CN105481363A - Large-discharge-current-capacity low-residual-voltage high-gradient zinc oxide piezoresistor ceramic - Google Patents

Large-discharge-current-capacity low-residual-voltage high-gradient zinc oxide piezoresistor ceramic Download PDF

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CN105481363A
CN105481363A CN201510998609.7A CN201510998609A CN105481363A CN 105481363 A CN105481363 A CN 105481363A CN 201510998609 A CN201510998609 A CN 201510998609A CN 105481363 A CN105481363 A CN 105481363A
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ball milling
zinc oxide
zno
preparation
discharge capacity
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CN105481363B (en
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何金良
胡军
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Tsinghua University
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Abstract

The invention relates to a large-discharge-current-capacity low-residual-voltage high-gradient zinc oxide piezoresistor ceramic. The invention is characterized in that the ceramic comprises the following formula components: zinc oxide ZnO, bismuth oxide Bi2O3, antimony trioxide Sb2O3, manganese peroxide MnO2, chromic oxide Cr2O3, cobaltic oxide Co2O3, silicon dioxide SiO2, silver oxide Ag2O, gallium nitrate Ga(NO3)3 and yttrium nitrate Y(NO3)3. By using the ceramic, the leakage current is inhibited; and by adding the Y and Ga elements, the ZnO piezoresistor prepared according to the formula has more stable aging resistance, thereby overcoming the defect that the leakage current can not be inhibited when the single Ag ions are added.

Description

A kind of large discharge capacity, low residual voltage, high-gradient zinc oxide piezoresistor ceramic
Technical field
The present invention relates to technical field of material chemistry, particularly a kind of pottery and preparation method thereof.
Background technology
ZnO varistor is main raw material with ZnO, adds a small amount of Bi2O3, Sb2O3, MnO2, Cr2O3, Co2O3 and silver glass powder etc. as auxiliary ingredients, adopts ceramic sintering process to be prepared from.The advantage of the non-linear behaviour good due to it and large discharge capacity, since 19 century 70s are found, ZnO varistor is widely used in the overvoltage protection of power system lightning protection and power equipment as the core parts of power system thunder arrester.
Along with improving constantly of transmission voltage grade, be particularly extra-high voltage system, apparatus insulated problem becomes increasingly conspicuous, and improves apparatus insulated paying through the nose comprehensively.Adopt the thunder arrester that assembles of ZnO varistor of high-gradient, low residual voltage can reduce the dielectric level of system, reduce the weight and volume of power transmission and transforming equipment, improve the reliability of transmission system.
The non-linear character of ZnO varistor can be divided into three regions: small area analysis district, middle Current Zone and big current district.(<10-4A/cm2) is also called prebreakdown district in small area analysis district, in this region, crystal boundary presents high-impedance state, I-V curve shows as ohm property, larger in the ohm property rate of curve in this region, then the power dissipation characteristics in leakage current region of ZnO varistor is more stable, and pressure sensitive voltage U1mA is also higher.Middle Current Zone is nonlinear resistance district, and this zone current sharply increases and voltage increases slowly, and this region I-V characteristic is determined by ZnO crystal grain and ZnO crystal boundary joint effect, is the workspace of voltage dependent resistor.(>103A/cm2) becomes ohm property again in big current district, the resistance of this region ZnO crystal grain determines the height of residual voltage, the position that occurs at I-V characteristic plane, this region, determines the size of ZnO varistor discharge capacity simultaneously.
