation method thereof Download PDF

Info

Publication number
CN106904968B
CN106904968B CN201710112251.2A CN201710112251A CN106904968B CN 106904968 B CN106904968 B CN 106904968B CN 201710112251 A CN201710112251 A CN 201710112251A CN 106904968 B CN106904968 B CN 106904968B
Authority
CN
China
Prior art keywords
powder
ball milling
niobium
nbo
microwave dielectric
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.)
Expired - Fee Related
Application number
CN201710112251.2A
Other languages
Chinese (zh)
Other versions
CN106904968A (en
Inventor
李玲霞
吕笑松
罗伟嘉
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.)
Tianjin University
Original Assignee
Tianjin University
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 Tianjin University filed Critical Tianjin University
Priority to CN201710112251.2A priority Critical patent/CN106904968B/en
Publication of CN106904968A publication Critical patent/CN106904968A/en
Application granted granted Critical
Publication of CN106904968B publication Critical patent/CN106904968B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • C04B35/6261—Milling
    • 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
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, 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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof

Landscapes

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

Abstract

The invention discloses a niobium-based composite microwave dielectric ceramic, which comprises the following composition expressions: (1-x) (Zn)0.95Ni0.05)3Nb2O8‑xNi0.5Ti0.5NbO4Wherein x is more than or equal to 0.5 and less than or equal to 0.7. Firstly ZnO, NiO and Nb2O5Proportioning according to the mol ratio of 2.85:0.15:1, performing ball milling, drying, sieving and pre-sintering, performing secondary ball milling, drying and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder; then NiO and TiO are added2And Nb2O5Mixing the materials according to the molar ratio of 1:1:1, and preparing Ni by the same method0.5Ti0.5NbO4And (3) pre-burning the powder. Will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-burning the powder, proportioning according to a stoichiometric ratio, and pressing and forming into a blank; sintering the blank at 1140-1180 ℃ to obtain the niobium-based composite microwave dielectric ceramic. Dielectric constant ε of the present inventionr32.8 to 44.1, quality factor Qxf of 37500 to 57600GHz, and temperature coefficient of resonance frequency taufIs-25.6 ppm/DEG C to +6.7 ppm/DEG C, and has important industrial application value.

