CN106904968A - A kind of niobium base composite microwave medium ceramic material and preparation method thereof - Google Patents

A kind of niobium base composite microwave medium ceramic material and preparation method thereof Download PDF

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CN106904968A
CN106904968A CN201710112251.2A CN201710112251A CN106904968A CN 106904968 A CN106904968 A CN 106904968A CN 201710112251 A CN201710112251 A CN 201710112251A CN 106904968 A CN106904968 A CN 106904968A
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李玲霞
吕笑松
罗伟嘉
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Tianjin University
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Abstract

The invention discloses a kind of niobium base composite microwave medium ceramic, its composition expression formula is：(1‑x)(Zn0.95Ni0.05)3Nb2O8‑xNi0.5Ti0.5NbO4, wherein 0.5≤x≤0.7.First by ZnO, NiO and Nb2O5In molar ratio 2.85:0.15:1 carries out dispensing, through ball milling, drying, sieving, pre-burning, then obtains (Zn after secondary ball milling, drying, sieving0.95Ni0.05)3Nb2O8Pre-burning powder；Again by NiO, TiO2And Nb2O5In molar ratio 1:1:1 dispensing, Ni is obtained by above-mentioned same procedure0.5Ti0.5NbO4Pre-burning powder.By (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, stoichiometrically dispensing, compressing is base substrate；Base substrate is obtained niobium base composite microwave medium ceramic in 1140 DEG C~1180 DEG C sintering.Permittivity ε of the inventionrIt is 32.8~44.1, quality factor q × f values are 37500GHz~57600GHz, temperature coefficient of resonance frequency τfIt it is 25.6ppm/ DEG C~+6.7ppm/ DEG C, with important industrial application value.

Description

A kind of niobium base composite microwave medium ceramic material and preparation method thereof
Technical field
The invention belongs to a kind of ceramic composition being characterized with composition, more particularly to a kind of two-phase is combined and resonant frequency Niobium-based microwave dielectric ceramic material of temperature coefficient nearly zero and preparation method thereof.
Background technology
With the fast development of microwave communication techniques, the performance to microwave device proposes higher and higher requirement.Microwave is situated between The crucial composition material as microwave device of matter ceramics, has developed a series of microwaves with differing dielectric constant and has been situated between at present Ceramics to meet different purposes, media ceramic of its medium dielectric constant microwave medium between 20~50 be mainly used in communications satellite, The field such as navigation antenna and military radar.Such microwave dielectric ceramic materials should typically meet the following requirements：(1) seriation Permittivity εr, to meet the various sizes of requirement of microwave device, typically require εr＞ 20；(2) quality factor q × f high, To reduce the insertion loss etc. of microwave device, Q × f ＞ 10000GHz are typically required；(3) nearly zero temperature coefficient of resonance frequency τf, to improve the job stability of microwave device, typically require -10ppm/ DEG C of ＜ τf+ 10ppm/ DEG C of ＜.
Niobium base AB2O6(A=Zn, Ni, Mg, Co；B=Nb) system with excellent microwave dielectric property due to being subject to extensive Concern.Researcher is by changing columbite ZnNb2O6The mol ratio of middle zinc position ion, finds Zn3Nb2O8Still there is columbite Structure, but its quality factor uprises (Q × f~83300GHz), and frequency-temperature coefficient changes (τ toward negative directionf~-71ppm/ ℃)；Recently we《Journal of Materials Science:Materials in Electronics》Periodical is reported Road (Zn is prepared with solid reaction process by trace doped nickel ion0.95Ni0.05)3Nb2O8Ceramics, the crystal structure of ceramics Without change, the microwave dielectric property at a temperature of 1160 DEG C：εr~21.81, Q × f~123558GHz, τf~-78.45ppm/ DEG C, it can be seen that the quality factor of system are further greatly improved, but frequency-temperature coefficient change not substantially, absolute value still compared with Greatly, it is impossible to meet the application needs of microwave device.Additionally, we《Materials Letters》In report another kind and mix Miscellaneous mode, i.e., to columbite NiNb2O6Ceramics pass through 1:1 addition TiO2, equally using solid sintering technology, when sintering for 1100 DEG C We have found that the Ni for preparing0.5Ti0.5NbO4Microwave-medium ceramics frequency-temperature coefficient τfBecome larger on the occasion of+79.1ppm/ DEG C, permittivity εr56.8 are increased to, quality factor q × f is down to 21100GHz, ceramics become rutile knot by columbite structure Structure, crystal structure changes, and causes the change of microwave dielectric property.
