CN106278192B - A kind of preparation method of the multi-phase microwave dielectric ceramic with jujube cake model structure - Google Patents

A kind of preparation method of the multi-phase microwave dielectric ceramic with jujube cake model structure Download PDF

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CN106278192B
CN106278192B CN201610713052.2A CN201610713052A CN106278192B CN 106278192 B CN106278192 B CN 106278192B CN 201610713052 A CN201610713052 A CN 201610713052A CN 106278192 B CN106278192 B CN 106278192B
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顾永军
李丽华
胡伟
黄金亮
李谦
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Henan University of Science and Technology
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Abstract

A kind of preparation method of the multi-phase microwave dielectric ceramic with jujube cake model structure, ceramics are BaCu (B by molecular formula2O5)‑xCaTiO3Material composition, wherein 0 x≤0.8 <；Preparation method includes BaCu (B2O5) preparation, CaTiO3Preparation and the multi-phase microwave dielectric ceramic with jujube cake model structure preparation.The present invention is formed using above-mentioned formula and technique, and permittivity ε can be obtainedrBetween 15 ~ 50, Qf value is quality factor not less than 50000GHz(Q), temperature coefficient of resonance frequency τ f Close to zero and adjustable, and the novel multi-phase microwave dielectric ceramic material of intrinsic sintering temperature lower (< 950 DEG C).

Description

A kind of preparation method of the multi-phase microwave dielectric ceramic with jujube cake model structure
Technical field
The present invention relates to microwave-medium ceramics fields, and in particular to a kind of multi-phase microwave dielectric with jujube cake model structure The preparation method of ceramics.
Background technique
Microwave-medium ceramics are the new function electronic ceramics that recent decades develop rapidly, and have and low, dielectric is lost The features such as constant is high, frequency-temperature coefficient is small, may be utilized in fabricating filter, dielectric resonator, diectric antenna etc., is widely used in The various fields such as mobile communication, satellite broadcasting television communication, radar are the novel-sections of a kind of great application value and development potentiality Material.In recent years, as modern mobile communication equipment is towards miniaturization, integrated, chip type, high reliability and low cost, environmental protection Direction develop, can be total with low melting point electrodes in base metal material C u, Ag or Cu/Ag alloy of high conductivity and environment-friendly type with development The microwave-medium ceramics (Low Temperature Co-fired Ceramic, abbreviation LTCC) of burning are sent out as microwave dielectric material The mainstream of exhibition.
LTCC material requirements dielectric constant is suitable, quality factor are high by nearly with temperature coefficient of resonance frequency zero, and can be lower At a temperature of be sintered (generally answering < 900 DEG C), so as to can be with electrode cofiring in the copper or silver metal of high conductivity.
The sintering temperature of most of commercial microwave-medium ceramics is at 1200~1500 DEG C at present, such as BaTi4O9、 Ba2Ti9O20、BaO-MgO-Ta2O5、(Zn,Sn)TiO4(Pb, Ca) (Zr, Ti) O3, it is difficult to meet the requirement of cofiring therewith.Mesh Before, although the admixture of the sintering aids such as low melting point oxide, compound or low softening point glass can be effectively reduced ceramic material Sintering temperature, but since the amount that need to be added is bigger, and different degrees of deterioration is brought to the microwave dielectric property of material； Preparing Ultramicro-powder using chemical synthesis process, then technique is generally all more complicated, and higher cost, subsequent technique is difficult to control, and difficult To guarantee stable microwave dielectric property, it is difficult to realize industrialized production.Generally speaking, many microwave dielectric properties are excellent at present Material system due to material self character, high, material at low temperature sintering that there are sintering temperatures with microwave dielectric property not The problems such as capable of having both, the microwave dielectric ceramic materials that can be really used as LTCC material are seldom.Therefore develop the third method, Finding the low new material of intrinsic sintering temperature becomes one of emphasis and hot spot of microwave dielectric material research in recent years.
