CN108863349A - A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof - Google Patents

A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof Download PDF

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CN108863349A
CN108863349A CN201810832289.1A CN201810832289A CN108863349A CN 108863349 A CN108863349 A CN 108863349A CN 201810832289 A CN201810832289 A CN 201810832289A CN 108863349 A CN108863349 A CN 108863349A
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temperature
tio
bafe
barium titanate
ceramic material
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蒲永平
李欣
彭鑫
张磊
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C04B2235/3255—Niobates or tantalates, e.g. silver niobate

Abstract

The present invention provides a kind of barium titanate-based lead-free height Jie temperature-stable ceramic materials, are made of matrix components and doping component, matrix components include BaTiO3And BaFe0.5Nb0.5O3, doping component Bi0.5Na0.5TiO3.The chemical expression of barium titanate-based lead-free height Jie temperature-stable ceramic material is (1-x)BaFe0.05Nb0.05Ti0.9O3‑xBi0.5Na0.5TiO3,x=0.04~0.1.The present invention also provides the preparation methods of this barium titanate-based lead-free height Jie temperature-stable ceramic material.Preparation process of the present invention is simple, and the cost of material is low, and ceramics obtained have preferable temperature stability, higher dielectric constant, is expected to become multilayer ceramic capacitor excellent important candidate material simultaneous technically and economically.

Description

A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof
Technical field
The present invention relates to ceramic dielectric material fields, and in particular to barium titanate-based lead-free height Jie's temperature-stable ceramics material Material and preparation method thereof.
Background technique
Ceramic capacitor is widely used in fields such as pulse power system, electric car, aerospace, defense techniques, is Extremely critical electronic component.With electronic component miniaturization in recent years, lightweight and the diversification of application field, to pottery The temperature stability of porcelain condenser proposes requirements at the higher level, in such as novel on-vehicle electronic control unit, aerospace equipment In the application of the Military Electronic Equipments such as engine system, high-power phased-array radar, it is desirable that the operating temperature of component in system The upper limit is increased to 175 DEG C even 200 DEG C or more.Barium phthalate base dielectric ceramics is due to dielectric constant with higher, lower Dielectric loss is the main environment-friendly materials for preparing MLCC.But the Curie temperature of barium titanate is at 125 DEG C or so, attached in Curie temperature Nearly change in dielectric constant is bigger, and temperature coefficient of capacitance is larger, it is therefore desirable to pass through the modes such as doping, process optimization, structure control Jie's temperature characteristics for improving barium titanate, to obtain the ideal ceramic material of temperature-stable.
BaFe0.5Nb0.5O3Ceramics have unique giant dielectric performance and good temperature and frequency stability, have very Important potential application.Its phase can be regulated and controled with other ions especially its A or B ions of Fe ion exchange in barium titanate Temperature, spontaneous polarization ability etc., make Curie temperature close to room temperature, and can substantially reduce its temperature dependency.
Bi0.5Na0.5TiO3It is a kind of A compound substituted ABO3 type perovskite ferroelectric body, there is high Curie temperature（Tc= 320℃）, relatively low sintering temperature also has the low temperature coefficient of capacitance as caused by " Diffuse phase transition ".In barium titanate matrix Bi is added0.5Na0.5TiO3It can make dielectric peak further widthization, and the Curie temperature of system is mobile to high temperature direction, raising makes Ceiling temperature makes it have high-temperature stability.