Therefore, in (Zn0.95Ni0.05)3Nb2O8Ni is added in ceramics0.5Ti0.5NbO4Ceramics, are expected to by adjusting addition Regulation coupled resonance frequency-temperature coefficient is moved to negative direction, obtains a kind of nearly zero τfThe niobium base multi-phase microwave dielectric ceramic of value, The temperature-stable of microwave device is improved, while improving permittivity εr, reduce the size of microwave device.
The content of the invention
The purpose of the present invention, is to provide a kind of frequency-temperature coefficient nearly zero, dielectric constant 30~45, with quality high The composite microwave medium ceramic of factor, with microwave device centering dielectric constant microwave in meeting telecommunication satellite, navigation media antenna The demand of medium ceramic material.Another object of the present invention is to provide the preparation method of above-mentioned microwave-medium ceramics.
The present invention is achieved by following technical solution.
A kind of niobium base composite microwave medium ceramic, its composition expression formula is (1-x) (Zn0.95Ni0.05)3Nb2O8- xNi0.5Ti0.5NbO4, wherein x is molar fraction, and 0.5≤x≤0.7 is by (Zn0.95Ni0.05)3Nb2O8With Ni0.5Ti0.5NbO4As matrix material, addition is combined in proportion and is formed；
The niobium base composite microwave medium ceramic is prepared using simple conventional solid reaction method, is comprised the following steps that：
(1) by ZnO, NiO and Nb2O5As raw material, in molar ratio 2.85:0.15:1 carries out weighing dispensing, then will weigh Good ZnO, NiO and Nb2O5It is put into ball grinder, addition zirconia ball and deionized water, the ball milling 12h on ball mill, then Dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, and burn-in time is 3h；After pre-burning (Zn is obtained after secondary ball milling, drying, sieving0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) by NiO, TiO2And Nb2O5As raw material, in molar ratio 1:1:1 carries out weighing dispensing, then will be load weighted NiO、TiO2And Nb2O5It is put into ball grinder, adds zirconia ball and deionized water, the ball milling 12h on ball mill, then 100 Dried at DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, and burn-in time is 3h；Pre-burning By secondary ball milling, dry, sieve rear to Ni0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, will be load weighted Powder is placed in ball grinder, the ball milling 12h on ball mill, and 80 mesh sieves are crossed after then being dried at 100 DEG C, recycles tablet press machine pressure System is shaped to base substrate；
(4) ceramic body that will be obtained rises to 1140 DEG C~1180 DEG C by the heating rate of 3 DEG C/min, is incubated 4h, then with 1 DEG C/rate of temperature fall of min is down to 900 DEG C, and afterwards with stove natural cooling, final prepared niobium base composite microwave medium ceramic.
The raw material of the step (1) and (2) is the analysis pure raw material of purity >=99%.
The volume ratio of raw material and ball-milling medium, deionized water described in the step (1), (2) and (3) is 1:1:1.
The step (1), (2) and (3) carries out ball milling using planetary ball mill, and drum's speed of rotation is 400 revs/min.
The step (3) is unidirectionally press-formed using tablet press machine under 4MPa, and base substrate is the cylinder of Φ 10mm × 5mm.