Currently, reporting that the low microwave dielectric ceramic materials of more intrinsic sintering temperature mainly have BiNbO4System, Bi2O3- ZnO-Nb2O5System, ZnO-TiO2System and lead base composite perofskite ceramics Pb (Fe1/3Nb1/3)O3(PFW)、(Pb1-xCax)(Fe1/ 2Nb1/2)O3(PCFN)、Pb(Fe1/2Nb1/2)O3(PFN) ceramic materials such as system.Although these systems can be burnt within 950 DEG C Knot, but there is variety of problems, limit its functionization.Such as BiNbO4Be ceramics Bi volatile ratio it is more serious, and with metal Ag It can react when electrode cofiring, lead to the dielectric properties severe exacerbation of material；Typical low-temperature sintering Bi2(Zn1/3Nb2/3)2O7 Ceramics, which exist, is lost the problems such as higher, frequency-temperature coefficient τ f is excessive；ZnO-TiO2Based material phase stability is poor, it is difficult to obtain Pure phase；Lead base composite perofskite system ceramics contain lead and are unfavorable for environmental protection.
Take a broad view of above-mentioned, the low ceramic material of existing intrinsic sintering temperature, dielectric constant range is narrow, dielectric properties are opposite It is poor, and such microwave dielectric material system compares shortage, both at home and abroad about the system of Temperature Firing Microwave Dielectric Ceramics, complete The research in face is also few.Therefore, research and develop potential microwave-medium ceramics new material have far-reaching theory significance and Practical value.
Summary of the invention
The present invention is situated between to overcome material at low temperature existing for existing microwave dielectric ceramic materials technology to be sintered with excellent microwave The problem of electrical property cannot have both, provides a kind of preparation method of multi-phase microwave dielectric ceramic with jujube cake model structure, and And designed by composition proportion, the temperature coefficient of resonance frequency of ceramics is successfully adjusted to nearly zero and sintering temperature < 900 DEG C.
The present invention in order to solve the above problem used by technical solution are as follows: a kind of multi-phase microwave with jujube cake model structure Media ceramic is BaCu (B by molecular formula2O5)-xCaTiO3Material composition, wherein 0 x≤0.8 <.
A kind of preparation method of the multi-phase microwave dielectric ceramic with jujube cake model structure, comprising the following steps: Step 1: According to BaCO3: H3BO3: the molar ratio of Cu=1:2:1.25 mixes after carrying out feeding, and mixture A is made, is added in mixture A Weight accounts for the deionized water of 1.5 times of mixture A total weight, is placed in 24 ~ 36h of mixing in ball mill, then dries at 100 ~ 150 DEG C It is dry；Mixture A after drying is packed into high-purity corundum crucible, under oxygen atmosphere, is heated up with the heating rate of 0.5 ~ 2 DEG C/min To 200 ~ 500 DEG C, then under argon atmosphere, 700 ~ 900 DEG C are warming up to the heating rate of 3 ~ 5 DEG C/min, and keep A certain temperature pre-burning 8 in the section ~ for 24 hours, synthesize BaCu (B2O5) crystal phase, it is spare；
Step 2: according to CaCO3: TiO2The molar ratio of=1:1 mixes after carrying out feeding, mixture B is made, in mixture B The middle deionized water that weight is added and accounts for 1.5 times of mixture B total weight, is placed in 24 ~ 36h of mixing in ball mill, then 100 ~ 150 It is dried at DEG C；Mixture B after drying is packed into high-purity corundum crucible, 900 are warming up to the heating rate of 3 ~ 5 DEG C/min ~ 1200 DEG C, and a certain temperature pre-burning 3 ~ for 24 hours is kept, synthesize CaTiO3Crystal phase, it is spare；
Step 3: by CaTiO made from step 23After surface treatment, according to aforementioned middle BaCu (B2O5)-xCaTiO3 BaCu (B made from the step of carrying out ingredient, molar ratio is taken to be 1:x one2O5) and step 2 made from CaTiO3, the two is mixed Mixture C is formed afterwards, and the ethyl alcohol that weight accounts for 1.2 times of mixture total weight is added in mixture C, discharges after 24 ~ 48h of ball milling, Then it is dried at 100 ~ 150 DEG C, is pressed into green body after granulation at 100 ~ 200MPa and naturally cools to room after dumping, sintering The multi-phase microwave dielectric ceramic with jujube cake model structure is made in temperature.
