CN105837211A - Wolframite microwave dielectric ceramic doped with cobalt ion and preparation method thereof - Google Patents
Wolframite microwave dielectric ceramic doped with cobalt ion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses wolframite microwave dielectric ceramic doped with cobalt ion and a preparation method thereof. The chemical formula of the ceramic is Zn<1-x>Co<x>ZrNb2O8, 0 <= x <= 0.1. The preparation method includes the steps of: burdening the materials, including ZnO, ZrO2, Nb2O5 and CoO, according to the chemical formula; and mixing the materials, drying and sieving the mixed materials, performing pre-sintering, granulation and press moulding and the like operations, sintering the mixture at 1100-1200 DEG C to prepare the Zn<1-x>Co<x>ZrNb2O8 ceramic doped with cobalt ion. In the method, zinc ion in ZnZrNb2O8 is doped by the cobalt ion, so that the ceramic material is reduced significantly in sintering temperature on the basis of ensuring stable microwave dielectric performance of the ceramic. The ceramic is 25.73-27.26 in dielectric constant, is 55600-61000 GHz in quality factor Qf, and is -11.3 - -15.2 ppm/DEG C in resonance frequency temperature coefficient. The preparation method is simple, employs low-cost device and environment-friendly process, and has great application value in industry.
Description
Technical field
The invention belongs to a kind of ceramic compound being characterized with composition, wolframite microwave-medium ceramics relating to a kind of ZnO thin film and preparation method thereof.
Background technology
Microwave-medium ceramics (MWDC) refers to complete as dielectric material a kind of pottery of microwave signal process in microwave frequency band circuit, is a kind of novel electric function ceramic.Along with the fast development of Internet technology, information capacity exponentially property increases, and applying frequency develops towards higher frequency range, and portable terminal and mobile communication develop further towards directions such as miniaturization, highly integrated and high stabilizabilities.Simultaneously, the devices such as dielectric resonator, wave filter, capacitor need further to be improved in terms of the acceptance of electromagnetic wave couples with transmission, energy with signal and screens frequency, this just proposes requirements at the higher level to the components and parts in microwave circuit, and exploitation miniaturization, high stable, cheap and highly integrated Novel microwave dielectric ceramic have become the focus place of current research and development.
Microwave-medium ceramics, as manufacturing the key component of microwave device, should meet following performance requirement: (1) relative dielectric constant εrHeight to be tried one's best, this can allow device more miniaturization；(2) temperature coefficient of resonance frequency τfDevice the most just can be made when working, to have preferable stability as close as 0；(3) quality factor q f value wants height, the most just can have excellent selecting frequency characteristic.According to relative dielectric constant εrSize different from use frequency range, generally can will have been developed that and the microwave-medium ceramics developed be divided into ultralow dielectric microwave dielectric ceramic, low εrWith the microwave dielectric ceramic of high q-factor, medium εrWith the microwave dielectric ceramic of Q-value, high εrLow reactance-resistance ratio microwave dielectric ceramic 4 class.
In the recent period, the ZnZrNb of monocline wolframite2O8Series microwave dielectric ceramic is because the microwave dielectric property of its excellence and relatively low sintering temperature are by the extensive concern of scientific research personnel.ZnZrNb2O8Microwave-medium ceramics is at ZnNb2O6On the basis of add ZrO2Generation has monocline, the Novel microwave dielectric ceramic consistent with tetragonal lattice structure.China domestic Liao Qing Wei et al. and India S.D. Ramarao et al. utilizes solid phase method to pass through ZnO, ZrO2And Nb2O5Stoichiometrically it is mixed with out ZnZrNb2O8, result of study finds ZnZrNb2O8Possess medium dielectric constant microwave medium (about 30), the excellent properties of high quality factor (about 60,000 GHz), there is miniaturization, high stable, the advantage such as cheap and integrated.On this basis, improve its microwave dielectric property further, reduce preparation temperature, reduction dielectric loss and raising temperature stability and become the emphasis of such ceramic material commercialization research.