Beneficial effects of the present invention are as follows：
(1)(Zn0.95Ni0.05)3Nb2O8Powder and Ni0.5Ti0.5NbO4The respective preparation process is simple of powder, and sintering temperature Degree is low, there is certain power savings advantages；Raw material country rich reserves, it is cheap, it is possible to decrease high-performance in modern communications technology The preparation cost of microwave device.
(2) the toxic heavy metal material such as not leaded, chromium or the stronger material of volatility in formula of the invention, are a kind of rings The microwave-medium ceramics of border friendly；
(3) dielectric properties of multi-phase microwave dielectric ceramic of the present invention are excellent, particularly with near-zero resonance frequency temperature system While number, ceramics can also keep Q × f values higher, and the energy consumption of device can be greatly reduced.
The present invention is combined by two-phase and the niobium-based microwave dielectric ceramic material with medium dielectric constant microwave medium, its temperature stabilization is obtained Property improved, when 1140 DEG C~1180 DEG C sinter when, the permittivity ε of productrIt is 32.8~44.1, quality factor q × f It is 37500GHz~57600GHz to be worth, temperature coefficient of resonance frequency τfIt is -25.6ppm/ DEG C~+6.7ppm/ DEG C, is to prepare property high The core material of the electronic components such as energy microwave dielectric resonator, microwave filter, oscillator and capacitor, therefore the present invention With important industrial application value.
Specific embodiment
Below by specific embodiment, the invention will be further described, and specific embodiment is as follows.
Embodiment 1
To analyze ZnO, NiO, the TiO of pure (purity >=99%)2And Nb2O5As raw material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(wherein x be molar fraction, and x=0.5) stoichiometric proportion carry out dispensing.
Specific preparation process is as follows：
(1) pure ZnO, NiO and Nb will be analyzed2O5As raw material (purity >=99%), in molar ratio 2.85:0.15:1 is carried out Dispensing is weighed, then by load weighted ZnO, NiO and Nb2O5It is put into nylon ball grinder, raw material and ball-milling medium, deionized water Volume ratio is 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, the ball milling on ball mill 12h, then dries at 100 DEG C, crosses 80 mesh sieves, is pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, pre-burning Time is 3h, and (Zn is obtained after secondary ball milling, drying, sieving after pre-burning0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) pure NiO, TiO will be analyzed2And Nb2O5As raw material (purity >=99%), in molar ratio 1:1:1 carries out weighing matches somebody with somebody Material, by load weighted NiO, TiO2And Nb2O5It is put into nylon ball grinder, raw material is with the volume ratio of ball-milling medium, deionized water 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, ball milling 12h, Ran Hou on ball mill Dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, and burn-in time is 3h, in advance After burning Ni is obtained after secondary ball milling, drying, sieving0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by 0.5 (Zn0.95Ni0.05)3Nb2O8-0.5Ni0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, load weighted powder is placed in In nylon ball grinder, raw material is 1 with the volume ratio of ball-milling medium, deionized water:1:1, ball milling is carried out using planetary ball mill, Drum's speed of rotation is 400 revs/min, and then the ball milling 12h on ball mill is dried at 100 DEG C, then powder is crossed into 40 and 80 respectively After mesh sieve, recycle tablet press machine unidirectionally to be pressurizeed under 4MPa pressure, be pressed into the cylinder green compact of Φ 10mm × 5mm；
(4) ceramic body that will be obtained rises to 1140 DEG C by the heating rate of 3 DEG C/min, and soaking time is 4h, by 1 DEG C/ The rate of temperature fall of min is down to 900 DEG C, afterwards with stove natural cooling, niobium base composite microwave medium ceramic is obtained.
(5) microwave dielectric property of the ceramic that test is sintered.
Test result：εr~32.8, Q × f~57600GHz, τf~-25.6ppm/ DEG C.
