CN108863348A - A kind of dielectric ceramic material and preparation method thereof of ultra-wide temperature stability - Google Patents

A kind of dielectric ceramic material and preparation method thereof of ultra-wide temperature stability Download PDF

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CN108863348A
CN108863348A CN201810832257.1A CN201810832257A CN108863348A CN 108863348 A CN108863348 A CN 108863348A CN 201810832257 A CN201810832257 A CN 201810832257A CN 108863348 A CN108863348 A CN 108863348A
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tio
powder
bimg
temperature
ultra
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蒲永平
李欣
张磊
彭鑫
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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
    • 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
    • C04B2235/3251—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 dielectric ceramic materials of ultra-wide temperature stability, are made of matrix components and doping component, and matrix components include BaTiO3、BaFe0.5Nb0.5O3And Bi0.5Na0.5TiO3, doping component BiMg2/3Nb1/3O3.Chemical expression is (1-x)(0.94BaFe0.05Nb0.05Ti0.9O3‑0.06Bi0.5Na0.5TiO3)‑xBiMg2/3Nb1/3O3,x=0.05~0.2.The present invention also provides the preparation methods of the dielectric ceramic material of this ultra-wide temperature stability.Preparation process of the present invention is simple, and the cost of material is low, and ceramics obtained have the temperature stability of ultra-wide, is expected to become multilayer ceramic capacitor excellent important candidate material simultaneous technically and economically.

Description

A kind of dielectric ceramic material and preparation method thereof of ultra-wide temperature stability
Technical field
The present invention relates to ceramic dielectric material fields, and in particular to a kind of dielectric ceramic material of ultra-wide temperature stability And preparation method thereof.
Background technique
With electronic component miniaturization in recent years, lightweight and the diversification of application field, to the temperature of ceramic capacitor Stability proposes requirements at the higher level, in such as engine system of novel on-vehicle electronic control unit, aerospace equipment, greatly In the application of the Military Electronic Equipments such as power phased-array radar, it is desirable that the operating temperature upper limit of component is increased to 175 in system DEG C even 200 DEG C or more.Barium phthalate base dielectric ceramics is system due to dielectric constant with higher, lower dielectric loss The main environment-friendly materials of standby MLCC.But the Curie temperature of barium titanate is at 125 DEG C or so, near Curie temperature change in dielectric constant Bigger, temperature coefficient of capacitance is larger, therefore can be solved by two schemes：1, Curie temperature is adjusted, Curie temperature is moved To using other than warm area；2, force down or broaden Curie peak.
The present invention passes through doping BaFe0.5Nb0.5O3, make Curie temperature close to room temperature, reduce the temperature-independent of dielectric properties Property；By adulterating Bi0.5Na0.5TiO3, since " Diffuse phase transition " makes dielectric peak broadening, and by the Curie temperature of system to high temperature Direction is mobile, improves the ceiling temperature used, makes it have high-temperature stability；By adulterating material not the ferroelectric BiMg2/3Nb1/ 3O3, Curie peak can be further forced down, so that its dielectric constant curve is become flat within the temperature range of ultra-wide, to be surpassed The ideal MLCC ceramic material of temperature-stable.