Summary of the invention
The purpose of the present invention, is for improving ZnZrNb2O8Microwave dielectric property, it is provided that a kind of with ZnO, ZrO2And Nb2O5For primary raw material, Co ion doping method is used to prepare Zn1-xCoxZrNb2O8Microwave-medium ceramics, thus reduce preparation temperature further, improve dielectric constant, it is achieved the reasonable application under microwave or even higher frequency section, and with appropriate ZnO thin film zinc ion, prepare the microwave-medium ceramics with excellent microwave dielectric property.Above-mentioned ceramic material is according to Zn1-xCoxZrNb2O8(x=0-0.1) chemical formula dispensing, twice batch mixing about 24 hours, calcined temperature 1050 DEG C.Ceramic material dominant is ZnZrNb mutually2O8, its dielectric constant range is 25.73 ~ 27.26, and quality factor q f scope is 55,600 ~ 61,000
GHz, temperature coefficient of resonance frequency scope is-11.3 ~-15.2 ppm/ DEG C.
The present invention is achieved by following technical solution.
(1) batch mixing: purity is more than the material powder of 99.99% according to formula Zn1-xCoxZrNb2O8Chemical general formula carry out dispensing, by powder, zirconium oxide balls, dehydrated alcohol adds in mixing bottle, batch mixing about 24 hours in batch mixer；Slurry after batch mixing is placed in drying baker drying；
(2) step (1) dried powders mixture loading crucible is placed in high temperature furnace, pre-burning 4 hours under 1050 ° of C, obtains pre-burning powder body;
(3) rerolling
By the powder after step (2) pre-burning, zirconium oxide balls, dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer；Slurry after batch mixing is placed in drying baker drying；
(4) pelletize, molding
The powder dried in (3) is added paraffin and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200MPa；
(5) binder removal
Green compact are placed in high temperature furnace, binder removal four hours under 500 ° of C, discharge paraffin component；
(6) sintering
By the green compact after binder removal in 1100 ° of C-1200
° C sintering, is incubated 4 hours.
The invention has the beneficial effects as follows: the present invention uses price the cheapest ceramic alumina powder to be raw material.Preparation process stoichiometric proportion controls accurately, and technique is simple, reproducible；The microwave ceramic powder granule of synthesis is tiny, uniform, and synthesis temperature is relatively low, it is easy to sintering, has good microwave dielectric property, it is possible to meet the needs of future microwave components and parts development.
Accompanying drawing explanation
Fig. 1 is Zn of the present invention1-xCoxZrNb2O8The each embodiment related process parameters of pottery and microwave dielectric property chart.
Detailed description of the invention
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1.
(1) batch mixing: according to Zn1-xCoxZrNb2O8(x=0.02) stoichiometric proportion of microwave-medium ceramics thing phase, uses precision balance to weigh zinc oxide (ZnO) 3.3924g that purity is 99.99%, cobalt oxide (CoO) 0.0637 g, zirconium oxide (ZrO2) 5.2407
G and niobium pentaoxide (Nb2O5) 11.3052 g.Powder after weighing is poured in mixing bottle, and adds 40g dehydrated alcohol and 400g zirconium oxide balls.The most a diameter of 1cm and a diameter of 0.5cm abrading-ball example in mass ratio are that 2:1 loads；The mixing bottle of powder, abrading-ball and dehydrated alcohol is positioned on batch mixer batch mixing about 24 hours continuously, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(2) pre-burning: the powder after step (1) being dried is placed in Muffle furnace pre-burning 4 hours at 1050 DEG C, can obtain the Zn after pre-burning0.98Co0.02ZrNb2O8Powder body.
(3) rerolling: by the powder after step (2) pre-burning and 400g zirconium oxide balls, 40g dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(4) pelletize, molding: the powder dried in step (3) is added the paraffin that mass percent is 8% and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200MPa.
(5) binder removal: green compact are placed in high temperature furnace, binder removal four hours at 500 DEG C, discharge paraffin component.