Description

Niobium-based composite microwave dielectric ceramic material and preparation method thereof
Technical Field
The invention belongs to a ceramic composition characterized by components, and particularly relates to a niobium-based microwave dielectric ceramic material which is compounded in two phases and has a temperature coefficient of resonance frequency close to zero and a preparation method thereof.
Background
With the rapid development of microwave communication technology, higher and higher requirements are put forward on the performance of microwave devices. As a key component material of a microwave device, a series of microwave dielectric ceramic materials with different dielectric constants have been developed so as to meet different purposes, wherein the dielectric ceramic with the dielectric constant of 20-50 is mainly used in the fields of communication satellites, navigation antennas, military radars and the like. Such microwave dielectric ceramic materials should generally meet the following requirements: (1) serialized dielectric constant εrTo satisfy different scales of microwave devicesThe cun requirement is usually epsilonrIs more than 20; (2) the high quality factor Qxf is used for reducing the insertion loss of a microwave device, and the Qxf is generally required to be more than 10000 GHz; (3) near zero temperature coefficient of resonance frequencyfTo improve the working stability of microwave devices, generally requires-10 ppm/DEG C < tauf＜+10ppm/℃。
Niobium based AB2O6The (A ═ Zn, Ni, Mg, Co; B ═ Nb) system has attracted much attention because of its excellent microwave dielectric properties. Researchers have changed ZnNb in columbite2O6The molar ratio of the zinc ions in the middle, Zn is found3Nb2O8The niobium-iron ore structure is still provided, but the quality factor is high (Q multiplied by f-83300 GHz), and the frequency temperature coefficient changes towards the negative direction (tau)f-71 ppm/. degree.C.); recently, we reported that it is prepared by solid phase reaction method by doping nickel ion in minute amount in Journal of Materials Science: Materials in Electronics (Zn)0.95Ni0.05)3Nb2O8Ceramic, the crystal structure of which is not altered, microwave dielectric properties at a temperature of 1160 ℃: epsilonr～21.81，Q×f～123558GHz，τfThe quality factor of the system is further greatly improved, but the frequency temperature coefficient is not obviously changed, the absolute value is still larger, and the application requirement of the microwave device cannot be met. In addition, we report another doping method in Materials Letters, namely NiNb for niobite2O6Ceramic by 1:1 addition of TiO2Also by solid phase sintering, we have found that Ni is produced when sintering at 1100 deg.C0.5Ti0.5NbO4Microwave dielectric ceramic frequency temperature coefficient taufBecomes a large positive value of +79.1 ppm/DEG C, and a dielectric constant of epsilonrWhen the quality factor Qxf is increased to 56.8 and reduced to 21100GHz, the niobium-iron ore structure of the ceramic is changed into a rutile structure, and the crystal structure is changed, so that the dielectric property of the microwave is changed.
Thus, in (Zn)0.95Ni0.05)3Nb2O8Addition of Ni to ceramics0.5Ti0.5NbO4Ceramics by conditioningThe addition amount is expected to adjust the temperature coefficient of the coupling resonance frequency to move towards the negative direction to obtain a nearly zero taufThe niobium-based complex phase microwave dielectric ceramic improves the temperature stability of microwave devices and simultaneously improves the dielectric constant epsilonrThe size of the microwave device is reduced.
Disclosure of Invention
The invention aims to provide a composite microwave dielectric ceramic with a frequency-temperature coefficient close to zero, a dielectric constant of 30-45 and a high quality factor, so as to meet the requirement of microwave devices in communication satellites and navigation dielectric antennas on the dielectric constant microwave dielectric ceramic material. The invention also aims to provide a preparation method of the microwave dielectric ceramic.
The invention is realized by the following technical scheme.
A niobium-based composite microwave dielectric ceramic with the composition expression of (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4Wherein x is a mole fraction, x is more than or equal to 0.5 and less than or equal to 0.7, is (Zn)0.95Ni0.05)3Nb2O8Phase with Ni0.5Ti0.5NbO4The phase is used as a base material and is formed by compounding and adding the phases in proportion;
the niobium-based composite microwave dielectric ceramic is prepared by adopting a simple traditional solid-phase reaction method, and comprises the following specific steps:
(1) ZnO, NiO and Nb2O5Weighing and mixing the raw materials according to the mol ratio of 2.85:0.15:1, and then weighing ZnO, NiO and Nb2O5Putting into a ball milling tank, adding zirconia balls and deionized water, ball milling for 12h in a ball mill, drying at 100 ℃, sieving with a 80-mesh sieve, and presintering to obtain the product (Zn)0.95Ni0.05)3Nb2O8Presintering at 1100 deg.c for 3 hr; pre-sintering, ball-milling for the second time, drying and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) NiO and TiO are mixed2And Nb2O5AsThe raw materials are weighed and mixed according to the mol ratio of 1:1:1, and then the weighed NiO and TiO are added2And Nb2O5Putting into a ball milling tank, adding zirconia balls and deionized water, ball milling for 12h in a ball mill, drying at 100 ℃, sieving with a 80-mesh sieve, and presintering to obtain the product (Zn)0.95Ni0.05)3Nb2O8Presintering at 900 deg.c for 3 hr; pre-sintering, ball-milling for the second time, drying and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering of powder material according to (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, putting the weighed powder into a ball milling tank, carrying out ball milling on the powder for 12 hours in a ball mill, drying the powder at 100 ℃, sieving the powder by a 80-mesh sieve, and carrying out compression molding by a tablet press to obtain a blank;
