CN104230329A - Low-temperature sintered microwave ceramic material and preparation method thereof - Google Patents
Low-temperature sintered microwave ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-temperature sintered microwave ceramic material and a preparation method thereof and belongs to the field of electronic materials and devices. The low-temperature sintered microwave ceramic material comprises a main material, namely Li2O-ZnO-TiO2, and an additive, wherein the main material, namely Li2O-ZnO-TiO2, has main crystal phases of TiO2 and Li2ZnTi3O8, and the molar ratio of Li2O to ZnO to TiO2 is 1 to 1 to (3-4); the additive is a composite oxide, namely aA+bB+cC, wherein A represents an alkali metal oxide, B represents a metal oxide, and C represents a nonmetallic oxide; a, b and c are coefficients, and calculated in percentage by weight, a+b+c=100% by weight, a is not less than 5% by weight and not more than 15% by weight, b is not less than 0% by weight and not more than 85% by weight, and c is not less than 0% by weight and not more than 55% by weight; one or more types of additives can be used, and the total percentage by weight of the additive is 0.2% by weight-4% by weight of the main material, namely Li2O-ZnO-TiO2. The preparation method has the advantages of low cost, good environmental friendliness, simple process, good repeatability and easiness in implementation; by adopting the preparation method, the medium and high-dielectric constant microwave ceramic material which has low loss, near-zero-series frequency temperature coefficients and stable performance and can realize low-temperature sintering with a silver electrode material can be prepared. The low-temperature sintered microwave ceramic material provided by the invention is suitable for manufacturing low-temperature co-fired multi-layer ceramic filters and resonators.
Description
Technical field
The invention belongs to electronic material and devices field, be specifically related to a kind of microwave ceramic material and preparation method thereof, especially relate to a kind of low temperature sintering microwave ceramic material and preparation method thereof.
Background technology
Along with information technology is rapidly towards high frequency, high-power, integrated, multifunction future development, the fast development of microelectronic device and integrated device is had higher requirement to electronics miniaturization and lightweight, the integrated application requiring that can not meet in current communication system of single active part, traditional bulk metal resonator cavity makes the integrated of microstrip circuit become difficulty, and the miniaturization of passive device has become a kind of trend.Microwave Multichip Module (MMCM) module is widely used because of it is lightweight, volume is little, cost is low and reliability is high advantage, and the effective way realizing this technology is development multilayer chip element.LTCC (Low Temperature Co-fired ceramic, LTCC) technology, because its integration density is high, high frequency characteristics is good, has been widely used in and has manufactured among integrated electronic component.What LTCC technology adopted is Miltilayer wiring structure, passive device integration and the passive and active device hybrid integrated technology of the assembling of a kind of 3 D stereo, ((resistance, electric capacity, inductance and wave filter) is integrated with transmission line can to realize passive element, again can surface mount IC element, to realize the miniaturization of device, the modularization of multi-functional and to improve the reliability of signal.The interconnecting conductor that LTCC technology uses is generally the silver metal with excellent conductive characteristic, and its fusing point is about 961 DEG C, and this just requires that the sintering temperature of the stupalith be used in LTCC technology must lower than 950 DEG C.But, the low-temperature co-burning ceramic material of Current commercialization application mostly belongs to glass-ceramic (glass-ceramic) system, and its specific inductivity is less than normal, and dielectric loss is bigger than normal, be mainly used in medium substrate material, as the A6 (ε of Ferro company of the U.S.
r=5.7, tg δ=0.0012), 951 (ε of Dupont company
r=7.85, tg δ=0.0063), and the low temperature co-fired medium ceramic material of commercialization with the microwave dielectric property excellence of middle high-k is also deficienter.In addition, other microwave dielectric ceramic materials of Current commercialization application, as CaTiO
3-SmAlO
3(CT-SA), BaO – Nd
2o
3– TiO
2(BNT), ZrTiO
4– ZnNb
2o
6, its sintering temperature is too high, is often greater than 1300 DEG C, and can not be implemented in argent and carry out common burning.
