CN108975911A - Complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials and preparation method thereof - Google Patents

Complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials and preparation method thereof Download PDF

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CN108975911A
CN108975911A CN201810990286.0A CN201810990286A CN108975911A CN 108975911 A CN108975911 A CN 108975911A CN 201810990286 A CN201810990286 A CN 201810990286A CN 108975911 A CN108975911 A CN 108975911A
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rock salt
salt structure
ball
ceramic materials
dielectric ceramic
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唐斌
张星
袁颖
钟朝位
张树人
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University of Electronic Science and Technology of China
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Abstract

The present invention provides a kind of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials and preparation method thereof, and composition general formula is Li3+aMg2‑b/3X1‑2b/3Yb+cO6+2cDZ, X Nb5+Or Ta5+, Y Ti4+、Sn4+Or Zr4+, Z is ZnO or LiF, 0.03≤a≤0.12,0.12≤b≤0.38,0≤c≤0.15,0wt%≤d≤5wt%, preparation method are according to general formula ingredient, by first time ball milling mixing, drying, sieving, pre-burning, using second of ball milling mixing, it is dry, it is granulated, dumping, sintering is made in air；The crystal phase of its manufactured goods is the compound phase of orderly orthorhombic phase rock salt structure and unordered cubic phase rock salt structure；Microwave dielectric ceramic materials provided by the invention present more excellent performance: its relative dielectric constant ε in two kinds of adjustable situations of different rock salt structure ingredientsrAdjustable between 8.8~17.9, Q × f value is 82000GHz~128000GHz, temperature coefficient of resonance frequency τfAdjustable between -33ppm/ DEG C~+11ppm/ DEG C, preparation process is simple, and performance is stablized, and the application demand of modern microwave device is met.

Description

Complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials and preparation method thereof
Technical field
The invention belongs to electronic information function material and device arts, in particular to be a kind of frequency-temperature coefficient Nearly adjustable ultra-low loss microwave dielectric ceramic materials in zero end and preparation method thereof.
Background technique
Microwave-medium ceramics are resonator, filter, Jie used in modern mobile communication, satellite communication and military radar etc. The critical material of the microwave devices such as matter substrate.State Council was early in 2009 " planning outline is revitalized in electronics and information industry adjustment " File proposes the importance of the excellent media ceramic of development dielectric constant seriation, microwave dielectric property.High frequency is digital production The inevitable trend of product development, miniaturization, collection with electronic information technology constantly to high frequency and digital development, to component Cheng Hua, modular demand are also more more and more urgent.In high-frequency microwave circuit, many microwave devices are needed using media ceramic material Material is used as substrate, so that microwave ceramics medium baseplate material more and more becomes used in microwave device, component and machine system Key basic material.Dielectric constant is the key performance of medium ceramic substrate, and the range of dielectric constant often determines substrate material The applicable direction of material.For example, substrate of the relative dielectric constant lower than 15 is suitable for the design of high-speed digital circuit；Opposite dielectric is normal The substrate of number 15~80 can complete the design of HF link well；Relative dielectric constant is up to 20000 substrate, then can make height Capacitive device is integrated into multilayered structure.And develop the microwave dielectric ceramic materials of low-k (lower than 20) to meet high frequency Requirement with high speed is the primary study developing direction of microwave-medium ceramics.Due to the quality factor q of microwave dielectric ceramic materials × f value is bigger, and the insertion loss of filter is lower, therefore high quality factor is advantageously implemented the good frequency-selecting of microwave device, and Close to zero frequency-temperature coefficient τfMean that the centre frequency of device is small with variation of ambient temperature, job stability is high.Cause This, developing has a tunable dielectric constant in a certain range simultaneously at microwave frequencies, ultra-low loss and close to zero frequency temperature The microwave dielectric ceramic materials for spending coefficient have very big application value.