(4) and raising the temperature of the obtained ceramic blank to 1140-1180 ℃ according to the heating rate of 3 ℃/min, preserving the heat for 4h, reducing the temperature to 900 ℃ according to the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to finally obtain the niobium-based composite microwave dielectric ceramic.
The raw materials of the steps (1) and (2) are analytically pure raw materials with the purity of more than or equal to 99 percent.
The volume ratio of the raw materials, the ball milling medium and the deionized water in the steps (1), (2) and (3) is 1:1: 1.
And (3) performing ball milling by adopting a planetary ball mill in the steps (1), (2) and (3), wherein the rotating speed of the ball mill is 400 r/m.
And (3) performing single-direction pressure forming by using a tablet press under 4MPa, wherein the blank is a cylinder with the diameter of phi 10mm multiplied by 5 mm.
The invention has the following beneficial effects:
(1)(Zn0.95Ni0.05)3Nb2O8powder and Ni0.5Ti0.5NbO4The respective preparation process of the powder is simple and the sintering temperature is highThe degree is low, and certain energy-saving advantage is achieved; the raw materials are abundant in domestic reserves and low in price, and the preparation cost of high-performance microwave components in modern communication technology can be reduced.
(2) The formula of the invention does not contain toxic heavy metal substances such as lead, chromium and the like or substances with strong volatility, and is environment-friendly microwave dielectric ceramic;
(3) the complex phase microwave dielectric ceramic has excellent dielectric property, particularly has near-zero temperature coefficient of resonant frequency, can keep higher Q x f value, and can greatly reduce the energy consumption of devices.
The invention prepares the niobium-based microwave dielectric ceramic material with the medium dielectric constant by two-phase compounding, the temperature stability of the material is improved, and when the material is sintered at 1140-1180 ℃, the dielectric constant epsilon of the product isr32.8 to 44.1, quality factor Qxf of 37500 to 57600GHz, and temperature coefficient of resonance frequency taufIs-25.6 ppm/DEG C to +6.7 ppm/DEG C, and is a core material for preparing electronic components such as high-performance microwave dielectric resonators, microwave filters, oscillators, capacitors and the like, so the invention has important industrial application value.
Detailed Description
The present invention is further illustrated by the following specific examples, which follow.
Example 1
ZnO, NiO and TiO with analytical purity (the purity is more than or equal to 99 percent)2And Nb2O5As a raw material, (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(where x is the mole fraction and x is 0.5) are dosed.
The preparation method comprises the following specific steps:
(1) will analyze pure ZnO, NiO, and Nb2O5Weighing and mixing the raw materials (the purity is more than or equal to 99%) according to the mol ratio of 2.85:0.15:1, and then weighing the ZnO, NiO and Nb2O5Putting the mixture into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, and planetary ball milling is adoptedBall milling with a ball mill at 400 rpm for 12 hr, oven drying at 100 deg.C, sieving with 80 mesh sieve, and presintering to obtain Zn0.95Ni0.05)3Nb2O8Presintering at 1100 deg.C for 3 hr, ball milling twice, oven drying, and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) will analyze pure NiO and TiO2And Nb2O5Weighing and proportioning the raw materials (the purity is more than or equal to 99%) according to the molar ratio of 1:1:1, and mixing the weighed NiO and TiO2And Nb2O5Putting the raw materials into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 r/m, ball milling is carried out for 12h on the ball mill, then drying is carried out at 100 ℃, sieving by a 80-mesh sieve, and presintering is carried out to obtain the finished product (Zn is prepared by Zn)0.95Ni0.05)3Nb2O8Presintering at 900 deg.c for 3 hr, ball milling twice, stoving and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering of powder in 0.5 (Zn)0.95Ni0.05)3Nb2O8-0.5Ni0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, placing the weighed powder in a nylon ball milling tank, wherein the volume ratio of the raw materials to the ball milling medium and the deionized water is 1:1:1, performing ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 rpm, performing ball milling for 12 hours on the ball mill, drying at 100 ℃, respectively sieving the powder with 40-80 meshes of sieve, and performing unidirectional pressurization by utilizing a tablet press under the pressure of 4MPa to press the powder into a cylinder green body with phi 10mm multiplied by 5 mm;
(4) and (3) heating the obtained ceramic blank to 1140 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 4h, cooling to 900 ℃ at the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to obtain the niobium-based composite microwave dielectric ceramic.
(5) And testing the microwave dielectric property of the sintered ceramic product.
And (3) testing results: epsilonr～32.8，Q×f～57600GHz，τf～-25.6ppm/℃。
Example 2
ZnO, NiO and TiO with analytical purity (the purity is more than or equal to 99 percent)2And Nb2O5As a raw material, (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(where x is the mole fraction and x is 0.55) were dosed.
The preparation method comprises the following specific steps:
(1) will analyze pure ZnO, NiO, and Nb2O5Weighing and mixing the raw materials (purity is more than or equal to 99%) according to the mol ratio of 2.85:0.15:1, and weighing ZnO, NiO and Nb2O5Putting the raw materials into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 r/m, ball milling is carried out for 12h on the ball mill, then drying is carried out at 100 ℃, sieving by a 80-mesh sieve, and presintering is carried out to obtain the finished product (Zn is prepared by Zn)0.95Ni0.05)3Nb2O8Presintering at 1100 deg.C for 3 hr, ball milling twice, oven drying, and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) will analyze pure NiO and TiO2And Nb2O5Weighing and proportioning the raw materials (the purity is more than or equal to 99%) according to the molar ratio of 1:1:1, and mixing the weighed NiO and TiO2And Nb2O5Putting the raw materials into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 r/m, ball milling is carried out for 12h on the ball mill, then drying is carried out at 100 ℃, sieving by a 80-mesh sieve, and presintering is carried out to obtain the finished product (Zn is prepared by Zn)0.95Ni0.05)3Nb2O8Presintering at 900 deg.C for 3 hr, ball milling twice, and bakingDrying and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering the powder in 0.45 (Zn)0.95Ni0.05)3Nb2O8-0.55Ni0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, placing the weighed powder in a nylon ball milling tank, wherein the volume ratio of the raw materials to the ball milling medium and the deionized water is 1:1:1, performing ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 rpm, performing ball milling for 12 hours on the ball mill, drying at 100 ℃, respectively sieving the powder by using 40-80 meshes of sieve, and performing unidirectional pressurization by using a tablet press under the pressure of 4MPa to press the powder into a cylinder green body with phi 10mm multiplied by 5 mm;
(4) and (3) heating the obtained ceramic blank to 1140 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 4h, cooling to 900 ℃ at the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to obtain the niobium-based composite microwave dielectric ceramic.
(5) And testing the microwave dielectric property of the sintered ceramic product.
And (3) testing results: epsilonr～34.2，Q×f～52500GHz，τf～-14.1ppm/℃。
Example 3
ZnO, NiO and TiO with analytical purity (the purity is more than or equal to 99 percent)2And Nb2O5As a raw material, (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(where x is the mole fraction and x is 0.6) are dosed.
The preparation method comprises the following specific steps:
(1) will analyze pure ZnO, NiO, and Nb2O5Weighing and mixing the raw materials (purity is more than or equal to 99%) according to the mol ratio of 2.85:0.15:1, and weighing ZnO, NiO and Nb2O5Putting the mixture into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, and adopting a planetBall milling in a ball mill at 400 rpm for 12 hr, stoving at 100 deg.c, 80 mesh sieving and pre-sintering to obtain Zn powder0.95Ni0.05)3Nb2O8Presintering at 1100 deg.C for 3 hr, ball milling twice, oven drying, and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) will analyze pure NiO and TiO2And Nb2O5Weighing and proportioning the raw materials (the purity is more than or equal to 99%) according to the molar ratio of 1:1:1, and mixing the weighed NiO and TiO2And Nb2O5Putting the raw materials into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 r/m, ball milling is carried out for 12h on the ball mill, then drying is carried out at 100 ℃, sieving by a 80-mesh sieve, and presintering is carried out to obtain the finished product (Zn is prepared by Zn)0.95Ni0.05)3Nb2O8Presintering at 900 deg.c for 3 hr, ball milling twice, stoving and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering of powder in 0.4 (Zn)0.95Ni0.05)3Nb2O8-0.6Ni0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, placing the weighed powder in a nylon ball milling tank, wherein the volume ratio of the raw materials to the ball milling medium and the deionized water is 1:1:1, performing ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 rpm, performing ball milling for 12 hours on the ball mill, drying at 100 ℃, respectively sieving the powder by using 40-80 meshes of sieve, and performing unidirectional pressurization by using a tablet press under the pressure of 4MPa to press the powder into a cylinder green body with phi 10mm multiplied by 5 mm;
(4) and (3) heating the obtained ceramic blank to 1140 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 4h, cooling to 900 ℃ at the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to obtain the niobium-based composite microwave dielectric ceramic.
(5) And testing the microwave dielectric property of the sintered ceramic product.
And (3) testing results: epsilonr～36.8，Q×f～48400GHz，τf～-8.5ppm/℃。
Example 4
ZnO, NiO and TiO with analytical purity (the purity is more than or equal to 99 percent)2And Nb2O5As a raw material, (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(where x is the mole fraction and x is 0.65) were dosed.
The preparation method comprises the following specific steps:
(1) will analyze pure ZnO, NiO, and Nb2O5Weighing and mixing the raw materials (purity is more than or equal to 99%) according to the mol ratio of 2.85:0.15:1, and weighing ZnO, NiO and Nb2O5Putting the raw materials into a nylon ball milling tank, ball milling media and deionized water in a volume ratio of 1:1:1, ball milling by adopting a planetary ball mill at the rotating speed of 400 r/min for 12h, drying at 100 ℃, sieving by using a 80-mesh sieve, and presintering to obtain the finished product (Zn)0.95Ni0.05)3Nb2O8Presintering at 1100 deg.C for 3 hr, ball milling twice, oven drying, and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) will analyze pure NiO and TiO2And Nb2O5Weighing and proportioning the raw materials (the purity is more than or equal to 99%) according to the molar ratio of 1:1:1, and mixing the weighed NiO and TiO2And Nb2O5Putting the raw materials into a nylon ball milling tank, ball milling media and deionized water in a volume ratio of 1:1:1, ball milling by adopting a planetary ball mill at the rotating speed of 400 r/min for 12h, drying at 100 ℃, sieving by using a 80-mesh sieve, and presintering to obtain the finished product (Zn)0.95Ni0.05)3Nb2O8The presintering temperature is 900 ℃, the presintering time is 3 hours,pre-sintering, performing secondary ball milling, drying and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering of powder in 0.35 (Zn)0.95Ni0.05)3Nb2O8-0.65Ni0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, placing the weighed powder in a nylon ball milling tank, wherein the volume ratio of the raw materials to the ball milling medium and the deionized water is 1:1:1, performing ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 rpm, performing ball milling for 12 hours on the ball mill, drying at 100 ℃, respectively sieving the powder by using 40-80 meshes of sieve, and performing unidirectional pressurization by using a tablet press under the pressure of 4MPa to press the powder into a cylinder green body with phi 10mm multiplied by 5 mm;
(4) and (3) heating the obtained ceramic blank to 1140 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 4h, cooling to 900 ℃ at the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to obtain the niobium-based composite microwave dielectric ceramic.
(5) And testing the microwave dielectric property of the sintered ceramic product.
And (3) testing results: epsilonr～39.5，Q×f～42600GHz，τf～-2.3ppm/℃。
Example 5
ZnO, NiO and TiO with analytical purity (the purity is more than or equal to 99 percent)2And Nb2O5As a raw material, (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(where x is the mole fraction and x is 0.7) are dosed.
The preparation method comprises the following specific steps:
(1) will analyze pure ZnO, NiO, and Nb2O5Weighing and mixing the raw materials (purity is more than or equal to 99%) according to the mol ratio of 2.85:0.15:1, and weighing ZnO, NiO and Nb2O5Putting the mixture into a nylon ball milling tank, and mixing the raw materials with ball milling medium and deionized waterThe volume ratio is 1:1:1, a planetary ball mill is adopted for ball milling, the rotating speed of the ball mill is 400 r/min, the ball milling is carried out for 12h on the ball mill, then the drying is carried out at the temperature of 100 ℃, the product is sieved by a 80-mesh sieve and presintering is carried out to prepare the Zn0.95Ni0.05)3Nb2O8Presintering at 1100 deg.C for 3 hr, ball milling twice, oven drying, and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) will analyze pure NiO and TiO2And Nb2O5Weighing and proportioning the raw materials (the purity is more than or equal to 99%) according to the molar ratio of 1:1:1, and mixing the weighed NiO and TiO2And Nb2O5Putting the raw materials into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 r/m, ball milling is carried out for 12h on the ball mill, then drying is carried out at 100 ℃, sieving by a 80-mesh sieve, and presintering is carried out to obtain the finished product (Zn is prepared by Zn)0.95Ni0.05)3Nb2O8Presintering at 900 deg.c for 3 hr, ball milling twice, stoving and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering of powder in 0.3 (Zn)0.95Ni0.05)3Nb2O8-0.7Ni0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, placing the weighed powder in a nylon ball milling tank, wherein the volume ratio of the raw materials to the ball milling medium and the deionized water is 1:1:1, performing ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 rpm, performing ball milling for 12 hours on the ball mill, drying at 100 ℃, respectively sieving the powder by using 40-80 meshes of sieve, and performing unidirectional pressurization by using a tablet press under the pressure of 4MPa to press the powder into a cylinder green body with phi 10mm multiplied by 5 mm;
(4) and (3) heating the obtained ceramic blank to 1140 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 4h, cooling to 900 ℃ at the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to obtain the niobium-based composite microwave dielectric ceramic.
(5) And testing the microwave dielectric property of the sintered ceramic product.
And (3) testing results: epsilonr～44.1，Q×f～39200GHz，τf～+6.7ppm/℃。
Example 6
ZnO, NiO and TiO with analytical purity (the purity is more than or equal to 99 percent)2And Nb2O5As a raw material, (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(where x is the mole fraction and x is 0.65) were dosed.
The preparation method comprises the following specific steps:
(1) will analyze pure ZnO, NiO, and Nb2O5Weighing and mixing the raw materials (purity is more than or equal to 99%) according to the mol ratio of 2.85:0.15:1, and weighing ZnO, NiO and Nb2O5Putting the raw materials into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 r/m, ball milling is carried out for 12h on the ball mill, then drying is carried out at 100 ℃, sieving by a 80-mesh sieve, and presintering is carried out to obtain the finished product (Zn is prepared by Zn)0.95Ni0.05)3Nb2O8Presintering at 1100 deg.C for 3 hr, ball milling twice, oven drying, and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) will analyze pure NiO and TiO2And Nb2O5Weighing and proportioning the raw materials (the purity is more than or equal to 99%) according to the molar ratio of 1:1:1, and mixing the weighed NiO and TiO2And Nb2O5Putting the raw materials into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 r/m, ball milling is carried out for 12h on the ball mill, then drying is carried out at 100 ℃, sieving by a 80-mesh sieve, and presintering is carried out to obtain the finished product (Zn is prepared by Zn)0.95Ni0.05)3Nb2O8The presintering temperature is 900 ℃, and the presintering time is 3hPre-sintering, ball-milling for the second time, drying and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering of powder in 0.35 (Zn)0.95Ni0.05)3Nb2O8-0.65Ni0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, placing the weighed powder in a nylon ball milling tank, wherein the volume ratio of the raw materials to the ball milling medium and the deionized water is 1:1:1, performing ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 rpm, performing ball milling for 12 hours on the ball mill, drying at 100 ℃, respectively sieving the powder by using 40-80 meshes of sieve, and performing unidirectional pressurization by using a tablet press under the pressure of 4MPa to press the powder into a cylinder green body with phi 10mm multiplied by 5 mm;