No matter be that ZnO grain resistance all affects I-V characteristic in middle Current Zone or big current district.Reduce the residual voltage of ZnO varistor, the resistivity of ZnO varistor must be reduced.Show according to research in the past, add the resistivity that a certain amount of donor ion can significantly improve ZnO crystal grain, thus reach the object reducing residual voltage.In the industrial production of reality, mostly adopt Al ion to add in ZnO varistor material as donor ion, but the interpolation of Al ion is often along with the increase of leakage current, cause the reduction of nonlinear factor, the aging property of ZnO varistor also become unstable simultaneously.In industrial application, also have the mode adopting ZnO and the presintering of part adjunct, make the pre-reaction of part mixing raw material, to improve potential barrier and the stability of pressure sensitive, this mode makes complex manufacturing.At present mainly through improving the degree of uniformity of crystal grain, make electric current can uniform flow whole varistor valve, thus improve the discharge capacity of ZnO varistor, but the degree of uniformity of crystal grain is comparatively large by the impact of sintering process and raw material mixed grinding technique etc., accomplishes that the homogenization of crystal grain is difficult larger.
Summary of the invention
The object of the invention is to solve the problem, devising the preparation method of a kind of large discharge capacity, low residual voltage, high-gradient zinc oxide piezoresistor ceramic.Specific design scheme is:
A kind of large discharge capacity, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, it is characterized in that, system component comprises zinc oxide ZnO, bismuth oxide Bi 2o 3, antimonous oxide Sb 2o 3, Manganse Dioxide MnO 2, chromic oxide Cr 2o 3, cobalt sesquioxide Co 2o 3, silicon-dioxide SiO 2, nitre silver suboxide Ag 2o, gallium nitrate Ga (NO 3) 3, Yttrium trinitrate Y (NO 3) 3.
Mol ratio between each system component is:
ZnO：Bi 2O 3：Sb 2O 3：MnO 2：Cr 2O 3：Co 2O 3：SiO 2：Ag 2O：Ga(NO 3) 3：Y(NO 3) 3＝87.5～95.8:0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0:0.1-1.0:0.1-1.0：1.0-1.5。
The preparation method of a kind of large discharge capacity, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, preparation process comprises that preparation is auxiliary adds slurry, shaping, sintering, and described preparation is auxiliary to be added sauce step and comprise first ball milling, secondary ball milling, three ball millings, mist projection granulating, automatically moisture.
In described first ball milling step, the composition of described first ball milling comprises Bi 2o 3, MnO 2, Sb 2o 3, Co 2o 3, SiO 2, Cr 2o 3, deionized water, described first Ball-milling Time is greater than 6h, obtains first ball milling and assists mixed slurry,
The Bi added 2o 3, MnO 2, Cr 2o 3, Co 2o 3, SiO 2the mol ratio of composition is: 0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0.
Described forming step is compression molding, and use the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, molding time 3min.
Use high temperature circuit to complete described sintering step, in described sintering step, temperature controls and time controling is:
From room temperature to 400 DEG C, heating-up time 2h;
At 400 DEG C of insulation binder removal 4h;
From 400 DEG C to 1000 DEG C, heating-up time 3h;
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h;
At 1200 DEG C of insulation 3h;
Temperature fall;
In secondary ball milling step, assist in mixed slurry to described first ball milling and add ZnO, PVAC polyvinylalcohol, pulvis, deionized water, and ball milling is mixed to and is uniformly dispersed, obtain secondary ball milling and assist mixed slurry, described in add ZnO and first ball milling assists Bi in mixed slurry 2o 3mol ratio be 87.5 ~ 95.8:0.5-2.0.
In three ball milling step, assist in mixed slurry to described secondary ball milling and add Ag 2o:Ga (NO 3) 3: Y (NO 3) 3, carry out three ball millings after deionized water, the time of described three ball millings is 2h, obtains slurry, described in add Ag 2o:Ga (NO 3) 3: Y (NO 3) 3the mol ratio of the ZnO added in mixed slurry is assisted to be 0.1-1.0:0.1-1.0:0.5 ~ 1.5:87.5 ~ 95.8 with secondary ball milling.