Li
2o-AO-TiO
2(A=Mg, Zn) series microwave dielectric ceramic is just newfound microwave dielectric material recently, is paid close attention to widely because it has excellent microwave dielectric property.The people such as S.George " have the Novel microwave dielectric ceramic Li of excellent temperature stability and high quality factor at the article of 2010 " American Ceramics association magazine " (Journal of the American Ceramic Society)
2aTi
3o
8the synthesis of (A=Mg, Zn) " (Synthesis and Microwave Dielectric Properties of Novel Temperature Stable High Q, Li
2aTi
3o
8(A=Mg, Zn) Ceramics) in report Li the earliest
2o-AO-TiO
2the microwave-medium ceramics of (A=Zn, Mg, Co) system, wherein Li
2znTi
3o
8the microwave dielectric property of pottery: ε
r~ 26.2, Q × f ~ 72,000GHz, τ
f=-15ppm/ DEG C.And then, scholar both domestic and external is to Li
2o-ZnO-TiO
2base microwave dielectric ceramics has carried out low-temperature sintering research, Li
2o-ZnO-TiO
2the sintering temperature of system pottery is at about 1100 DEG C, and its low-temperature sintering mainly adopts the approach of annex solution phase sintering auxiliary agent to realize.As " investigation of materials bulletin " (Materials Research Bulletin) article " BaCu (B of 2011
2o
5) the low-temperature sintering Li that adulterates
2znTi
3o
8ceramic microwave dielectric properties " (Low-firing Li
2znTi
3o
8microwave dielectric ceramics with BaCu (B
2o
5) additive) and in report BaCu (B
2o
5) glass can reduce Li
2znTi
3o
8the sintering temperature to 925 DEG C of pottery, but the dephasign that the generation that can react between them is new, havoc microwave dielectric property, 1.5wt%BaCu (B
2o
5) Li of glass-doped
2znTi
3o
8base microwave dielectric ceramics obtains microwave dielectric property under 925 DEG C/4h: ε
r=23.1, Q × f=2,2732GHz, τ
f=-17.6ppm/ DEG C." Materials science magazine-electronic material " (Journal of Materials Science-Materials in Electronics) article of 2012 " low-temperature sintering Li of LBS doping
2znTi
3o
8pottery and add TiO
2ceramic microwave dielectric properties " (Low-temperature firing and microwave dielectric properties of LBS glass-added Li
2znTi
3o
8ceramics with TiO
2) in report 1.0wt%Li
2o – B
2o
3– SiO
2+ 3.5wt%TiO
2the Li of doping
2znTi
3o
8pottery, at 875 DEG C of sintering 4h, can obtain microwave dielectric property: ε
r=36.0, Q × f=4,4023GHz, τ
f=-4.4ppm/ DEG C.TiO
2add and effectively can regulate Li
2znTi
3o
8the frequency-temperature coefficient of ceramic systems and can good microwave dielectric property be kept.Thereafter, the people such as Y.X.Li is at the article " TiO of 2013 " electronic material magazine " (Journal of Electronic Materials)
2ratio is to Li
2znTi
3+xo
8+2xthe impact of ceramic phase composition and microwave dielectric property " (Effect of TiO
2ratio on the Phase and Microwave Dielectric Properties of Li
2znTi
3+xo
8+2xceramics) Li is reported in
2o-ZnO-TiO
2in system, adopt the technique of single sintering pottery, TiO
2the change of ratio can regulate its frequency-temperature coefficient to zero effectively, and keeps the microwave dielectric property of this system excellence.The display of XRD material phase analysis which form the Li with stable two phase structure
2znTi
3o
8-TiO
2stupalith.The complex phase Li obtained
2znTi
3o
8-TiO
2the microwave dielectric property of pottery: ε
r~ 28.51, Q × f ~ 58,511GHz, τ
f=+2.3ppm/ DEG C.Its reason is TiO
2existence can reduce void content in ceramic body, improve relative density and itself just there is excellent microwave dielectric property (ε
r=105, Q × f=40000GHz, τ
f=+400ppm/ DEG C).Before to Li
2aTi
3o
8the research of (A=Mg, Zn) ceramic systems major part mainly concentrates on and reduces sintering temperature aspect, can find, for low melting point oxide or glass-doped, most researchers all concentrates on selects B
2o
3, B
2o
3– SiO
2, B
2o
3– ZnO, BaCu (B
2o
5) etc.Wherein have part to adulterate to demonstrate Li
2o-ZnO-TiO
2base microwave dielectric ceramics has unique liquid phase sintering effect, effectively can reduce sintering temperature, above-mentioned Temperature Firing Microwave Dielectric Ceramics has the also few of excellent comprehensive microwave dielectric property, be mainly manifested in Q × f value not high, mostly at below 20000GHz, or temperature coefficient of resonance frequency τ
fvalue is higher cannot meet practical application request.