Summary of the invention
The purpose of the present invention is to provide a kind of dielectric ceramic material and preparation method thereof of ultra-wide temperature stability, with gram Take 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 have ultra-wide Temperature stability, it is possible to technically and economically and excellent important candidate material as multilayer ceramic capacitor.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of dielectric ceramic material of ultra-wide temperature stability, is made of, matrix components are matrix components and doping component BaTiO3、BaFe0.5Nb0.5O3、Bi0.5Na0.5TiO3, doping component BiMg2/3Nb1/3O3, Jie of the ultra-wide temperature stability The chemical expression of electroceramics material is (1-x) (0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3,x=0.05~0.2。
The dielectric ceramic material preparation method of above-mentioned ultra-wide temperature stability, includes the following steps：
Step 1：According to the chemical expression (1- of the dielectric ceramic material of ultra-wide temperature stabilityx) (0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3（x=0.05~0.2）Middle metallic atom Stoichiometric ratio weighs matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5、 Bi2O3And NaCO3And doping component raw material Bi2O3, MgO and Nb2O5, 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 matrix components raw material Bi2O3、NaCO3、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：By weighed doping component raw material Bi2O3、MgO、Nb2O5Ball milling, drying, briquetting in deionized water Afterwards, 2 ~ 3 hours are kept the temperature in 800 DEG C, obtains BiMg2/3Nb1/3O3Powder, it is spare；
Step 5：The powder that step 2 to step 4 is obtained is according to (1-x) (0.94BaFe0.05Nb0.05Ti0.9O3- 0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3In deionized water after ball milling, drying, it is put into mold and is pressed into disk, Whereinx=0.05 ~ 0.2, sample is made under the pressure of 200MPa in disk；
Step 6：Sample obtained by step 5 is carried out once sintered；
Step 7：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) (0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/ 3Nb1/3O3Ceramics sample.
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, pre-burning condition described in step 4 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 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 5x) (0.94BaFe0.05Nb0.05Ti0.9O3- 0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3The mold that powder is put into diameter 12mm is pressed into disk taking-up, then disk is put Enter after gum cover vacuumizes, carries out isostatic cool pressing under the pressure of 200MPa, pressure maintaining 5 minutes.
According to the above scheme, once sintered condition is in step 6：200 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 7：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：
The dielectric ceramic material of ultra-wide temperature stability of the invention has excellent temperature stability, in super-wide temperature range Interior satisfaction（xMeet X9R condition when=0.05,xAt -40 DEG C -450 DEG C when=0.2 Super-wide temperature range in meet。
The present invention is by BaFe0.5Nb0.5O3、Bi0.5Na0.5TiO3、BiMg2/3Nb1/3O3It is doped to BaTiO3The inside, Bi3+With Na+Replace BaTiO3The position A, Fe3+And Nb5+Replace BaTiO3The position B, pass through doping occur relaxation phenomena, realize BaTiO3's The widthization at Curie peak, by adulterating material not the ferroelectric BiMg2/3Nb1/3O3Generate micro- different with integral macroscopic concentration of microscopic concentration Area forms different microcell with slightly different Curie temperature, causes undulating composition phase transformation, macroscopically generates the phase transformation of widthization Warm area, to obtain the ideal MLCC ceramic material of ultra-wide temperature stability.The method of the present invention uses conventional solid Method preparation, technical maturity are suitble to industrialization production, by adulterating BaFe0.5Nb0.5O3, Curie temperature is adjusted, Curie temperature is moved Move near room temperature；By adulterating Bi0.5Na0.5TiO3, cause Diffuse phase transition, so that dielectric peak broadening, improves the upper limit used Temperature；By adulterating material not the ferroelectric BiMg2/3Nb1/3O3, Curie peak is further forced down, makes its dielectric constant curve in ultra-wide Become flat in temperature range, to obtain the ideal MLCC ceramic material of ultra-wide temperature stability.Side of the present invention Not only preparation process is simple for the temperature-stable ceramic material of method preparation, and the cost of material is low, and dielectric constant with higher, Temperature stability is good, and it is technically and economically and excellent to become temperature-stable multilayer ceramic capacitor to substitution lead base ceramic material Important candidate material.
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 the dielectric ceramic material of ultra-wide temperature stability, includes the following steps：
Step 1：According to the chemical expression (1- of the dielectric ceramic material of ultra-wide temperature stabilityx) (0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3（x=0.05~0.2）Middle metallic atom Stoichiometric ratio weighs matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5、 Bi2O3And NaCO3And doping component raw material Bi2O3, MgO and Nb2O5, 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 matrix components raw material Bi2O3、NaCO3、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：By weighed doping component raw material Bi2O3、MgO、Nb2O5Ball milling, drying, briquetting in deionized water Afterwards, 2 ~ 3 hours are kept the temperature in 800 DEG C, obtains BiMg2/3Nb1/3O3Powder, it is spare；
Step 5：The powder that step 2 to step 4 is obtained is according to (1-x) (0.94BaFe0.05Nb0.05Ti0.9O3- 0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3In deionized water after ball milling, drying, it is put into mold and is pressed into disk, Whereinx=0.05 ~ 0.2, sample is made under the pressure of 200MPa in disk；
Step 6：Sample obtained by step 5 is carried out once sintered；
Step 7：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) (0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/ 3Nb1/3O3Ceramics sample.