The performance superiority and inferiority of microwave-medium ceramics is dependent firstly on the performance of selected materials.In order to meet the needs of above-mentioned, one The binary or ternary Li base microwave ceramics system of series high-performance developed in succession." American Ceramic Society's proceedings " (Journal of the American Ceramic Society) was in article " Li in 2011(3-3x)M4xNb(1-x)O4(M= Mg, Zn) system phase transformation and microwave dielectric property " in have studied Li2O-MgO-Nb2O3The phase-change mechanism of ternary system and its right The influence of microwave dielectric property, wherein Li3Mg2NbO6For the orthorhombic phase with higher order structures, because its have it is excellent Dielectric properties (ε r=16.8, Q × f=79642GHz, τf=-22ppm/ DEG C) and cause the attention of numerous scholars.Although Li3Mg2NbO6Microwave-medium ceramics have compared with low-loss, but have common defect as most of raw microwave ceramics.Its One, under 1300 DEG C or so of high temperature sintering environment, Li+The serious volatilization of ion leads to Li3Mg2NbO6Structure in exist compared with More stomatas increase the dielectric loss of material；Second, biggish negative frequency temperature coefficient makes Li3Mg2NbO6Original ceramic material It is more difficult to meet industrial applicability；Third, higher firing temperature increases industrial cost.It is put into using by material rich in Li The atmosphere sintering of volatile matter or to be put into confined space calcining to inhibit the volatilization of lithium be two kinds of common methods, the former often technique Complexity, the latter generally burn powder manufacture confined space using platinum crucible or burying for discord raw material reaction, but because of platinum price It is expensive and bury firing technique complexity, all it is difficult to apply in actual industrial production.Bian et al. is in " Li2+xTiO3(0≤x≤ 0.2) sintering character, microstructure and microwave dielectric property " (Sintering behavior, microstructure and microwave dielectric properties of Li2+xTiO3(0≤x≤0.2)) Li element is successfully utilized in a text Non-stoichiometric realizes Li2+xTiO3The significantly promotion of the comprehensive microwave property of ceramics, at the same to a certain degree under effectively inhibit The volatilization of lithium in stoichiometric ratio raw material.And adjusting the most effective method of frequency-temperature coefficient at present is to introduce and base-material body It is the opposite phase of frequency-temperature coefficient, such as introduces TiO in negative frequency temperature coefficient system2(450ppm/ DEG C) etc. has positive frequency Temperature coefficient and easily controllable phase.And the conventional method of microwave ceramic material sintering temperature is reduced as sintering aid, such as " electricity is added Sub- component " 2008 years article " Mg1-xZnxTiO3Be the research of ceramic microwave dielectric properties " in point out, add it is suitable ZnO can effectively reduce sintering temperature, and can further decrease the dielectric loss loss of ceramic material script.Bian et al. In article " (1-x) Li of " investigation of materials bulletin " (Material Research Bulletin) periodical2TiO3- xLiF ceramics Structural evolution, sintering temperature and microwave property " in point out, do not influence material to LiF too much while reducing sintering temperature The performance of material, possible cause are LiF and Li2TiO3With similar structure, while liquid-phase sintering, LiF is entered Li2TiO3Solid solution is formed in structure therewith, eliminates influence of the miscellaneous phase to dielectric loss.Moreover, it is noted that in " Europe Continent ceramics association proceedings " (Journal of the European Ceramic Society) article in 2010 " new high Q It is worth rock salt structure microwave dielectric material: (1-x) Li2TiO3- xMgO " in report, the method for the charge recombinations such as utilizing to replace, (1-x) Li2TiO3- xMgO material produces phase transformation of the monocline rock salt structure to cube rock salt structure, and phase with the increase of MgO amount Change process makes Q × f huge increase occur.
In conclusion with YO2(Y=Ti, Sn, Zr) is substituent group to Li2O-MgO-X2O5(X=Nb, Ta) is low damage microwave Ceramic material carries out the modified (Mg of equal charge-dopings2++2X5+→3Y4+) on the basis of, integrated use non-stoichiometric was added Measure Li2It O and rock salt structure is added helps the method for burning dopant, study a kind of lower sintering temperature, ultra high quality factor (ultralow damage Consumption), close to zero frequency-temperature coefficient, while can adjust in a certain range dielectric properties Novel microwave dielectric ceramic tool There is good application prospect, is able to satisfy microwave communication industry requirement.
Summary of the invention
The shortcomings that in order to overcome prior art described above, the purpose of the present invention is to provide a kind of lower sintering temperature, Ultra high quality factor (ultra-low loss), close to zero frequency-temperature coefficient, while dielectric properties can be adjusted in a certain range Novel microwave dielectric ceramic, the present invention passes through in Li2O-MgO-XO2(X=Nb, Ta) is that YO is added in low damage microwave ceramic material2 (Y=Ti, Sn, Zr) substituent group carries out equal charge-dopingsIt is successfully realized orderly orthorhombic phase rock salt structure Excess Li is added with the two-phase content controllable variations of unordered cubic phase rock salt structure, and utilization non-stoichiometric2O and addition Rock salt structure helps the method for burning dopant, the microwave dielectric ceramic materials ε preparedrIt is adjustable between 8.8~17.9, Q × f value Between 82000GHz~128000GHz, temperature coefficient of resonance frequency τfIt is controllable between -33ppm/ DEG C~+11ppm/ DEG C, system Standby simple process, and performance is stablized, it is easy to industrialized production.
