CN102432291B - Capacitor antiferroelectric ceramic material with positive voltage coefficient, and manufacturing method thereof - Google Patents
Capacitor antiferroelectric ceramic material with positive voltage coefficient, and manufacturing method thereof Download PDFInfo
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- CN102432291B CN102432291B CN201110259284.2A CN201110259284A CN102432291B CN 102432291 B CN102432291 B CN 102432291B CN 201110259284 A CN201110259284 A CN 201110259284A CN 102432291 B CN102432291 B CN 102432291B
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Abstract
The invention discloses a capacitor antiferroelectric ceramic material with a positive voltage coefficient, and a manufacturing method thereof. The capacitor antiferroelectric ceramic material with a positive voltage coefficient has a chemical formula of Pb(1-x)Lax(ZryTi(1-y))1-x/4O3, wherein x is great than or equal to 0.08 and less than or equal to 0.12 and y is great than or equal to 0.75 and less than or equal to 0.85. The manufacturing method comprises the following steps of selecting raw materials, accurately extracting components, grinding the extracted components, drying, carrying out granulation, putting the granules obtained by the previous step into an alumina crucible, carrying out heat-insulation sealing calcination, then cooling, grinding, drying, mixing with wax, carrying out tabletting to obtain blanks, putting the blanks into a crucible, carrying out sealing sintering, heating, carrying out heat preservation, then cooling, carrying out coating of silver electrodes, and testing electrical properties. The manufacturing method of the capacitor antiferroelectric ceramic material with a positive voltage coefficient has a simple and clear manufacturing flow, good stability and good repeatability. A pulse energy-storage capacitor prepared from the capacitor antiferroelectric ceramic material with a positive voltage coefficient has a large positive voltage coefficient, low medium loss, a long service life, a small volume, a large capacity and good voltage resistance.
Description
Technical field
The present invention relates to a kind of electric capacity positive voltage coefficient antiferroelectric ceramics material and preparation method thereof.
Background technology
As everyone knows, dielectric capacitor dielectric specific inductivity under same voltage is higher, and the energy of capacitor stores is just larger, and energy storage density is just higher.Equally, in the time of voltage that releasing applies, the electric flux that electrical condenser discharges is also larger.But, there is following problem for the generic media stupalith of making electrical condenser: (1) linear (being I class) ceramic dielectric constant is very little, although according to energy storage density concept (electric flux storing in unit volume), can improve energy storage density by improving strength of electric field, but this brings a difficult problem to electrical isolation protection problem; (2) non-linear (being II class) ferroelectric ceramic material, in the time of low electric field, relatively there is very high specific inductivity, but its specific inductivity sharply declines and reaches more than 75% under high electric field, the ability of the resistance to electrical breakdown of ferroelectric ceramic(s) of high-k is also poor simultaneously.Common linearity and nonlinear ceramics material, capacitor deposited energy density, within the scope of 0.2～0.4 joule/square centimeter, has suppressed the raising of energy storage capacitor energy storage density.
As far back as the seventies, just carry out the research to the application of antiferroelectric ceramics material abroad.Recent year has also carried out a large amount of research work to antiferroelectric ceramics material and application.And traditional single Pb-based lanthanumdoped zirconate titanates antiferroelectric ceramics exists antiferroelectricly in ferroelectric phase phase transition process, the problem such as transformation temperature scope is narrow, electric hysteresis is wide and dependent variable is large, can not meet electrical condenser service requirements.Traditional ferroelectric ceramic material condenser dielectric loss is large, is easy to agingly after repeatedly discharging and recharging, and work-ing life is shorter, and traditional ferroelectric ceramic material also has that volume is large, capacity is little simultaneously, and resistance to pressure, stability and security be the shortcoming such as poor all.
Summary of the invention
The object of the invention is to solve the deficiency of existing ferroelectric ceramic material, a kind of novel electric capacity positive voltage coefficient antiferroelectric ceramics material and preparation method thereof is provided, overcome traditional ferroelectric ceramic material condenser dielectric loss large, after repeatedly discharging and recharging, be easy to aging, work-ing life is shorter, simultaneously traditional ferroelectric ceramic material also have that volume is large, capacity is little, all shortcomings such as poor of resistance to pressure, stability and security.
The object of the invention is to be achieved through the following technical solutions: electric capacity positive voltage coefficient antiferroelectric ceramics material, its chemical formula is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3, in formula, 0.08≤x≤0.12,0.75≤y≤0.85.
Electric capacity positive voltage coefficient antiferroelectric ceramics material of the present invention, its chemical formula is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3+ A, in formula, A is ZnO, Ag
2o, Bi
2o
3and SiO
2, 0.08≤x≤0.12,0.75≤y≤0.85,0.5wt%≤A≤1.0wt%.