Embodiment 2
To analyze ZnO, NiO, the TiO of pure (purity >=99%)2And Nb2O5As raw material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(wherein x be molar fraction, and x=0.55) stoichiometric proportion matched somebody with somebody Material.
Specific preparation process is as follows：
(1) pure ZnO, NiO and Nb will be analyzed2O5As raw material (purity >=99%), in molar ratio 2.85:0.15:1 is carried out Dispensing is weighed, by load weighted ZnO, NiO and Nb2O5It is put into nylon ball grinder, raw material and ball-milling medium, the body of deionized water Product is than being 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, the ball milling 12h on ball mill, Then dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, burn-in time It is 3h, (Zn is obtained after secondary ball milling, drying, sieving after pre-burning0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) pure NiO, TiO will be analyzed2And Nb2O5As raw material (purity >=99%), in molar ratio 1:1:1 carries out weighing matches somebody with somebody Material, by load weighted NiO, TiO2And Nb2O5It is put into nylon ball grinder, raw material is with the volume ratio of ball-milling medium, deionized water 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, ball milling 12h, Ran Hou on ball mill Dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, and burn-in time is 3h, in advance After burning Ni is obtained after secondary ball milling, drying, sieving0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by 0.45 (Zn0.95Ni0.05)3Nb2O8-0.55Ni0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, will weigh Good powder is placed in nylon ball grinder, and raw material is 1 with the volume ratio of ball-milling medium, deionized water:1:1, using planetary ball Grinding machine carries out ball milling, and drum's speed of rotation is 400 revs/min, and then the ball milling 12h on ball mill dries at 100 DEG C, then by powder Body is crossed after 40 and 80 mesh sieves respectively, is unidirectionally pressurizeed under 4MPa pressure using tablet press machine, is pressed into the cylinder of Φ 10mm × 5mm Green compact；
(4) ceramic body that will be obtained rises to 1140 DEG C by the heating rate of 3 DEG C/min, and soaking time is 4h, by 1 DEG C/ The rate of temperature fall of min is down to 900 DEG C, afterwards with stove natural cooling, niobium base composite microwave medium ceramic is obtained.
(5) microwave dielectric property of the ceramic that test is sintered.
Test result：εr~34.2, Q × f~52500GHz, τf~-14.1ppm/ DEG C.
Embodiment 3
To analyze ZnO, NiO, the TiO of pure (purity >=99%)2And Nb2O5As raw material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(wherein x be molar fraction, and x=0.6) stoichiometric proportion carry out dispensing.
Specific preparation process is as follows：
(1) pure ZnO, NiO and Nb will be analyzed2O5As raw material (purity >=99%), in molar ratio 2.85:0.15:1 is carried out Dispensing is weighed, by load weighted ZnO, NiO and Nb2O5It is put into nylon ball grinder, raw material and ball-milling medium, the body of deionized water Product is than being 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, the ball milling 12h on ball mill, Then dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, burn-in time It is 3h, (Zn is obtained after secondary ball milling, drying, sieving after pre-burning0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) pure NiO, TiO will be analyzed2And Nb2O5As raw material (purity >=99%), in molar ratio 1:1:1 carries out weighing matches somebody with somebody Material, by load weighted NiO, TiO2And Nb2O5It is put into nylon ball grinder, raw material is with the volume ratio of ball-milling medium, deionized water 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, ball milling 12h, Ran Hou on ball mill Dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, and burn-in time is 3h, in advance After burning Ni is obtained after secondary ball milling, drying, sieving0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by 0.4 (Zn0.95Ni0.05)3Nb2O8-0.6Ni0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, load weighted powder is placed in In nylon ball grinder, raw material is 1 with the volume ratio of ball-milling medium, deionized water:1:1, ball milling is carried out using planetary ball mill, Drum's speed of rotation is 400 revs/min, and then the ball milling 12h on ball mill is dried at 100 DEG C, then powder is crossed into 40 and 80 respectively After mesh sieve, unidirectionally pressurizeed under 4MPa pressure using tablet press machine, be pressed into the cylinder green compact of Φ 10mm × 5mm；
(4) ceramic body that will be obtained rises to 1140 DEG C by the heating rate of 3 DEG C/min, and soaking time is 4h, by 1 DEG C/ The rate of temperature fall of min is down to 900 DEG C, afterwards with stove natural cooling, niobium base composite microwave medium ceramic is obtained.