Further, in step 3, in step 3, CaTiO3Surface treatment method are as follows: in CaTiO3It is middle be added 0.3 ~ Then citric acid and ammonium hydroxide that molar ratio is 1:1 are added simultaneously, adds ethanol solution for the sodium alkyl benzene sulfonate of 0.5% weight, Butyl titanate is added after sonic oscillation, after stirring 2 ~ 8h, is dried at 300 ~ 550 DEG C.
Further, in step 3, prilling are as follows: it is its weight 4 ~ 10% that weight is added in mixture C after the drying Poly-vinyl alcohol solution the pelletizing that water content is 0 ~ 0.2% is made using spray dryer；Wherein, poly-vinyl alcohol solution Mass concentration is 5 ~ 10%.
Further, the binder removal in step 3 is in 550 ~ 700 DEG C of 1 ~ 4h of heat preservation；Sintering process are as follows: set green body It is sintered in high-purity corundum aluminium crucible, 1 ~ 6h is kept the temperature at 700 ~ 900 DEG C.
CaCO in the present invention3、TiO2、BaCO3、H3BO3It is that analysis is pure.
The utility model has the advantages that the 1, present invention is formed using above-mentioned formula and technique, permittivity ε can be obtainedrBetween 15 ~ 50, Quality factor q × f is not less than 50000GHz, temperature coefficient of resonance frequency τ f Close to zero and adjustable, and intrinsic sintering temperature compared with The novel multi-phase microwave dielectric ceramic material of low (< 950 DEG C)；In addition, by changing BaCu (B2O5) and CaTiO3The ratio of two-phase Example, sintering temperature can be reduced to 825 DEG C or so, while keep excellent microwave dielectric property, after being sintered at a temperature of 825 DEG C Obtain the diphase ceramic material with excellent microwave dielectric property.
2、BaCu(B2O5) be a kind of sintering temperature low (800 DEG C) material system, and its microwave dielectric property is excellent: being situated between Electric constant εr50000GHz, temperature coefficient of resonance frequency τ are up to for 7.4, quality factor q × f f =-32 ppm/℃；CaTiO3It is A kind of good (ε of dielectric propertiesr=175, Q × f=3600 GHz, TCF=+ 800ppm/ DEG C) high-permittivity microwave medium ceramics Material.By BaCu (B2O5) it is used as principal crystalline phase, CaTiO3The two as secondary crystal phase is compound, and available sintering temperature is low and micro- The excellent multi-phase microwave dielectric ceramic material of wave dielectric properties, the ceramics are jujube cake model structure on the micro level, and secondary crystal phase is equal The even inside for being embedded in principal crystalline phase.
3, it in step 1, is previously added after copper simple substance and carries out oxidation processes again, avoid BaCO3、H3BO3And CuO is Friable structure is difficult to uniformly mixed problem, is added as copper simple substance, aoxidizes in-situ preparation under subsequent oxidizing atmosphere CuO, toughness is preferable, is conducive to mixing.
4, device therefor is commonly used equipment, such as baking oven, ball mill, resistance furnace in material preparation process in the present invention, Process route is simple and easy, and the cost of material is low, simple process is stable, favorable reproducibility, is conducive to industrialized production, meets low temperature co-fired The technical requirements of ceramics, suitable for making using base metals such as silver, copper as the multilayers such as the dielectric resonator of interior electrode and filter Slice component is with a wide range of applications.
