CN103803967A - Microwave dielectric ceramic and preparation method thereof - Google Patents

Microwave dielectric ceramic and preparation method thereof Download PDF

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CN103803967A
CN103803967A CN201410054015.6A CN201410054015A CN103803967A CN 103803967 A CN103803967 A CN 103803967A CN 201410054015 A CN201410054015 A CN 201410054015A CN 103803967 A CN103803967 A CN 103803967A
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powder
microwave
medium ceramics
preburning
preparation
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CN103803967B (en
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岑远清
方静
付振晓
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GUANGDONG GOVA ADVANCED MATERIAL TECHNOLOGY Co Ltd
Guangdong Fenghua Advanced Tech Holding Co Ltd
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GUANGDONG GOVA ADVANCED MATERIAL TECHNOLOGY Co Ltd
Guangdong Fenghua Advanced Tech Holding Co Ltd
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Abstract

The invention provides microwave dielectric ceramic which has the chemical formula (1-x)ZrTi2O(6-x)ZnaCabMncNbeWfO6.y(ZnCu2)Nb2O8.mZn2SiO4, in which x is greater than 0 but less than or equal to 0.12, (a+b+c) is equal to 1, a is greater than or equal to 0.7 and less than or equal to 0.95, b is greater than or equal to 0 and less than or equal to 0.2, c is greater than or equal to 0 and less than or equal to 0.2, (e+f) is equal to 2, e is greater than or equal to 1.8 and less than or equal to 2, f is greater than or equal to 0 but less than or equal to 0.2, y is greater than or equal to 0 but less than or equal to 0.5, m is greater than or equal to 0 and less than or equal to 0.6, c and f are not 0 at the same time, and b, y and m are not 0 at the same time. The microwave dielectric ceramic is modified by doping at least one of Mn and W and at least one of Ca, Cu and Si so as to effectively reduce the content of b in the microwave dielectric ceramic, so that use of Nb2O5 is effectively reduced, and the cost of the microwave dielectric ceramic is lowered. In addition, the invention further provides a preparation method of the microwave dielectric ceramic.

Description

Microwave-medium ceramics and preparation method thereof
Technical field
The present invention relates to microwave-medium ceramics field, particularly relate to a kind of microwave-medium ceramics and preparation method thereof.
Background technology
Microwave-medium ceramics refers to and is applied in microwave frequency band (being mainly UHF, SHF frequency range, 300MHz～300GHz) circuit as dielectric material and completes the pottery of one or more functions.Microwave-medium ceramics is mainly used in as microwave devices such as resonator, wave filter, polyrod antenna, medium guided wave loops.Can be used for the aspects such as mobile communication, satellite communication and military radar.But traditional microwave-medium ceramics contains more niobium, cost is higher.
Summary of the invention
Based on this, be necessary to provide a kind of lower-cost microwave-medium ceramics and preparation method thereof.
A kind of microwave-medium ceramics, described microwave-medium ceramics has chemical general formula (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6y (ZnCu 2) Nb 2o 8mZn 2siO 4, (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6, (ZnCu 2) Nb 2o 8and Zn 2siO 4mol ratio be 1:y:m, (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6in, ZrTi 2o 6and Zn aca bmn cnb ew fo 6mol ratio be 1-x:x, wherein, 0<x≤0.12, a+b+c=1,0.7≤a≤0.95,0≤b≤0.2,0≤c≤0.2, e+f=2,1.8≤e≤2,0≤f≤0.2,0≤y≤0.5,0≤m≤0.6, is that 0, b, y are 0 when different with m when c is different with f.
In one embodiment, 0.09≤x≤0.12,0.80≤a≤0.90,0≤b≤0.20,0≤c≤0.20,1.80≤e≤1.92,0.08≤f≤0.20,0.08≤y≤0.20,0.10≤m≤0.40.
