CN102976751A - Low-temperature sintering microwave dielectric ceramic material and preparation method thereof - Google Patents

Low-temperature sintering microwave dielectric ceramic material and preparation method thereof Download PDF

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CN102976751A
CN102976751A CN2012104785505A CN201210478550A CN102976751A CN 102976751 A CN102976751 A CN 102976751A CN 2012104785505 A CN2012104785505 A CN 2012104785505A CN 201210478550 A CN201210478550 A CN 201210478550A CN 102976751 A CN102976751 A CN 102976751A
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microwave dielectric
low
dielectric ceramic
milling
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CN102976751B (en
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雒文博
杨晓战
刘明龙
朱红伟
刘晏君
杜富贵
江林
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Chongqing Yuntianhua hanen New Material Development Co Ltd
Yunnan Yuntianhua Co Ltd
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Yunnan Yuntianhua Co Ltd
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Abstract

The invention discloses a low-temperature sintering microwave dielectric ceramic material and a preparation method thereof. The low-temperature sintering microwave dielectric ceramic material comprises ywt%[(1-x)Ba5Nb4O15-xBaNb2O6]+zwt%A, wherein A is a product of reaction between CuO and HBO3; x=0.1-0.3; 0<z<20; and y+z=100. According to the invention, A is obtained by the reaction between CuO and HBO3; the product is insoluble in solvents such as water, ethanol and the like and does not generate a gelling reaction with binders such as PVA (polyvinyl acetate), PVB (polyvinyl butyral) and the like, thus the requirements of the LTCC (low temperature co-fired ceramic) technology are met, and a high-density ceramic membrane can be obtained; the problem of the reaction with the barium element in the Ba5Nb4O15 ceramic is avoided so that the content of the BaNb2O6 phase is accurately controlled; and the material has good adjustability of resonant frequency temperature coefficient, low dielectric loss and high material quality factor, and the sintering temperature is lower than 880 DEG C. According to the invention, rare earth elements are not involved, the raw materials are cheap, and the cost is relatively low, thus the material is suitable for industrial production of microwave dielectric ceramic devices.

Description

Low-temperature sintered microwave dielectric ceramic material and preparation method thereof
Technical field
The present invention relates to micro-wave communication with the microwave-medium ceramics technical field of the microwave devices such as dielectric resonator, vibrator, be specifically related to a kind of low-temperature sintered microwave dielectric ceramic material and preparation method.
Background technology
Along with modern communication technology to miniaturization, integrated, modularization and the cheaply active demand of components and parts, LTCC (Low Temperature Co-fired Ceramics, LTCC) technology with excellent electricity, machinery, thermal characteristics and high reliability has become the one preferred technique that communication is made with components and parts.LTCC technology maximum is characterised in that and adopts base metal (such as Ag) as the multilayer wiring conductor material, improves signal transmission rate and reliability, and a plurality of microwave electron components and parts can be embedded in that sintering improves at double packing density in the substrate.Adopt the components and parts of this technology preparation to have that dielectric loss is low, reliability is high, low cost and other advantages, have a wide range of applications.
Because the fusing point of metal A g electrode is at 960 ℃, in order to realize that with ceramic co-fired the sintering temperature of LTCC technical requirements pottery is lower than 900 ℃.The microwave-medium ceramics sintering temperature that most has excellent properties is higher than 1200 ℃, has the Ba of excellent microwave dielectric property 5Nb 4O 15Pottery also is like this.It is reported Ba 5Nb 4O 15The specific inductivity of microwave-medium ceramics is ε r=41, quality factor q * f=57000GHz, temperature coefficient of resonance frequency τ f=50ppm/ ℃, but sintering temperature is higher than 1380 ℃.In order to realize low temperature co-fired with the Ag electrode, the people such as Kin.J.R are at " Journal of the American Society " 85 volumes " Microwave Dielectric Properties ofLow-Fired Ba in 2002 5Nb 4O 15" point out in the literary composition to add low melting point oxide B at pottery 2O 3Sintering temperature can be down to 900 ℃, quality factor q * f=18700GHz also can make temperature coefficient of resonance frequency approach zero simultaneously.