Detailed description of the invention
Fig. 1 is the XRD diagram of microwave-medium ceramics prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of microwave-medium ceramics prepared by embodiment 1.
Specific embodiment
The present invention is further explained in the light of specific embodiments, so that those skilled in the art can be better Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
A kind of multi-phase microwave dielectric ceramic with jujube cake model structure is BaCu (B by molecular formula2O5)-xCaTiO3Material Material composition, wherein 0 x≤0.8 <.
Embodiment 1
A kind of preparation method of the multi-phase microwave dielectric ceramic with jujube cake model structure, comprising the following steps: Step 1: According to BaCO3: H3BO3: the molar ratio of Cu=1:2:1.25 mixes after carrying out feeding, and mixture A is made, is added in mixture A Weight accounts for the deionized water of 1.5 times of mixture A total weight, is placed in ball mill and mixes 36h, then dries at 110 DEG C；It will dry Mixture A after dry is packed into high-purity corundum crucible and is warming up to 350 DEG C under oxygen atmosphere with the heating rate of 0.5 DEG C/min, Then under argon atmosphere, 700 DEG C are warming up to the heating rate of 5 DEG C/min, and keeps the temperature pre-burning for 24 hours, is synthesized BaCu(B2O5) crystal phase, it is spare；
Step 2: according to CaCO3: TiO2The molar ratio of=1:1 mixes after carrying out feeding, mixture B is made, in mixture B The middle deionized water that weight is added and accounts for 1.5 times of mixture B total weight, is placed in ball mill and mixes for 24 hours, then dry at 100 DEG C It is dry；Mixture B after drying is packed into high-purity corundum crucible, is warming up to 900 DEG C with the heating rate of 4.5 DEG C/min, and keep A certain temperature pre-burning 3h synthesizes CaTiO3Crystal phase, it is spare；
Step 3: by CaTiO made from step 23After surface treatment, according to aforementioned middle BaCu (B2O5)-xCaTiO3 BaCu (B made from the step of carrying out ingredient, molar ratio is taken to be 1:0.8 one2O5) and step 2 made from CaTiO3, the two is mixed Mixture C is formed after conjunction, and the ethyl alcohol that weight accounts for 1.2 times of mixture total weight is added in mixture C, discharges after ball milling 48h, so It is dried at 100 DEG C afterwards；The poly-vinyl alcohol solution that weight is its weight 4% is added in mixture C after the drying, using by spraying The pelletizing that water content is 0.2% is made in drying machine；Wherein, the mass concentration of poly-vinyl alcohol solution is 10%；After granulation It is pressed into green body under 200MPa, by green body in 550 DEG C of heat preservation 4h, then green body is placed in high-purity corundum aluminium crucible and is burnt Knot, keeps the temperature 2.5h at 825 DEG C, and the multi-phase microwave dielectric ceramic with jujube cake model structure is made in cooled to room temperature.Its In, CaTiO3Surface treatment method are as follows: in CaTiO3Middle addition weight is CaTiO3The alkyl benzene sulphonate of weight 0.3 ~ 0.5% Then citric acid and ammonium hydroxide that molar ratio is 1:1 is added in sodium simultaneously, add ethanol solution, metatitanic acid fourth is added after sonic oscillation Ester is dried at 300 ~ 550 DEG C after stirring 2 ~ 8h.