Summary of the invention
The purpose of the present invention is to provide a kind of barium titanate-based lead-free height Jie's temperature-stable ceramic material and its preparation sides Method, to overcome the problems of the above-mentioned prior art.Preparation process of the present invention is simple, and the cost of material is low, and ceramics obtained With preferable temperature stability, higher dielectric constant, low dielectric loss, it is possible to become multilayer ceramic capacitor in skill Art and economically simultaneous excellent important candidate material.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material, is made of, matrix components matrix components and doping component For BaTiO3、BaFe0.5Nb0.5O3, doping component Bi0.5Na0.5TiO3, barium titanate-based lead-free height Jie's temperature-stable pottery The chemical expression of ceramic material is (1-x) BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3,x=0.04~0.1。
Above-mentioned barium titanate-based lead-free height Jie temperature-stable ceramic material preparation method, includes the following steps：
Step 1：According to the chemical expression (1- of barium titanate-based lead-free height Jie's temperature-stable ceramic materialx) BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3（x=0.04~0.1）The stoichiometric ratio of middle metallic atom weighs matrix group Divide raw material BaCO3、TiO2、Fe2O3And Nb2O5With doping component raw material Bi2O3、NaCO3And TiO2It is spare；
Step 2：By weighed matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5Ball milling, baking in deionized water After dry, briquetting, 2 ~ 3 hours are kept the temperature in 1100 DEG C, obtains the BaFe of pure phase0.05Nb0.05Ti0.9O3Powder, it is spare；
Step 3：By weighed doping component raw material Bi2O3、NaCO3And TiO2Ball milling, drying, pressure in deionized water After block, 2 ~ 3 hours are kept the temperature in 800 ~ 850 DEG C, obtains the Bi of pure phase0.5Na0.5TiO3Powder, it is spare；
Step 4：The BaFe that step 2 is obtained0.05Nb0.05Ti0.9O3The Bi that powder and step 3 obtain0.5Na0.5TiO3Powder According to (1-x)BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3It is put into mold and is pressed into disk, whereinx=0.04 ~ 0.1, it will Sample is made under the pressure of 200MPa in disk；
Step 5：Sample obtained by step 4 is carried out once sintered；
Step 6：In polishing, cleaning step four after once sintered good sample, silver electrode slurry is uniformly coated in sample tow sides Material carries out double sintering, obtains (1-x)BaFe0.05Nb0.05Ti0.9O3-x Bi0.5Na0.5TiO3Ceramics.
According to the above scheme, the Ball-milling Time is 4h-8h.
According to the above scheme, pre-burning condition described in step 2 is：200 DEG C are warming up to 2 DEG C/min, with 3 DEG C/min liter When temperature is to 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, 1100 DEG C is warming up to 2 DEG C/min and keeps the temperature 2 ~ 3 hours.
According to the above scheme, pre-burning condition described in step 3 is：200 DEG C are warming up to 2 DEG C/min, with 3 DEG C/min liter When temperature is to 500 DEG C, 800 ~ 850 DEG C are warming up to 5 DEG C/min and keeps the temperature 2 ~ 3 hours.
According to the above scheme, by (1- described in step 4x)BaFe0.05Nb0.05Ti0.9O3-xBi0.5Na0.5TiO3Powder is put The mold for entering diameter 12mm is pressed into disk taking-up, then disk is put into after gum cover vacuumizes, and carries out under the pressure of 200MPa Isostatic cool pressing, pressure maintaining 5 minutes.
According to the above scheme, once sintered condition is in step 5：200 DEG C are warming up to 2 DEG C/min, with 3 DEG C/min heating When to 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, keeps the temperature 2 hours when being warming up to 1200 ~ 1230 DEG C with 2 DEG C/min, later, with 2 DEG C/min is cooled to 1000 DEG C, after being cooled to 500 DEG C with 5 DEG C/min, cools to room temperature with the furnace.
According to the above scheme, the condition of double sintering is in step 6：Temperature is 600 ~ 620 DEG C, and the time is 20 ~ 30 minutes.
Compared with prior art, the invention has the following beneficial technical effects：
High Jie's temperature-stable ceramics of the invention, dielectric constant with higher（xDielectric constant is 3496 when=0.04,x= Dielectric constant is 2962 when 0.06,xDielectric constant is 2584 when=0.08,xDielectric constant is 2335 when=0.1）, good temperature is steady It is qualitative, meet X8R condition, it is possible to as temperature-stable multilayer ceramic capacitor excellent important time simultaneous technically and economically Material selection.