The making method of electric capacity positive voltage coefficient antiferroelectric ceramics material, it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2and TiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and accurately weighs, and extracts each component;
(2) be 1: 5: 1.0～1.2 to put into milling apparatus and grind, milling time 40～50 hours each component according to the ratio of material, ball and water;
(3) mixture after grinding is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 850～950 ℃ in alumina crucible, then cool to room temperature with the furnace;
(4) grind putting into milling apparatus after the burning piece weighing after calcining, grinding according to the ratio of material, ball and water is 1: 5: 0.8～1.0 to carry out, milling time 80 hours, reach slip median size and be not more than 0.5 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after grinding;
(5) ratio that is 100: 7～8 according to material powder and paraffin ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200Mpa;
(6) blank after moulding is placed on zirconium white zirconium plate, then be placed in the alumina crucible of high-content aluminum oxide together with zirconium white zirconium plate, covered and enclosed sintering, is incubated 3 hour, then furnace cooling after being heated to 1130～1150 ℃ by the temperature rise rate of 150 ℃/h;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
The making method of electric capacity positive voltage coefficient antiferroelectric ceramics material of the present invention, it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2, TiO
2, ZnO, Ag
2o, Bi
2o
3and SiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and accurately weighs, and extracts each component;
(2) be 1: 5: 1.0～1.2 to put into milling apparatus and grind, milling time 40～50 hours each component according to the ratio of material, ball and water;
(3) mixture after grinding is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 850～950 ℃ in alumina crucible, then cool to room temperature with the furnace;
(4) grind in putting into milling apparatus after the accurate weighing of the ratio of the burning piece after calcining and A value, grinding according to the ratio of material, ball and water is 1: 5: 0.8～1.0 to carry out, milling time 80 hours, reaching slip median size is 0.4～0.5 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after grinding;
(5) ratio that is 100: 7～8 according to material powder and paraffin ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200Mpa;
(6) blank after moulding is placed on zirconium white zirconium plate, then be placed in the alumina crucible of high-content aluminum oxide together with zirconium white zirconium plate, covered and enclosed sintering, is incubated 3 hour, then furnace cooling after being heated to 1130～1150 ℃ by the temperature rise rate of 150 ℃/h;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
Milling apparatus of the present invention is ball mill device.
Milling apparatus of the present invention is vertical vibrating mill apparatus.
Blank in step of the present invention (6) takes the mode keeping flat to be placed on zirconium white zirconium plate.
High-content aluminum oxide in step of the present invention (6) is the aluminum oxide that content is greater than 95%.
The invention has the beneficial effects as follows: adopt simple flow process, stability and the repeated all good antiferroelectric ceramics making methods of making clearly to produce the high-performance antiferroelectric ceramics material with larger positive voltage coefficient, the pulse energy storage MLCC (laminated ceramic capacitor) that antiferroelectric ceramics material of the present invention is made has that positive voltage coefficient is large, dielectric loss is very low, multiple discharge keeps good characteristic, long service life, and energy storage density is high, output rating is large, volume is little, capacity is large and the feature such as good pressure-resistant performance.
Accompanying drawing explanation
Fig. 1 is that antiferroelectric pulse energy storage MLCC (laminated ceramic capacitor) electric capacity that representative formula production porcelain is made varies with temperature curve
Fig. 2 be representative formula produce porcelain make antiferroelectric pulse energy storage MLCC (laminated ceramic capacitor) electric capacity with voltage change curve
Fig. 3 is the proportioning information slip of representative formula of the present invention
Fig. 4 is the electrical property information slip of each representative formula.
Embodiment
Further describe technical scheme of the present invention below in conjunction with embodiment:
[embodiment 1]
Electric capacity positive voltage coefficient antiferroelectric ceramics material, its chemical formula is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/40
3, in formula, 0.08≤x≤0.12,0.75≤y≤0.85.