(6) sintering: using high temperature sintering furnace with 5 DEG C/min of programming rate, can realize it for 4 hours in 1200 DEG C of insulations and sinter porcelain into, its dielectric constant is 27.26, and quality factor q f is 5.67 × 104 GHz, temperature coefficient of resonance frequency is-15.2
ppm/℃。
Embodiment 2.
(1) batch mixing: according to Zn1-xCoxZrNb2O8(x=0.04) stoichiometric proportion of microwave-medium ceramics thing phase, uses precision balance to weigh zinc oxide (ZnO) 3.3241 g that purity is 99.99%, cobalt oxide (CoO) 0.1275 g, zirconium oxide (ZrO2) 5.2421
G and niobium pentaoxide (Nb2O5) 11.3083 g.Powder after weighing is poured in mixing bottle, and adds 40g dehydrated alcohol and 400g zirconium oxide balls.The most a diameter of 1cm and a diameter of 0.5cm abrading-ball example in mass ratio are that 2:1 loads；The mixing bottle of powder, abrading-ball and dehydrated alcohol is positioned on batch mixer batch mixing about 24 hours continuously, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(2) pre-burning: the powder after step (1) being dried is placed in Muffle furnace pre-burning 4 hours at 1050 DEG C, can obtain the Zn after pre-burning0.96Co0.04ZrNb2O8Powder body.
(3) rerolling: by the powder after step (2) pre-burning and 400g zirconium oxide balls, 40g dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(4) pelletize, molding: the powder dried in step (3) is added the paraffin that mass percent is 8% and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200MPa.
(5) binder removal: green compact are placed in high temperature furnace, binder removal four hours at 500 DEG C, discharge paraffin component.
(6) sintering: using high temperature sintering furnace with 5 DEG C/min of programming rate, can realize it for 4 hours in 1100 DEG C of insulations and sinter porcelain into, its dielectric constant is 26.76, and quality factor q f is 5.63 × 104 GHz, temperature coefficient of resonance frequency is-12.4
ppm/℃。
Embodiment 3.
(1) batch mixing: according to Zn1-xCoxZrNb2O8(x=0.06) stoichiometric proportion of microwave-medium ceramics thing phase, uses precision balance to weigh zinc oxide (ZnO) 3.2557 g that purity is 99.99%, cobalt oxide (CoO) 0.1913 g, zirconium oxide (ZrO2) 5.2436
G and niobium pentaoxide (Nb2O5) 11.3114 g.Powder after weighing is poured in mixing bottle, and adds 40g dehydrated alcohol and 400g zirconium oxide balls.The most a diameter of 1cm and a diameter of 0.5cm abrading-ball example in mass ratio are that 2:1 loads；The mixing bottle of powder, abrading-ball and dehydrated alcohol is positioned on batch mixer batch mixing about 24 hours continuously, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(2) pre-burning: the powder after step (1) being dried is placed in Muffle furnace pre-burning 4 hours at 1050 DEG C, can obtain the Zn after pre-burning0.94Co0.06ZrNb2O8Powder body.
(3) rerolling: by the powder after step (2) pre-burning and 400g zirconium oxide balls, 40g dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(4) pelletize, molding: the powder dried in step (3) is added the paraffin that mass percent is 8% and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200MPa.
(5) binder removal: green compact are placed in high temperature furnace, binder removal four hours at 500 DEG C, discharge paraffin component.
(6) sintering: using high temperature sintering furnace with 5 DEG C/min of programming rate, can realize it for 4 hours in 1200 DEG C of insulations and sinter porcelain into, its dielectric constant is 27.17, and quality factor q f is 5.83 × 104 GHz, temperature coefficient of resonance frequency is-11.3ppm/ DEG C.
Embodiment 4.