(4) and raising the temperature of the obtained ceramic blank to 1160 ℃ according to the heating rate of 3 ℃/min, keeping the temperature for 4h, lowering the temperature to 900 ℃ according to the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to obtain the niobium-based composite microwave dielectric ceramic.
(5) And testing the microwave dielectric property of the sintered ceramic product.
And (3) testing results: epsilonr～39.9，Q×f～39400GHz，τf～-0.8ppm/℃。
Example 7
ZnO, NiO and TiO with analytical purity (the purity is more than or equal to 99 percent)2And Nb2O5As a raw material, (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(where x is the mole fraction and x is 0.65) were dosed.
The preparation method comprises the following specific steps:
(1) will analyze pure ZnO, NiO, and Nb2O5Weighing and mixing the raw materials (purity is more than or equal to 99%) according to the mol ratio of 2.85:0.15:1, and weighing ZnO, NiO and Nb2O5Putting the mixture into a nylon ball milling tank, and mixing the raw materials with a ball milling medium and deionized waterThe volume ratio of the zinc oxide to the zinc oxide is 1:1:1, a planetary ball mill is adopted for ball milling, the rotating speed of the ball mill is 400 r/m, the ball milling is carried out on the ball mill for 12h, then the zinc oxide is dried at the temperature of 100 ℃, sieved by a 80-mesh sieve and presintered to prepare the zinc oxide (Zn)0.95Ni0.05)3Nb2O8Presintering at 1100 deg.C for 3 hr, ball milling twice, oven drying, and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) will analyze pure NiO and TiO2And Nb2O5Weighing and proportioning the raw materials (the purity is more than or equal to 99%) according to the molar ratio of 1:1:1, and mixing the weighed NiO and TiO2And Nb2O5Putting the raw materials into a nylon ball milling tank, wherein the volume ratio of the raw materials to ball milling media and deionized water is 1:1:1, ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 r/m, ball milling is carried out for 12h on the ball mill, then drying is carried out at 100 ℃, sieving by a 80-mesh sieve, and presintering is carried out to obtain the finished product (Zn is prepared by Zn)0.95Ni0.05)3Nb2O8Presintering at 900 deg.c for 3 hr, ball milling twice, stoving and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering of powder in 0.35 (Zn)0.95Ni0.05)3Nb2O8-0.65Ni0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, placing the weighed powder in a nylon ball milling tank, wherein the volume ratio of the raw materials to the ball milling medium and the deionized water is 1:1:1, performing ball milling by adopting a planetary ball mill, the rotating speed of the ball mill is 400 rpm, performing ball milling for 12 hours on the ball mill, drying at 100 ℃, respectively sieving the powder by using 40-80 meshes of sieve, and performing unidirectional pressurization by using a tablet press under the pressure of 4MPa to press the powder into a cylinder green body with phi 10mm multiplied by 5 mm;
(4) and (3) heating the obtained ceramic blank to 1180 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 4 hours, cooling to 900 ℃ at the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to obtain the niobium-based composite microwave dielectric ceramic.
(5) And testing the microwave dielectric property of the sintered ceramic product.
And (3) testing results: epsilonr～40.2，Q×f～37500GHz，τf～+1.6ppm/℃。
The detection method of each of the above embodiments is as follows:
(1) the diameter and thickness of the product were measured using a micrometer;
(2) according to the Hakki-Coleman dielectric resonance method, the dielectric properties of the samples in the microwave frequency range were tested using an Agilent 8720ES vector network analyzer. Temperature coefficient of frequency τfThe value is measured at 25 ℃ to 85 ℃.
As can be seen from the above examples, the epsilon of the composite niobium-based microwave dielectric ceramic of the inventionr32.8 to 44.1, quality factor Qxf of 37500 to 57600GHz, and temperature coefficient of resonance frequency taufCan be adjusted within the range of-25.6 ppm/DEG C to +6.7 ppm/DEG C. Especially for 0.35 (Zn)0.95Ni0.05)3Nb2O8-0.65Ni0.5Ti0.5NbO4When the microwave dielectric ceramic is sintered at 1160 ℃, the temperature coefficient of the resonant frequency is-0.8 ppm/DEG C, the quality factor is 39400GHz, and the use requirement of a high-performance microwave device can be met. Secondly, the above-mentioned examples only represent some embodiments of the present invention, and the description thereof is more specific and detailed, which should not be construed as limiting the patent of the present invention. It should be noted that a person skilled in the art may make several modifications and further improvements without departing from the inventive concept, which falls within the scope of protection of the present invention. Therefore, the protection scope of the present patent shall be subject to the claims.

