CN101318815B - Bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature and manufacture of the same - Google Patents

Bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature and manufacture of the same Download PDF

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CN101318815B
CN101318815B CN2008100183454A CN200810018345A CN101318815B CN 101318815 B CN101318815 B CN 101318815B CN 2008100183454 A CN2008100183454 A CN 2008100183454A CN 200810018345 A CN200810018345 A CN 200810018345A CN 101318815 B CN101318815 B CN 101318815B
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microwave
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porcelain
bismuth
preparation
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CN101318815A (en
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汪宏
周迪
姚熹
庞利霞
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Xian Jiaotong University
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Xian Jiaotong University
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Abstract

The invention discloses a bismuthino molybdenum ultralow temperature sintering microwave medium ceramic material. A phase map of Bi2O3-MoO3 binary system is taken as a beginning, a single-phase compound is taken as a basis, and a series of microwave medium material which has good microwave dielectric property (the permittivity is between 10 and 45, and the Qf is between 4,000 and 25,000GHz) and can be sintered into ceramics at a low temperature of between 550 and 900 DEG C is prepared through the methods of adjusting the proportion of the binary system and substitution for equivalent and unequivalent ions. The structural formula is (1-x)[(Bi1-yAy)2O3]-x[(Mo1-zBz)O3], wherein, A is equal to La<3+>, Nd<3+>, and Sm<3+>, B is equal to W<6+>, Nb<5+>, Ta<5+>, Sb<5+>, Ti<4+>, Zr<4+>, and Sn<4+>,x is more than or equal to 0.01 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.20, and z is more than or equal to 0 and less than or equal to 0.20.

Description

Bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature and preparation thereof
Technical field
The invention belongs to electronic ceramics and preparation field thereof, particularly a kind of bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature of agglomerating at low temperatures and preparation thereof.
Background technology
Along with the development of radio communication, facility communication system has been proposed portable requirement, from the microwave device to the machine system, move towards integrated, in the hope of obtaining small volume, light weight, high reliability, product cheaply.
To microwave device (band logical device, resonator, wave filter etc.) the integrated requirement of miniaturization, make LTCC Technology (Low-temperature co-fired ceramic (LTCC)) develop rapidly.LTCC Technology can provide high-density, high band, high digitized encapsulation technology and good thermal treatment process.The common burning temperature of LTCC system (LTCC) generally is lower than 950 ℃.Because sintering temperature is low, the low metal of available resistivity is as the conductor material of multilayer wiring, thereby improve packing density, signaling rate, and can in be embedded in the various laminar microwave electronic devices of multilager base plate once-firing, therefore be widely used in the interconnected mcm of high-speed and high-density (MCM).Since altogether burning technology have packing density height, dielectric loss low, can be used for characteristics such as high microwave frequency band, monolithic structure high reliability and IC heat match, so have a wide range of applications.Thereby have high-k, high quality factor (Qf), research focus that the well behaved microwave-medium ceramics that approaches zero temperature coefficient of resonance frequency (TCF) becomes present field of functional materials.In order to realize low temperature co-fired technology, microwave-medium ceramics must will be followed low-loss, low-melting electrode (as silver electrode, copper electrode, gold electrode or aluminium electrode) co-sintered.
But, the sintering temperature of the microwave ceramics of the overwhelming majority is all more than 1000 ℃, though they also have very good microwave dielectric property, be not suitable for the LTCC technical requirements, so microwave material system just very meaningful of R and D with sintering temperature and low.For the microwave-medium ceramics that higher sintering temperature will be arranged is applied to the LTCC technology, need lower the temperature to its material system, the method for cooling has following several: 1, adopt the method for chemical preparation, make become the to coordinate temperature of porcelain reduce; 2, use the tiny oxide compound of particle to react; 3, add low-melting oxide compound as sintering agent; 4, add special oxide compound and lower the temperature by the mode of reaction sintering; 5, add glassy phase and lower the temperature in the mode of liquid phase sintering; 6, use itself has low-temperature sintering and becomes the oxide compound of porcelain characteristic as the pivot system.