(5) microwave dielectric property of the ceramic that test is sintered.
Test result：εr~36.8, Q × f~48400GHz, τf~-8.5ppm/ DEG C.
Embodiment 4
To analyze ZnO, NiO, the TiO of pure (purity >=99%)2And Nb2O5As raw material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(wherein x be molar fraction, and x=0.65) stoichiometric proportion matched somebody with somebody Material.
Specific preparation process is as follows：
(1) pure ZnO, NiO and Nb will be analyzed2O5As raw material (purity >=99%), in molar ratio 2.85:0.15:1 is carried out Dispensing is weighed, by load weighted ZnO, NiO and Nb2O5It is put into nylon ball grinder, raw material and ball-milling medium, the matter of deionized water Amount is than being 1 for volume ratio:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, on ball mill Ball milling 12h, then dries at 100 DEG C, crosses 80 mesh sieves, is pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, Burn-in time is 3h, and (Zn is obtained after secondary ball milling, drying, sieving after pre-burning0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) pure NiO, TiO will be analyzed2And Nb2O5As raw material (purity >=99%), in molar ratio 1:1:1 carries out weighing matches somebody with somebody Material, by load weighted NiO, TiO2And Nb2O5It is put into nylon ball grinder, raw material is with the mass ratio of ball-milling medium, deionized water Volume ratio is 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, the ball milling on ball mill 12h, then dries at 100 DEG C, crosses 80 mesh sieves, is pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, pre-burning Time is 3h, and Ni is obtained after secondary ball milling, drying, sieving after pre-burning0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by 0.35 (Zn0.95Ni0.05)3Nb2O8-0.65Ni0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, will weigh Good powder is placed in nylon ball grinder, and raw material is 1 with the volume ratio of ball-milling medium, deionized water:1:1, using planetary ball Grinding machine carries out ball milling, and drum's speed of rotation is 400 revs/min, and then the ball milling 12h on ball mill dries at 100 DEG C, then by powder Body is crossed after 40 and 80 mesh sieves respectively, is unidirectionally pressurizeed under 4MPa pressure using tablet press machine, is pressed into the cylinder of Φ 10mm × 5mm Green compact；
(4) ceramic body that will be obtained rises to 1140 DEG C by the heating rate of 3 DEG C/min, and soaking time is 4h, by 1 DEG C/ The rate of temperature fall of min is down to 900 DEG C, afterwards with stove natural cooling, niobium base composite microwave medium ceramic is obtained.
(5) microwave dielectric property of the ceramic that test is sintered.
Test result：εr~39.5, Q × f~42600GHz, τf~-2.3ppm/ DEG C.
Embodiment 5
To analyze ZnO, NiO, the TiO of pure (purity >=99%)2And Nb2O5As raw material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(wherein x be molar fraction, and x=0.7) stoichiometric proportion carry out dispensing.