Claims (5)

1. A niobium-based composite microwave dielectric ceramic material comprises the following composition expressions: (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4Wherein x is a mole fraction, x is more than or equal to 0.5 and less than or equal to 0.7, is (Zn)0.95Ni0.05)3Nb2O8Phase with Ni0.5Ti0.5NbO4The phase is used as a base material and is formed by compounding and adding the phases in proportion;
the niobium-based composite microwave dielectric ceramic is prepared by adopting a simple traditional solid-phase reaction method, and comprises the following specific steps:
(1) ZnO, NiO and Nb2O5Weighing and mixing the raw materials according to the mol ratio of 2.85:0.15:1, and then weighing ZnO, NiO and Nb2O5Putting into a ball milling tank, adding zirconia balls and deionized water, ball milling for 12h in a ball mill, drying at 100 ℃, sieving with a 80-mesh sieve, and presintering to obtain the product (Zn)0.95Ni0.05)3Nb2O8Presintering at 1100 deg.c for 3 hr; pre-sintering, ball-milling for the second time, drying and sieving to obtain (Zn)0.95Ni0.05)3Nb2O8Pre-burning the powder;
(2) NiO and TiO are mixed2And Nb2O5Weighing and proportioning the raw materials according to the molar ratio of 1:1:1, and then weighing NiO and TiO2And Nb2O5Putting into a ball milling tank, adding zirconia balls and deionized water, ball milling for 12h in a ball mill, drying at 100 ℃, sieving with a 80-mesh sieve, and presintering to obtain the product (Zn)0.95Ni0.05)3Nb2O8Presintering at 900 deg.c for 3 hr; pre-sintering, ball-milling for the second time, drying and sieving to obtain Ni0.5Ti0.5NbO4Pre-burning the powder;
(3) will (Zn)0.95Ni0.05)3Nb2O8Pre-sintering powder and Ni0.5Ti0.5NbO4Pre-sintering of powder material according to (1-x) (Zn)0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4Weighing the powder in a stoichiometric ratio of x being more than or equal to 0.5 and less than or equal to 0.7, putting the weighed powder into a ball milling tank, carrying out ball milling on the powder for 12 hours in a ball mill, drying the powder at 100 ℃, sieving the powder by a 80-mesh sieve, and carrying out compression molding by a tablet press to obtain a blank;
(4) and raising the temperature of the obtained ceramic blank to 1140-1180 ℃ according to the heating rate of 3 ℃/min, preserving the heat for 4h, reducing the temperature to 900 ℃ according to the cooling rate of 1 ℃/min, and naturally cooling along with the furnace to finally obtain the niobium-based composite microwave dielectric ceramic.
2. The niobium-based composite microwave dielectric ceramic material as claimed in claim 1, wherein the raw materials in steps (1) and (2) are analytically pure raw materials with purity not less than 99%.
3. The niobium-based composite microwave dielectric ceramic material as claimed in claim 1, wherein the volume ratio of the raw materials, the ball milling medium and the deionized water in steps (1) and (2) is 1:1: 1.
4. The niobium-based composite microwave dielectric ceramic material as claimed in claim 1, wherein the steps (1) and (2) are ball-milled by a planetary ball mill, and the rotation speed of the ball mill is 400 rpm.
5. The niobium-based composite microwave dielectric ceramic material as claimed in claim 1, wherein the step (3) is performed by single-direction pressing under 4MPa by using a tablet press, and the blank is a cylinder with the diameter of 10mm x 5 mm.
CN201710112251.2A 2017-02-28 2017-02-28 Niobium-based composite microwave dielectric ceramic material and preparation method thereof Expired - Fee Related CN106904968B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710112251.2A CN106904968B (en) 2017-02-28 2017-02-28 Niobium-based composite microwave dielectric ceramic material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710112251.2A CN106904968B (en) 2017-02-28 2017-02-28 Niobium-based composite microwave dielectric ceramic material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106904968A CN106904968A (en) 2017-06-30
CN106904968B true CN106904968B (en) 2020-02-07