The present invention is by BaFe0.5Nb0.5O3And Bi0.5Na0.5TiO3It is doped to BaTiO3The inside, Bi3+And Na+Replace BaTiO3The position A, Fe3+And Nb5+Replace BaTiO3The position B, pass through doping occur relaxation phenomena, realize BaTiO3Curie peak Widthization, to reach the requirement of X8R.The method of the present invention is prepared using conventional solid-state method, technical maturity, is suitble to industry metaplasia It produces, using BaFe0.5Nb0.5O3It is doped, passes through Fe3+And Nb5+Compound action, have adjusted the residence of barium phthalate base dielectric material In temperature, using Bi0.5Na0.5TiO3Doping reduces the sintering temperature of ceramics, realizes the Diffuse phase transition of barium titanate ceramics, mention The ceiling temperature that height uses, makes it have high-temperature stability.The temperature-stable ceramic material of the method for the present invention preparation is not only made Standby simple process, the cost of material is low, and dielectric constant with higher, temperature stability are good, to substitution lead base ceramic material As temperature-stable multilayer ceramic capacitor excellent important candidate material simultaneous technically and economically.
Detailed description of the invention
Fig. 1 is the phase composition figure of sample made from embodiment 1-4；
Fig. 2 is the micro-structure diagram of sample made from embodiment 1-4；
Fig. 3 is the characteristic curve of the dielectric constant with temperature variation of sample made from embodiment 1；
Fig. 4 is the characteristic curve of the dielectric constant with temperature variation of sample made from embodiment 2；
Fig. 5 is the characteristic curve of the dielectric constant with temperature variation of sample made from embodiment 3；
Fig. 6 is the characteristic curve of the dielectric constant with temperature variation of sample made from embodiment 4；
Fig. 7 is that the temperature coefficient of capacitance of sample made from embodiment 1-4 varies with temperature figure；
Fig. 8 is the ln of sample made from embodiment 1-4f~T m Curve.
Specific embodiment
In order to be best understood from the present invention, embodiments of the present invention are described in further detail below：
A kind of preparation method of barium titanate-based lead-free height Jie temperature-stable ceramic material, includes the following steps：
Step 1：According to the chemical expression (1- of barium titanate-based lead-free height Jie's temperature-stable ceramic materialx) BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3（x=0.04~0.1）The stoichiometric ratio of middle metallic atom weighs matrix group Divide raw material BaCO3、TiO2、Fe2O3And Nb2O5With doping component raw material Bi2O3、NaCO3And TiO2It is spare；
Step 2：By weighed matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5Ball milling, baking in deionized water After dry, briquetting, 2 ~ 3 hours are kept the temperature in 1100 DEG C, obtains the BaFe of pure phase0.05Nb0.05Ti0.9O3Powder, it is spare；
Step 3：By weighed doping component raw material Bi2O3、NaCO3And TiO2Ball milling, drying, pressure in deionized water After block, 2 ~ 3 hours are kept the temperature in 800 ~ 850 DEG C, obtains the Bi of pure phase0.5Na0.5TiO3Powder, it is spare；
Step 4：The BaFe that step 2 is obtained0.05Nb0.05Ti0.9O3The Bi that powder and step 3 obtain0.5Na0.5TiO3Powder According to (1-x)BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3It is put into mold and is pressed into disk, whereinx=0.04 ~ 0.1, it will Sample is made under the pressure of 200MPa in disk；
Step 5：Sample obtained by step 4 is carried out once sintered；
Step 6：In polishing, cleaning step four after once sintered good sample, silver electrode slurry is uniformly coated in sample tow sides Material carries out double sintering, obtains (1-x)BaFe0.05Nb0.05Ti0.9O3-x Bi0.5Na0.5TiO3Ceramics.