(1) batch mixing: according to Zn1-xCoxZrNb2O8(x=0.08) stoichiometric proportion of microwave-medium ceramics thing phase, uses precision balance to weigh zinc oxide (ZnO) 3.1873 g that purity is 99.99%, cobalt oxide (CoO) 0.2552 g, zirconium oxide (ZrO2) 5.2450
G and niobium pentaoxide (Nb2O5) 11.3145 g.Powder after weighing is poured in mixing bottle, and adds 40g dehydrated alcohol and 400g zirconium oxide balls.The most a diameter of 1cm and a diameter of 0.5cm abrading-ball example in mass ratio are that 2:1 loads；The mixing bottle of powder, abrading-ball and dehydrated alcohol is positioned on batch mixer batch mixing about 24 hours continuously, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(2) pre-burning: the powder after step (1) being dried is placed in Muffle furnace pre-burning 2 hours at 1000 DEG C, can obtain the Zn after pre-burning0.92Co0.08ZrNb2O8Powder body.
(3) rerolling: by the powder after step (2) pre-burning and 400g zirconium oxide balls, 40g dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(4) pelletize, molding: the powder dried in step (3) is added the paraffin that mass percent is 8% and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200MPa.
(5) binder removal: green compact are placed in high temperature furnace, binder removal four hours at 500 DEG C, discharge paraffin component.
(6) sintering: using high temperature sintering furnace with 5 DEG C/min of programming rate, can realize it for 4 hours in 1200 DEG C of insulations and sinter porcelain into, its dielectric constant is 27.10, and quality factor q f is 6.10 × 104 GHz, temperature coefficient of resonance frequency is-13.7ppm/ DEG C.
Embodiment 5.
(1) batch mixing: according to Zn1-xCoxZrNb2O8(x=0.10) stoichiometric proportion of microwave-medium ceramics thing phase, uses precision balance to weigh zinc oxide (ZnO) 3.1189 g that purity is 99.99%, cobalt oxide (CoO) 0.3190 g, zirconium oxide (ZrO2) 5.2465
G and niobium pentaoxide (Nb2O5) 11.3176 g.Powder after weighing is poured in mixing bottle, and adds 40g dehydrated alcohol and 400g zirconium oxide balls.The most a diameter of 1cm and a diameter of 0.5cm abrading-ball example in mass ratio are that 2:1 loads；The mixing bottle of powder, abrading-ball and dehydrated alcohol is positioned on batch mixer batch mixing about 24 hours continuously, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(2) pre-burning: the powder after step (1) being dried is placed in Muffle furnace pre-burning 2 hours at 1000 DEG C, can obtain the Zn after pre-burning0.9Co0.1ZrNb2O8Powder body.
(3) rerolling: by the powder after step (2) pre-burning and 400g zirconium oxide balls, 40g dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(4) pelletize, molding: the powder dried in step (3) is added the paraffin that mass percent is 8% and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200MPa.
(5) binder removal: green compact are placed in high temperature furnace, binder removal four hours at 500 DEG C, discharge paraffin component.
(6) sintering: using high temperature sintering furnace with 5 DEG C/min of programming rate, can realize it for 4 hours in 1200 DEG C of insulations and sinter porcelain into, its dielectric constant is 26.64, and quality factor q f is 5.61 × 104 GHz, temperature coefficient of resonance frequency is-11.4
ppm/℃。
Embodiment 6.
(1) batch mixing: according to Zn1-xCoxZrNb2O8(x=0.06) stoichiometric proportion of microwave-medium ceramics thing phase, uses precision balance to weigh zinc oxide (ZnO) 3.2557 g that purity is 99.99%, cobalt oxide (CoO) 0.1913 g, zirconium oxide (ZrO2) 5.2436
G and niobium pentaoxide (Nb2O5) 11.3114 g.Powder after weighing is poured in mixing bottle, and adds 40g dehydrated alcohol and 400g zirconium oxide balls.The most a diameter of 1cm and a diameter of 0.5cm abrading-ball example in mass ratio are that 2:1 loads；The mixing bottle of powder, abrading-ball and dehydrated alcohol is positioned on batch mixer batch mixing about 24 hours continuously, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(2) pre-burning: the powder after step (1) being dried is placed in Muffle furnace pre-burning 2 hours at 1000 DEG C, can obtain the Zn after pre-burning0.94Co0.06ZrNb2O8Powder body.
(3) rerolling: by the powder after step (2) pre-burning and 400g zirconium oxide balls, 40g dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(4) pelletize, molding: the powder dried in step (3) is added the paraffin that mass percent is 8% and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200MPa.