In sum, along with the fast development of microwave mobile communication, new requirement has been proposed for portable, the microminiaturization of microwave device.Microwave dielectric resonator with the high-dielectric constant microwave material preparation can greatly reduce the microwave circuit size, but further microminiaturized outlet is the development of MCM.When making MCM and use Mulitilayer circuit board, the LTCC technology demonstrates peculiar advantage, so has just obtained paying attention to widely and studying with multilayered medium device and material that the LTCC technology adapts.Be applicable to LTCC technology, microwave property excellence, can with silver or copper electrode altogether the simple novel microwave dielectric ceramic material of burning, chemical constitution and preparation technology be the novel material that a class has application prospect.
Summary of the invention
The objective of the invention is to overcome above-mentioned prior art deficiency, a kind of bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature and preparation method thereof is provided, this stupalith be a kind of do not need to add any sintering agent just at low temperatures agglomerating can be applicable to the high-performance bismuthino molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature of LTCC, its minimum sintering temperature is low to moderate 550 ℃.
First purpose of the present invention provides a kind of bismuth-based molybdenum-based low-temperature sintered microwave dielectric ceramic material, and the relative permittivity behind its sintering is 10～45, low low-frequency dielectric loss (tan δ＜5 * 10 -41MHz), good microwave property (Qf=4000GHz～25000GHz), temperature coefficient of resonance frequency is adjustable (TCF=-230ppm/ ℃～+ 31ppm/ ℃), its principal feature is (550 ℃～900 ℃) to carry out sintering under low-down sintering temperature in addition, and chemical constitution and preparation technology are simple.
Second purpose of the present invention provides the preparation method of the bismuth-based molybdenum-based microwave dielectric ceramic materials of above-mentioned sintered at ultra low temperature.
The present invention has adopted the most simple and effective solid state reaction agglomerating method to realize the foregoing invention purpose.It at first is the prescription of choosing proper ratio, choose suitable initial oxide and suitable substituent, make oxide compound mix by a ball milling, make oxide compound carry out preliminary reaction by the presintering process, by the particle size of secondary ball milling refinement reactant, obtain needed ceramics sample by sintering process at last again.By a kind of so simple effective preparation method, the specific inductivity of the ceramics sample that obtains changes between 10～45 with composition and changes, Qf is distributed in 4000GHz～25000GHz, temperature coefficient of resonance frequency-230ppm/ ℃～+ 31ppm/ is ℃ adjustable, can realize 0ppm/ ℃ requirement, 550 ℃～900 ℃ of sintering temperatures make it to be applicable to the needs of LTCC technology to enlarge its range of application.
Technical scheme of the present invention is achieved in that the structure expression of bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature is: (1-x) [(Bi 1-yA y) 2O 3]-x[(Mo 1-zB z) O 3], A=La wherein 3+, Nd 3+, Sm 3+, B=W 6+, Nb 5+, Ta 5+, Sb 5+, Ti 4+, Zr 4+, Sn 4+, 0.01≤x≤1,0≤y≤0.20,0≤z≤0.20.
Described microwave-medium ceramics is based on Bi 2O 3-MoO 3Single-phase compound in the binary system.
Described A is La 3+, Nd 3+, Sm 3+A kind of in the ion.
Described B is W 6+, Nb 5+, Ta 5+, Sb 5+, Ti 4+, Zr 4+, Sn 4+In a kind of.
Bismuth-based molybdenum-based low-temperature sintered microwave dielectric ceramic material preparation method of the present invention, carry out according to the following steps:
1) with chemical feedstocks Bi 2O 3, MoO 3, WO 3, Nb 2O 5, Ta 2O 5, Sb 2O 3, TiO 2, ZrO 2, SnO 2, La 2O 3, Nd 2O 3, Sm 2O 3By prescription general formula (1-x) [(Bi 1-yA y) 2O 3]-x[(Mo 1-zB z) O 3] weighing preparation, wherein A=La 3+, Nd 3+, Sm 3+, B=W 6+, Nb 5+, Ta 5+, Sb 5+, Ti 4+, Zr 4+, Sn 4+, 0.01≤x≤1,0≤y≤0.20,0≤z≤0.20.