For achieving the above object, technical solution of the present invention is as follows:
A kind of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials, the composition general formula of the ceramics are as follows: Li3+aMg2-b/ 3X1-2b/3Yb+cO6+2cDZ, wherein X Nb5+Or Ta5+, Y Ti4+、Sn4+Or Zr4+, Z be ZnO or LiF, 0.03≤a≤ 0.12,0.12≤b≤0.38,0≤c≤0.15；0wt%≤d≤5wt%, when preparation first will raw material carry out pre-burning after obtain sample Product burning block, d are the percentage of sample burning block after shared pre-burning.
It is preferred that the raw material of the microwave ceramics includes basic magnesium carbonate Mg (OH)2·4MgCO3·5H2O, Li2CO3, the rare earth oxide of Nb or Ta, titanium, the oxide of tin or zirconium and ZnO, LiF any one of them additive.
It is preferred that the microwave dielectric ceramic materials crystal phase is orderly orthorhombic phase rock salt structure and unordered cubic phase The compound phase of rock salt structure.
It is preferred that the firing temperature of the microwave ceramics is 960~1280 DEG C, relative dielectric constant 8.8 ~17.9, Q × f value reaches 82000GHz~128000GHz, temperature coefficient of resonance frequency τfAt -33ppm/ DEG C~+11ppm/ DEG C Between.
For achieving the above object, the present invention also provides any one of the above complex phase rock salt structure ultra-low loss microwave Jie The preparation method of ceramics, comprising the following steps:
Step 1: by basic magnesium carbonate Mg (OH)2·4MgCO3·5H2O, Li2CO3, the rare earth oxide of Nb or Ta, titanium, tin Or the oxide of zirconium, according to Li3+aMg2-b/3X1-2b/3Yb+cO6+2cThe molar ratio of chemical general formula is stocked up, and wherein X is Nb5+Or Ta5+, Y Ti4+、Sn4+Or Zr4+, 0.03≤a≤0.12,0.12≤b≤0.38,0≤c≤0.15, by obtained mixture with Zirconia balls are ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is 1:(5~7): (2~4) carry out grinding 5~8 hours, finally obtain uniformly mixed mixture；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, obtains dry powder, then 900~ Pre-burning keeps the temperature 3~5h at 1050 DEG C, obtains sample burning block；
Step 3: sample burning block being crushed, dopant is not added or ZnO, LiF wherein a certain dopant is added, with titanium dioxide Zirconium ball is ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is 1:(5~7): (2~ 4) it grinds 2~3 hours, is dried, granulation processing, is granulated size Control in 120 mesh, pellet is put into dry-pressing in molding die Molding obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 960~1280 DEG C, keep the temperature 4~6h, are made finally Microwave dielectric ceramic materials.
It is preferred that the basic magnesium carbonate Mg (OH) of the step 12·4MgCO3·5H2O material purity is greater than 99.95%, Li2CO3, rare earth oxide, titanium or the tin of Nb or Ta or the oxide raw material purity of zirconium be greater than 99.99%.
It is preferred that the ball mill of the step 1 and step 3 is planetary ball mill.
It is preferred that wherein a certain dopant dosage is obtained by step 2 by the step 3 ZnO, LiF for being added 0wt%≤d of sample burning block≤5wt%.
It is preferred that the raw embryo briquetting pressure of the step 3 is 20MPa, raw embryo specification is the circle of Φ 15mm × 7mm Cylinder.