The low-temperature sintered microwave dielectric ceramic material of current use is all in its high-k of strain after, low-loss and near-zero resonance frequency temperature coefficient feature, from material dielectric constant seriation and reduction electronic devices and components size aspect, need badly a kind of with low cost, technique simple, have middle high-k, low-loss, can burn altogether with argent and the stupalith of the not biochemical reaction with silver hair, to meet the application demand of micro-wave communication industry under lower sintering temperature (lower than 950 DEG C) condition.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind ofly to be had middle high-k, low-loss, can burn altogether with argent and low temperature sintering microwave ceramic material of the not biochemical reaction with silver hair and preparation method thereof, to overcome the defect that the poor and frequency-temperature coefficient of existing low temperature sintered microwave dielectric spillage of material characteristic not easily returns to zero.
The technical solution adopted for the present invention to solve the technical problems is: a kind of low temperature sintering microwave ceramic material, comprises Li
2o-ZnO-TiO
2major ingredient and additive, described Li
2o-ZnO-TiO
2the principal crystalline phase of major ingredient is TiO
2and Li
2znTi
3o
8, wherein Li
2o:ZnO:TiO
2mol ratio is 1:1:(3 ~ 4); Described additive is composite oxides aA+bB+cC, and wherein, A represents alkalimetal oxide, and B represents metal oxide, and C represents nonmetal oxide; A, b, c are coefficients, calculate by weight percentage, a+b+c=100wt%, 5wt%≤a≤15wt%, 0wt%≤b≤85wt%, 0wt%≤c≤55wt%, and the kind of described additive is one or more, and total mass percent of additive is Li
2o-ZnO-TiO
20.2wt% ~ the 4wt% of major ingredient.
Concrete, described alkalimetal oxide is Li
2o, CaO, MgO, La
2o
3in one or more.
Concrete, described metal oxide is Al
2o
3, WO
3, one or more in ZnO.
Concrete, described nonmetal oxide is B
2o
3, SiO
2or B
2o
3with SiO
2mixture.
Preferably, described additive is CaO-MgO-B
2o
3-SiO
2, Li
2o-Al
2o
3-B
2o
3, La
2o
3-ZnO-B
2o
3and Li
2wO
4.
Another technical scheme that the present invention solves its technical problem is: a kind of preparation method of low temperature sintering microwave ceramic material, comprises the following steps:
A. Li is selected
2cO
3, ZnO and TiO
2as raw material, be 1:1:(3 ~ 4 according to mol ratio) get the raw materials ready, will get the raw materials ready with deionized water is that medium carries out ball milling, and dries at 100 DEG C and cross 40 mesh sieves, then pre-burning 3 ~ 5 hours under 850 DEG C ~ 920 DEG C temperature condition, obtaining principal crystalline phase is TiO
2and Li
2znTi
3o
8li
2o-ZnO-TiO
2major ingredient;
B. select one or more in alkalimetal oxide, metal oxide and nonmetal oxide as raw material, and get the raw materials ready according to a certain percentage, obtain composite oxides aA+bB+cC, wherein, A represents alkalimetal oxide, and B represents metal oxide, and C represents nonmetal oxide; A, b, c are coefficients, calculate by weight percentage, a+b+c=100wt%, 5wt%≤a≤15wt%, 0wt%≤b≤85wt%, 0wt%≤c≤55wt%; To get the raw materials ready with alcohol is that medium carries out ball milling, and dries at 75 DEG C and cross 40 mesh sieves; Then wish scorification system, then ball milling 3h under certain temperature condition, dry and obtain pulverous additive;
C. at Li
2o-ZnO-TiO
2add the additive that step B obtains in major ingredient, total mass percent of additive is Li
2o-ZnO-TiO
20.2wt% ~ the 4wt% of major ingredient take deionized water as medium mixing and ball milling;
D. by the mixture drying obtained after step C ball milling, sieve, granulation, shaping rear binder removal;
E. sinter in atmosphere, obtain low temperature sintering microwave ceramic material after naturally cooling, described sintering temperature is 840 ~ 940 DEG C, sinters 120 ~ 180 minutes.