Embodiment 2
A kind of preparation method of low-temperature sintering multi-phase microwave dielectric ceramic, comprising the following steps: Step 1: according to BaCO3: H3BO3: the molar ratio of Cu=1:2:1.25 mixes after carrying out feeding, and mixture A is made, and weight is added in mixture A and accounts for mixing The deionized water of 1.5 times of A total weight of material, is placed in ball mill and mixes for 24 hours, then dry at 150 DEG C；By the mixing after drying Material A is packed into high-purity corundum crucible and 500 DEG C is warming up to the heating rate of 0.5 DEG C/min, then in argon gas under oxygen atmosphere Under protective atmosphere, 850 DEG C are warming up to the heating rate of 4.5 DEG C/min, and keeps temperature pre-burning 18h, synthesizes BaCu (B2O5) Crystal phase, it is spare；
Step 2: according to CaCO3: TiO2The molar ratio of=1:1 mixes after carrying out feeding, mixture B is made, in mixture B The middle deionized water that weight is added and accounts for 1.5 times of mixture B total weight, is placed in ball mill and mixes 32h, then dry at 110 DEG C It is dry；Mixture B after drying is packed into high-purity corundum crucible, is warming up to 1050 DEG C with the heating rate of 3 DEG C/min, and keep certain One temperature pre-burning for 24 hours, synthesizes CaTiO3Crystal phase, it is spare；
Step 3: by CaTiO made from step 23After surface treatment, according to aforementioned middle BaCu (B2O5)-xCaTiO3 BaCu (B made from the step of carrying out ingredient, molar ratio is taken to be 1:0.7 one2O5) and step 2 made from CaTiO3, the two is mixed Mixture C is formed after conjunction, and the ethyl alcohol that weight accounts for 1.2 times of mixture total weight is added in mixture C, discharges after ball milling 33h, so It is dried at 120 DEG C afterwards；The poly-vinyl alcohol solution that weight is its weight 10% is added in mixture C after the drying, using by spraying The pelletizing that water content is 0.1% is made in drying machine；Wherein, the mass concentration of poly-vinyl alcohol solution is 8%；After granulation It is pressed into green body under 100MPa, by green body in 700 DEG C of heat preservation 1h, then green body is placed in high-purity corundum aluminium crucible and is burnt Knot, keeps the temperature 6h at 700 DEG C, and low-temperature sintering multi-phase microwave dielectric ceramic is made in cooled to room temperature.Wherein, CaTiO3's Surface treatment method is the same as embodiment 1.
Embodiment 3
A kind of preparation method of low-temperature sintering multi-phase microwave dielectric ceramic, comprising the following steps: Step 1: according to BaCO3: H3BO3: the molar ratio of Cu=1:2:1.25 mixes after carrying out feeding, and mixture A is made, and weight is added in mixture A and accounts for mixing The deionized water of 1.5 times of A total weight of material, is placed in ball mill and mixes 32h, then dry at 100 DEG C；By the mixing after drying Material A is packed into high-purity corundum crucible and is warming up to 280 DEG C under oxygen atmosphere with the heating rate of 2 DEG C/min, then protects in argon gas It protects under atmosphere, is warming up to 900 DEG C with the heating rate of 3 DEG C/min, and keep temperature pre-burning 8h, synthesize BaCu (B2O5) brilliant Phase, it is spare；
Step 2: according to CaCO3: TiO2The molar ratio of=1:1 mixes after carrying out feeding, mixture B is made, in mixture B The middle deionized water that weight is added and accounts for 1.5 times of mixture B total weight, is placed in ball mill and mixes 36h, then dry at 150 DEG C It is dry；Mixture B after drying is packed into high-purity corundum crucible, is warming up to 1200 DEG C with the heating rate of 5 DEG C/min, and keep certain One temperature pre-burning 16h synthesizes CaTiO3Crystal phase, it is spare；
Step 3: by CaTiO made from step 23After surface treatment, according to aforementioned middle BaCu (B2O5)-xCaTiO3 BaCu (B made from the step of carrying out ingredient, molar ratio is taken to be 1:0.1 one2O5) and step 2 made from CaTiO3, the two is mixed Mixture C is formed after conjunction, the ethyl alcohol that weight accounts for 1.2 times of mixture total weight is added in mixture C, and ball milling discharges afterwards for 24 hours, so It is dried at 150 DEG C afterwards；The poly-vinyl alcohol solution that weight is its weight 6.5% is added in mixture C after the drying, utilizes spray The pelletizing that water content is 0 is made in mist drying machine；Wherein, the mass concentration of poly-vinyl alcohol solution is 5%；In 160MPa after granulation Under be pressed into green body, by green body in 620 DEG C of heat preservation 2.5h, then green body is placed in high-purity corundum aluminium crucible and is sintered, 1h is kept the temperature at 850 DEG C, low-temperature sintering multi-phase microwave dielectric ceramic is made in cooled to room temperature.Wherein, CaTiO3Surface at Reason method is the same as embodiment 1.