Family

ID=59209192

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710112251.2A Expired - Fee Related CN106904968B (en) 2017-02-28 2017-02-28 Niobium-based composite microwave dielectric ceramic material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106904968B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107777997A (en) * 2017-09-06 2018-03-09 天津大学 A kind of preparation method of the high Qf values microwave-medium ceramics of medium dielectric constant microwave medium
CN110451959A (en) * 2019-09-25 2019-11-15 哈尔滨工业大学 A kind of adjustable high-Q microwave dielectric ceramics of dielectric properties and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010235345A (en) * 2009-03-30 2010-10-21 Tdk Corp Dielectric ceramic composition and oscillator
CN103435347A (en) * 2013-08-28 2013-12-11 天津大学 Zinc oxide-doped niobium nickel titanate microwave dielectric ceramic as well as preparation method thereof
CN103951430A (en) * 2014-04-23 2014-07-30 天津大学 Low-temperature-sintered niobate high-quality-factor microwave dielectric ceramic material
CN105000881A (en) * 2015-07-21 2015-10-28 天津大学 Niobate medium-dielectric constant microwave dielectric ceramic material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6445372B2 (en) * 2015-03-31 2018-12-26 日本碍子株式会社 Piezoelectric / electrostrictive material, piezoelectric / electrostrictive body, and resonance driving device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010235345A (en) * 2009-03-30 2010-10-21 Tdk Corp Dielectric ceramic composition and oscillator
CN103435347A (en) * 2013-08-28 2013-12-11 天津大学 Zinc oxide-doped niobium nickel titanate microwave dielectric ceramic as well as preparation method thereof
CN103951430A (en) * 2014-04-23 2014-07-30 天津大学 Low-temperature-sintered niobate high-quality-factor microwave dielectric ceramic material
CN105000881A (en) * 2015-07-21 2015-10-28 天津大学 Niobate medium-dielectric constant microwave dielectric ceramic material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Structure and properties analysis for Zn3Nb2O8;Lingxia Li et al.;《J Mater Sci》;20150611;第7026–7031页 *
The microwavedielectricpropertiesof(Ni,Zn)0.5Ti0.5NbO4;Tiankai Chen et al.;《MaterialsLetters》;20131231;第111–113页 *

Also Published As

Publication number Publication date
CN106904968A (en) 2017-06-30

Similar Documents

Publication Publication Date Title
CN102442823A (en) Microwave dielectric ceramic material and preparation method thereof
CN109836149B (en) Garnet ferrite material with low magnetic moment, small loss and high temperature stability
CN104692795B (en) A kind of ultra-low loss magnesium titanate lithium microwave dielectric ceramic materials and preparation method thereof
CN103073281A (en) Lithium-zinc-titanium-tin series microwave dielectric ceramics material and preparation method thereof
CN108911746B (en) Low-loss tungsten-based ultralow-temperature sintered microwave dielectric ceramic material and preparation method and application thereof
CN106904968B (en) Niobium-based composite microwave dielectric ceramic material and preparation method thereof
CN108191426B (en) Medium-temperature sintered high-Q-value microwave dielectric material
CN108358633B (en) Low-temperature sintered Ca5Mn4-xMgxV6O24Microwave dielectric material and preparation method thereof
CN111943671A (en) Wide-sintering temperature zone low-loss microwave dielectric ceramic and preparation method thereof
CN107382313B (en) Microwave dielectric ceramic with ultrahigh quality factor, medium-low dielectric constant and near-zero temperature coefficient and preparation method thereof
CN113896530B (en) Modified NiO-Ta with stable temperature 2 O 5 Microwave-based dielectric ceramic material and preparation method thereof
CN110015894A (en) The bismuth-sodium titanate base ceramics and its preparation method and application of dielectric stable under a kind of high temperature
CN104671773B (en) A kind of low dielectric constant microwave dielectric ceramic material and preparation method thereof
CN107382317A (en) A kind of magnesium nickel zirconium niobium series microwave dielectric ceramic
CN108455986B (en) Composite microwave dielectric ceramic material and preparation method thereof
CN109251028A (en) A kind of low high Q lithium magnesium niobium series microwave dielectric ceramic and preparation method thereof that is situated between
CN107352998B (en) Ultralow-loss lithium-magnesium-titanium-based microwave dielectric ceramic and preparation method thereof
CN105152649A (en) Temperature-stable high-Q-value niobium tantalite microwave dielectric ceramic and preparation method thereof
CN109721359A (en) A kind of lithium titanium is co-doped with high q-factor lithium magnesium niobium system dielectric material and preparation method thereof
CN112851347A (en) Low-temperature sintered low-loss oxyfluoride microwave dielectric ceramic and preparation method thereof
CN108439968A (en) A kind of microwave-medium ceramics and preparation method thereof of low-k and ultra-low loss
CN110357618B (en) Low-temperature sintering temperature-stable zirconate microwave dielectric ceramic material and preparation method thereof
CN104710175B (en) A kind of low-k magnesium zirconate lithium microwave dielectric ceramic materials and preparation method thereof
CN101462872A (en) Low frequency microstrip aerial substrate material and preparation thereof
CN100534949C (en) Yttrium niobate solid-phase reaction synthetic sintering method capable of being used for microwave dielectric ceramic

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
CB03 Change of inventor or designer information

Inventor after: Li Lingxia

Inventor after: Lv Xiaosong

Inventor after: Deng Hao

Inventor after: Luo Weijia

Inventor before: Li Lingxia

Inventor before: Lv Xiaosong

Inventor before: Luo Weijia

CB03 Change of inventor or designer information
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200207

Termination date: 20210228

CF01 Termination of patent right due to non-payment of annual fee