The making method of electric capacity positive voltage coefficient antiferroelectric ceramics material, it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2and TiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and accurately weighs, and extracts each component;
(2) be to put into ball mill device at 1: 5: 1.0 to carry out ball milling by each component according to the ratio of material, ball and water, Ball-milling Time 40 hours;
(3) mixture after ball milling is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 850 ℃ in alumina crucible, then cool to room temperature with the furnace;
(4) carry out ball milling by putting into ball mill device after the burning piece weighing after calcining, ball milling is 1: 5: 0.8～0.8 to carry out according to the ratio of material, ball and water, Ball-milling Time 80 hours, reach slip median size and be not more than 0.5 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after grinding;
(5) ratio that is 100: 7 according to material powder and paraffin ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200Mpa;
(6) blank after moulding being taked to keep flat mode is placed on zirconium white zirconium plate, then be placed in the alumina crucible of high-content aluminum oxide together with zirconium white zirconium plate, covered and enclosed sintering, is incubated 3 hour, then furnace cooling after being heated to 1130 ℃ by the temperature rise rate of 150 ℃/h;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
[embodiment 2]
Electric capacity positive voltage coefficient antiferroelectric ceramics material, its chemical formula is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3, in formula, 0.08≤x≤0.12,0.75≤y≤0.85.
The making method of electric capacity positive voltage coefficient antiferroelectric ceramics material, it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2and TiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and Measurement accuracy, extracts each component;
(2) be to put into ball mill device at 1: 5: 1.1 to carry out ball milling by each component according to the ratio of material, ball and water, Ball-milling Time 45 hours;
(3) mixture after ball milling is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 900 ℃ in alumina crucible, then cool to room temperature with the furnace;
(4) carry out vertical vibration grinder by putting into vertical vibrating mill apparatus after the burning piece weighing after calcining, be to carry out at 1: 5: 0.9 according to the ratio of material, ball and water, vertical vibrating time consuming 80 hours, reach slip median size and be not more than 0.4 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after ball milling;
(5) ratio that is 100: 8 according to material powder and paraffin ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200Mpa;
(6) blank after moulding being taked to keep flat mode is placed on zirconium white zirconium plate, then be placed in the alumina crucible of high-content aluminum oxide together with zirconium white zirconium plate, covered and enclosed sintering, is incubated 3 hour, then furnace cooling after being heated to 1140 ℃ by the temperature rise rate of 150 ℃/h;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
[embodiment 3]
Electric capacity positive voltage coefficient antiferroelectric ceramics material, its chemical formula is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3+ A, in formula, A is ZnO, Ag
2o, Bi
2o
3and SiO
2, 0.08≤x≤0.12,0.75≤y≤0.85,0.5wt%≤A≤1.0wt%.
The making method of electric capacity positive voltage coefficient antiferroelectric ceramics material, it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2, TiO
2, ZnO, Ag
2o, Bi
2o
3and SiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and accurately weighs, and extracts each component;
(2) be to put into vertical vibrating mill apparatus at 1: 5: 1.2 to carry out vertical vibration grinder by each component according to the ratio of material, ball and water, vertical vibrating time consuming 50 hours;
(3) mixture after vertical vibration grinder is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 950 ℃ in alumina crucible, then cool to room temperature with the furnace;
(4) grind in putting into vertical vibrating mill apparatus after the accurate weighing of the ratio of the burning piece after calcining and A value, vertical vibration grinder is to carry out at 1: 5: 1.0 according to the ratio of material, ball and water, vertical vibrating time consuming 80 hours, reach slip median size and be not more than 0.4 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after vertical vibration grinder;
(5) ratio that is 100: 8 according to material powder and paraffin ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200Mpa;
(6) blank after moulding being taked to keep flat mode is placed on zirconium white zirconium plate, then be placed in the alumina crucible of high-content aluminum oxide together with zirconium white zirconium plate, covered and enclosed sintering, is incubated 3 hour, then furnace cooling after being heated to 1150 ℃ by the temperature rise rate of 150 ℃/h;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
[embodiment 4]
Electric capacity positive voltage coefficient antiferroelectric ceramics material, its chemical formula is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3+ A, in formula, A is ZnO, Ag
2o, Bi
2o
3and SiO
2, 0.08≤x≤0.12,0.75≤y≤0.85,0.5wt%≤A≤1.0wt%.
The making method of electric capacity positive voltage coefficient antiferroelectric ceramics material, it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2, TiO
2, ZnO, Ag
2o, Bi
2o
3and SiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and accurately weighs, and extracts each component;
(2) be to put into vertical vibrating mill apparatus at 1: 5: 1.2 to carry out vertical vibration grinder by each component according to the ratio of material, ball and water, vertical vibrating time consuming 40 hours;
(3) mixture after vertical vibration grinder is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 850 in alumina crucible, then cool to room temperature with the furnace;
(4) grind in putting into vertical vibrating mill apparatus after the accurate weighing of the ratio of the burning piece after calcining and A value, vertical vibration grinder is to carry out at 1: 5: 0.8 according to the ratio of material, ball and water, vertical vibrating time consuming 80 hours, reach slip median size and be not more than 0.5 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after vertical vibration grinder;
(5) ratio that is 100: 8 according to material powder and paraffin ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200Mpa;
(6) blank after moulding being taked to keep flat mode is placed on zirconium white zirconium plate, then be placed in the alumina crucible of high-content aluminum oxide together with zirconium white zirconium plate, covered and enclosed sintering, is incubated 3 hour, then furnace cooling after being heated to 1130 ℃ by the temperature rise rate of 150 ℃/h;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
[embodiment 5]
Electric capacity positive voltage coefficient antiferroelectric ceramics material, its chemical formula is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3+ A, in formula, A is ZnO, Ag
2o, Bi
2o
3and SiO
2, 0.08≤x≤0.12,0.75≤y≤0.85,0.5wt%≤A≤1.0wt%.