2) chemical feedstocks after will preparing mixes, and puts into the nylon jar, adds the alcohol ball milling 4～5 hours, and thorough mixing is levigate, takes out 100 ℃～200 ℃ of flash bakings, is pressed into bulk behind 200 orders that sieve;
3) Ya Zhi block is through 500 ℃～800 ℃ pre-burnings, and is incubated 5～8 hours, can obtain sample and burn piece;
4) sample is burnt piece and pulverize, and through 4～8 hours secondary ball milling, thorough mixing was levigate, oven dry 100 ℃～200 ℃, granulation, granulation obtains required porcelain small-particle after 60 orders and 120 eye mesh screen bilayers sieve;
5) with porcelain compression moulding on demand, became porcelain in 2～8 hours at 550 ℃～900 ℃ following sintering, can obtain bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature.
The bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature of the present invention has following characteristics: relative permittivity higher (10～45), little (tan δ＜5 * 10 of dielectric loss under the low frequency -4, 1MHz), microwave property good (Qf=4000～25000GHz), temperature coefficient of resonance frequency is adjustable (TCF=-230ppm/ ℃～+ 31ppm/ ℃), sintering temperature very low (550 ℃～900 ℃), chemical constitution and preparation technology are simple.
Embodiment
Below content of the present invention is described in further detail.
The recipe formulation of bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature of the present invention is: (1-x) [(Bi 1-yA y) 2O 3]-x[(Mo 1-zB z) O 3], A=La wherein 3+, Nd 3+, Sm 3+, B=W 6+, Nb 5+, Ta 5+, Sb 5+, Ti 4+, Zr 4+, Sn 4+, 0.01≤x≤1,0≤y≤0.20,0≤z≤0.20.
The concrete preparation process of the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature of the present invention is: with chemical feedstocks Bi 2O 3, MoO 3, WO 3, Nb 2O 5, Ta 2O 5, Sb 2O 3, TiO 2, ZrO 2, SnO 2, La 2O 3, Nd 2O 3, Sm 2O 3Deng by prescription general formula (1-x) [(Bi 1-yA y) 2O 3]-x[(Mo 1-zB z) O 3] weighing preparation, wherein A=La 3+, Nd 3+, Sm 3+, B=W 6+, Nb 5+, Ta 5+, Sb 5+, Ti 4+, Zr 4+, Sn 4+, 0.01≤x≤1,0≤y≤0.20,0≤z≤0.20.
Thorough mixing ball milling 4～5 hours is dried after levigate, is sieved, briquetting, then through 500 ℃～800 ℃ pre-burnings, and be incubated 5～8 hours, the block after the pre-burning is carried out secondary ball milling, granulation after the levigate oven dry, sieve through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand, became porcelain in 2～8 hours at 550 ℃～900 ℃ following sintering then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature of the present invention is owing to comprised Bi 2O 3, MO 3Deng low melting point oxide and with it as pivot, make that this medium ceramic material of sintering becomes possibility at low temperatures.The present invention is relevant with dielectric medium theoretical according to the crystal chemistry principle, with Bi 2O 3-MO 3The simple single-phase compound of binary system is the basis, by changing the pivot component and coming bismuth-based molybdenum-based microwave dielectric ceramic materials is carried out modification by the method for non-equivalence ionic replacement of equal value, under the prerequisite of not adding any sintering aid, can go out fine and close and new function pottery that good microwave dielectric property is arranged by sintering in low-down temperature range (550 ℃～900 ℃), this class pottery can be used as the radio frequency laminated ceramic capacitor, chip microwave dielectric resonator or wave filter, LTCC system (LTCC), ceramic antenna, mcm dielectric materials such as (MCM) uses.
Embodiment 1:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zNb z) O 3Preparation, x=0.125 wherein, z=0.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 750 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 800 ℃～900 ℃ air then, can obtain low temp, sintered bismuth base molybdenum base microwave medium ceramic material.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 800 ℃～900 ℃ air r=29.7 (6.24GHz), quality factor q=300, the temperature coefficient of resonance frequency TCF under the Qf=1868GHz, microwave～+ 19.7ppm/ ℃ (25 ℃～85 ℃).
Embodiment 2:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zNb z) O 3Preparation, x=0.25 wherein, z=0.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 600 ℃～640 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 600 ℃～640 ℃ air r～19 (7.56GHz), quality factor q～2886, the temperature coefficient of resonance frequency TCF under the Qf～21818GHz, microwave～-220ppm/ ℃ (25 ℃～85 ℃).