Suitable raw material can be used to form chemical general formula Li for the present invention3+aMg2-b/3X1-2b/3Yb+cO6+2cThe microwave-medium of dZ Ceramic material, wherein X Nb5+Or Ta5+, Y Ti4+、Sn4+Or Zr4+, Z is ZnO or LiF, 0.03≤a≤0.12,0.12≤b ≤ 0.38,0≤c≤0.15,0wt%≤d≤5wt%, when preparation first will raw material carry out pre-burning after obtain sample burning block, d is to account for The percentage of sample burning block.In YO2When tetravalent oxide additive amount is less, the content of orderly orthogonal rock salt structure in system It is less, with YO2Content gradually increases, and cube rock salt mutually increases, and orthogonal rock salt is mutually reduced.Generally speaking, this two-phase is in dielectric Constant, dielectric loss have different parameters on frequency-temperature coefficient, and the value for adjusting b, which can reach comprehensive adjustment, improves microwave property Purpose.Meanwhile introducing excessive Li2O adjusts the value of a to control Li element evaporation；Introduce excess YO2, the value for adjusting c is reachable To the purpose for adjusting frequency-temperature coefficient nearly zero；It is appropriate to reduce sintering temperature by adjusting the value of d to control the content of additive Degree.Ultra-low loss microwave dielectric ceramic materials with complex phase rock salt structure of the invention measure its electrical property at microwave frequencies Are as follows: εr=8.8~17.9, Q × f is between 82000GHz~128000GHz, temperature coefficient of resonance frequency τf- 33ppm/ DEG C~ Adjustable between+11ppm/ DEG C, sintering temperature is 960~1280 DEG C.
Compared with prior art, the invention has the following advantages:
1, microwave dielectric ceramic materials provided by the invention realize larger promotion in performance, prepared by the prior art Related system microwave dielectric ceramic materials, εrBetween 13~17, Q × f value is between 79000~95000GHz, resonance Frequency-temperature coefficient is at -22ppm/ DEG C or so；In contrast, the opposite dielectric of microwave dielectric ceramic materials provided by the invention is normal Number εrAdjustable between 8.8~17.9, Q × f value is 82000GHz~128000GHz, temperature coefficient of resonance frequency τfMeet- 33ppm/ DEG C~+11ppm/ DEG C, and performance is stablized, and can satisfy the application demand of modern microwave device.
2, Pb is free of in microwave dielectric ceramic materials of the invention, the volatility toxic metals such as Cd, Bi can be widely applied to It is applied in the microwave devices such as dielectric resonator, filter, oscillator in satellite communication, it is green and pollution-free, meet the European Community The RHOS (" limitation uses certain Hazardous Substances Directives in electrical, electronic equipment ") and recovery processing management rules of newest appearance (WEEE) strict standard requirement.
3, biggish Q × f value is realized while the present invention uses medium temperature or low-temperature sintering, has saved time and the energy Cost, application prospect are extensive.
4, present invention gained complex phase rock salt structure microwave ceramic dielectric material uses single sintering method, and technique is relatively simple； Additive is simple oxide and fluoride, is added in secondary ball milling, not will increase complex process degree, is easy to control System.
Detailed description of the invention
Fig. 1 is the XRD analysis result of microwave ceramic dielectric material prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD analysis result of microwave ceramic dielectric material prepared by the embodiment of the present invention 3；
Fig. 3 is the scanning electron microscope sem figure of microwave ceramic dielectric material prepared by the embodiment of the present invention 11；
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from Various modifications or alterations are carried out under spirit of the invention.
A kind of ultra-low loss microwave dielectric ceramic materials with complex phase rock salt structure, chemical general formula Li3+aMg2-b/ 3X1-2b/3Yb+cO6+2cDZ, wherein X is Nb5+Or Ta5+, Y Ti4+、Sn4+Or Zr4+, Z be ZnO or LiF in it is any, 0.03≤ A≤0.12,0.12≤b≤0.38,0≤c≤0.15,0wt%≤d≤5wt%, d are the percentage of sample burning block after shared pre-burning Than.
The raw material of the microwave ceramics includes basic magnesium carbonate Mg (OH)2·4MgCO3·5H2O, Li2CO3, Nb or Ta's is dilute Native oxide, titanium, the oxide of tin or zirconium and ZnO, LiF any one of them additive.
The microwave dielectric ceramic materials crystal phase is answering for orderly orthorhombic phase rock salt structure and unordered cubic phase rock salt structure Close phase.
The firing temperature of the microwave ceramics is 960~1280 DEG C, and relative dielectric constant is 8.8~17.9, Q × f value Reach 82000GHz~128000GHz, temperature coefficient of resonance frequency τfBetween -33ppm/ DEG C~+11ppm/ DEG C.