Still there is more deficiency but adopt such scheme to prepare LTCC, is in particular in:
(1) because B 2O 3Soluble in water, ethanol equal solvent, and with the most frequently used binding agent generation gelling reactions such as PVA, PVB so that ceramic powder can not obtain highdensity ceramic diaphragm after curtain coating.
(2) in the technique scheme, the mechanism that reduces sintering temperature is B 2O 3With Ba 5Nb 4O 15The barium element reaction generates the low melting point oxide of barium, boron, oxygen system in the pottery, but the oxide compound fusing point of all barium, boron, oxygen system is all greater than 890 ℃, and this technology can not further reduce sintering temperature.Simultaneously, temperature coefficient of resonance frequency reduced be since system barium element disappearance cause more than the niobium element and a small amount of barium Element generation BaNb 2O 6Phase, but because barium, boron, oxygen system oxide compound kind are numerous, BaNb 2O 6The actual content of phase is difficult to control, and temperature coefficient of resonance frequency is difficult to control in the actual production.
Therefore, need a kind of low-temperature sintered microwave dielectric ceramic material, water insoluble, the ethanol equal solvent of low melting point oxide in this material, and not with the binding agent generation gelling reactions such as PVA, PVB, to obtain highdensity ceramic diaphragm; Do not exist and Ba 5Nb 4O 15The problem of barium element reaction makes BaNb in the pottery 2O 6It is precisely controlled to get mutually content, further reduces simultaneously sintering temperature; And have lower cost, be fit to the industrialization production of microwave-medium ceramics device.
Summary of the invention
In view of this, the purpose of this invention is to provide a kind of low-temperature sintered microwave dielectric ceramic material and preparation method thereof, water insoluble, the ethanol equal solvent of low melting point oxide in this material, and not with the binding agent generation gelling reactions such as PVA, PVB, to obtain highdensity ceramic diaphragm; Do not exist and Ba 5Nb 4O 15The problem of barium element reaction makes BaNb in the pottery 2O 6It is precisely controlled to get mutually content, further reduces simultaneously sintering temperature; And have lower cost, be fit to the industrialization production of microwave-medium ceramics device.
Low-temperature sintered microwave dielectric ceramic material of the present invention comprises: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3Reacted product; X=0.1 ~ 0.3,0＜z＜20, y+z=100.
Further, described A is CuO and HBO 3In molar weight than 1:(5 ~ 9) ratio at the product of 1000 ℃ ~ 1200 ℃ lower reactions after 1 ~ 4 hour;
Further, described A is CuB 8O 13
Further, x=0.1 ~ 0.2,0＜z＜10.
The invention also discloses a kind of preparation method of low-temperature sintered microwave dielectric ceramic material, may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A;
D. press ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, x=0.1 ~ 0.3,0＜z＜20, y+z=100 takes by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, form microwave dielectric ceramic materials behind the sintering.
Further, among the step c, press CuO and HBO 3Molar weight than for 1:(5 ~ 9) the ratio proportioning, add and adopted dry type ball milled mixing and ball milling in the ball grinder 2 ~ 6 hours, obtain product A after 1 ~ 4 hour and pulverize 1000 ℃ ~ 1200 ℃ insulations;
Further, among the step a, press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 20 ~ 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 1 ~ 6 hour 1000 ℃ ~ 1200 ℃ insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
Among the step b, press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 20 ~ 24 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1000 ℃ ~ 1200 ℃ insulations 1 ~ 4 hour, cool to 900 ℃ ~ 950 ℃ insulations with the speed of 2 ~ 5 ℃/min and obtained BaNb in 1 ~ 6 hour 2O 6Ceramic powder;
In the steps d, press ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, x=0.1 ~ 0.3,0＜z＜20, the prescription of y+z=100 takes by weighing the Ba of step a gained 5Nb 4O 15The BaNb of ceramic powder, step b gained 2O 6The product A powder of ceramic powder and step c gained in ball grinder adopts wet ball-milling method mixing and ball milling 22 ~ 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and oven dry obtains mixed powder in baking oven;
Among the step e, the addition of caking agent is the 1wt% ~ 3.5wt% of mixed powder massfraction in the steps d, obtains moulding at 1 ~ 3 hour binder removal of 500 ℃ ~ 600 ℃ insulations after the compression moulding and gives birth to stock; Described living stock places the muffle furnace sintering, obtains microwave dielectric ceramic materials.