Below with reference to embodiment, the invention will be described in further detail：
Embodiment 1
Step 1：According to molar ratio 1:0.9:0.025:0.025 weighs matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5? It is 1 according to mass ratio by powder, zirconium oxide ballstone and deionized water in deionized water:5:2 mixing after carry out ball milling, drying, After briquetting, 2 ~ 3 hours are kept the temperature in 1100 DEG C, obtains the BaFe of pure phase0.05Nb0.05Ti0.9O3Powder, it is spare；
Step 2：According to molar ratio 0.25:0.5:1 weighs doping component raw material Bi2O3、NaCO3、TiO2In deionized water will Powder, zirconium oxide ballstone and deionized water are 1 according to mass ratio:5:Ball milling, drying are carried out after 2 mixing, after briquetting, in 800 ~ 850 DEG C keep the temperature 2 ~ 3 hours, obtain the Bi of pure phase0.5Na0.5TiO3Powder, it is spare；
Step 3：The BaFe that step 1 is obtained0.05Nb0.05Ti0.9O3The Bi that powder and step 2 obtain0.5Na0.5TiO3Powder According to molar ratio 0.96:0.04 in deionized water by powder, zirconium oxide ballstone and deionized water, is 1 according to mass ratio:5:2 After carrying out ball milling, drying after mixing, it is put into mold and is pressed into disk, sample is made under the pressure of 200MPa in disk；
Step 4：Sample obtained by step 4 is placed in using zirconium oxide to carry out in high temperature box furnace in the aluminium oxide saggar of backing plate It is once sintered：200 DEG C are warming up to 2 DEG C/min, when being warming up to 500 DEG C with 3 DEG C/min, is warming up to 1000 DEG C with 5 DEG C/min, with 2 DEG C/min keeps the temperature 2 hours when being warming up to 1200 ~ 1230 DEG C, later, is cooled to 1000 DEG C with 2 DEG C/min, with 5 DEG C/min cooling To after 500 DEG C, room temperature is cooled to the furnace.
Step 5：In polishing, cleaning step four after once sintered good sample, silver-colored electricity is uniformly coated in sample tow sides Pole slurry, in 600 DEG C double sintering 20 minutes, obtain blank sample.
Embodiment 2
Step 1：According to molar ratio 1:0.9:0.025:0.025 weighs matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5? It is 1 according to mass ratio by powder, zirconium oxide ballstone and deionized water in deionized water:5:2 mixing after carry out ball milling, drying, After briquetting, 2 ~ 3 hours are kept the temperature in 1100 DEG C, obtains the BaFe of pure phase0.05Nb0.05Ti0.9O3Powder, it is spare；
Step 2：According to molar ratio 0.25:0.5:1 weighs doping component raw material Bi2O3、NaCO3、TiO2In deionized water will Powder, zirconium oxide ballstone and deionized water are 1 according to mass ratio:5:Ball milling, drying are carried out after 2 mixing, after briquetting, in 800 ~ 850 DEG C keep the temperature 2 ~ 3 hours, obtain the Bi of pure phase0.5Na0.5TiO3Powder, it is spare；
Step 3：The BaFe that step 1 is obtained0.05Nb0.05Ti0.9O3The Bi that powder and step 2 obtain0.5Na0.5TiO3Powder According to molar ratio 0.94:0.06 in deionized water by powder, zirconium oxide ballstone and deionized water, is 1 according to mass ratio:5:2 After carrying out ball milling, drying after mixing, it is put into mold and is pressed into disk, sample is made under the pressure of 200MPa in disk；
Step 4：Sample obtained by step 4 is placed in using zirconium oxide to carry out in high temperature box furnace in the aluminium oxide saggar of backing plate It is once sintered：200 DEG C are warming up to 2 DEG C/min, when being warming up to 500 DEG C with 3 DEG C/min, is warming up to 1000 DEG C with 5 DEG C/min, with 2 DEG C/min keeps the temperature 2 hours when being warming up to 1200 ~ 1230 DEG C, later, is cooled to 1000 DEG C with 2 DEG C/min, with 5 DEG C/min cooling To after 500 DEG C, room temperature is cooled to the furnace.
Step 5：In polishing, cleaning step four after once sintered good sample, silver-colored electricity is uniformly coated in sample tow sides Pole slurry, in 600 DEG C double sintering 20 minutes, obtain blank sample.
