CN103803967B - Microwave-medium ceramics and preparation method thereof - Google Patents

Microwave-medium ceramics and preparation method thereof Download PDF

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CN103803967B
CN103803967B CN201410054015.6A CN201410054015A CN103803967B CN 103803967 B CN103803967 B CN 103803967B CN 201410054015 A CN201410054015 A CN 201410054015A CN 103803967 B CN103803967 B CN 103803967B
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microwave
medium ceramics
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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

A kind of 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, 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, when c with f is different be 0, b, y with m different time be 0.Above-mentioned microwave-medium ceramics to microwave-medium ceramics modification by least one in doped with Mn and W and at least one in Ca, Cu and Si, effectively can be reduced the content of Nb in microwave-medium ceramics, thus effectively reduce Nb 2o 5use, reduce the cost of microwave-medium ceramics.In addition, a kind of preparation method of microwave-medium ceramics is also provided.

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 to be applied in microwave frequency band (mainly UHF, SHF frequency range, 300MHz ~ 300GHz) circuit as dielectric material and to complete the pottery of one or more functions.Microwave-medium ceramics is mainly used in being used as the microwave devices such as resonator, wave filter, polyrod antenna, medium wave circuit.Can be used for the aspects such as mobile communication, satellite communication and military radar.But traditional microwave-medium ceramics contains more niobium, and 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, when c with f is different be 0, b, y with m different time be 0.
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, when c with f is different be 0, b, y with m different time be 0;
By described mixed powder at 850 DEG C ~ 1000 DEG C pre-burning 2h ~ 4h, obtain preburning powder;
In described preburning powder, add sizing agent granulation, compression moulding obtains ceramic green;
Having in oxygen atmosphere, described ceramic green is being sintered 4h ~ 10h under the condition of 1200 DEG C ~ 1300 DEG C, obtains described microwave-medium ceramics.
In one embodiment, the particle diameter of described mixed powder is 20 order ~ 80 orders.
In one embodiment, add sizing agent granulation in described preburning powder before, also comprise and 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 described preburning powder being carried out the step of grinding, before crossing the step of 60 order ~ 120 object sieves, also comprises the operation of being dried at 100 DEG C ~ 250 DEG C by the powder that grinding obtains.
In one embodiment, described preburning powder is ground, before then crossing the operation of 60 order ~ 120 object sieves, also comprise the operation of described preburning powder being crossed 20 order ~ 60 object sieves.
In one embodiment, described granulation be operating as that the described preburning powder adding described sizing agent is made 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 in doped with Mn and W and at least one in Ca, Cu and Si, modification is carried out to microwave-medium ceramics, while ensureing that microwave-medium ceramics has better performance, effectively can reduce the content of Nb in microwave-medium ceramics, thus effectively can reduce Nb 2o 5use, thus reduce the cost of microwave-medium ceramics.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the microwave-medium ceramics of an embodiment;
Fig. 2 is the X-ray diffractogram of microwave-medium ceramics prepared by embodiment 6;
Fig. 3 is the scanning electron microscope (SEM) photograph of microwave-medium ceramics prepared by embodiment 6.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by 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, when c with f is different be 0, b, y with m different time be 0.
Above-mentioned microwave-medium ceramics comprises (1-x) ZrTi that mol ratio is 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, when c with f is different be 0, b, y with m different time be 0.
In above-mentioned microwave-medium ceramics, (1-x) ZrTi 2o 6-xZn aca bmn cnb ew fo 6for main body base-material, comprise the ZrTi that mol ratio is 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 43 ~ 47, Q × F value be 38000GHz ~ 42000GHz, temperature drift coefficient τ ffor-5ppm/ DEG C ~+10ppm/ DEG C.
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 in doped with Mn and W and at least one in Ca, Cu and Si, modification is carried out to microwave-medium ceramics, while ensureing that microwave-medium ceramics has better performance, effectively can reduce the content of Nb in microwave-medium ceramics, thus effectively can reduce Nb 2o 5use, thus reduce the cost of microwave-medium ceramics.
Concrete, above-mentioned microwave-medium ceramics can suppress Ti to reduce by least one in doped with Mn and W, prevents Ti in sintering process 4+be reduced to Ti 3+thus cause product microwave property to worsen.Both can regulate sintering temperature by least one in doped with Cu, Ca and Si, can temperature drift coefficient be regulated again, thus make above-mentioned microwave-medium ceramics have good performance.
In above-mentioned microwave-medium ceramics, ZrTiO 4specific inductivity be 43, Q × F be 31000, temperature drift coefficient is 58ppm/ DEG C.ZnNb 2o 6specific inductivity be 25, Q × F be 83000, temperature drift coefficient is-56ppm/ DEG C.MnNb 2o 6specific inductivity be 20.9, Q × F be 13000, temperature drift coefficient is-74ppm/ DEG C.CaNb 2o 6specific inductivity be 17.3, Q × F be 49600, temperature drift coefficient is-53ppm/ DEG C.(ZnCu 2) Nb 2o 8specific inductivity be 22.1, Q × F be 59500, temperature drift coefficient is-66ppm/ DEG C, synthesis temperature 950 ~ 1000 DEG C.Zn 2siO 4specific inductivity be 6.5, have high q-factor, Q × F is greater than 100000, and temperature drift coefficient is-63ppm/ DEG C.(ZnCu 2) Nb 2o 8, Zn 2siO 4the temperature drift coefficient of above-mentioned microwave-medium ceramics can be adjusted etc. the high q-factor material with negative temperature coefficient of deviation, make its temperature drift coefficient be-5ppm/ DEG C ~+10ppm/ DEG C.
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, when c with f is different be 0, b, y with m different time be 0.
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 by difference ball milling ZrO 2, ZnO, Nb 2o 5, TiO 2, CuO, MnO, CaCO 3, SiO 2and WO 3100 DEG C ~ 250 DEG C oven dry after 1h ~ 10h, and 20 order ~ 80 object sieves obtain excessively.
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 DEG C ~ 1000 DEG C pre-burning 2h ~ 4h, obtain preburning powder.