A preparation method for microwave-medium ceramics, comprises the steps:
According to (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6y (ZnCu 2) Nb 2o 8mZn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder, wherein, and 0<x≤0.12, a+b+c=1,0.7≤a≤0.95,0≤b≤0.2,0≤c≤0.2, e+f=2,1.8≤e≤2,0≤f≤0.2,0≤y≤0.5,0≤m≤0.6, is that 0, b, y are 0 when different with m when c is different with f;
Described mixed powder, at 850 ℃～1000 ℃ pre-burning 2h～4h, is obtained to preburning powder;
In described preburning powder, add sizing agent granulation, compression moulding obtains ceramic green;
Having in oxygen atmosphere, by described ceramic green sintering 4h～10h under the condition of 1200 ℃～1300 ℃, obtain described microwave-medium ceramics.
In one embodiment, the particle diameter of described mixed powder is 20 order～80 orders.
In one embodiment, in described preburning powder, add before sizing agent granulation, also comprise described preburning powder is ground, then cross the operation of 60 order～120 object sieves.
In one embodiment, the operation of described grinding adopts ball milled, after the step that described preburning powder is ground, crosses before the step of 60 order～120 object sieves, also comprises the operation that the powder that grinding is obtained is dried at 100 ℃～250 ℃.
In one embodiment, described preburning powder is ground, then cross before the operation of 60 order～120 object sieves, also comprise the operation of described preburning powder being crossed to 20 order～60 object sieves.
In one embodiment, described granulation be operating as that the described preburning powder that has added described sizing agent is made to particle diameter is 60 order～100 object particles.
In one embodiment, described sizing agent is polyvinyl alcohol, paraffin or phenolic varnish.
In one embodiment, the mass ratio of described polyvinyl alcohol and described preburning powder is 10%～30%.
Nb in the raw material of above-mentioned microwave-medium ceramics 2o 5price more expensive, by at least one at least one and Ca, Cu and Si in doped with Mn and W, microwave-medium ceramics is carried out to modification, in guaranteeing that microwave-medium ceramics has better performance, can effectively reduce the content of Nb in microwave-medium ceramics, thereby can effectively reduce Nb 2o 5use, thereby reduce the cost of microwave-medium ceramics.
Accompanying drawing explanation
Fig. 1 is the preparation method's of the microwave-medium ceramics of an embodiment schema;
Fig. 2 is the X-ray diffractogram of the microwave-medium ceramics prepared of embodiment 6;
Fig. 3 is the scanning electron microscope (SEM) photograph of the microwave-medium ceramics prepared of embodiment 6.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
The microwave-medium ceramics of one embodiment, microwave-medium ceramics has chemical general formula (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6y (ZnCu 2) Nb 2o 8mZn 2siO 4, (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6, (ZnCu 2) Nb 2o 8and Zn 2siO 4mol ratio be 1:y:m, (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6in, ZrTi 2o 6and Zn aca bmn cnb ew fo 6mol ratio be 1-x:x, wherein, 0<x≤0.12, a+b+c=1,0.7≤a≤0.95,0≤b≤0.2,0≤c≤0.2, e+f=2,1.8≤e≤2,0≤f≤0.2,0≤y≤0.5,0≤m≤0.6, is that 0, b, y are 0 when different with m when c is different with f.
Above-mentioned microwave-medium ceramics comprises that mol ratio is (1-x) ZrTi of 1:y:m 2o 6-xZn aca bmn cnb ew fo 6, (ZnCu 2) Nb 2o 8and Zn 2siO 4.Wherein, 0<x≤0.12, a+b+c=1,0.7≤a≤0.95,0≤b≤0.2,0≤c≤0.2, e+f=2,1.8≤e≤2,0≤f≤0.2,0≤y≤0.5,0≤m≤0.6, is that 0, b, y are 0 when different with m when c is different with f.
In above-mentioned microwave-medium ceramics, (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6for main body base-material, comprise that mol ratio is the ZrTi of 1-x:x 2o 6and Zn aca bmn cnb ew fo 6, 0<x≤0.12.The DIELECTRIC CONSTANT ε of above-mentioned microwave-medium ceramics rbe that 43～47, Q × F value is 38000GHz～42000GHz, temperature drift coefficient τ ffor-5ppm/ ℃～+ 10ppm/ ℃.
In a preferred embodiment, 0.09≤x≤0.12,0.80≤a≤0.90,0≤b≤0.20,0≤c≤0.20,1.80≤e≤1.92,0.08≤f≤0.20,0.08≤y≤0.20,0.10≤m≤0.40.