Embodiment 4
A kind of preparation method of low-temperature sintering multi-phase microwave dielectric ceramic, using the preparation method of embodiment 1, wherein Step 3 green body is placed in the temperature being sintered in high-purity corundum aluminium crucible and is set as 725 DEG C；In step 3, in aforementioned BaCu(B2O5)-xCaTiO3BaCu (B made from the step of carrying out ingredient, molar ratio is taken to be 1:0.4 one2O5) and step 2 be made CaTiO3。
Embodiment 5
A kind of preparation method of low-temperature sintering multi-phase microwave dielectric ceramic, using the preparation method of embodiment 1, wherein Step 3 green body is placed in the temperature being sintered in high-purity corundum aluminium crucible and is set as 900 DEG C；In step 3, in aforementioned BaCu(B2O5)-xCaTiO3BaCu (B made from the step of carrying out ingredient, molar ratio is taken to be 1:0.2 one2O5) and step 2 be made CaTiO3。
To low-temperature sintering multi-phase microwave dielectric ceramic made from 1 ~ embodiment of embodiment 5 through sand paper is two-sided polish after it is to be measured Examination, tests its dielectric properties (room temperature) with cylindrical dielectric the resonance method, wherein temperature coefficient of resonance frequency is within the scope of 25 ~ 85 DEG C It obtains.Microwave dielectric property of the composition material under different sintering temperatures such as the following table 1.
The microwave dielectric property of 11 ~ embodiment of embodiment 5 of table
For low-temperature sintering multi-phase microwave dielectric ceramic made from embodiment 1, the pottery being sintered at 825 DEG C is identified with XRD The object phase composition (as shown in Figure 1) of porcelain sample, and it is utilized respectively the highest peak (I zero and I ■) of two-phase in XRD diagram, according to equation: BaCu(B2O5)/CaTiO3Zero/I of=I ■ carrys out preresearch estimates BaCu (B2O5) mutually and CaTiO3The relative volume fraction of phase.XRD result Display: the ceramics are by BaCu (B2O5) mutually and CaTiO3Phase two-phase is constituted, and BaCu (B2O5) mutually and CaTiO3The volume of phase point Number is than about 0.81；The scanning electron microscopic picture of 825 DEG C of agglomerated materials is shown in Fig. 2.In conjunction with XRD diagram it is found that the ceramic material is by A phase- BaCu(B2O5) and B phase-CaTiO3It is mutually combined, shows special institutional framework and well-developed grain form.Its In, the potsherd being sintered in the present embodiment through 825 DEG C, with fairly small temperature coefficient of resonance frequency: τ f =3.2ppm/℃。
Novel B aCu (B of the invention2O5)-xCaTiO3Multi-phase microwave dielectric material, sintering temperature is low (< 1000 DEG C), And microwave dielectric property is very excellent: the resonance frequency (f) in table 1 is 8 ~ 10, dielectric constant (εr) be 15~50, Q ×fValue (Q is quality factor) is not less than 50000GHz and small and adjustable temperature coefficient of resonance frequency (τ f )；And by adjusting CaTiO3Relative amount, sintering temperature can be reduced to 825 DEG C, while keep excellent microwave dielectric property.The present invention The cost of material is low, simple process and stabilization, favorable reproducibility, meets the technical requirements of low-temperature co-fired ceramics, be suitable for production with silver, The base metals such as copper are with a wide range of applications as multilayer chip elements such as the dielectric resonator of interior electrode and filters.