Specific preparation process is as follows：
(1) pure ZnO, NiO and Nb will be analyzed2O5As raw material (purity >=99%), in molar ratio 2.85:0.15:1 is carried out Dispensing is weighed, by load weighted ZnO, NiO and Nb2O5It is put into nylon ball grinder, raw material and ball-milling medium, the body of deionized water Product is than being 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, the ball milling 12h on ball mill, Then dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, burn-in time It is 3h, (Zn is obtained after secondary ball milling, drying, sieving after pre-burning0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) pure NiO, TiO will be analyzed2And Nb2O5As raw material (purity >=99%), in molar ratio 1:1:1 carries out weighing matches somebody with somebody Material, by load weighted NiO, TiO2And Nb2O5It is put into nylon ball grinder, raw material is with the volume ratio of ball-milling medium, deionized water 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, ball milling 12h, Ran Hou on ball mill Dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, and burn-in time is 3h, in advance After burning Ni is obtained after secondary ball milling, drying, sieving0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by 0.3 (Zn0.95Ni0.05)3Nb2O8-0.7Ni0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, load weighted powder is placed in In nylon ball grinder, raw material is 1 with the volume ratio of ball-milling medium, deionized water:1:1, ball milling is carried out using planetary ball mill, Drum's speed of rotation is 400 revs/min, and then the ball milling 12h on ball mill is dried at 100 DEG C, then powder is crossed into 40 and 80 respectively After mesh sieve, unidirectionally pressurizeed under 4MPa pressure using tablet press machine, be pressed into the cylinder green compact of Φ 10mm × 5mm；
(4) ceramic body that will be obtained rises to 1140 DEG C by the heating rate of 3 DEG C/min, and soaking time is 4h, by 1 DEG C/ The rate of temperature fall of min is down to 900 DEG C, afterwards with stove natural cooling, niobium base composite microwave medium ceramic is obtained.
(5) microwave dielectric property of the ceramic that test is sintered.
Test result：εr~44.1, Q × f~39200GHz, τf~+6.7ppm/ DEG C.
Embodiment 6
To analyze ZnO, NiO, the TiO of pure (purity >=99%)2And Nb2O5As raw material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(wherein x be molar fraction, and x=0.65) stoichiometric proportion matched somebody with somebody Material.
Specific preparation process is as follows：
(1) pure ZnO, NiO and Nb will be analyzed2O5As raw material (purity >=99%), in molar ratio 2.85:0.15:1 is carried out Dispensing is weighed, by load weighted ZnO, NiO and Nb2O5It is put into nylon ball grinder, raw material and ball-milling medium, the body of deionized water Product is than being 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, the ball milling 12h on ball mill, Then dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, burn-in time It is 3h, (Zn is obtained after secondary ball milling, drying, sieving after pre-burning0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) pure NiO, TiO will be analyzed2And Nb2O5As raw material (purity >=99%), in molar ratio 1:1:1 carries out weighing matches somebody with somebody Material, by load weighted NiO, TiO2And Nb2O5It is put into nylon ball grinder, raw material is with the volume ratio of ball-milling medium, deionized water 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, ball milling 12h, Ran Hou on ball mill Dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, and burn-in time is 3h, in advance After burning Ni is obtained after secondary ball milling, drying, sieving0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by 0.35 (Zn0.95Ni0.05)3Nb2O8-0.65Ni0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, will weigh Good powder is placed in nylon ball grinder, and raw material is 1 with the volume ratio of ball-milling medium, deionized water:1:1, using planetary ball Grinding machine carries out ball milling, and drum's speed of rotation is 400 revs/min, and then the ball milling 12h on ball mill dries at 100 DEG C, then by powder Body is crossed after 40 and 80 mesh sieves respectively, is unidirectionally pressurizeed under 4MPa pressure using tablet press machine, is pressed into the cylinder of Φ 10mm × 5mm Green compact；
(4) ceramic body that will be obtained rises to 1160 DEG C by the heating rate of 3 DEG C/min, and soaking time is 4h, by 1 DEG C/ The rate of temperature fall of min is down to 900 DEG C, afterwards with stove natural cooling, niobium base composite microwave medium ceramic is obtained.
(5) microwave dielectric property of the ceramic that test is sintered.
Test result：εr~39.9, Q × f~39400GHz, τf~-0.8ppm/ DEG C.
Embodiment 7
To analyze ZnO, NiO, the TiO of pure (purity >=99%)2And Nb2O5As raw material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4(wherein x be molar fraction, and x=0.65) stoichiometric proportion matched somebody with somebody Material.