The large discharge capacity obtained by technique scheme of the present invention, low residual voltage, high-gradient zinc oxide piezoresistor ceramic and preparation method thereof, its beneficial effect is:
In ZnO and mixed slurry, with the addition of Ag and Y element, the acting in conjunction of Ag and Y ion makes the grain resistance in big current district decline, and reduces the residual voltage level of ZnO varistor simultaneously; On V-I rational curve, the flex point in big current district moves to right, and improves ZnO varistor that this formula makes and to release the ability of electric charge; Under the acting in conjunction of Y and Ga ion, the ZnO varistor that this formula is made is more stable in the V-I characteristic in small area analysis district, and voltage gradient is improved, and nonlinear factor increases, and adds Ag Ion Phase ratio merely, and leakage current is inhibited; The aging resistance of the ZnO varistor that the common interpolation of Y and Ga element makes this formula make is more stable, eliminates the weak point that leakage current that the simple Ag of interpolation ion brings can not get suppressing.
Embodiment
A kind of large discharge capacity, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, it is characterized in that, system component comprises zinc oxide ZnO, bismuth oxide Bi 2o 3, antimonous oxide Sb 2o 3, Manganse Dioxide MnO 2, chromic oxide Cr 2o 3, cobalt sesquioxide Co 2o 3, silicon-dioxide SiO 2, nitre silver suboxide Ag 2o, gallium nitrate Ga (NO 3) 3, Yttrium trinitrate Y (NO 3) 3.
Mol ratio between each system component is:
ZnO：Bi 2O 3：Sb 2O 3：MnO 2：Cr 2O 3：Co 2O 3：SiO 2：Ag 2O：Ga(NO 3) 3：Y(NO 3) 3＝87.5～95.8:0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0:0.1-1.0:0.1-1.0：1.0-1.5。
The preparation method of a kind of large discharge capacity, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, preparation process comprises that preparation is auxiliary adds slurry, shaping, sintering, and described preparation is auxiliary to be added sauce step and comprise first ball milling, secondary ball milling, three ball millings, mist projection granulating, automatically moisture.
In described first ball milling step, the composition of described first ball milling comprises Bi 2o 3, MnO 2, Sb 2o 3, Co 2o 3, SiO 2, Cr 2o 3, deionized water, described first Ball-milling Time is greater than 6h, obtains first ball milling and assists mixed slurry,
The Bi added 2o 3, MnO 2, Cr 2o 3, Co 2o 3, SiO 2the mol ratio of composition is: 0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0.
Described forming step is compression molding, and use the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, molding time 3min.
Use high temperature circuit to complete described sintering step, in described sintering step, temperature controls and time controling is:
From room temperature to 400 DEG C, heating-up time 2h;
At 400 DEG C of insulation binder removal 4h;
From 400 DEG C to 1000 DEG C, heating-up time 3h;
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h;
At 1200 DEG C of insulation 3h;
Temperature fall;
In secondary ball milling step, assist in mixed slurry to described first ball milling and add ZnO, PVAC polyvinylalcohol, pulvis, deionized water, and ball milling is mixed to and is uniformly dispersed, obtain secondary ball milling and assist mixed slurry, described in add ZnO and first ball milling assists Bi in mixed slurry 2o 3mol ratio be 87.5 ~ 95.8:0.5-2.0.
In three ball milling step, assist in mixed slurry to described secondary ball milling and add Ag 2o:Ga (NO 3) 3: Y (NO 3) 3, carry out three ball millings after deionized water, the time of described three ball millings is 2h, obtains slurry, described in add Ag 2o:Ga (NO 3) 3: Y (NO 3) 3the mol ratio of the ZnO added in mixed slurry is assisted to be 0.1-1.0:0.1-1.0:0.5 ~ 1.5:87.5 ~ 95.8 with secondary ball milling.
Embodiment one
According to the large discharge capacity of a kind of system for ultra-high voltage transmission of patent specification introduction of the present invention, the preparation method of low residual voltage zinc oxide piezoresistor ceramic, carry out the actual preparation of high-performance ZnO based varistor.