In the present invention, the TiO of step 22It could alternatively be MgO, SiO2, remaining preparation step is with embodiment 1, in embodiment Being adapted to property of the parameter adjustment being related to, to achieve the purpose that reduce cost.

Claims (4)

1. a kind of preparation method of the multi-phase microwave dielectric ceramic with jujube cake model structure, it is characterised in that: be by molecular formula BaCu(B2O5)-xCaTiO3Material composition, wherein 0 x≤0.8 <, preparation method the following steps are included:
Step 1: according to BaCO3: H3BO3: the molar ratio of Cu=1:2:1.25 mixes after carrying out feeding, and mixture A is made, mixed It closes and the deionized water that weight accounts for 1.5 times of mixture A total weight is added in material A, be placed in 24 ~ 36h of mixing in ball mill, then exist It is dried at 100 ~ 150 DEG C；Mixture A after drying is packed into high-purity corundum crucible, under oxygen atmosphere, with 0.5 ~ 2 DEG C/min Heating rate be warming up to 200 ~ 500 DEG C, then under argon atmosphere, be warming up to 700 with the heating rate of 3 ~ 5 DEG C/min ~ 900 DEG C, and a certain temperature pre-burning 8 in the section ~ for 24 hours is kept, synthesize BaCu (B2O5) crystal phase, it is spare；
Step 2: according to CaCO3: TiO2The molar ratio of=1:1 mixes after carrying out feeding, and mixture B is made, and adds in mixture B Enter the deionized water that weight accounts for 1.5 times of mixture B total weight, 24 ~ 36h of mixing in ball mill is placed in, then at 100 ~ 150 DEG C Drying；Mixture B after drying is packed into high-purity corundum crucible, is warming up to 900 ~ 1200 DEG C with the heating rate of 3 ~ 5 DEG C/min, And a certain temperature pre-burning 3 ~ for 24 hours is kept, synthesize CaTiO3Crystal phase, it is spare；
Step 3: by CaTiO made from step 23After surface treatment, according to BaCu (B2O5)-xCaTiO3Ingredient is carried out, is taken BaCu (B made from the step of molar ratio is 1:x one2O5) and step 2 made from CaTiO3, mixture is formed after the two is mixed The ethyl alcohol that weight accounts for 1.2 times of mixture total weight is added in mixture C, discharges after 24 ~ 48h of ball milling, then 100 ~ 150 by C It is dried at DEG C, is pressed into green body after granulation at 100 ~ 200MPa, after dumping, sintering, cooled to room temperature, being made has jujube The multi-phase microwave dielectric ceramic of cake model structure.
2. a kind of preparation method of multi-phase microwave dielectric ceramic with jujube cake model structure according to claim 1, It is characterized in that: in step 3, CaTiO3Surface treatment method are as follows: in CaTiO3The middle benzene sulfonamide that 0.3 ~ 0.5% weight is added Then citric acid and ammonium hydroxide that molar ratio is 1:1 are added simultaneously, adds ethanol solution, metatitanic acid is added after sonic oscillation for sour sodium Butyl ester is dried at 300 ~ 550 DEG C after stirring 2 ~ 8h.
3. a kind of preparation method of multi-phase microwave dielectric ceramic with jujube cake model structure according to claim 1, It is characterized in that: in step 3, prilling are as follows: the polyethylene that weight is its weight 4 ~ 10% is added in mixture C after the drying The pelletizing that water content is 0 ~ 0.2% is made using spray dryer in alcoholic solution；Wherein, the mass concentration of poly-vinyl alcohol solution It is 5 ~ 10%.
4. a kind of preparation method of multi-phase microwave dielectric ceramic with jujube cake model structure according to claim 1, Be characterized in that: the binder removal in step 3 is in 550 ~ 700 DEG C of 1 ~ 4h of heat preservation；Sintering process are as follows: be placed in green body high-purity rigid It is sintered in beautiful aluminium crucible, 1 ~ 6h is kept the temperature at 700 ~ 900 DEG C.
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