Preferably, step B is specially and selects CaCO
3, MgO, SiO
2and B
2o
3as raw material, get the raw materials ready by Ca:Mg:Si:B=1:1:2:4 mol ratio, will get the raw materials ready with alcohol is that medium carries out ball milling, and dry at 75 DEG C and cross 40 mesh sieves, then fusion cast glass under 1250 DEG C of temperature condition, then ball milling 3h, dries and obtains glass powder CaO-MgO-B
2o
3-SiO
2additive.
Preferably, step B is specially and selects Li
2o, Al
2o
3and B
2o
3as raw material, get the raw materials ready according to certain mol proportion, will get the raw materials ready with alcohol is that medium carries out ball milling, and dries at 75 DEG C and cross 40 mesh sieves, then fusion cast glass under 1250 DEG C of temperature condition, then ball milling 3h, dries and obtains glass powder Li
2o-Al
2o
3-B
2o
3additive.
Preferably, step B is specially and selects La
2o
3, ZnO and B
2o
3as raw material, get the raw materials ready by certain mol proportion, will get the raw materials ready using alcohol as medium and carry out ball milling, and dry at 75 DEG C and cross 40 mesh sieves, then fusion cast glass under 1250 DEG C of temperature condition, and ball milling 3h, obtain Powdered La after oven dry
2o
3-ZnO-B
2o
3additive.
Further, step B is specially and selects Li
2cO
3and H
2wO
4as raw material, get the raw materials ready by Li:W=2:1 mol ratio, will get the raw materials ready with alcohol is that medium carries out ball milling, and dries at 75 DEG C and cross 40 mesh sieves, and then pre-burning 3 ~ 5 hours under 500 DEG C of temperature condition, obtains pulverous Li
2wO
4additive.
The invention has the beneficial effects as follows: the raw material of microwave ceramic material is sufficient, with low cost, and not containing volatility or heavy metals such as Pb, Cd, Bi, the feature of environmental protection is good; Additive significantly can reduce sintering temperature, not with argent generation chemical reaction, and can realize good mating with pottery, reduces the loss degradation factors that sintering agent brings, and realizes low temperature sintering; Technique is simple, reproducible, be easy to realize, low-loss, the frequency-temperature coefficient of nearly zero seriation and stable performance can be prepared, can realize with silver electrode material the microwave ceramic material with middle high-k that low temperature (lower than 950 DEG C) sinters.The present invention is applicable to micro-wave communication industry.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention;
Fig. 2 is the X ray diffracting spectrum of low temperature sintering microwave ceramic material of the present invention;
Fig. 3 is low temperature sintering microwave ceramic material SEM scanning electron microscope (SEM) photograph of the present invention.
Embodiment
Below in conjunction with drawings and Examples, describe technical scheme of the present invention in detail.
As shown in Figure 1, a kind of low temperature sintering microwave ceramic material of the present invention, comprises Li
2o-ZnO-TiO
2major ingredient and additive, Li
2o-ZnO-TiO
2the principal crystalline phase of major ingredient is TiO
2and Li
2znTi
3o
8, wherein Li
2o:ZnO:TiO
2mol ratio is 1:1:(3 ~ 4); Described additive is composite oxides aA+bB+cC, and wherein, A represents alkalimetal oxide, comprises Li
2o, CaO, MgO, La
2o
3in one or more, B represents metal oxide, comprises Al
2o
3, WO
3, one or more in ZnO, C represents nonmetal oxide, comprises B
2o
3, SiO
2or B
2o
3with SiO
2mixture; A, b, c are coefficients, calculate by weight percentage, a+b+c=100wt%, 5wt%≤a≤15wt%, 0wt%≤b≤85wt%, 0wt%≤c≤55wt%, and the kind of described additive is one or more, and total percent mass specific mass of additive is Li
2o-ZnO-TiO
20.2wt% ~ the 4wt% of major ingredient.