Preparation method includes the following steps:
Step 1: by basic magnesium carbonate Mg (OH)2·4MgCO3·5H2O, Li2CO3, the rare earth oxide of Nb or Ta, titanium, tin Or the oxide of zirconium, according to Li3+aMg2-b/3X1-2b/3Yb+cO6+2cThe molar ratio of chemical general formula is stocked up, and wherein X is Nb5+Or Ta5+, Y Ti4+、Sn4+Or Zr4+, 0.03≤a≤0.12,0.12≤b≤0.38,0≤c≤0.15, by obtained mixture with Zirconia balls are ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is 1:(5~7): (2~4) carry out grinding 5~8 hours, finally obtain uniformly mixed mixture；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, obtains dry powder, then 900~ Pre-burning keeps the temperature 3~5h at 1050 DEG C, obtains sample burning block；
Step 3: sample burning block being crushed, dopant is not added or ZnO, LiF wherein a certain dopant is added, with titanium dioxide Zirconium ball is ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is 1:(5~7): (2~ 4) it grinds 2~3 hours, is dried, granulation processing, is granulated size Control in 120 mesh, pellet is put into dry-pressing in molding die Molding obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 960~1280 DEG C, keep the temperature 4~6h, are made finally Microwave dielectric ceramic materials.
The basic magnesium carbonate Mg (OH) of the step 12·4MgCO3·5H2O material purity is greater than 99.95%, Li2CO3、Nb Or rare earth oxide, titanium or the tin of Ta or the oxide raw material purity of zirconium are greater than 99.99%.
Preferably, the ball mill of the step 1 and step 3 is planetary ball mill.
Preferably, wherein a certain dopant dosage is that step 2 gained sample is burnt to ZnO, LiF that the step 3 is added 0wt%≤d of block≤5wt%.
Preferably, the raw embryo briquetting pressure of the step 3 is 20MPa, and raw embryo specification is the cylindrical body of Φ 15mm × 7mm.
Below in conjunction with specific embodiment, invention is further explained, and table 1 is that chemical general formula of the present invention is Li3+ aMg2-b/3X1-2b/3Yb+cO6+2cThe each component mass percentage data of the specific embodiment of the microwave dielectric ceramic materials of dZ Table, wherein X is Nb5+Or Ta5+, Y Ti4+、Sn4+Or Zr4+, Z is any in ZnO or LiF, and 0.03≤a≤0.12, 0.12≤b≤0.38,0≤c≤0.15；0wt%≤d≤5wt%, wherein the amount d of dopant is to account for sample obtained in step 2 The weight percent of burning block.
Table 1.
Embodiment 1:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Nb2O5And TiO2, respectively according to 43.66%, 25.93%, 27.09% and 3.32% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:2 carries out grinding 6 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 1000 DEG C Lower pre-burning keeps the temperature 3h, obtains sample burning block；
Step 3: sample burning block being crushed, using zirconia balls as ball-milling medium, to go dehydrated alcohol as solvent, according to mixed Close material: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:2 is ground 2 hours, is dried, granulation processing, is granulated size Control in 120 mesh, Pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1260 DEG C, final microwave-medium is made in heat preservation 4h Ceramic material.
Embodiment 2:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Nb2O5And TiO2, respectively according to 43.34%, 26.27%, 25.94% and 4.45% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:3 carries out grinding 7 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 900 DEG C Lower pre-burning keeps the temperature 4h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the ZnO doping agent of sample burning block 0.8wt% is added, with zirconia balls For ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:3 is ground 3 hours, into Row drying, granulation processing, are granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1200 DEG C, 6h is kept the temperature, final microwave-medium is made Ceramic material.
Embodiment 3:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Nb2O5And TiO2, respectively according to 42.92%, 26.80%, 24.72% and 5.57% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:7:4 carries out grinding 6 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 950 DEG C Lower pre-burning keeps the temperature 5h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the LiF dopant of sample burning block 4wt% is added, is with zirconia balls Ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:7:4 is ground 2 hours, is carried out Dry, granulation processing, is granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1050 DEG C, final microwave-medium is made in heat preservation 5h Ceramic material.
Embodiment 4:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Nb2O5And TiO2, respectively according to 52.43%, 32.95%, 5.86% and 8.76% mass ratio is stocked up, by obtained mixture using zirconia balls as ball Grinding media, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:3 carries out grinding 8 hours, finally Obtain uniformly mixed mixture；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 910 DEG C Lower pre-burning keeps the temperature 3h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the ZnO doping agent of sample burning block 3wt% is added, is with zirconia balls Ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:3 is ground 3 hours, is carried out Dry, granulation processing, is granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1150 DEG C, final microwave-medium is made in heat preservation 5h Ceramic material.