Specific preparation process is as follows：
(1) pure ZnO, NiO and Nb will be analyzed2O5As raw material (purity >=99%), in molar ratio 2.85:0.15:1 is carried out Dispensing is weighed, by load weighted ZnO, NiO and Nb2O5It is put into nylon ball grinder, raw material and ball-milling medium, the body of deionized water Product is than being 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, the ball milling 12h on ball mill, Then dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, burn-in time It is 3h, (Zn is obtained after secondary ball milling, drying, sieving after pre-burning0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) pure NiO, TiO will be analyzed2And Nb2O5As raw material (purity >=99%), in molar ratio 1:1:1 carries out weighing matches somebody with somebody Material, by load weighted NiO, TiO2And Nb2O5It is put into nylon ball grinder, raw material is with the volume ratio of ball-milling medium, deionized water 1:1:1, ball milling is carried out using planetary ball mill, drum's speed of rotation is 400 revs/min, ball milling 12h, Ran Hou on ball mill Dried at 100 DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, and burn-in time is 3h, in advance After burning Ni is obtained after secondary ball milling, drying, sieving0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by 0.35 (Zn0.95Ni0.05)3Nb2O8-0.65Ni0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, will weigh Good powder is placed in nylon ball grinder, and raw material is 1 with the volume ratio of ball-milling medium, deionized water:1:1, using planetary ball Grinding machine carries out ball milling, and drum's speed of rotation is 400 revs/min, and then the ball milling 12h on ball mill dries at 100 DEG C, then by powder Body is crossed after 40 and 80 mesh sieves respectively, is unidirectionally pressurizeed under 4MPa pressure using tablet press machine, is pressed into the cylinder of Φ 10mm × 5mm Green compact；
(4) ceramic body that will be obtained rises to 1180 DEG C by the heating rate of 3 DEG C/min, and soaking time is 4h, by 1 DEG C/ The rate of temperature fall of min is down to 900 DEG C, afterwards with stove natural cooling, niobium base composite microwave medium ceramic is obtained.
(5) microwave dielectric property of the ceramic that test is sintered.
Test result：εr~40.2, Q × f~37500GHz, τf~+1.6ppm/ DEG C.
The detection method of various embodiments above is as follows：
(1) diameter and thickness of product are measured using micrometer；
(2) according to Hakki-Coleman dielectric resonance methods, Agilent 8720ES vector network analyzer test specimens are used Dielectric properties under product microwave frequency band.Frequency-temperature coefficient τfValue is determined at 25 DEG C~85 DEG C.
By above example as can be seen that the ε of compound niobium-based microwave dielectric ceramic of the inventionrIt is 32.8~44.1, Quality factor q × f values are 37500GHz~57600GHz, temperature coefficient of resonance frequency τfIn -25.6ppm/ DEG C~+6.7ppm/ It is adjustable in the range of DEG C.Especially for 0.35 (Zn0.95Ni0.05)3Nb2O8-0.65Ni0.5Ti0.5NbO4Microwave-medium ceramics, During 1160 DEG C of sintering, its temperature coefficient of resonance frequency is -0.8ppm/ DEG C, and quality factor are 39400GHz, can meet high-performance The use demand of microwave device.Secondly, embodiment described above only expresses several embodiments of the invention, and its description is more Specific and detailed, this can not be therefore understands that be the limitation to patent of the present invention.It should be pointed out that those skilled in the art are not On the premise of departing from present inventive concept, some adjustment and further improvement can also be made, these belong to protection of the invention Scope.So, the protection domain of patent of the present invention should be defined by the claim.