By adjustment Li
2o-ZnO-TiO
2middle TiO
2ratio, and add above-mentioned additive, make the high-performance that microwave ceramic material can realize at about 860 DEG C low-temperature sintering ceramics: there is higher Q × f value (16000 ~ 60000), the frequency-temperature coefficient (-16 ~ 6) of Medium dielectric constant (24 ~ 30) and seriation nearly zero.
Based on cost and realize effect consider, described additive is four kinds, such as CaO-MgO-B
2o
3-SiO
2, Li
2o-Al
2o
3-B
2o
3, La
2o
3-ZnO-B
2o
3and Li
2wO
4.
Be the material phase analysis low temperature sintering microwave ceramic sample after burning till carried out with XRD diffraction approach as shown in Figure 2, can confirm that obtained ceramic principal crystalline phase is Li
2znTi
3o
8and TiO
2, principal phase is not subject to the impact of sintering agent doping.Observe as shown in Figure 3 with scanning electron microscope sem to ceramic surface, can find out ceramic surface crystal grain more greatly and comparatively even compact, the pottery burnt till after cooling does not occur that sintering agent introduces the large-area glass phase and crystal grain misgrowth brought.
For preparing above-mentioned low temperature sintering microwave ceramic material, the preparation method of use, comprises the following steps:
A. Li is prepared
2o-ZnO-TiO
2major ingredient.Select Li
2cO
3, ZnO and TiO
2as raw material, be 1:1:(3 ~ 4 according to mol ratio) get the raw materials ready, will get the raw materials ready with deionized water is that medium carries out ball milling, and dries at 100 DEG C and cross 40 mesh sieves, then pre-burning 3 ~ 5 hours under 850 DEG C ~ 920 DEG C temperature condition, obtaining principal crystalline phase is TiO
2and Li
2znTi
3o
8li
2o-ZnO-TiO
2major ingredient;
B. composite oxides additive is prepared.One or more in selection alkalimetal oxide, metal oxide and nonmetal oxide as raw material, and are got the raw materials ready according to a certain percentage, obtain composite oxides aA+bB+cC, wherein, A represents alkalimetal oxide, and B represents metal oxide, and C represents nonmetal oxide; A, b, c are coefficients, calculate by weight percentage, a+b+c=100wt%, 5wt%≤a≤15wt%, 0wt%≤b≤85wt%, 0wt%≤c≤55wt%; To get the raw materials ready with alcohol is that medium carries out ball milling, and dries at 75 DEG C and cross 40 mesh sieves; Then wish scorification system, then ball milling 3h under certain temperature condition, dry and obtain pulverous additive;
Described additive can be one or more.Preferably, add four kinds of additives: the CaO-MgO-B of low melting point simultaneously
2o
3-SiO
2, Li
2o-Al
2o
3-B
2o
3, La
2o
3-ZnO-B
2o
3and Li
2wO
4, to improve preparation effect.
C. at Li
2o-ZnO-TiO
2add the additive that step B obtains in major ingredient, total mass percent of additive is Li
2o-ZnO-TiO
20.2wt% ~ the 4wt% of major ingredient take deionized water as medium mixing and ball milling;
D. by the mixture drying obtained after step C ball milling, sieve, granulation, shaping rear binder removal;
E. sinter in atmosphere, obtain low temperature sintering microwave ceramic material after naturally cooling, described sintering temperature is 840 ~ 940 DEG C, sinters 120 ~ 180 minutes.
Embodiment 1: addition of C aO-MgO-B
2o
3-SiO
2doping change is compared
According to Li
2o:ZnO:TiO
2=1:1:3.17 synthesizes major ingredient, and ceramic formula is pressed Li
2o-ZnO-TiO
2major ingredient is fixed as 100g, the first addition of C aO-MgO-B
2o
3-SiO
2be respectively the weighing of 0.5g, 1g, 2g, 3g, 4g proportioning.Wet-milling, material after oven dry adds polyvinyl alcohol water solution and carries out granulation, type is made at 25Mpa pressure, obtaining diameter is 15mm, and thickness is the cylinder green compact of 8mm, is then placed in air and sinters, slightly change according to the different sintering condition of major ingredient proportioning, temperature rise rate is 3 DEG C/min, and furnace cooling can obtain Temperature Firing Microwave Dielectric Ceramics, and ceramic main formula changing conditions, sintering process and dielectric properties parameter are in table 1.