Embodiment 3:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zNb z) O 3Preparation, x=0.5 wherein, z=0.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 700 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 730 ℃～780 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 730 ℃～780 ℃ air r～30.6 (6.43GHz), quality factor q～2592, the temperature coefficient of resonance frequency TCF under the Qf～16678GHz, microwave～-114ppm/ ℃ (25 ℃～85 ℃).
Embodiment 4:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zNb z) O 3Preparation, x=2/3 wherein, z=0.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 600 ℃～650 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 620 ℃～645 ℃ air r～38 (5.05GHz), quality factor q～2050, the temperature coefficient of resonance frequency TCF under the Qf～10352GHz, microwave～+ 31ppm/ ℃ (25 ℃～85 ℃).
Embodiment 5:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zNb z) O 3Preparation, x=0.8 wherein, z=0.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 580 ℃～620 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 580 ℃～620 ℃ air r～16.8 (8.37GHz), quality factor q～1115, the temperature coefficient of resonance frequency TCF under the Qf～9331GHz, microwave～-160ppm/ ℃ (25 ℃～85 ℃).
Embodiment 6:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zNb z) O 3Preparation, x=2/3 wherein, z=0.10.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 640 ℃～670 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 640 ℃～670 ℃ air r～41 (4.81GHz), quality factor q～1960, the temperature coefficient of resonance frequency TCF under the Qf～9428GHz, microwave～+ 35ppm/ ℃ (25 ℃～85 ℃).
Embodiment 7:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zTa z) O 3Preparation, x=2/3 wherein, z=0.20.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 640 ℃～670 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 640 ℃～670 ℃ air r～31.1 (6.43GHz), quality factor q～1891, the temperature coefficient of resonance frequency TCF under the Qf～12171GHz, microwave～+ 13.1ppm/ ℃ (25 ℃～85 ℃).
Embodiment 8:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zSb z) O 3Preparation, x=2/3 wherein, 0≤z≤0.15.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 640 ℃～670 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 640 ℃～670 ℃ air r=28.2～35 (6.43～6.80GHz), quality factor q=1750～2011, the temperature coefficient of resonance frequency TCF=+29 under the Qf=11805～14201GHz, microwave～-10.2ppm/ ℃ (25 ℃～85 ℃).
Embodiment 9:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zTi z) O 3Preparation, x=2/3 wherein, z=0.2.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 640 ℃～670 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 640 ℃～670 ℃ air r=31.5 (6.33GHz), quality factor q=1952, the temperature coefficient of resonance frequency TCF=+12.8ppm/ under the Qf=12438GHz, microwave ℃ (25 ℃～85 ℃).
Embodiment 10:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zZr z) O 3Preparation, x=2/3 wherein, z=0.2.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 640 ℃～670 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 640 ℃～670 ℃ air r=29.2 (6.58GHz), quality factor q=1386, the temperature coefficient of resonance frequency TCF=-13.4ppm/ under the Qf=9061GHz, microwave ℃ (25 ℃～85 ℃).
Embodiment 11:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zSn z) O 3Preparation, x=2/3 wherein, 0.0≤z≤0.1.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 640 ℃～670 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 640 ℃～670 ℃ air r=28.5～34 (6.58～6.78GHz), quality factor q=1244～1860, the temperature coefficient of resonance frequency TCF=+29.5 under the Qf=9450～12807GHz, microwave～-11.4ppm/ ℃ (25 ℃～85 ℃).
Embodiment 12:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) Bi 2O 3-x (Mo 1-zW z) O 3Preparation, x=2/3 wherein, 0.0≤z≤0.2.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 650 ℃～750 ℃ air then, can obtain the bismuth-based molybdenum-based microwave dielectric ceramic materials of sintered at ultra low temperature.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 650 ℃～750 ℃ air r=37～39 (6.24～6.37GHz), quality factor q=1174～1950, the temperature coefficient of resonance frequency TCF=+30 under the Qf=7478～12168GHz, microwave～+ 24.5ppm/ ℃ (25 ℃～85 ℃).