Embodiment 3
Step 1：According to molar ratio 1:0.9:0.025:0.025 weighs matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5? It is 1 according to mass ratio by powder, zirconium oxide ballstone and deionized water in deionized water:5:2 mixing after carry out ball milling, drying, After briquetting, 2 ~ 3 hours are kept the temperature in 1100 DEG C, obtains the BaFe of pure phase0.05Nb0.05Ti0.9O3Powder, it is spare；
Step 2：According to molar ratio 0.25:0.5:1 weighs doping component raw material Bi2O3、NaCO3、TiO2In deionized water will Powder, zirconium oxide ballstone and deionized water are 1 according to mass ratio:5:Ball milling, drying are carried out after 2 mixing, after briquetting, in 800 ~ 850 DEG C keep the temperature 2 ~ 3 hours, obtain the Bi of pure phase0.5Na0.5TiO3Powder, it is spare；
Step 3：The BaFe that step 1 is obtained0.05Nb0.05Ti0.9O3The Bi that powder and step 2 obtain0.5Na0.5TiO3Powder According to molar ratio 0.92:0.08 in deionized water by powder, zirconium oxide ballstone and deionized water, is 1 according to mass ratio:5:2 After carrying out ball milling, drying after mixing, it is put into mold and is pressed into disk, sample is made under the pressure of 200MPa in disk；
Step 4：Sample obtained by step 4 is placed in using zirconium oxide to carry out in high temperature box furnace in the aluminium oxide saggar of backing plate It is once sintered：200 DEG C are warming up to 2 DEG C/min, when being warming up to 500 DEG C with 3 DEG C/min, is warming up to 1000 DEG C with 5 DEG C/min, with 2 DEG C/min keeps the temperature 2 hours when being warming up to 1200 ~ 1230 DEG C, later, is cooled to 1000 DEG C with 2 DEG C/min, with 5 DEG C/min cooling To after 500 DEG C, room temperature is cooled to the furnace.
Step 5：In polishing, cleaning step four after once sintered good sample, silver-colored electricity is uniformly coated in sample tow sides Pole slurry, in 600 DEG C double sintering 20 minutes, obtain blank sample.
Embodiment 4
Step 1：According to molar ratio 1:0.9:0.025:0.025 weighs matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5? It is 1 according to mass ratio by powder, zirconium oxide ballstone and deionized water in deionized water:5:2 mixing after carry out ball milling, drying, After briquetting, 2 ~ 3 hours are kept the temperature in 1100 DEG C, obtains the BaFe of pure phase0.05Nb0.05Ti0.9O3Powder, it is spare；
Step 2：According to molar ratio 0.25:0.5:1 weighs doping component raw material Bi2O3、NaCO3、TiO2In deionized water will Powder, zirconium oxide ballstone and deionized water are 1 according to mass ratio:5:Ball milling, drying are carried out after 2 mixing, after briquetting, in 800 ~ 850 DEG C keep the temperature 2 ~ 3 hours, obtain the Bi of pure phase0.5Na0.5TiO3Powder, it is spare；
Step 3：The BaFe that step 1 is obtained0.05Nb0.05Ti0.9O3The Bi that powder and step 2 obtain0.5Na0.5TiO3Powder According to molar ratio 0.9:0.1 in deionized water by powder, zirconium oxide ballstone and deionized water, is 1 according to mass ratio:5:2 is mixed After carrying out ball milling, drying after conjunction, it is put into mold and is pressed into disk, sample is made under the pressure of 200MPa in disk；
Step 4：Sample obtained by step 4 is placed in using zirconium oxide to carry out in high temperature box furnace in the aluminium oxide saggar of backing plate It is once sintered：200 DEG C are warming up to 2 DEG C/min, when being warming up to 500 DEG C with 3 DEG C/min, is warming up to 1000 DEG C with 5 DEG C/min, with 2 DEG C/min keeps the temperature 2 hours when being warming up to 1200 ~ 1230 DEG C, later, is cooled to 1000 DEG C with 2 DEG C/min, with 5 DEG C/min cooling To after 500 DEG C, room temperature is cooled to the furnace.
Step 5：In polishing, cleaning step four after once sintered good sample, silver-colored electricity is uniformly coated in sample tow sides Pole slurry, in 600 DEG C double sintering 20 minutes, obtain blank sample.
Embodiment 5
XRD, SEM test are carried out to the sample that embodiment 1 ~ 4 obtains, obtain Fig. 1, Fig. 2 result；According to EIA standardized test specimen Dielectric constant temperature characterisitic, obtain Fig. 3 ~ 7 as a result, obtaining Fig. 8 according to EIA standard analysis.