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 matrix components 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：According to molar ratio 3:4:1 weighs doping component raw material Bi2O3、MgO、Nb2O5In deionized water by powder, oxygen Change zirconium ballstone and deionized water, is 1 according to mass ratio:5:After carrying out ball milling, drying, briquetting after 2 mixing, protected in 800 ~ 850 DEG C Temperature 2 ~ 3 hours, obtains the BiMg of pure phase2/3Nb1/3O3Powder, it is spare；
Step 4：The powder BaFe that step 1 to step 3 is obtained0.05Nb0.05Ti0.9O3、Bi0.5Na0.5TiO3、BiMg2/ 3Nb1/3O3According to molar ratio 0.893:0.057:0.05 in deionized water after ball milling, drying, is put into mold and is pressed into circle Sample is made under the pressure of 200MPa in disk by piece；
Step 5：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 6：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 matrix components 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：According to molar ratio 3:4:1 weighs doping component raw material Bi2O3、MgO、Nb2O5In deionized water by powder, oxygen Change zirconium ballstone and deionized water, is 1 according to mass ratio:5:After carrying out ball milling, drying, briquetting after 2 mixing, protected in 800 ~ 850 DEG C Temperature 2 ~ 3 hours, obtains the BiMg of pure phase2/3Nb1/3O3Powder, it is spare；
Step 4：The powder BaFe that step 1 to step 3 is obtained0.05Nb0.05Ti0.9O3、Bi0.5Na0.5TiO3、BiMg2/ 3Nb1/3O3According to molar ratio 0.846:0.054:0.1 in deionized water after ball milling, drying, is put into mold and is pressed into circle Sample is made under the pressure of 200MPa in disk by piece；
Step 5：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 6：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 matrix components 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：According to molar ratio 3:4:1 weighs doping component raw material Bi2O3、MgO、Nb2O5In deionized water by powder, oxygen Change zirconium ballstone and deionized water, is 1 according to mass ratio:5:After carrying out ball milling, drying, briquetting after 2 mixing, protected in 800 ~ 850 DEG C Temperature 2 ~ 3 hours, obtains the BiMg of pure phase2/3Nb1/3O3Powder, it is spare；
Step 4：The powder BaFe that step 1 to step 3 is obtained0.05Nb0.05Ti0.9O3、Bi0.5Na0.5TiO3、BiMg2/ 3Nb1/3O3According to molar ratio 0.799:0.051:0.15 in deionized water after ball milling, drying, is put into mold and is pressed into circle Sample is made under the pressure of 200MPa in disk by piece；
Step 5：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 6：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 matrix components 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：According to molar ratio 3:4:1 weighs doping component raw material Bi2O3、MgO、Nb2O5In deionized water by powder, oxygen Change zirconium ballstone and deionized water, is 1 according to mass ratio:5:After carrying out ball milling, drying, briquetting after 2 mixing, protected in 800 ~ 850 DEG C Temperature 2 ~ 3 hours, obtains the BiMg of pure phase2/3Nb1/3O3Powder, it is spare；
Step 4：The powder BaFe that step 1 to step 3 is obtained0.05Nb0.05Ti0.9O3、Bi0.5Na0.5TiO3、BiMg2/ 3Nb1/3O3According to molar ratio 0.752:0.048:0.2 in deionized water after ball milling, drying, is put into mold and is pressed into circle Sample is made under the pressure of 200MPa in disk by piece；
Step 5：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 6：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)(0.94BaFe0.05Nb0.05Ti0.9O3- 0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3（x=0.05~0.2）The T of ceramicsm、 Tc、 Tcw、△Tm, lower limit temperature, the upper limit Temperature（C/C25℃≤±15%）（Unit：℃）And εm。
In table, TmIt is the corresponding temperature of dielectric constant maximum value；TcIt is Curie-point temperature；TcwIt is that change in dielectric constant starts to follow Temperature corresponding to Curie-Weiss law；△Tm=Tcw-Tm；εmIt is dielectric constant maximum value.