Further, among the step c, CuO and HBO 3Molar weight than for 1:(6 ~ 8);
Further, among the step e, described binding agent is polyvinyl alcohol water solution, and concentration is 1.0wt% ~ 5.0wt%;
Further, among the step e, 1.5 ~ 6 ℃/min of temperature rise rate of sintering process, sintering temperature is 830 ~ 880 ℃, and soaking time is 1 ~ 4 hour under this temperature.
The invention has the beneficial effects as follows: low-temperature sintered microwave dielectric ceramic material of the present invention, low melting point oxide adopts CuO and HBO 3The product that reaction obtains, this product is water insoluble, the ethanol equal solvent, and not with the binding agent generation gelling reactions such as PVA, PVB, meet the LTCC processing requirement, can obtain highdensity ceramic diaphragm; Do not exist and Ba 5Nb 4O 15The problem of barium element reaction makes BaNb in the pottery 2O 6Mutually content is precisely controlled, have good temperature coefficient of resonance frequency adjustability, low dielectric loss, high material quality factor, microwave dielectric ceramic materials specific inductivity 42＜ε of the present invention r＜44, quality factor q * f〉8000GHz, temperature coefficient of resonance frequency-7ppm/ ℃＜τ f＜5ppm/ ℃; Further reduce simultaneously sintering temperature, sintering temperature is lower than 880 ℃; And the present invention does not relate to rare earth element, and cost of material is cheap, has lower cost, is fit to the industrialization production of microwave-medium ceramics device.
Embodiment
Low-temperature sintered microwave dielectric ceramic material of the present invention comprises: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3Reacted product; X=0.1 ~ 0.3,0＜z＜20, y+z=100; Wt% is weight percentage.
In the present embodiment, described A is CuO and HBO 3In molar weight than 1:(5 ~ 9) ratio at the product of 1000 ℃ ~ 1200 ℃ lower reactions after 1 ~ 4 hour.
In the present embodiment, described A is CuB 8O 13
In the present embodiment, x=0.1 ~ 0.2,0＜z＜10.
The invention also discloses a kind of preparation method of low-temperature sintered microwave dielectric ceramic material, may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A;
D. press ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, x=0.1 ~ 0.3,0＜z＜20, y+z=100 takes by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, form microwave dielectric ceramic materials behind the sintering.
In the present embodiment, among the step c, press CuO and HBO 3Molar weight than for 1:(5 ~ 9) the ratio proportioning, add and adopted dry type ball milled mixing and ball milling in the ball grinder 2 ~ 6 hours, obtain product A after 1 ~ 4 hour and pulverize 1000 ℃ ~ 1200 ℃ insulations;
In the present embodiment, among the step a, press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 20 ~ 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 1 ~ 6 hour 1000 ℃ ~ 1200 ℃ insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
Among the step b, press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 20 ~ 24 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1000 ℃ ~ 1200 ℃ insulations 1 ~ 4 hour, cool to 900 ℃ ~ 950 ℃ insulations with the speed of 2 ~ 5 ℃/min and obtained BaNb in 1 ~ 6 hour 2O 6Ceramic powder;
In the steps d, press ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, x=0.1 ~ 0.3,0＜z＜20, the prescription of y+z=100 takes by weighing the Ba of step a gained 5Nb 4O 15The BaNb of ceramic powder, step b gained 2O 6The product A powder of ceramic powder and step c gained in ball grinder adopts wet ball-milling method mixing and ball milling 22 ~ 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and oven dry obtains mixed powder in baking oven;
Among the step e, the addition of caking agent is the 1wt% ~ 3.5wt% of mixed powder massfraction in the steps d, obtains moulding at 1 ~ 3 hour binder removal of 500 ℃ ~ 600 ℃ insulations after the compression moulding and gives birth to stock; Described living stock places the muffle furnace sintering, obtains microwave dielectric ceramic materials.