Embodiment 5:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Ta2O5And TiO2, respectively according to 36.17%, 21.89%, 38.60% and 3.34% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:4 carries out grinding 7 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 1000 DEG C Lower pre-burning keeps the temperature 4h, obtains sample burning block；
Step 3: sample burning block being crushed, using zirconia balls as ball-milling medium, to go dehydrated alcohol as solvent, according to mixed Close material: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:4 is ground 2 hours, is dried, granulation processing, is granulated size Control in 120 mesh, Pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1280 DEG C, final microwave-medium is made in heat preservation 6h Ceramic material.
Embodiment 6:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Ta2O5And SnO2, respectively according to 36.11%, 21.45%, 37.25% and 5.19% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:7:4 carries out grinding 6 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 1020 DEG C Lower pre-burning keeps the temperature 5h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the ZnO doping agent of sample burning block 5wt% is added, is with zirconia balls Ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:7:4 is ground 3 hours, is carried out Dry, granulation processing, is granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1120 DEG C, final microwave-medium is made in heat preservation 6h Ceramic material.
Embodiment 7:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Ta2O5And SnO2, respectively according to 34.94%, 21.51%, 32.37% and 11.18% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:4 carries out grinding 7 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 980 DEG C Lower pre-burning keeps the temperature 4h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the LiF dopant of sample burning block 1.5wt% is added, with zirconia balls For ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:4 is ground 2 hours, into Row drying, granulation processing, are granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1180 DEG C, final microwave-medium is made in heat preservation 4h Ceramic material.
Embodiment 8:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Ta2O5And ZrO2, respectively according to 36.02%, 22.28%, 34.49% and 7.21% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:2 carries out grinding 5 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 970 DEG C Lower pre-burning keeps the temperature 5h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the LiF dopant of sample burning block 2wt% is added, is with zirconia balls Ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:2 is ground 3 hours, is carried out Dry, granulation processing, is granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1160 DEG C, final microwave-medium is made in heat preservation 6h Ceramic material.
Embodiment 9:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Ta2O5And ZrO2, respectively according to 35.38%, 21.64%, 36.50% and 6.84% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:3 carries out grinding 7 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 1030 DEG C Lower pre-burning keeps the temperature 3h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the ZnO doping agent of sample burning block 1.5wt% is added, with zirconia balls For ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:3 is ground 2 hours, into Row drying, granulation processing, are granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1220 DEG C, final microwave-medium is made in heat preservation 5h Ceramic material.
Embodiment 10:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Nb2O5And SnO2, respectively according to 39.78%, 23.87%, 23.81% and 12.53% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:7:3 carries out grinding 6 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 940 DEG C Lower pre-burning keeps the temperature 5h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the LiF dopant of sample burning block 3wt% is added, is with zirconia balls Ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:7:3 is ground 3 hours, is carried out Dry, granulation processing, is granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1000 DEG C, final microwave-medium is made in heat preservation 6h Ceramic material.
Embodiment 11:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Nb2O5And SnO2, respectively according to 41.10%, 25.17%, 23.67% and 10.06% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:2 carries out grinding 8 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 1050 DEG C Lower pre-burning keeps the temperature 4h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the ZnO doping agent of sample burning block 2.5wt% is added, with zirconia balls For ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:2 is ground 2 hours, into Row drying, granulation processing, are granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 1210 DEG C, final microwave-medium is made in heat preservation 5h Ceramic material.
Embodiment 12:
Step 1: by basic magnesium carbonate (Mg (OH)2·4MgCO3·5H2O)、Li2CO3、Nb2O5And ZrO2, respectively according to 41.29%, 25.94%, 23.25% and 9.52% mass ratio is stocked up, and is with zirconia balls by obtained mixture Ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:5:3 carries out grinding 7 hours, most Uniformly mixed mixture is obtained afterwards；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then at 1040 DEG C Lower pre-burning keeps the temperature 4h, obtains sample burning block；
Step 3: sample burning block being crushed, is weighed, the LiF dopant of sample burning block 5wt% is added, is with zirconia balls Ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is that 1:6:2 is ground 2 hours, is carried out Dry, granulation processing, is granulated size Control in 120 mesh, and pellet is put into and dry-pressing formed in molding die obtains green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 960 DEG C, final microwave-medium pottery is made in heat preservation 5h Ceramic material.
Table 2 show the performance parameter for the microwave dielectric ceramic materials that embodiment cited by the present invention is prepared.
Table 2
From table 2 it can be seen that the microwave dielectric ceramic materials that the present invention prepares have the quality factor of superelevation, Q × f value For 82000GHz~128000GHz, temperature coefficient of resonance frequency τfIt is -33ppm/ DEG C~+11ppm/ DEG C, and relative dielectric constant εrAdjustable, value is between 8.8~17.9.