Embodiment 13:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) (Bi 1-yLa y) 2O 3-xMoO 3Preparation, x=0.5 wherein, y=0.2.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 750 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 800 ℃～900 ℃ air then, can obtain low temp, sintered bismuth base molybdenum base microwave medium ceramic material.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 800 ℃～900 ℃ air r=23.9 (8.08GHz), quality factor q=3042, the temperature coefficient of resonance frequency TCF under the Qf=24581GHz, microwave～-102ppm/ ℃ (25 ℃～85 ℃).
Embodiment 14:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) (Bi 1-ySm y) 2O 3-xMoO 3Preparation, x=2/3 wherein, 0≤y≤0.2.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 600 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 640 ℃～670 ℃ air then, can obtain low temp, sintered bismuth base molybdenum base microwave medium ceramic material.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 640 ℃～670 ℃ air r=30～35 (6.70～6.99GHz), quality factor q=1810～1920, the temperature coefficient of resonance frequency TCF=+30 under the Qf=12400～13420GHz, microwave～-5.2ppm/ ℃ (25 ℃～85 ℃).
Embodiment 15:
Raw material MoO with purity assay 3And Bi 2O 3By prescription (1-x) (Bi 1-yNd y) 2O 3-xMoO 3Preparation, x=0.5 wherein, y=0.2.Preparation back thorough mixing ball milling 4 hours was dried then, is sieved, briquetting, through 750 ℃ of pre-burnings 4 hours, carried out secondary ball milling again 5 hours after then the bulk sample after the pre-burning being pulverized, levigate oven dry back granulation is sieved through 60 orders and 120 eye mesh screen bilayers, can obtain required porcelain.With porcelain compression moulding on demand (sheet or column), sintering 2～3h becomes porcelain under 840 ℃～900 ℃ air then, can obtain low temp, sintered bismuth base molybdenum base microwave medium ceramic material.
The performance of this group stupalith reaches following index:
Sinter porcelain into, the dielectric properties ε under the microwave in 840 ℃～900 ℃ air r=23.8 (8.26GHz), quality factor q=3401, the temperature coefficient of resonance frequency TCF under the Qf=28100GHz, microwave～-94.9ppm/ ℃ (25 ℃～85 ℃).
It is pointed out that according to technical scheme of the present invention, the foregoing description can also be enumerated many, prove,, all can reach purpose of the present invention in the scope that claims of the present invention proposed according to applicant's lot of experiment results.

Claims (2)

1. a bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature is characterized in that, this stupalith structure expression is: (1-x) [(Bi 1-yA y) 2O 3]-x[(Mo 1-zB z) O 3],
The preparation technology of this material carries out according to the following steps:
1) with chemical feedstocks Bi 2O 3, MoO 3, WO 3, Nb 2O 5, Ta 2O 5, Sb 2O 3, TiO 2, ZrO 2, SnO 2, La 2O 3, Nd 2O 3, Sm 2O 3By prescription general formula (1-x) [(Bi 1-yA y) 2O 3]-x[(Mo 1-zB z) O 3] preparation, wherein A=La 3+, Nd 3+Or Sm 3+, B=W 6+, Nb 5+, Ta 5+, Sb 5+, Ti 4+, Zr 4+Or Sn 4+, a kind of preparation in described A, the B ion is adopted in 0.01≤x＜1,0≤y≤0.20,0≤z≤0.20;
2) chemical feedstocks after will preparing mixes, and puts into the nylon jar, adds the alcohol ball milling 4～5 hours, and thorough mixing is levigate, takes out 100 ℃～200 ℃ of flash bakings, is pressed into bulk behind 200 orders that sieve;
3) Ya Zhi block is through 500 ℃～800 ℃ pre-burnings, and is incubated 4～8 hours, can obtain sample and burn piece;
4) sample is burnt piece and pulverize, and through 4～8 hours secondary ball milling, thorough mixing was levigate, oven dry 100 ℃～200 ℃, granulation, granulation obtains required porcelain powder after 60 orders and 120 eye mesh screen bilayers sieve;
5) with the compression moulding on demand of porcelain powder, became porcelain in 2～8 hours at 550 ℃～900 ℃ following sintering, can obtain bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature.
2. bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature according to claim 1 is characterized in that described microwave-medium ceramics is based on Bi 2O 3-MoO 3Single-phase compound in the binary system.
CN2008100183454A 2008-05-30 2008-05-30 Bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature and manufacture of the same Expired - Fee Related CN101318815B (en)

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