In the present embodiment, among the step c, CuO and HBO 3Molar weight than for 1:(6 ~ 8);
In the present embodiment, among the step e, described binding agent is polyvinyl alcohol water solution, and concentration is 1.0wt% ~ 5.0wt%;
In the present embodiment, among the step e, 1.5 ~ 6 ℃/min of temperature rise rate of sintering process, sintering temperature is 830 ~ 880 ℃, and soaking time is 1 ~ 4 hour under this temperature.
The below is embodiments of the invention:
Embodiment one
Comprise: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3In ratio the product 1150 ℃ under react 1.5 hour after of molar weight than 1:5.5; X=0.2, z=4, y=96.
The preparation method of present embodiment low temperature sintering microwave dielectric ceramic materials may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder:
Press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 20 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 6 hours 1200 ℃ of insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder:
Press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 24 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1200 ℃ of ℃ of insulations 4 hours, cool to 950 ℃ of insulations with the speed of 2 ℃/min and obtained BaNb in 4 hours 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A:
Press CuO and HBO 3Molar weight than being the ratio proportioning of 1:5.5, add and adopted dry type ball milled mixing and ball milling in the ball grinder 5 hours, obtain product A after 1.5 hours and pulverize 1150 ℃ of insulations;
D. take by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder; The raw material that takes by weighing was adopted wet ball-milling method mixing and ball milling 22 hours take dehydrated alcohol or deionized water as ball-milling medium adds in the ball grinder, oven dry obtains mixed powder in baking oven;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, obtain moulding at 1 hour binder removal of 500 ℃ of insulations and give birth to stock, to give birth to stock and place muffle furnace to be raised to 870 ℃ of insulations 3.5 hours with the speed of 5 ℃/min from room temperature, form microwave dielectric ceramic materials behind the sintering; The binding agent of present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase that employing x x ray diffractometer x (XRD) is analyzed the ceramics sample behind the sintering is Ba 5Nb 4O 15Phase and BaNb 2O 6The phase two-phase adopts Agilent H98722ET vector network analysis instrument test result: DIELECTRIC CONSTANT ε r=43.4, quality factor q * f=8910.9GHz has very high quality factor.Temperature coefficient of resonance frequency τ f=-3ppm/ ℃, satisfy real requirement.Compared with prior art, sintering temperature is reduced to 870 ℃ from 900 ℃, has avoided simultaneously and the polyvinyl alcohol water solution reaction, and the finer and close ceramic diaphragm of preparation can be arranged; Also avoided and the containing barium compound reaction, temperature coefficient of resonance frequency-3ppm/ ℃ and more stable, satisfied the LTCC Technology Need.
Embodiment two
Comprise: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3In ratio the product 1100 ℃ under react 2 hour after of molar weight than 1:8; X=0.15, z=10, y=90.
The preparation method of present embodiment low temperature sintering microwave dielectric ceramic materials may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder:
Press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 2 hours 1200 ℃ of insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder:
Press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 24 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1200 ℃ of ℃ of insulations 2 hours, cool to 950 ℃ of insulations with the speed of 2 ℃/min and obtained BaNb in 3 hours 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A:
Press CuO and HBO 3Molar weight than being the ratio proportioning of 1:8, add and adopted dry type ball milled mixing and ball milling in the ball grinder 5 hours, obtain product A after 2 hours and pulverize 1100 ℃ of insulations; In the present embodiment, CuO and HBO 3Product under these conditions is CuB 8O 13
D. take by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder; The raw material that takes by weighing was adopted wet ball-milling method mixing and ball milling 24 hours take dehydrated alcohol or deionized water as ball-milling medium adds in the ball grinder, oven dry obtains mixed powder in baking oven;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, obtain moulding at 2 hours binder removals of 600 ℃ of insulations and give birth to stock, to give birth to stock and place muffle furnace to be raised to 830 ℃ of insulations 3 hours with the speed of 5 ℃/min from room temperature, form microwave dielectric ceramic materials behind the sintering; The binding agent of present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase that employing x x ray diffractometer x (XRD) is analyzed the ceramics sample behind the sintering is Ba 5Nb 4O 15Phase and BaNb 2O 6The phase two-phase.Adopt Agilent H98722ET vector network analysis instrument test result: DIELECTRIC CONSTANT ε r=42.5, quality factor q * f=13710.9GHz has very high quality factor; Temperature coefficient of resonance frequency τ f=0ppm/ ℃, compare with embodiment 1, quality factor have had more obviously raising, and temperature coefficient of resonance frequency is zero; Compared with prior art, sintering temperature is reduced to 830 ℃ from 900 ℃, has avoided simultaneously and the polyvinyl alcohol water solution reaction, and the finer and close ceramic diaphragm of preparation can be arranged; Also avoided and the containing barium compound reaction, better met the LTCC Technology Need.