Claims (5)

1. a kind of niobium base composite microwave medium ceramic material, its composition expression formula is：(1-x)(Zn0.95Ni0.05)3Nb2O8- xNi0.5Ti0.5NbO4, wherein x is molar fraction, and 0.5≤x≤0.7 is by (Zn0.95Ni0.05)3Nb2O8With Ni0.5Ti0.5NbO4As matrix material, addition is combined in proportion and is formed；
The niobium base composite microwave medium ceramic is prepared using simple conventional solid reaction method, is comprised the following steps that：
(1) by ZnO, NiO and Nb2O5As raw material, in molar ratio 2.85:0.15:1 carries out weighing dispensing, then will be load weighted ZnO, NiO and Nb2O5It is put into ball grinder, adds zirconia ball and deionized water, the ball milling 12h on ball mill, then 100 Dried at DEG C, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 1100 DEG C, and burn-in time is 3h；Pre-burning By secondary ball milling, drying, sieving after obtain (Zn0.95Ni0.05)3Nb2O8Pre-burning powder；
(2) by NiO, TiO2And Nb2O5As raw material, in molar ratio 1:1:1 carries out weighing dispensing, then by load weighted NiO, TiO2 And Nb2O5It is put into ball grinder, adds zirconia ball and deionized water, then the ball milling 12h on ball mill dries at 100 DEG C Do, cross 80 mesh sieves, be pre-fired into (Zn0.95Ni0.05)3Nb2O8, calcined temperature is 900 DEG C, and burn-in time is 3h；Through two after pre-burning Secondary ball milling, dry, sieve rear to Ni0.5Ti0.5NbO4Pre-burning powder；
(3) by (Zn0.95Ni0.05)3Nb2O8Preburning powdered material and Ni0.5Ti0.5NbO4Preburning powdered material, by (1-x) (Zn0.95Ni0.05)3Nb2O8-xNi0.5Ti0.5NbO4, wherein the stoichiometric proportion of 0.5≤x≤0.7 is weighed, load weighted powder is placed in ball In grinding jar, the ball milling 12h on ball mill crosses 80 mesh sieves after then being dried at 100 DEG C, and it is base to recycle tablet press machine compressing Body；
(4) ceramic body that will be obtained rises to 1140 DEG C~1180 DEG C by the heating rate of 3 DEG C/min, is incubated 4h, then with 1 DEG C/ The rate of temperature fall of min is down to 900 DEG C, afterwards with stove natural cooling, niobium base composite microwave medium ceramic is finally obtained.
2. a kind of niobium base composite microwave medium ceramic material according to claim 1, it is characterised in that the step (1) (2) raw material is the analysis pure raw material of purity >=99%.
3. a kind of niobium base composite microwave medium ceramic material according to claim 1, it is characterised in that the step (1), (2) raw material and the volume ratio of ball-milling medium, deionized water and described in (3) are 1:1:1.
4. a kind of niobium base composite microwave medium ceramic material according to claim 1, it is characterised in that the step (1), (2) and (3) carry out ball milling using planetary ball mill, drum's speed of rotation is 400 revs/min.
5. a kind of niobium base composite microwave medium ceramic material according to claim 1, it is characterised in that the step (3) Unidirectionally it is press-formed under 4MPa using tablet press machine, base substrate is the cylinder of Φ 10mm × 5mm.
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Cited By (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 (5)

* 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
US20160293832A1 (en) * 2015-03-31 2016-10-06 Ngk Insulators, Ltd. Piezoelectric/electrostrictive material, piezoelectric/electrostrictive body, and resonance driving device

Patent Citations (5)

* 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
US20160293832A1 (en) * 2015-03-31 2016-10-06 Ngk Insulators, Ltd. Piezoelectric/electrostrictive material, piezoelectric/electrostrictive body, and resonance driving device
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
LINGXIA LI ET AL.: "Structure and properties analysis for Zn3Nb2O8", 《J MATER SCI》 *
TIANKAI CHEN ET AL.: "The microwavedielectricpropertiesof(Ni,Zn)0.5Ti0.5NbO4", 《MATERIALSLETTERS》 *

Cited By (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

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