By mixed powder 850 DEG C ~ 1000 DEG C pre-burnings, effectively can improve the structure of the composition of mixed powder, ensure 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 20 order ~ 60 object sieves, then the preburning powder after sieving is ground, after drying at 100 DEG C ~ 250 DEG C, cross 60 order ~ 120 object sieves.The operation of grinding adopts ball milled.Preburning powder is crossed 20 order ~ 60 object sieves preburning powder to be disperseed effectively, thus milling time below can be shortened.
It is 60 order ~ 100 object particles that the preburning powder adding 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 also can be 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 formed is that diameter height is than the cylinder green being 2.
S40, having in oxygen atmosphere, ceramic green is being sintered 4h ~ 10h under the condition of 1200 DEG C ~ 1300 DEG C, obtains microwave-medium ceramics.
There is 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 Ti can be suppressed to reduce by least one in doped with Mn and W in the preparation method of above-mentioned microwave-medium ceramics, prevent Ti in sintering process 4+be reduced to Ti 3+thus cause product microwave property to worsen.Both can regulate sintering temperature by least one in doped with Cu, Ca and Si, can temperature drift coefficient be regulated again, and material be sintered under air ambient namely there is good microwave property, reduce the requirement to agglomerating plant, 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 DEG C, obtain preburning powder.Preburning powder is crossed 40 object sieves, then the preburning powder after sieving is adopted ball milled grinding 5h, after drying at 100 DEG C, cross 80 object sieves.Add polyvinyl alcohol granulation afterwards, obtaining particle diameter is 60 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and preburning powder is 20%.
In atmosphere, by ceramic green at 1250 DEG C of sintering 10h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, 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 DEG C, obtain preburning powder.Preburning powder is crossed 40 object sieves, then the preburning powder after sieving is adopted ball milled grinding 1h, after drying at 150 DEG C, cross 60 object sieves, add polyvinyl alcohol granulation afterwards, obtaining particle diameter is 40 object particles, and compression moulding obtains ceramic green.The mass ratio of PVA and preburning powder is 10%.
In atmosphere, by ceramic green at 1200 DEG C of sintering 4h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, 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 DEG C, obtain preburning powder.Preburning powder is crossed 20 object sieves, then the preburning powder after sieving is adopted ball milled grinding 10h, after drying at 250 DEG C, cross 120 object sieves, add polyvinyl alcohol granulation afterwards, 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 atmosphere, by ceramic green at 1300 DEG C of sintering 5h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, 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 DEG C, obtain preburning powder.Preburning powder is crossed 50 object sieves, then the preburning powder after sieving is adopted ball milled grinding 5h, after drying at 200 DEG C, cross 80 object sieves, add phenolic varnish granulation afterwards, obtaining particle diameter is 60 object particles, and compression moulding obtains ceramic green.
In atmosphere, by ceramic green at 1250 DEG C of sintering 5h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, 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 DEG C, obtain preburning powder.Preburning powder is crossed 20 object sieves, then the preburning powder after sieving is adopted ball milled grinding 10h, after drying at 250 DEG C, cross 120 object sieves, add paraffin granulation afterwards, obtaining particle diameter is 100 object particles, and compression moulding obtains ceramic green.
In atmosphere, by ceramic green at 1300 DEG C of sintering 5h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, 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 DEG C, obtain preburning powder.Preburning powder is crossed 20 object sieves, then the preburning powder after sieving is adopted ball milled grinding 10h, after drying at 250 DEG C, cross 120 object sieves, add polyvinyl alcohol granulation afterwards, 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 atmosphere, by ceramic green at 1300 DEG C of sintering 5h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
X-ray diffraction (XRD) figure of microwave-medium ceramics prepared by embodiment 6 as shown in Figure 2.Fig. 3 is the scanning electron microscope (SEM) photograph of microwave-medium ceramics prepared by 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 DEG C, obtain preburning powder.Preburning powder is crossed 20 object sieves, then the preburning powder after sieving is adopted ball milled grinding 10h, after drying at 250 DEG C, cross 120 object sieves, add polyvinyl alcohol granulation afterwards, 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 atmosphere, by ceramic green at 1300 DEG C of sintering 5h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, 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 DEG C, obtain preburning powder.Preburning powder is crossed 20 object sieves, then the preburning powder after sieving is adopted ball milled grinding 10h, after drying at 250 DEG C, cross 120 object sieves, add polyvinyl alcohol granulation afterwards, 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 atmosphere, by ceramic green at 1300 DEG C of sintering 5h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, 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 DEG C, obtain preburning powder.Preburning powder is crossed 20 object sieves, then the preburning powder after sieving is adopted ball milled grinding 10h, after drying at 250 DEG C, cross 120 object sieves, add polyvinyl alcohol granulation afterwards, 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 atmosphere, by ceramic green at 1300 DEG C of sintering 5h, microwave-medium ceramics is obtained.
According to Hakki-Coleman dielectric resonance method, by 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 DEG C, t 2=85 DEG C, f t2and f t1for the resonant frequency of these two temperature spots, test result is as shown in table 1.
Table 1
As can be seen from Table 1, embodiment 1 ~ embodiment 9 suppresses Ti reduction by least one in doped with Mn and W, prevents Ti in calcination process 4+be reduced to Ti 3+thus cause product microwave property to worsen.Both can regulate calcining temperature by least one in doped with Cu, Ca and Si, can temperature drift coefficient be regulated again.Thus make the temperature drift coefficient τ of the microwave-medium ceramics obtained ffor-5ppm/ DEG C ~+10ppm/ DEG C, make microwave-medium ceramics have higher specific inductivity and Q × F value simultaneously.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 (9)