As shown in Figures 1 to 7, dielectric properties test shows：Ceramic medium material prepared by embodiment 1-4 meets temperature Stable type ceramic material is spent, specific parameters are as shown in table 1.Table 1 is (1-x)BaFe0.05Nb0.05Ti0.9O3-xBi0.5Na0.5TiO3（x=0.04~0.1）The T of ceramicsm、 Tc、 Tcw、△Tm, lower limit temperature, ceiling temperature（Unit：℃）And εm。
In table, TmIt is dielectric constant maximum value corresponding temperature；TcIt is Curie-point temperature；TcwIt is that change in dielectric constant starts to follow residence In-weiss law corresponding to temperature；△Tm=Tcw-Tm；εmIt is dielectric constant maximum value.
By adulterating BaFe0.5Nb0.5O3And Bi0.5Na0.5TiO3, with BaTiO3Solid solution is formed, makes Curie peak to low temperature side To movement, and reduce sintering temperature；With Bi0.5Na0.5TiO3The increase of content can promote ceramic densifying.The present invention Using BaFe0.5Nb0.5O3It is doped, passes through Fe3+And Nb5+Compound action, using peak drifting effect have adjusted barium phthalate base be situated between The Curie temperature of material, using Bi0.5Na0.5TiO3Doping, causes undulating composition phase transformation, by broadening effect, realizes metatitanic acid The Diffuse phase transition of barium-based ceramic, so that the warm curve that makes to be situated between becomes more flat.The temperature-stable ceramics of the method for the present invention preparation Not only preparation process is simple for material, and the cost of material is low, and dielectric constant with higher, temperature stability are good, to substitution lead Base ceramic material becomes temperature-stable multilayer ceramic capacitor excellent important candidate material simultaneous technically and economically.

Claims (10)

1. a kind of barium titanate-based lead-free height Jie temperature-stable ceramic material, it is characterised in that：By matrix components and doping component Composition, matrix components include BaTiO3And BaFe0.5Nb0.5O3, doping component Bi0.5Na0.5TiO3。
2. a kind of barium titanate-based lead-free height Jie temperature-stable ceramic material according to claim 1, it is characterised in that：Institute The chemical expression for stating barium titanate-based lead-free height Jie's temperature-stable ceramic material is (1-x) BaFe0.05Nb0.05Ti0.9O3-xBi0.5Na0.5TiO3,x=0.04~0.1。
3. a kind of preparation method of barium titanate-based lead-free height Jie temperature-stable ceramic material of any of claims 1 or 2, special Sign is, includes the following steps：
By BaFe0.05Nb0.05Ti0.9O3Powder and Bi0.5Na0.5TiO3Powder is according to chemical formula (1-x) BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3、x=0.04 ~ 0.1 measures and is uniformly mixed, and is put into mold compression moulding, Then sample is made under the pressure of 200MPa；Sample is once sintered in 1200 ~ 1230 DEG C of progress；It is equal in sample tow sides Even coating silver electrode paste obtains (1- in 600 ~ 620 DEG C of progress double sinteringsx)BaFe0.05Nb0.05Ti0.9O3-xBi0.5Na0.5TiO3Ceramics.
4. a kind of preparation method of barium titanate-based lead-free height Jie temperature-stable ceramic material according to claim 3, It is characterized in that, the BaFe0.05Nb0.05Ti0.9O3It is obtained by method comprising the following steps：
According to BaFe0.05Nb0.05Ti0.9O3The stoichiometric ratio of middle metallic atom weighs BaCO3、TiO2 、Fe2O3And Nb2O5, In deionized water after ball milling, drying, briquetting, 2 ~ 3 hours are kept the temperature in 1100 DEG C, obtains pure phase BaFe0.05Nb0.05Ti0.9O3Powder.
5. a kind of preparation method of barium titanate-based lead-free height Jie temperature-stable ceramic material according to claim 3, It is characterized in that, the Bi0.5Na0.5TiO3It is obtained by method comprising the following steps：
According to Bi0.5Na0.5TiO3The stoichiometric ratio of middle metallic atom weighs Bi2O3、NaCO3And TiO2, ball in deionized water Mill is uniform, dries, after briquetting, keeps the temperature 2 ~ 3 hours in 800 ~ 850 DEG C, obtains the Bi of pure phase0.5Na0.5TiO3Powder.