Embodiment three
Comprise: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3In ratio the product 1000 ℃ under react 4 hour after of molar weight than 1:5; X=0.1, z=19.7, y=80.3.
The preparation method of present embodiment low temperature sintering microwave dielectric ceramic materials may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder:
Press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 22 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 6 hours 1000 ℃ of insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder:
Press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 20 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1000 ℃ of insulations 4 hours, cool to 900 ℃ of insulations with the speed of 5 ℃/min and obtained BaNb in 6 hours 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A:
Press CuO and HBO 3Molar weight than being the ratio proportioning of 1:5, add and adopted dry type ball milled mixing and ball milling in the ball grinder 2 hours, obtain product A after 4 hours and pulverize 1000 ℃ of insulations;
D. take by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder; The raw material that takes by weighing was adopted wet ball-milling method mixing and ball milling 22 hours take dehydrated alcohol or deionized water as ball-milling medium adds in the ball grinder, oven dry obtains mixed powder in baking oven;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, obtain moulding at 3 hours binder removals of 550 ℃ of insulations and give birth to stock, to give birth to stock and place muffle furnace to be raised to 830 ℃ of insulations 2 hours with the speed of 1.5 ℃/min from room temperature, form microwave dielectric ceramic materials behind the sintering; The binding agent of present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase that employing x x ray diffractometer x (XRD) is analyzed the ceramics sample behind the sintering is Ba 5Nb 4O 15Phase and BaNb 2O 6The phase two-phase.Adopt Agilent H98722ET vector network analysis instrument test result: DIELECTRIC CONSTANT ε r=42.9, quality factor q * f=8321.5GHz has very high quality factor; Temperature coefficient of resonance frequency τ f=5ppm/ ℃, quality factor are compared low with embodiment 2; Compared with prior art, sintering temperature is reduced to 830 ℃ from 900 ℃, has avoided simultaneously and the polyvinyl alcohol water solution reaction, and the finer and close ceramic diaphragm of preparation can be arranged; Also avoided and the containing barium compound reaction, can satisfy the LTCC Technology Need.
Embodiment four
Comprise: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3 is in ratio the product 1200 ℃ under react 1 hour after of molar weight than 1:9; X=0.3, z=0.05, y=99.5.