The making method of electric capacity positive voltage coefficient antiferroelectric ceramics material, it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2, TiO
2, ZnO, Ag
2o, Bi
2o
3and SiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and accurately weighs, and extracts each component;
(2) be to put into ball mill device at 1: 5: 1.2 to carry out ball milling by each component according to the ratio of material, ball and water, Ball-milling Time 45 hours;
(3) mixture after ball milling is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 850 ℃ in alumina crucible, then cool to room temperature with the furnace;
(4) grind in putting into ball mill device after the accurate weighing of the ratio of the burning piece after calcining and A value, ball milling is to carry out at 1: 5: 0.9 according to the ratio of material, ball and water, Ball-milling Time 80 hours, reach slip median size and be not more than 0.45 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after ball milling;
(5) ratio that is 100: 7.5 according to material powder and paraffin ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200Mpa;
(6) blank after moulding being taked to keep flat mode is placed on zirconium white zirconium plate, then be placed in the alumina crucible of high-content aluminum oxide together with zirconium white zirconium plate, covered and enclosed sintering, is incubated 3 hour, then furnace cooling after being heated to 1145 ℃ by the temperature rise rate of 150 ℃/h;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
The chemical constitution formula of antiferroelectric ceramics material is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o3, in formula, 0.08≤x≤0.12,0.75≤y≤0.85, the lead element that the lanthanum element part substituted compound valency that is positive trivalent with valency is positive divalence, and the ratio of to adjust valency be positive tetravalence zr element and the titanium elements of positive tetravalence, to adjust antiferroelectric ceramics material Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3fundamental property, especially electric capacity positive voltage coefficient.
Obtaining after the fundamental property of approval, then adding modifier A and further improve its performance, especially significantly reducing maturing temperature (being down to 1130 ℃ from 1350 ℃) and dielectric loss, can also further improve electric capacity positive voltage coefficient.
Fig. 3 provides the various proportioning situations of representative formula of the present invention, and Fig. 4 provides the electrical property of patent representative formula of the present invention.Select 8
#formula, according to above-mentioned starting material and processing requirement, adopt vertical vibration grinder abrasive material mode, produce 200 kilograms of porcelains, and porcelain is produced to the antiferroelectric pulse energy storage MLCC (laminated ceramic capacitor) of CP41L-7860-1250V-104K model according to common MLCC (laminated ceramic capacitor) production technique.
Comprehensive all round properties, selects 8
#formula is produced porcelain and is made the antiferroelectric pulse energy storage MLCC (laminated ceramic capacitor) of CP41L-7860-1250V-104K model, and test-results is as follows: dielectric loss is 0.12%; While applying voltage 1250V, discharging current 1300A, discharge time is more than 1500 times; Electric capacity varies with temperature curve as figure mono-; Electric capacity with voltage change curve as figure bis-.
In compositing range of the present invention, all there is the electric capacity positive voltage coefficient that numerical value does not wait, in composition, add Bi
2o
3, ZnO, SiO
2and Ag
2o helps after burning and properties-correcting agent, and its sintering temperature has significantly reduced by 180 ℃, and the voltage coefficient (VCC) of dielectric loss, dielectric strength, insulation resistance, percentage of capacitance variation with temperature, especially electric capacity has all obtained extremely significantly improving.Therefore antiferroelectric capacitor ceramic material of the present invention has successfully solved the ferroelectric ceramic(s) problem that specific inductivity significantly reduces with the increase of strength of electric field in the time of high-voltage; also overcome linear (being I class) stupalith and organic dielectric and need to improve the electrical isolation protection difficult problem that energy storage density brings by improving strength of electric field because specific inductivity is low, thereby providing a kind of has high energy storage density, high-output power, height is withstand voltage, the nonlinear capacitor antiferroelectric ceramics material of ultralow dielectric loss simultaneously.The positive voltage coefficient of capacitance of antiferroelectric ceramics material of the present invention, except filling a prescription composition adjustment by adjustment, can also be adjusted by adjusting sinter process.In addition, pulse energy storage capacitor charging/discharging voltage and the electric current of making, can fill a prescription to form by adjustment and design, and also can be adjusted by the series parallel circuits mode that changes electrical condenser.