(5) binder removal: green compact are placed in high temperature furnace, binder removal four hours at 500 DEG C, discharge paraffin component.
(6) sintering: using high temperature sintering furnace with 5 DEG C/min of programming rate, can realize it for 4 hours in 1150 DEG C of insulations and sinter porcelain into, its dielectric constant is 27.05, and quality factor q f is 5.63 × 104 GHz, temperature coefficient of resonance frequency is-12.4
ppm/℃。
Embodiment 7.
(1) batch mixing: according to Zn1-xCoxZrNb2O8(x=0.08) stoichiometric proportion of microwave-medium ceramics thing phase, uses precision balance to weigh zinc oxide (ZnO) 3.1873 g that purity is 99.99%, cobalt oxide (CoO) 0.2552 g, zirconium oxide (ZrO2) 5.2450
G and niobium pentaoxide (Nb2O5) 11.3145 g.Powder after weighing is poured in mixing bottle, and adds 40g dehydrated alcohol and 400g zirconium oxide balls.The most a diameter of 1cm and a diameter of 0.5cm abrading-ball example in mass ratio are that 2:1 loads；The mixing bottle of powder, abrading-ball and dehydrated alcohol is positioned on batch mixer batch mixing about 24 hours continuously, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(2) pre-burning: the powder after step (1) being dried is placed in Muffle furnace pre-burning 4 hours at 1050 DEG C, can obtain the Zn after pre-burning0.9Co0.1ZrNb2O8Powder body.
(3) rerolling: by the powder after step (2) pre-burning and 400g zirconium oxide balls, 40g dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer, and batch mixer rotating speed is 200 r/min；With coarse mesh, the slurry after batch mixing is separated with abrading-ball, will separate after slurry be placed in 70-90 DEG C at drying baker in dry.
(4) pelletize, molding: the powder dried in step (3) is added the paraffin that mass percent is 8% and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200MPa.
(5) binder removal: green compact are placed in high temperature furnace, binder removal four hours at 500 DEG C, discharge paraffin component.
(6) sintering: using high temperature sintering furnace with 5 DEG C/min of programming rate, can realize it for 4 hours in 1100 DEG C of insulations and sinter porcelain into, its dielectric constant is 25.73, and quality factor q f is 5.56 × 104 GHz, temperature coefficient of resonance frequency is-11.3ppm/ DEG C.
Claims (8)
1. the wolframite microwave-medium ceramics of a ZnO thin film, it is characterised in that the composition expression formula of this ceramic material is: Zn1-xCoxZrNb2O8, wherein 0≤x≤0.1.
The wolframite microwave-medium ceramics of a kind of ZnO thin film the most according to claim 1, it is characterised in that the relative dielectric constant ε of described ceramic materialr=25.73 ~ 27.26, quality factor q f=55,600 ~ 61,000 GHz, temperature coefficient of resonance frequency-11.3 ~-15.2 ppm/ DEG C.
3. the preparation method of the wolframite microwave-medium ceramics of a ZnO thin film, it is characterised in that comprise the following steps:
(1) batch mixing: purity is more than the material powder of 99.99% according to formula Zn1-xCoxZrNb2O8Chemical general formula carry out dispensing, by powder, zirconium oxide balls, dehydrated alcohol adds in mixing bottle, batch mixing about 24 hours in batch mixer；Slurry after batch mixing is placed in drying baker drying；
(2) being placed in high temperature furnace by step (1) dried powders mixture loading crucible, at a temperature of about 1050 ° of C, pre-burning 4 hours, obtains pre-burning powder body;
(3) rerolling
By the powder after step (2) pre-burning, zirconium oxide balls, dehydrated alcohol adds mixing bottle again, batch mixing about 24 hours in batch mixer；Slurry after batch mixing is placed in drying baker drying；
(4) pelletize, molding
The powder dried in (3) is added paraffin and carries out pelletize as binding agent, after crossing 80 mesh standard sieves, then be pressed into green compact with powder compressing machine with the pressure of 200 MPa；
(5) binder removal
Green compact are placed in high temperature furnace, 500
Binder removal four hours under ° C, discharges paraffin component；
(6) sintering
By the green compact after binder removal in 1100-1200
° C sintering, is incubated 4 hours.