Table 1
Embodiment 2: additive Li
2o-Al
2o
3-B
2o
3doping change is compared
According to Li
2o:ZnO:TiO
2=1:1:3.17 synthesizes major ingredient, and ceramic formula is pressed Li
2o-ZnO-TiO
2major ingredient is fixed as 100g, Second addition Li
2o-Al
2o
3-B
2o
3be respectively the weighing of 0.2g, 0.5g, 1g, 2g, 4g proportioning.Wet-milling, material after oven dry adds polyvinyl alcohol water solution and carries out granulation, type is made at 25Mpa pressure, obtaining diameter is 15mm, thickness is the cylinder green compact of 8mm, is then placed in air and sinters, and temperature rise rate is 3 DEG C/min, furnace cooling can obtain Temperature Firing Microwave Dielectric Ceramics, and ceramic main formula changing conditions, sintering process and dielectric properties parameter are in table 2.
Table 2
Embodiment 3: additive La
2o
3-ZnO-B
2o
3doping change is compared
According to Li
2o:ZnO:TiO
2=1:1:3.24 synthesizes major ingredient, and ceramic formula is pressed Li
2o-ZnO-TiO
2major ingredient is fixed as 100g, the 3rd additive La
2o
3-ZnO-B
2o
3be respectively the weighing of 0.5g, 1g, 2g, 4g proportioning.Wet-milling, material after oven dry adds polyvinyl alcohol water solution and carries out granulation, type is made at 25Mpa pressure, obtaining diameter is 15mm, and thickness is the cylinder green compact of 8mm, is then placed in air and sinters, slightly change according to the different sintering condition of major ingredient proportioning, temperature rise rate is 3 DEG C/min, and furnace cooling can obtain Temperature Firing Microwave Dielectric Ceramics, and ceramic main formula changing conditions, sintering process and dielectric properties parameter are in table 3.
Table 3
Embodiment 4: additive Li
2wO
4doping change is compared
According to Li
2o:ZnO:TiO
2=1:1:3.2 synthesizes major ingredient, and ceramic formula is pressed Li
2o-ZnO-TiO
2major ingredient is fixed as 100g, the 4th additive Li
2wO
4be respectively the weighing of 0.5g, 1g, 2g, 4g proportioning.Wet-milling, material after oven dry adds polyvinyl alcohol water solution and carries out granulation, type is made at 25Mpa pressure, obtaining diameter is 15mm, thickness is the cylinder green compact of 8mm, is then placed in air and sinters, and temperature rise rate is 3 DEG C/min, furnace cooling can obtain Temperature Firing Microwave Dielectric Ceramics, and ceramic main formula changing conditions, sintering process and dielectric properties parameter are in table 4.
Table 4
Claims (10)
1. a low temperature sintering microwave ceramic material, is characterized in that, comprises Li
2o-ZnO-TiO
2major ingredient and additive, described Li
2o-ZnO-TiO
2the principal crystalline phase of major ingredient is TiO
2and Li
2znTi
3o
8, wherein Li
2o:ZnO:TiO
2mol ratio is 1:1:(3 ~ 4); Described additive is composite oxides aA+bB+cC, and wherein, A represents alkalimetal oxide, and B represents metal oxide, and C represents nonmetal oxide; A, b, c are coefficients, calculate by weight percentage, a+b+c=100wt%, 5wt%≤a≤15wt%, 0wt%≤b≤85wt%, 0wt%≤c≤55wt%, and the kind of described additive is one or more, and total mass percent of additive is Li
2o-ZnO-TiO
20.2wt% ~ the 4wt% of major ingredient.
2. a kind of low temperature sintering microwave ceramic material as claimed in claim 1, is characterized in that, described alkalimetal oxide is Li
2o, CaO, MgO, La
2o
3in one or more.
3. a kind of low temperature sintering microwave ceramic material as claimed in claim 1 or 2, is characterized in that, described metal oxide is Al
2o
3, WO
3, one or more in ZnO.
4. a kind of low temperature sintering microwave ceramic material as claimed in claim 3, is characterized in that, described nonmetal oxide is B
2o
3, SiO
2or B
2o
3with SiO
2mixture.