In a more excellent embodiment, x=0.12, a=0.80, b=0.12, c=0.08, e=1.91, f=0.09, y=0.50, m=0.15.
Nb in the raw material of above-mentioned microwave-medium ceramics 2o 5price more expensive, by at least one at least one and Ca, Cu and Si in doped with Mn and W, microwave-medium ceramics is carried out to modification, in guaranteeing that microwave-medium ceramics has better performance, can effectively reduce the content of Nb in microwave-medium ceramics, thereby can effectively reduce Nb 2o 5use, thereby reduce the cost of microwave-medium ceramics.
Concrete, above-mentioned microwave-medium ceramics can suppress Ti reduction by least one in doped with Mn and W, prevents Ti in sintering process 4+be reduced to Ti 3+thereby cause product microwave property to worsen.Both can regulate sintering temperature by least one in doped with Cu, Ca and Si, and can regulate again temperature drift coefficient, thereby make above-mentioned microwave-medium ceramics there is good performance.
In above-mentioned microwave-medium ceramics, ZrTiO 4specific inductivity be that 43, Q × F is 31000, temperature drift coefficient is 58ppm/ ℃.ZnNb 2o 6specific inductivity be that 25, Q × F is 83000, temperature drift coefficient is-56ppm/ ℃.MnNb 2o 6specific inductivity be that 20.9, Q × F is 13000, temperature drift coefficient is-74ppm/ ℃.CaNb 2o 6specific inductivity be that 17.3, Q × F is 49600, temperature drift coefficient is-53ppm/ ℃.(ZnCu 2) Nb 2o 8specific inductivity be that 22.1, Q × F is 59500, temperature drift coefficient is-66ppm/ ℃, 950～1000 ℃ of synthesis temperatures.Zn 2siO 4specific inductivity be 6.5, there is high Q value, Q × F is greater than 100000, temperature drift coefficient is-63ppm/ ℃.(ZnCu 2) Nb 2o 8, Zn 2siO 4can adjust the temperature drift coefficient of above-mentioned microwave-medium ceramics Deng the high Q value material with negative temperature coefficient of deviation, make its temperature drift coefficient for-5ppm/ ℃～+ 10ppm/ ℃.
As shown in Figure 1, the preparation method of above-mentioned microwave-medium ceramics, comprises the steps:
S10, according to (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6. y(ZnCu 2) Nb 2o 8mZn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder, wherein, and 0<x≤0.12, a+b+c=1,0.7≤a≤0.95,0≤b≤0.2,0≤c≤0.2, e+f=2,1.8≤e≤2,0≤f≤0.2,0≤y≤0.5,0≤m≤0.6, is that 0, b, y are 0 when different with m when c is different with f.
The particle diameter of mixed powder can be 20 order～80 orders.
ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder can be by difference ball milling ZrO 2, ZnO, Nb 2o 5, TiO 2, CuO, MnO, CaCO 3, SiO 2and WO 3after 1h～10h 100 ℃～250 ℃ oven dry, and cross 20 order～80 object sieves obtain.
ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3the purity of powder is all more than or equal to 99%.
In a preferred embodiment, 0.09≤x≤0.12,0.80≤a≤0.90,0≤b≤0.20,0≤c≤0.20,1.80≤e≤1.92,0.08≤f≤0.20,0.08≤y≤0.20,0.10≤m≤0.40.
In a more excellent embodiment, x=0.10, a=0.86, b=0.06, c=0.08, e=1.92, f=0.08, y=0.30, m=0.60.
S20, by mixed powder at 850 ℃～1000 ℃ pre-burning 2h～4h, obtain preburning powder.
Mixed powder, 850 ℃～1000 ℃ pre-burnings, can effectively be improved to the structure of the composition of mixed powder, guarantee the volume stability of product and the accuracy of physical dimension of preparation, improve the performance of product.
S30, in preburning powder, add sizing agent granulation, compression moulding obtains ceramic green.
Add the step of sizing agent granulation in preburning powder before, first preburning powder is crossed to 20 order～60 object sieves, then the preburning powder after sieving is ground, after 100 ℃～250 ℃ oven dry, cross 60 order～120 object sieves.The operation of grinding adopts ball milled.Preburning powder is crossed to 20 order～60 object sieves can be disperseed preburning powder effectively, thereby can shorten milling time below.