By adulterating BaFe0.5Nb0.5O3、 Bi0.5Na0.5TiO3、 BiMg2/3Nb1/3O3, with BaTiO3Solid solution is formed, is made Curie peak is mobile to low temperature direction, and reduces sintering temperature.The present invention uses BaFe0.5Nb0.5O3It is doped, passes through Fe3+ And Nb5+Compound action the Curie temperature of host material is reduced near room temperature using peak drifting effect；Using Bi0.5Na0.5TiO3Doping, causes undulating composition phase transformation, by broadening effect, realizes the Diffuse phase transition of barium titanate based ceramic, make The warm curve that is situated between becomes flat；By adulterating material not the ferroelectric BiMg2/3Nb1/3O3, generate and form different microcell, have slightly not Same Curie temperature macroscopically generates the transition temperature area of widthization, reduces the ferroelectricity of host material, force down Curie peak, make its Jie Electric constant curve becomes flat within the temperature range of ultra-wide, so that the ideal MLCC for obtaining ultra-wide temperature stability is used Ceramic material.Not only preparation process is simple for the temperature-stable ceramic material of the method for the present invention preparation, and the cost of material is low, and has Have that higher dielectric constant, temperature stability are good, temperature-stable multilayer ceramic capacitor is become to substitution lead base ceramic material Excellent important candidate material simultaneous technically and economically.

Claims (9)

1. a kind of dielectric ceramic material of ultra-wide temperature stability, it is characterised in that：It is made of matrix components and doping component, base Matter component includes BaTiO3、BaFe0.5Nb0.5O3And Bi0.5Na0.5TiO3, doping component BiMg2/3Nb1/3O3。
2. a kind of dielectric ceramic material of ultra-wide temperature stability according to claim 1, it is characterised in that：The ultra-wide The chemical expression of the dielectric ceramic material of temperature stability is (1-x)(0.94BaFe0.05Nb0.05Ti0.9O3- 0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3,x=0.05~0.2。
3. a kind of preparation method of the dielectric ceramic material of ultra-wide temperature stability of any of claims 1 or 2, feature exist In including the following steps：
By (1-x)(0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3、 x=0.05~0.2 Stoichiometric ratio weigh BaFe0.05Nb0.05Ti0.9O3Powder, Bi0.5Na0.5TiO3Powder and BiMg2/3Nb1/3O3Powder, ball milling Uniformly, after drying, it is put into mold compression moulding, sample then is made under the pressure of 200MPa；1200 ~ 1230 DEG C of sintering examinations Sample；Silver electrode paste is uniformly coated in sample tow sides, 600 ~ 620 DEG C of progress double sinterings obtain (1-x) (0.94BaFe0.05Nb0.05Ti0.9O3 -0.06Bi0.5Na0.5TiO3) -xBiMg2/3Nb1/3O3Ceramics sample.
4. a kind of preparation method of the dielectric ceramic material of ultra-wide temperature stability according to claim 3, feature exist In the BaFe0.05Nb0.05Ti0.9O3Powder 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 the dielectric ceramic material of ultra-wide temperature stability according to claim 3, feature exist In the Bi0.5Na0.5TiO3Powder 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. a kind of preparation method of the dielectric ceramic material of ultra-wide temperature stability according to claim 3, feature exist In the BiMg2/3Nb1/3O3Powder is obtained by method comprising the following steps：
According to BiMg2/3Nb1/3O3The stoichiometric ratio of middle metallic atom weighs Bi2O3, MgO and Nb2O5, ball in deionized water Mill is uniform, dries, after briquetting, keeps the temperature 2 ~ 3 hours in 800 DEG C, obtains BiMg2/3Nb1/3O3Powder.