Claims (4)
1. the preparation method of electric capacity positive voltage coefficient antiferroelectric ceramics material, the chemical formula of described electric capacity positive voltage coefficient antiferroelectric ceramics material is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3, in formula, 0.08≤x≤0.12,0.75≤y≤0.85;
It is characterized in that: it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2and TiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and accurately weighs, and extracts each component;
(2) be that 1:5:1.0～1.2 are put into milling apparatus and ground by each component according to the weight ratio of material, ball and water, milling time 40～50 hours;
(3) mixture after grinding is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 850～950 ℃ in alumina crucible, then cool to room temperature with the furnace;
(4) grind putting into milling apparatus after the burning piece weighing after calcining, grinding is that carry out 1:5:0.8～1.0 according to the weight ratio of material, ball and water, milling time 80 hours, reach slip median size and be not more than 0.5 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after grinding;
(5) ratio that is 100:7～8 according to material powder and paraffin weight ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200MPa;
(6) mode of the blank after moulding being taked keep flat is placed on zirconium white zirconium plate, then being placed on mass content together with zirconium white zirconium plate is greater than in 95% the alumina crucible of high-content aluminum oxide, covered and enclosed sintering, after being heated to 1130～1150 ℃ by the temperature rise rate of 150 ℃/h, be incubated 3 hours, then furnace cooling;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
2. the preparation method of electric capacity positive voltage coefficient antiferroelectric ceramics material according to claim 1, the chemical formula of described electric capacity positive voltage coefficient antiferroelectric ceramics material is Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3+ A, in formula, 0.08≤x≤0.12,0.75≤y≤0.85, A is ZnO, Ag
2o, Bi
2o
3and SiO
2, 0.5wt%≤A≤1.0wt%; It is characterized in that: it comprises the following steps:
(1) selecting purity is chemical pure or analytically pure PbO, La
2o
3, ZrO
2, TiO
2, ZnO, Ag
2o, Bi
2o
3and SiO
2as starting material, according to Pb
(1-x)la
x(Zr
yti
(1-y))
1-x/4o
3the value range of middle x and y calculates and accurately weighs, and extracts each component;
(2) be that 1:5:1.0～1.2 are put into milling apparatus and ground by each component according to the weight ratio of material, ball and water, milling time 40～50 hours;
(3) mixture after grinding is dried and granulation, be incubated airtight calcining in 3 hours by the temperature rise rate of 200 ℃/h temperature with 850～950 ℃ in alumina crucible, then cool to room temperature with the furnace;
(4) grind in putting into milling apparatus after the accurate weighing of the ratio of the burning piece after calcining and A value, grinding is that carry out 1:5:0.8～1.0 according to the weight ratio of material, ball and water, milling time 80 hours, reach slip median size and be not more than 0.5 μ m, when maximum particle diameter is not more than 2.0 μ m, dry the mixture after grinding;
(5) ratio that is 100:7～8 according to material powder and paraffin weight ratio is closed wax operation, is then shaped to the blank of Φ 14 × 1.5 disks at the pressure lower sheeting of 200Mpa;
(6) blank after moulding is placed on zirconium white zirconium plate, then be placed in the alumina crucible of high-content aluminum oxide together with zirconium white zirconium plate, covered and enclosed sintering, is incubated 3 hour, then furnace cooling after being heated to 1130～1150 ℃ by the temperature rise rate of 150 ℃/h;
(7) coat silver electrode and test its electrical property on the two sides of ceramic disks.
3. the preparation method of electric capacity positive voltage coefficient antiferroelectric ceramics material according to claim 1 and 2, is characterized in that: described milling apparatus is ball mill device.
4. the preparation method of electric capacity positive voltage coefficient antiferroelectric ceramics material according to claim 1 and 2, is characterized in that: described milling apparatus is vertical vibrating mill apparatus.
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| CN107216581B (en) * | 2017-06-11 | 2019-03-29 | 杭州电子科技大学 | Antiferroelectric ceramics/PVDF 0-3 structural composite material and its thermal treatment producing method |
| CN107995712A (en) * | 2017-12-08 | 2018-05-04 | 北京弗圣威尔科技有限公司 | Wireless power heating unit and heating means and placement thing and its preparation method |
| CN112142466B (en) * | 2019-06-26 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Lead niobate ytterbium acid based antiferroelectric ceramic material and preparation method thereof |
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