Fig. 1 is the XRD analysis of microwave ceramic dielectric material prepared by the embodiment of the present invention 1 as a result, as can be seen from Figure 1: The principal crystalline phase for the microwave dielectric ceramic materials that the inventive embodiments 1 are prepared is orderly orthorhombic phase rock salt structure and less The unordered cubic phase rock salt structure of amount.The diffraction maximum of cubic phase rock salt structure and the peak of orthorhombic phase partly overlap, actually herein Disordered structure cubic phase be orthorhombic phase subcell, but the two is variant in cell parameter, then in the angle of diffraction at peak Subtle offset is embodied, as shown in Fig. 1 (b).
Fig. 2 is the XRD analysis of microwave ceramic dielectric material prepared by the embodiment of the present invention 3 as a result, as can be seen from Figure 2: The crystal phase for the microwave dielectric ceramic materials that the inventive embodiments 3 are prepared remains as orthogonal and cube complex phase rock salt structure, but with The amount of Ti increase, the peak intensity of cubic phase has very big promotion, and the diffraction maximum relative intensity of orthorhombic phase gradually weakens, shows to pass through Control YO2Additive amount can control two kinds of phases relative amount.In addition to this, it is found, illustrates few without the peak of other miscellaneous phases Perhaps excessive TiO2Original lattice has all been dissolved into LiF, forms solid solution.
Fig. 3 is the scanning electron microscope sem figure of microwave ceramic dielectric material prepared by the embodiment of the present invention 11, because of two kinds of phase structures Lattice be super cell and subcell relationship, grain morphology is identical, is all irregular polygon.And it is bright without other Aobvious miscellaneous phase illustrates that ZnO has dissolved into original lattice and formd solid solution.The microwave ceramic material table prepared as can be seen from Figure 3 Face grain size distribution is uniform, CRYSTALLITE SIZES distribution it is regular, without stomata occur, structure is finer and close, disclose material compared with Good dielectric properties.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause This, all those of ordinary skill in the art are completed without departing from the spirit and technical ideas disclosed in the present invention All equivalent modifications or change, should be covered by the claims of the present invention.

Claims (9)

1. a kind of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials, which is characterized in that the composition general formula of the ceramics are as follows: Li3+aMg2-b/3X1-2b/3Yb+cO6+2cDZ, wherein X Nb5+Or Ta5+, Y Ti4+、Sn4+Or Zr4+, Z be ZnO or LiF, 0.03 ≤ a≤0.12,0.12≤b≤0.38,0≤c≤0.15；0wt%≤d≤5wt% first carries out raw material after pre-burning when preparation To sample burning block, d is the percentage for accounting for sample burning block.
2. a kind of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials as described in claim 1, it is characterised in that: institute The raw material for stating microwave ceramics includes basic magnesium carbonate Mg (OH)2·4MgCO3·5H2O, Li2CO3, the rare earth oxide of Nb or Ta, Titanium, the oxide of tin or zirconium and ZnO, LiF any one of them additive.
3. a kind of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials as described in claim 1, it is characterised in that: institute State the compound phase that microwave dielectric ceramic materials crystal phase is orderly orthorhombic phase rock salt structure and unordered cubic phase rock salt structure.
4. a kind of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials as described in claim 1, it is characterised in that: institute The firing temperature for stating microwave ceramics is 960~1280 DEG C, and relative dielectric constant is that 8.8~17.9, Q × f value reaches 82000GHz~128000GHz, temperature coefficient of resonance frequency τfBetween -33ppm/ DEG C~+11ppm/ DEG C.
5. the preparation method of any one complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials in Claims 1-4, It is characterized in that, comprising the following steps:
Step 1: by basic magnesium carbonate Mg (OH)2·4MgCO3·5H2O, Li2CO3, the rare earth oxide of Nb or Ta, titanium, tin or zirconium Oxide, according to Li3+aMg2-b/3X1-2b/3Yb+cO6+2cThe molar ratio of chemical general formula is stocked up, and wherein X is Nb5+Or Ta5+, Y For Ti4+、Sn4+Or Zr4+, 0.03≤a≤0.12,0.12≤b≤0.38,0≤c≤0.15, by obtained mixture with titanium dioxide Zirconium ball is ball-milling medium, using dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is 1:(5~7): (2~4) It carries out grinding 5~8 hours, finally obtains uniformly mixed mixture；
Step 2: 60 meshes are dried at 100 DEG C and crossed to the mixture after ball milling, dry powder is obtained, then 900~1050 Pre-burning keeps the temperature 3~5h at DEG C, obtains sample burning block；
Step 3: sample burning block being crushed, dopant is not added or ZnO, LiF wherein a certain dopant is added, with zirconia balls For ball-milling medium, to go dehydrated alcohol as solvent, according to mixture: abrading-ball: the weight ratio of ethyl alcohol is 1:(5~7): (2~4) are ground Mill 2~3 hours is dried, granulation processing, is granulated size Control in 120 mesh, pellet is put into dry-pressing formed in molding die Obtain green compact；
Step 4: the green compact that step 4 obtains being sintered at a temperature of 960~1280 DEG C, 4~6h is kept the temperature, final microwave is made Medium ceramic material.