The preparation method of present embodiment low temperature sintering microwave dielectric ceramic materials may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder:
Press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 2 hours 1100 ℃ of insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder:
Press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 22 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1100 ℃ of ℃ of insulations 3 hours, cool to 925 ℃ of insulations with the speed of 3 ℃/min and obtained BaNb in 4 hours 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A:
Press CuO and HBO 3Molar weight than being the ratio proportioning of 1:9, add and adopted dry type ball milled mixing and ball milling in the ball grinder 4 hours, obtain product A after 1 hour and pulverize 1200 ℃ of insulations;
D. take by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder; The raw material that takes by weighing was adopted wet ball-milling method mixing and ball milling 23 hours take dehydrated alcohol or deionized water as ball-milling medium adds in the ball grinder, oven dry obtains mixed powder in baking oven;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, obtain moulding at 2 hours binder removals of 600 ℃ of insulations and give birth to stock, to give birth to stock and place muffle furnace to be raised to 880 ℃ of insulations 4 hours with the speed of 6 ℃/min from room temperature, form microwave dielectric ceramic materials behind the sintering; The binding agent of present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase that employing x x ray diffractometer x (XRD) is analyzed the ceramics sample behind the sintering is Ba 5Nb 4O 15Phase and BaNb 2O 6The phase two-phase.Adopt Agilent H98722ET vector network analysis instrument test result: DIELECTRIC CONSTANT ε r=43.1, quality factor q * f=9631.8GHz has very high quality factor; Temperature coefficient of resonance frequency τ f=-7ppm/ ℃, quality factor increase than embodiment 1; Compare compared with prior art, sintering temperature is reduced to 880 ℃ from 900 ℃, has avoided simultaneously and the polyvinyl alcohol water solution reaction, and the finer and close ceramic diaphragm of preparation can be arranged; Also avoided and the containing barium compound reaction, can satisfy the LTCC Technology Need.
Embodiment five
Comprise: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3In ratio the product 1150 ℃ under react 3 hour after of molar weight than 1:6.5; X=0.15, z=13, y=87.
The preparation method of present embodiment low temperature sintering microwave dielectric ceramic materials may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder:
Press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 4 hours 1150 ℃ of insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder:
Press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 23 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1150 ℃ of ℃ of insulations 2 hours, cool to 940 ℃ of insulations with the speed of 4 ℃/min and obtained BaNb in 5 hours 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A:
Press CuO and HBO 3Molar weight than being the ratio proportioning of 1:6.5, add and adopted dry type ball milled mixing and ball milling in the ball grinder 4 hours, obtain product A after 3 hours and pulverize 1150 ℃ of insulations;
D. take by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder; The raw material that takes by weighing was adopted wet ball-milling method mixing and ball milling 23 hours take dehydrated alcohol or deionized water as ball-milling medium adds in the ball grinder, oven dry obtains mixed powder in baking oven;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, obtain moulding at 3 hours binder removals of 550 ℃ of insulations and give birth to stock, to give birth to stock and place muffle furnace to be raised to 840 ℃ of insulations 3 hours with the speed of 3 ℃/min from room temperature, form microwave dielectric ceramic materials behind the sintering; The binding agent of present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase that employing x x ray diffractometer x (XRD) is analyzed the ceramics sample behind the sintering is Ba 5Nb 4O 15Phase and BaNb 2O 6The phase two-phase.Adopt Agilent H98722ET vector network analysis instrument test result: DIELECTRIC CONSTANT ε r=42.6, quality factor q * f=10171.9GHz has very high quality factor; Temperature coefficient of resonance frequency τ f=0ppm/ ℃, quality factor are high with embodiment 1 ratio, and temperature coefficient of resonance frequency is zero; Compare compared with prior art, sintering temperature is reduced to 840 ℃ from 900 ℃, has avoided simultaneously and the polyvinyl alcohol water solution reaction, and the finer and close ceramic diaphragm of preparation can be arranged; Also avoided and the containing barium compound reaction, can satisfy the LTCC Technology Need.
Embodiment six
Comprise: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3In ratio the product 1150 ℃ under react 4 hour after of molar weight than 1:7.5; X=0.25, z=8, y=92.