6. according to a kind of described in any item preparations of barium titanate-based lead-free height Jie temperature-stable ceramic material of claim 3 ~ 5 Method, which is characterized in that specific steps include：
Step 1：According to the chemical expression (1- of barium titanate-based lead-free height Jie's temperature-stable ceramic materialx) BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3（x=0.04~0.1）The stoichiometric ratio of middle metallic atom weighs matrix group Divide raw material BaCO3、TiO2 、Fe2O3And Nb2O5With doping component raw material Bi2O3、NaCO3And TiO2It is spare；
Step 2：By weighed matrix components raw material BaCO3、TiO2 、Fe2O3、Nb2O5Ball milling, baking in deionized water After dry, briquetting, 2 ~ 3 hours are kept the temperature in 1100 DEG C, obtains the BaFe of pure phase0.05Nb0.05Ti0.9O3Powder, it is spare；Sintering condition For：200 DEG C are warming up to 2 DEG C/min, is warming up to 500 DEG C with 3 DEG C/min, 1000 DEG C are warming up to 5 DEG C/min, with 2 DEG C/min It is warming up to 1100 DEG C and keeps the temperature 2 ~ 3 hours；
Step 3：By weighed doping component raw material Bi2O3、NaCO3And TiO2Ball milling, drying, pressure in deionized water After block, 2 ~ 3 hours are kept the temperature in 800 ~ 850 DEG C, obtains the Bi of pure phase0.5Na0.5TiO3Powder, it is spare；Sintering condition is：With 2 DEG C/ Min is warming up to 200 DEG C, when being warming up to 500 DEG C with 3 DEG C/min, is warming up to 800 ~ 850 DEG C with 5 DEG C/min and keeps the temperature 2 ~ 3 hours；
Step 4：The BaFe that step 2 is obtained0.05Nb0.05Ti0.9O3The Bi that powder and step 3 obtain0.5Na0.5TiO3Powder is pressed According to (1-x)BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3It is put into mold and is pressed into disk, whereinx=0.04 ~ 0.1, it will Sample is made under the pressure of 200MPa in disk；
Step 5：Sample obtained by step 4 is carried out once sintered；
Step 6：In polishing, cleaning step four after once sintered good sample, silver electrode slurry is uniformly coated in sample tow sides Material carries out double sintering, obtains (1-x)BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3Ceramics.
7. a kind of preparation method of barium titanate-based lead-free height Jie temperature-stable ceramic material according to claim 6, It is characterized in that the Ball-milling Time is 4h-8h.
8. a kind of preparation method of barium titanate-based lead-free height Jie temperature-stable ceramic material according to claim 6, It is characterized in that (1- described in step 4x)BaFe0.05Nb0.05Ti0.9O3- xBi0.5Na0.5TiO3Powder is put into diameter 12mm Mold be pressed into disk taking-up, then disk is put into after gum cover vacuumizes, isostatic cool pressing is carried out under the pressure of 200MPa, is protected Pressure 5 minutes.
9. a kind of preparation method of barium titanate-based lead-free height Jie temperature-stable ceramic material according to claim 6, It is characterized in that in step 5 that once sintered condition is：200 DEG C are warming up to 2 DEG C/min, when being warming up to 500 DEG C with 3 DEG C/min, with 5 DEG C/min is warming up to 1000 DEG C, keeps the temperature 2 hours when being warming up to 1200 ~ 1230 DEG C with 2 DEG C/min, later, with 2 DEG C/min cooling To 1000 DEG C, after being cooled to 500 DEG C with 5 DEG C/min, room temperature is cooled to the furnace.
10. a kind of preparation method of barium titanate-based lead-free height Jie temperature-stable ceramic material according to claim 6, The condition for being characterized in that double sintering in step 6 is：Temperature is 600 ~ 620 DEG C, and the time is 20 ~ 30 minutes.
CN201810832289.1A 2018-07-26 2018-07-26 A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof Pending CN108863349A (en)

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Application publication date: 20181123