5. a kind of low temperature sintering microwave ceramic material as claimed in claim 1, is characterized in that, described additive is CaO-MgO-B
2o
3-SiO
2, Li
2o-Al
2o
3-B
2o
3, La
2o
3-ZnO-B
2o
3and Li
2wO
4.
6. a preparation method for low temperature sintering microwave ceramic material, is characterized in that, comprises the following steps:
A. Li is selected
2cO
3, ZnO and TiO
2as raw material, be 1:1:(3 ~ 4 according to mol ratio) get the raw materials ready, will get the raw materials ready with deionized water is that medium carries out ball milling, and dries at 100 DEG C and cross 40 mesh sieves, then pre-burning 3 ~ 5 hours under 850 DEG C ~ 920 DEG C temperature condition, obtaining principal crystalline phase is TiO
2and Li
2znTi
3o
8li
2o-ZnO-TiO
2major ingredient;
B. select one or more in alkalimetal oxide, metal oxide and nonmetal oxide as raw material, and get the raw materials ready according to a certain percentage, obtain composite oxides aA+bB+cC, wherein, A represents alkalimetal oxide, and B represents metal oxide, and C represents nonmetal oxide; A, b, c are coefficients, calculate by weight percentage, a+b+c=100wt%, 5wt%≤a≤15wt%, 0wt%≤b≤85wt%, 0wt%≤c≤55wt%; To get the raw materials ready with alcohol is that medium carries out ball milling, and dries at 75 DEG C and cross 40 mesh sieves; Then wish scorification system, then ball milling 3h under certain temperature condition, dry and obtain pulverous additive;
C. at Li
2o-ZnO-TiO
2add the additive that step B obtains in major ingredient, total mass percent of additive is Li
2o-ZnO-TiO
20.2wt% ~ the 4wt% of major ingredient take deionized water as medium mixing and ball milling;
D. by the mixture drying obtained after step C ball milling, sieve, granulation, shaping rear binder removal;
E. sinter in atmosphere, obtain low temperature sintering microwave ceramic material after naturally cooling, described sintering temperature is 840 ~ 940 DEG C, sinters 120 ~ 180 minutes.
7. the preparation method of a kind of low temperature sintering microwave ceramic material as claimed in claim 6, is characterized in that, step B is specially and selects CaCO
3, MgO, SiO
2and B
2o
3as raw material, get the raw materials ready by Ca:Mg:Si:B=1:1:2:4 mol ratio, will get the raw materials ready with alcohol is that medium carries out ball milling, and dry at 75 DEG C and cross 40 mesh sieves, then fusion cast glass under 1250 DEG C of temperature condition, then ball milling 3h, dries and obtains glass powder CaO-MgO-B
2o
3-SiO
2additive.
8. the preparation method of a kind of low temperature sintering microwave ceramic material as claimed in claim 6, is characterized in that, step B is specially and selects Li
2o, Al
2o
3and B
2o
3as raw material, get the raw materials ready according to certain mol proportion, will get the raw materials ready with alcohol is that medium carries out ball milling, and dries at 75 DEG C and cross 40 mesh sieves, then fusion cast glass under 1250 DEG C of temperature condition, then ball milling 3h, dries and obtains glass powder Li
2o-Al
2o
3-B
2o
3additive.
9. the preparation method of a kind of low temperature sintering microwave ceramic material as claimed in claim 6, is characterized in that, step B is specially and selects La
2o
3, ZnO and B
2o
3as raw material, get the raw materials ready by certain mol proportion, will get the raw materials ready using alcohol as medium and carry out ball milling, and dry at 75 DEG C and cross 40 mesh sieves, then fusion cast glass under 1250 DEG C of temperature condition, and ball milling 3h, obtain Powdered La after oven dry
2o
3-ZnO-B
2o
3additive.
10. the preparation method of a kind of low temperature sintering microwave ceramic material as claimed in claim 6, is characterized in that, step B is specially and selects Li
2cO
3and H
2wO
4as raw material, get the raw materials ready by Li:W=2:1 mol ratio, will get the raw materials ready with alcohol is that medium carries out ball milling, and dries at 75 DEG C and cross 40 mesh sieves, and then pre-burning 3 ~ 5 hours under 500 DEG C of temperature condition, obtains pulverous Li
2wO
4additive.
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