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, when a+b+c=1, e+f=2, c and f are different be 0, b, y with m different time be 0;
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。
2. 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, be 0 when a+b+c=1, e+f=2, c and f are different, be 0 when b, y are different with m, 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;
By described mixed powder at 850 DEG C ~ 1000 DEG C pre-burning 2h ~ 4h, obtain preburning powder;
In described preburning powder, add sizing agent granulation, compression moulding obtains ceramic green;
Having in oxygen atmosphere, described ceramic green is being sintered 4h ~ 10h under the condition of 1200 DEG C ~ 1300 DEG C, obtains described microwave-medium ceramics.
3. the preparation method of microwave-medium ceramics according to claim 2, is characterized in that, the particle diameter of described mixed powder is 20 order ~ 80 orders.
4. the preparation method of microwave-medium ceramics according to claim 2, is characterized in that, before adding sizing agent granulation, also comprises and being ground by described preburning powder in described preburning powder, then crosses the operation of 60 order ~ 120 object sieves.
5. the preparation method of microwave-medium ceramics according to claim 4, it is characterized in that, the operation of described grinding adopts ball milled, after described preburning powder being carried out the step of grinding, before crossing the step of 60 order ~ 120 object sieves, also comprise the operation of being dried at 100 DEG C ~ 250 DEG C by the powder that grinding obtains.
6. the preparation method of microwave-medium ceramics according to claim 4, is characterized in that, is ground by described preburning powder, before then crossing the operation of 60 order ~ 120 object sieves, also comprises the operation of described preburning powder being crossed 20 order ~ 60 object sieves.
7. the preparation method of microwave-medium ceramics according to claim 2, is characterized in that, it is 60 order ~ 100 object particles that the described preburning powder adding described sizing agent is made particle diameter by being operating as of described granulation.
8. the preparation method of microwave-medium ceramics according to claim 2, is characterized in that, described sizing agent is polyvinyl alcohol, paraffin or phenolic varnish.
9. the preparation method of microwave-medium ceramics according to claim 8, is characterized in that, the mass ratio of described polyvinyl alcohol and described preburning powder is 10% ~ 30%.
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