It is 60 order～100 object particles that the preburning powder that has added sizing agent is made particle diameter by being operating as of granulation.
Sizing agent can be polyvinyl alcohol (Polyvinyl alcohol, PVA), paraffin or phenolic varnish.Be appreciated that in actual applications, sizing agent can be also the sizing agent of other types.Preferably, sizing agent is polyvinyl alcohol.The mass ratio of polyvinyl alcohol and preburning powder can be 10%～30%.
Compression moulding obtains in the operation of ceramic green, and under the condition of 10MPa～30MPa, compacting forms ceramic green.The ceramic green forming is that diameter aspect ratio is 2 cylinder green compact body.
S40, having in oxygen atmosphere, by ceramic green sintering 4h～10h under the condition of 1200 ℃～1300 ℃, obtain microwave-medium ceramics.
Having oxygen atmosphere can be air.
The preparation method of above-mentioned microwave-medium ceramics, manufacture craft is simple, is adapted at sintering in long stove, is applicable to volume production.And in the preparation method of above-mentioned microwave-medium ceramics, can suppress Ti reduction by least one in doped with Mn and W, prevent Ti in sintering process 4+be reduced to Ti 3+thereby cause product microwave property to worsen.Both can regulate sintering temperature by least one in doped with Cu, Ca and Si, can regulate again temperature drift coefficient, and make material sintering under air ambient there is good microwave property, reduce the requirement to agglomerating plant, and be easy to apply.
Be specific embodiment part below.
Embodiment 1
According to 0.91ZrTi 2o 6-0.09Zn 0.95ca 0.02mn 0.03nb 1.99w 0.01o 60.1 (ZnCu 2) Nb 2o 8the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder and WO 3powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 20 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder and WO 3the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 3h under the condition of 850 ℃, obtain preburning powder.Preburning powder is crossed to 40 object sieves, then adopt ball milled to grind 5h the preburning powder after sieving, after 100 ℃ of oven dry, cross 80 object sieves.Add afterwards polyvinyl alcohol granulation, obtaining particle diameter is 60 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and preburning powder is 20%.
In air, ceramic green, at 1250 ℃ of sintering 10h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Embodiment 2
According to 0.91ZrTi 2o 6-0.09Zn 0.95ca 0.01mn 0.04nb 1.98w 0.02o 60.12Zn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, manganese, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 80 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 2h under the condition of 900 ℃, obtain preburning powder.Preburning powder is crossed to 40 object sieves, then adopt ball milled to grind 1h the preburning powder after sieving, after drying, cross 60 object sieves at 150 ℃, add afterwards polyvinyl alcohol granulation, obtaining particle diameter is 40 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and preburning powder is 10%.
In air, ceramic green, at 1200 ℃ of sintering 4h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Embodiment 3
According to 0.91ZrTi 2o 6-0.09Zn 0.9ca 0.08mn 0.02nb 1.99w 0.01o 60.08 (ZnCu 2) Nb 2o 80.1Zn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 60 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 4h under the condition of 1000 ℃, obtain preburning powder.Preburning powder is crossed to 20 object sieves, then adopt ball milled to grind 10h the preburning powder after sieving, after drying, cross 120 object sieves at 250 ℃, add afterwards polyvinyl alcohol granulation, obtaining particle diameter is 100 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and the 3rd powder is 30%.
In air, ceramic green, at 1300 ℃ of sintering 5h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Embodiment 4
According to 0.9ZrTi 2o 6-0.1Zn 0.9ca 0.04mn 0.06nb 2o 60.2 (ZnCu 2) Nb 2o 80.12Zn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium and silicon, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder and SiO 2powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 60 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder and SiO 2the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 3h under the condition of 900 ℃, obtain preburning powder.Preburning powder is crossed to 50 object sieves, then adopt ball milled to grind 5h the preburning powder after sieving, after drying, cross 80 object sieves at 200 ℃, add afterwards phenolic varnish granulation, obtaining particle diameter is 60 object particles, and compression moulding obtains ceramic green.