The preparation method of present embodiment low temperature sintering microwave dielectric ceramic materials may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder:
Press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 4 hours 1150 ℃ of insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder:
Press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 23 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1150 ℃ of ℃ of insulations 2 hours, cool to 940 ℃ of insulations with the speed of 4 ℃/min and obtained BaNb in 5 hours 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A:
Press CuO and HBO 3Molar weight than being the ratio proportioning of 1:7.5, add and adopted dry type ball milled mixing and ball milling in the ball grinder 4 hours, obtain product A after 4 hours and pulverize 1150 ℃ of insulations;
D. take by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder; The raw material that takes by weighing was adopted wet ball-milling method mixing and ball milling 24 hours take dehydrated alcohol or deionized water as ball-milling medium adds in the ball grinder, oven dry obtains mixed powder in baking oven;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, obtain moulding at 2 hours binder removals of 600 ℃ of insulations and give birth to stock, to give birth to stock and place muffle furnace to be raised to 850 ℃ of insulations 2 hours with the speed of 4 ℃/min from room temperature, form microwave dielectric ceramic materials behind the sintering; The binding agent of present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase that employing x x ray diffractometer x (XRD) is analyzed the ceramics sample behind the sintering is Ba 5Nb 4O 15Phase and BaNb 2O 6The phase two-phase.Adopt Agilent H98722ET vector network analysis instrument test result: DIELECTRIC CONSTANT ε r=42.3, quality factor q * f=11171.9GHz has very high quality factor; Temperature coefficient of resonance frequency τ f=-6ppm/ ℃, quality factor are high with embodiment 1 ratio; Compare compared with prior art, sintering temperature is reduced to 850 ℃ from 900 ℃, has avoided simultaneously and the polyvinyl alcohol water solution reaction, and the finer and close ceramic diaphragm of preparation can be arranged; Also avoided and the containing barium compound reaction, can satisfy the LTCC Technology Need.
According to the parameter comparison of above-described embodiment, microwave dielectric ceramic materials specific inductivity 42＜ε of the present invention r＜44, quality factor q * f〉8000GHz, temperature coefficient of resonance frequency-7ppm/ ℃＜τ f＜5ppm/ ℃; Further reduce simultaneously sintering temperature, sintering temperature is lower than 880 ℃; Embodiment two, embodiment five and embodiment six obviously are better than other embodiment, and embodiment two obviously is better than embodiment five and embodiment six, is best proportioning and processing parameter.
Among the embodiment two, CuO and HBO 3The product of reaction is CuB 8O 13, and this product is different from it among other embodiment, though can reach with respect to prior art effect preferably, compares with embodiment two and still has deficiency.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (10)

1. a low-temperature sintered microwave dielectric ceramic material is characterized in that: comprising: ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, wherein: A is CuO and HBO 3Reacted product; X=0.1 ~ 0.3,0＜z＜20, y+z=100.
2. low-temperature sintered microwave dielectric ceramic material according to claim 1, it is characterized in that: described A is CuO and HBO 3In molar weight than 1:(5 ~ 9) ratio at the product of 1000 ℃ ~ 1200 ℃ lower reactions after 1 ~ 4 hour.
3. low-temperature sintered microwave dielectric ceramic material according to claim 2, it is characterized in that: described A is CuB 8O 13
4. low-temperature sintered microwave dielectric ceramic material according to claim 3 is characterized in that: x=0.1 ~ 0.2,0＜z＜10.
5. the preparation method of a low-temperature sintered microwave dielectric ceramic material is characterized in that: may further comprise the steps:
A. prepare Ba 5Nb 4O 15Ceramic powder;
B. prepare BaNb 2O 6Ceramic powder;
C.CuO and HBO 3Reaction obtains product A;
D. press ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, x=0.1 ~ 0.3,0＜z＜20, y+z=100 takes by weighing Ba 5Nb 4O 15Ceramic powder, BaNb 2O 6Ceramic powder and product A also form mixed powder;
E. add compression moulding after binding agent and the granulation in the mixed powder of steps d, form microwave dielectric ceramic materials behind the sintering.
6. the preparation method of low-temperature sintered microwave dielectric ceramic material according to claim 5 is characterized in that: among the step c, press CuO and HBO 3Molar weight than for 1:(5 ~ 9) the ratio proportioning, add and adopted dry type ball milled mixing and ball milling in the ball grinder 2 ~ 6 hours, obtain product A after 1 ~ 4 hour and pulverize 1000 ℃ ~ 1200 ℃ insulations.