The preparation method of the wolframite microwave-medium ceramics of a kind of ZnO thin film the most according to claim 3, it is characterised in that described ceramic powder raw material is respectively ZnO, ZrO2、Nb2O5With CoO powder body.
The preparation method of the wolframite microwave-medium ceramics of a kind of ZnO thin film the most according to claim 3, it is characterised in that described step (1), the material of (3), abrading-ball, the mass ratio of dehydrated alcohol is 1:10:1；A diameter of 1cm and a diameter of 0.5cm mill ball quality ratio are 2:1, and batch mixer rotating speed is 200 r/min.
The preparation method of the wolframite microwave-medium ceramics of a kind of ZnO thin film the most according to claim 3, it is characterised in that described step (1), the temperature that (3) dry is 70～90 DEG C.
The preparation method of the wolframite microwave-medium ceramics of a kind of ZnO thin film the most according to claim 3, it is characterized in that, pelletize described in step (4) is to carry out adding hot mixing by ball milling and the paraffin that sample powder body and mass fraction are 8% after drying, heating mixing temperature is 55-65 DEG C, makes micron-sized spheroidal particle.
The preparation method of the wolframite microwave-medium ceramics of a kind of ZnO thin film the most according to claim 2, it is characterized in that, the cylindrical green body that step (5) obtains is sintered under 1100-1200 DEG C of air atmosphere by described step (6), heating gradient is 5 DEG C/min, and temperature retention time is 4h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250441A (en) * | 2020-10-28 | 2021-01-22 | 烟台大学 | Microwave dielectric ceramic with low sintering temperature and adjustable dielectric property |
| CN112374886A (en) * | 2020-10-29 | 2021-02-19 | 烟台大学 | Ion doping regulation and control high-quality factor microwave dielectric ceramic and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105000881A (en) * | 2015-07-21 | 2015-10-28 | 天津大学 | Niobate medium-dielectric constant microwave dielectric ceramic material and preparation method thereof |
| CN105060887A (en) * | 2015-07-24 | 2015-11-18 | 天津大学 | Low-temperature sintering low loss microwave dielectric ceramic material |
| CN105152649A (en) * | 2015-09-11 | 2015-12-16 | 天津大学 | Temperature-stable high-Q-value niobium tantalite microwave dielectric ceramic and preparation method thereof |
| CN105272245A (en) * | 2015-10-30 | 2016-01-27 | 天津大学 | Low-loss zinc zirconium and niobium series microwave dielectric ceramic prepared by reaction sintering method |
-
2016
- 2016-03-25 CN CN201610174896.4A patent/CN105837211A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105000881A (en) * | 2015-07-21 | 2015-10-28 | 天津大学 | Niobate medium-dielectric constant microwave dielectric ceramic material and preparation method thereof |
| CN105060887A (en) * | 2015-07-24 | 2015-11-18 | 天津大学 | Low-temperature sintering low loss microwave dielectric ceramic material |
| CN105152649A (en) * | 2015-09-11 | 2015-12-16 | 天津大学 | Temperature-stable high-Q-value niobium tantalite microwave dielectric ceramic and preparation method thereof |
| CN105272245A (en) * | 2015-10-30 | 2016-01-27 | 天津大学 | Low-loss zinc zirconium and niobium series microwave dielectric ceramic prepared by reaction sintering method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250441A (en) * | 2020-10-28 | 2021-01-22 | 烟台大学 | Microwave dielectric ceramic with low sintering temperature and adjustable dielectric property |
| CN112374886A (en) * | 2020-10-29 | 2021-02-19 | 烟台大学 | Ion doping regulation and control high-quality factor microwave dielectric ceramic and preparation method thereof |
| CN112374886B (en) * | 2020-10-29 | 2022-10-28 | 烟台大学 | Ion doping regulation and control high-quality factor microwave dielectric ceramic and preparation method thereof |
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