In air, ceramic green, at 1250 ℃ of sintering 5h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Embodiment 5
According to 0.9ZrTi 2o 6-0.1Zn 0.86ca 0.14nb 1.9w 0.1o 60.12 (ZnCu 2) Nb 2o 80.2Zn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 60 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, CaCO 3powder, SiO 2powder and WO 3the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 4h under the condition of 1000 ℃, obtain preburning powder.Preburning powder is crossed to 20 object sieves, then adopt ball milled to grind 10h the preburning powder after sieving, after drying, cross 120 object sieves at 250 ℃, add afterwards paraffin granulation, obtaining particle diameter is 100 object particles, and compression moulding obtains ceramic green.
In air, ceramic green, at 1300 ℃ of sintering 5h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Embodiment 6
According to 0.9ZrTi 2o 6-0.1Zn 0.86ca 0.06mn 0.08nb 1.92w 0.08o 60.3 (ZnCu 2) Nb 2o 80.6Zn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 60 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 4h under the condition of 1000 ℃, obtain preburning powder.Preburning powder is crossed to 20 object sieves, then adopt ball milled to grind 10h the preburning powder after sieving, after drying, cross 120 object sieves at 250 ℃, add afterwards polyvinyl alcohol granulation, obtaining particle diameter is 80 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and the 3rd powder is 30%.
In air, ceramic green, at 1300 ℃ of sintering 5h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
The X-ray diffraction (XRD) of microwave-medium ceramics prepared by embodiment 6 is schemed as shown in Figure 2.Fig. 3 is the scanning electron microscope (SEM) photograph of the microwave-medium ceramics prepared of embodiment 6.
Embodiment 7
According to 0.88ZrTi 2o 6-0.12Zn 0.8ca 0.12mn 0.08nb 1.91w 0.09o 60.5 (ZnCu 2) Nb 2o 80.15Zn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 60 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 4h under the condition of 1000 ℃, obtain preburning powder.Preburning powder is crossed to 20 object sieves, then adopt ball milled to grind 10h the preburning powder after sieving, after drying, cross 120 object sieves at 250 ℃, add afterwards polyvinyl alcohol granulation, obtaining particle diameter is 60 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and the 3rd powder is 30%.
In air, ceramic green, at 1300 ℃ of sintering 5h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Embodiment 8
According to 0.88ZrTi 2o 6-0.12Zn 0.8mn 0.2nb 1.85w 0.15o 60.4 (ZnCu 2) Nb 2o 80.3Zn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 60 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, SiO 2powder and WO 3the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 4h under the condition of 1000 ℃, obtain preburning powder.Preburning powder is crossed to 20 object sieves, then adopt ball milled to grind 10h the preburning powder after sieving, after drying, cross 120 object sieves at 250 ℃, add afterwards polyvinyl alcohol granulation, obtaining particle diameter is 100 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and the 3rd powder is 30%.
In air, ceramic green, at 1300 ℃ of sintering 5h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Embodiment 9
According to 0.88ZrTi 2o 6-0.12Zn 0.7ca 0.2mn 0.1nb 1.8w 0.2o 60.2 (ZnCu 2) Nb 2o 80.4Zn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder.The particle diameter of mixed powder is 60 orders.Wherein, ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3the purity of powder is all more than or equal to 99%.
By mixed powder pre-burning 4h under the condition of 1000 ℃, obtain preburning powder.Preburning powder is crossed to 20 object sieves, then adopt ball milled to grind 10h the preburning powder after sieving, after drying, cross 120 object sieves at 250 ℃, add afterwards polyvinyl alcohol granulation, obtaining particle diameter is 60 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and the 3rd powder is 30%.
In air, ceramic green, at 1300 ℃ of sintering 5h, is obtained to microwave-medium ceramics.