7. the preparation method of low-temperature sintered microwave dielectric ceramic material according to claim 6 is characterized in that: among the step a, press Ba 5Nb 4O 15Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material in ball grinder adopts wet ball-milling method mixing and ball milling 20 ~ 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and obtains Ba in 1 ~ 6 hour 1000 ℃ ~ 1200 ℃ insulations after the oven dry in baking oven 5Nb 4O 15Ceramic powder;
Among the step b, press BaNb 2O 6Stoichiometric ratio take by weighing BaCO 3And Nb 2O 5Raw material, the raw material that takes by weighing as adding, ball-milling medium was adopted wet ball-milling method mixing and ball milling 20 ~ 24 hours take dehydrated alcohol or deionized water in the ball grinder, in baking oven after the oven dry 1000 ℃ ~ 1200 ℃ insulations 1 ~ 4 hour, cool to 900 ℃ ~ 950 ℃ insulations with the speed of 2 ~ 5 ℃/min and obtained BaNb in 1 ~ 6 hour 2O 6Ceramic powder;
In the steps d, press ywt%[(1-x) Ba 5Nb 4O 15-xBaNb 2O 6]+zwt%A, x=0.1 ~ 0.3,0＜z＜20, the prescription of y+z=100 takes by weighing the Ba of step a gained 5Nb 4O 15The BaNb of ceramic powder, step b gained 2O 6The product A powder of ceramic powder and step c gained in ball grinder adopts wet ball-milling method mixing and ball milling 22 ~ 24 hour take dehydrated alcohol or deionized water as ball-milling medium adds with the raw material that takes by weighing, and oven dry obtains mixed powder in baking oven;
Among the step e, the addition of caking agent is the 1wt% ~ 3.5wt% of mixed powder massfraction in the steps d, obtains moulding at 1 ~ 3 hour binder removal of 500 ℃ ~ 600 ℃ insulations after the compression moulding and gives birth to stock; Described living stock places the muffle furnace sintering, obtains microwave dielectric ceramic materials.
8. according to claim 5, the preparation method of 6 or 7 described low-temperature sintered microwave dielectric ceramic materials, it is characterized in that: among the step c, CuO and HBO 3Molar weight than for 1:(6 ~ 8).
9. according to claim 5, the preparation method of 6,7 or 8 described low-temperature sintered microwave dielectric ceramic materials, it is characterized in that: among the step e, described binding agent is polyvinyl alcohol water solution, and concentration is 1.0wt% ~ 5.0wt%.
10. according to claim 5, the preparation method of 6,7 or 8 described low-temperature sintered microwave dielectric ceramic materials, it is characterized in that: among the step e, 1.5 ~ 6 ℃/min of temperature rise rate of sintering process, sintering temperature is 830 ~ 880 ℃, and soaking time is 1 ~ 4 hour under this temperature.
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CN103553610A (en) * 2013-10-30 2014-02-05 云南云天化股份有限公司 Low-temperature sintered microwave dielectric ceramic material, preparation method and microwave device
CN103553609A (en) * 2013-10-30 2014-02-05 云南云天化股份有限公司 Microwave dielectric ceramic material with high quality factor, preparation method and microwave device
CN103553609B (en) * 2013-10-30 2015-12-02 云南云天化股份有限公司 High-quality factor microwave medium ceramic material, preparation method and microwave device
CN104129993A (en) * 2014-07-10 2014-11-05 上海大学 Method for reducing KNbO3-based PTCR material sintering temperature
CN104129993B (en) * 2014-07-10 2015-10-07 上海大学 A kind of reduction KNbO 3the method of base PTCR material sintering temperature
CN106699178A (en) * 2015-11-18 2017-05-24 信昌电子陶瓷股份有限公司 Microwave dielectric ceramic by low-temperature co-fired ceramics
CN113690561A (en) * 2021-09-01 2021-11-23 深圳市动盈先进材料有限公司 Preparation method of filter for 5G signal conversion
CN113690561B (en) * 2021-09-01 2022-07-29 深圳市动盈先进材料有限公司 Preparation method of filter for 5G signal conversion
CN114105638A (en) * 2021-12-31 2022-03-01 嘉兴佳利电子有限公司 Medium dielectric constant low-temperature sintered microwave dielectric ceramic material and preparation method thereof
CN114105638B (en) * 2021-12-31 2022-12-23 嘉兴佳利电子有限公司 Medium dielectric constant low-temperature sintered microwave dielectric ceramic material and preparation method thereof

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