6. a kind of preparation method of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials as claimed in claim 5, It is characterized in that: the basic magnesium carbonate Mg (OH) of the step 12·4MgCO3·5H2O material purity is greater than 99.95%, Li2CO3、 Rare earth oxide, titanium or the tin of Nb or Ta or the oxide raw material purity of zirconium are greater than 99.99%.
7. a kind of preparation method of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials as claimed in claim 5, Be characterized in that: the ball mill of the step 1 and step 3 is planetary ball mill.
8. a kind of preparation method of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials as claimed in claim 5, Be characterized in that: wherein a certain dopant dosage is step 2 gained sample burning block to the ZnO or LiF that the step 3 is added 0wt%≤d≤5wt%.
9. a kind of preparation method of complex phase rock salt structure ultra-low loss microwave dielectric ceramic materials as claimed in claim 5, Be characterized in that: the raw embryo briquetting pressure of the step 3 is 20MPa, and raw embryo specification is the cylindrical body of Φ 15mm × 7mm.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112457010A (en) * 2020-12-02 2021-03-09 电子科技大学 Rock salt type reconstructed superlattice structure microwave dielectric ceramic material and preparation method thereof
CN112851347A (en) * 2021-03-09 2021-05-28 陕西师范大学 Low-temperature sintered low-loss oxyfluoride microwave dielectric ceramic and preparation method thereof
CN114874005A (en) * 2022-06-10 2022-08-09 安徽理工大学 Temperature-stable magnesium titanate base microwave dielectric composite ceramic and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5188993A (en) * 1991-01-23 1993-02-23 Sanyo Electric Co., Ltd. Microwave dielectric ceramic composition
CN102674828A (en) * 2012-05-16 2012-09-19 桂林电子科技大学 Low-dielectric-loss temperature stabilization type microwave dielectric ceramic material and preparation method thereof
CN104844204A (en) * 2015-04-15 2015-08-19 厦门万明电子有限公司 High-dielectric microwave ceramic dielectric material, and preparation method and use thereof
CN105503202A (en) * 2016-01-17 2016-04-20 济南大学 Novel low-loss Li2MgZrO4 microwave dielectric ceramic material and preparing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5188993A (en) * 1991-01-23 1993-02-23 Sanyo Electric Co., Ltd. Microwave dielectric ceramic composition
CN102674828A (en) * 2012-05-16 2012-09-19 桂林电子科技大学 Low-dielectric-loss temperature stabilization type microwave dielectric ceramic material and preparation method thereof
CN104844204A (en) * 2015-04-15 2015-08-19 厦门万明电子有限公司 High-dielectric microwave ceramic dielectric material, and preparation method and use thereof
CN105503202A (en) * 2016-01-17 2016-04-20 济南大学 Novel low-loss Li2MgZrO4 microwave dielectric ceramic material and preparing method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C.H.YANG等: "Effects of Ti-substitution on the crystal structures, micro-structures and microwave dielectric properties of Li2Mg3Zr1-xTixO6(0≤x≤1) ceramics", 《CERAMICS INTERNATIONAL》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112457010A (en) * 2020-12-02 2021-03-09 电子科技大学 Rock salt type reconstructed superlattice structure microwave dielectric ceramic material and preparation method thereof
CN112457010B (en) * 2020-12-02 2022-03-29 电子科技大学 Rock salt type reconstructed superlattice structure microwave dielectric ceramic material and preparation method thereof
CN112851347A (en) * 2021-03-09 2021-05-28 陕西师范大学 Low-temperature sintered low-loss oxyfluoride microwave dielectric ceramic and preparation method thereof
CN114874005A (en) * 2022-06-10 2022-08-09 安徽理工大学 Temperature-stable magnesium titanate base microwave dielectric composite ceramic and preparation method thereof

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