According to Hakki-Coleman dielectric resonance method, with the performance of network analyzer test microwave-medium ceramics, frequency-temperature coefficient τ fby τ f=(f t2-f t1)/((t 2-t 1) × f t1) calculate wherein t 1=25 ℃, t 2=85 ℃, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Table 1
Figure BDA0000466603900000111
As can be seen from Table 1, embodiment 1～embodiment 9, by least one the inhibition Ti reduction in doped with Mn and W, prevents Ti in calcination process 4+be reduced to Ti 3+thereby cause product microwave property to worsen.Both calcining temperature can be regulated by least one in doped with Cu, Ca and Si, temperature drift coefficient can be regulated again.Thereby make the temperature drift coefficient τ of the microwave-medium ceramics obtaining ffor-5ppm/ ℃～+ 10ppm/ ℃, make microwave-medium ceramics there is higher specific inductivity and Q × F value simultaneously.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a microwave-medium ceramics, is characterized in that, described microwave-medium ceramics has chemical general formula (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6y (ZnCu 2) Nb 2o 8mZn 2siO 4, (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6, (ZnCu 2) Nb 2o 8and Zn 2siO 4mol ratio be 1:y:m, (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6in, ZrTi 2o 6and Zn aca bmn cnb ew fo 6mol ratio be 1-x:x, wherein, 0<x≤0.12, a+b+c=1,0.7≤a≤0.95,0≤b≤0.2,0≤c≤0.2, e+f=2,1.8≤e≤2,0≤f≤0.2,0≤y≤0.5,0≤m≤0.6, is that 0, b, y are 0 when different with m when c is different with f.
2. microwave-medium ceramics according to claim 1, is characterized in that, 0.09≤x≤0.12,0.80≤a≤0.90,0≤b≤0.20,0≤c≤0.20,1.80≤e≤1.92,0.08≤f≤0.20,0.08≤y≤0.20,0.10≤m≤0.40.
3. a preparation method for microwave-medium ceramics as claimed in claim 1, is characterized in that, comprises the steps:
According to (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6y (ZnCu 2) Nb 2o 8mZn 2siO 4the stoichiometric ratio of middle zirconium, zinc, niobium, titanium, copper, manganese, calcium, silicon and tungsten, provides ZrO 2powder, ZnO powder, Nb 2o 5powder, TiO 2powder, CuO powder, MnO powder, CaCO 3powder, SiO 2powder and WO 3powder also mixes, and obtains mixed powder, wherein, and 0<x≤0.12, a+b+c=1,0.7≤a≤0.95,0≤b≤0.2,0≤c≤0.2, e+f=2,1.8≤e≤2,0≤f≤0.2,0≤y≤0.5,0≤m≤0.6, is that 0, b, y are 0 when different with m when c is different with f;
Described mixed powder, at 850 ℃～1000 ℃ pre-burning 2h～4h, is obtained to preburning powder;
In described preburning powder, add sizing agent granulation, compression moulding obtains ceramic green;
Having in oxygen atmosphere, by described ceramic green sintering 4h～10h under the condition of 1200 ℃～1300 ℃, obtain described microwave-medium ceramics.
4. the preparation method of microwave-medium ceramics according to claim 3, is characterized in that, the particle diameter of described mixed powder is 20 order～80 orders.
5. the preparation method of microwave-medium ceramics according to claim 3, is characterized in that, adds before sizing agent granulation in described preburning powder, also comprises described preburning powder is ground, and then crosses the operation of 60 order～120 object sieves.
6. the preparation method of microwave-medium ceramics according to claim 5, it is characterized in that, the operation of described grinding adopts ball milled, after the step that described preburning powder is ground, cross before the step of 60 order～120 object sieves, also comprise the operation that the powder that grinding is obtained is dried at 100 ℃～250 ℃.
7. the preparation method of microwave-medium ceramics according to claim 5, is characterized in that, described preburning powder is ground, and then crosses before the operation of 60 order～120 object sieves, also comprises the operation of described preburning powder being crossed to 20 order～60 object sieves.
8. the preparation method of microwave-medium ceramics according to claim 3, is characterized in that, it is 60 order～100 object particles that the described preburning powder that has added described sizing agent is made particle diameter by being operating as of described granulation.
9. the preparation method of microwave-medium ceramics according to claim 3, is characterized in that, described sizing agent is polyvinyl alcohol, paraffin or phenolic varnish.
10. the preparation method of microwave-medium ceramics according to claim 9, is characterized in that, the mass ratio of described polyvinyl alcohol and described preburning powder is 10%～30%.
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