7. according to a kind of described in any item preparation methods of the dielectric ceramic material of ultra-wide temperature stability of claim 3 ~ 6, It is characterized in that, specific steps include：
Step 1：According to the chemical expression (1- of the dielectric ceramic material of ultra-wide temperature stabilityx) (0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3、xMetallic atom in=0.05 ~ 0.2 Stoichiometric ratio weighs matrix components raw material BaCO3、TiO2、Fe2O3、Nb2O5、Bi2O3And NaCO3, and weigh doping component original Expect Bi2O3, MgO and Nb2O5, 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；Sintering condition is：With 2 DEG C/min is warming up to 200 DEG C, 500 DEG C are warming up to 3 DEG C/min, 1000 DEG C is warming up to 5 DEG C/min, is warming up to 2 DEG C/min 1100 DEG C keep the temperature 2 ~ 3 hours；
Step 3：By weighed matrix components raw material Bi2O3、NaCO3、TiO2Ball milling, drying, briquetting in deionized water Afterwards, 2 ~ 3 hours are kept the temperature in 800 ~ 850 DEG C, obtains the Bi of pure phase0.5Na0.5TiO3Powder；Sintering condition is：With 2 DEG C/min heating To 200 DEG C, 500 DEG C are warming up to 3 DEG C/min, 800 ~ 850 DEG C is warming up to 5 DEG C/min and keeps the temperature 2 ~ 3 hours；
Step 4：By weighed doping component raw material Bi2O3、MgO、Nb2O5Ball milling, drying, briquetting in deionized water Afterwards, 2 ~ 3 hours are kept the temperature in 800 DEG C, obtains BiMg2/3Nb1/3O3Powder；Sintering condition is：200 DEG C are warming up to 2 DEG C/min, with 3 DEG C/min is warming up to 500 DEG C, is warming up to 800 DEG C with 5 DEG C/min and keeps the temperature 2 ~ 3 hours；
Step 5：The powder that step 2 to step 4 is obtained is according to (1-x) (0.94BaFe0.05Nb0.05Ti0.9O3- 0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3In deionized water after ball milling, drying, it is put into mold and is pressed into disk, Whereinx=0.05 ~ 0.2, sample is made under the pressure of 200MPa in disk；
Step 6：Sample obtained by step 5 is carried out once sintered；Sintering condition is：200 DEG C are warming up to 2 DEG C/min, with 3 DEG C/min is when being warming up to 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, heat preservation 2 is small when being warming up to 1200 ~ 1230 DEG C with 2 DEG C/min When, later, 1000 DEG C are cooled to 2 DEG C/min, after being cooled to 500 DEG C with 5 DEG C/min, cools to room temperature with the furnace；
Step 7：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；The condition of sintering is：Temperature is 600 ~ 620 DEG C, and the time is 20 ~ 30 minutes；Obtain (1-x) (0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/3O3Ceramics sample.
8. a kind of preparation method of the dielectric ceramic material of ultra-wide temperature stability according to claim 7, feature exist In：The Ball-milling Time is 4h-8h.
9. a kind of preparation method of the dielectric ceramic material of ultra-wide temperature stability according to claim 7, feature exist In：By (1- described in step 5x) (0.94BaFe0.05Nb0.05Ti0.9O3-0.06Bi0.5Na0.5TiO3)-xBiMg2/3Nb1/ 3O3The mold that powder is put into diameter 12mm is pressed into disk taking-up, then disk is put into after gum cover vacuumizes, in the pressure of 200MPa Strong lower progress isostatic cool pressing, pressure maintaining 5 minutes.
CN201810832257.1A 2018-07-26 2018-07-26 A kind of dielectric ceramic material and preparation method thereof of ultra-wide temperature stability Pending CN108863348A (en)

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