(1) preparation of raw material:
In following ratio ZnO (87.5%), Bi 2o 3(2.0mol%), Sb 2o 3(1.5mol%), MnO 2(1.0mol%), Cr 2o 3(1.0mol%), Co 2o 3(1.5mol%), SiO 2, and Ag (2.0mol%) 2o (1.0mol%), Ga (NO 3) 3(1.0mol%), Y (NO 3) 3(1.5mol%) initial feed is prepared.
(2) slurry preparation
1) ball milling adjunct:
By Bi 2o 3(2.0mol%), Sb 2o 3(1.5mol%), MnO 2(1.0mol%), Cr 2o 3(1.0mol%), Co 2o 3(1.5mol%), SiO 2(2.0mol%) put into the ball grinder into planetary ball mill, add appropriate deionized water, ball milling 8 hours.
2) add the ZnO of (87.5mol%) in auxiliary mixed slurry after ball milling, add PVA, dispersion agent and appropriate deionized water, by all mixing raw material mixing and ball milling to being uniformly dispersed.
3) silver, aluminium plus gallium ion is added
In the ZnO mixed and adjunct, add Ag 2o (1.0mol%), Ga (NO 3) 3(1.0mol%), Y (NO 3) 3(1.5mol%), ball milling is continued 2 hours, after mist projection granulating, moisture.
(3) shaping
The powder obtained in previous step is sprayed, after automatically moisture, adopts tabletting molding process.Use the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, 3 minutes dwell times.
(4) sinter
With high-temperature electric resistance furnace sintered body in closed atmosphere, actual temp and the period as follows:
From room temperature to 400 DEG C, 2 hours heating-up times;
Binder removals 4 hours are incubated at 400 DEG C;
From 400 DEG C to 1000 DEG C, 3 hours heating-up times;
From 1000 DEG C to 1200 DEG C, 1.5 hours heating-up times;
1200 DEG C of insulations 3 hours;
Temperature fall.
Properties test is carried out to the sample of the ZnO varistor prepared.Its residual voltage ratio is that 1.47,2ms square wave discharge capacity reaches 535J/cm 3, breakdown voltage gradient average 440V/mm, in addition, its leakage current is less than 1 μ A/cm 2, nonlinear factor is greater than 70.Its performance has met industrial application requirement.
Embodiment two
According to the large discharge capacity of a kind of system for ultra-high voltage transmission of patent specification introduction of the present invention, the preparation method of low residual voltage zinc oxide piezoresistor ceramic, carry out the actual preparation of high-performance ZnO based varistor.
(1) preparation of raw material:
In following ratio ZnO (95.8mol%), Bi 2o 3(0.5mol%), Sb 2o 3(0.5mol%), MnO 2(0.5mol%), Cr 2o 3(0.5mol%), Co 2o 3(0.5mol%), SiO 2, and Ag (1.0mol%) 2o (0.1mol%), Ga (NO 3) 3(0.1mol%), Y (NO 3) 3(0.5mol%) initial feed is prepared.
(2) slurry preparation
1) ball milling adjunct:
By Bi 2o 3(0.5mol%), Sb 2o 3(0.5mol%), MnO 2(0.5mol%), Cr 2o 3(0.5mol%), Co 2o 3(0.5mol%), SiO 2(1.0mol%) put into the ball grinder into planetary ball mill, add appropriate deionized water, ball milling more than 6 hours.
2) add the ZnO of (87.5 ~ 95.8mol%) in auxiliary mixed slurry after ball milling, add PVA, dispersion agent and appropriate deionized water, by all mixing raw material mixing and ball milling to being uniformly dispersed.
3) silver, aluminium plus gallium ion is added
In the ZnO mixed and adjunct, add Ag 2o (0.1 ~ 1.0mol%), Ga (NO 3) 3(0.1 ~ 1.0mol%), Y (NO 3) 3(0.5 ~ 1.5mol%), continues ball milling 2 hours, after mist projection granulating, moisture.
(3) shaping
The powder obtained in previous step is sprayed, after automatically moisture, adopts tabletting molding process.Use the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, 3 minutes dwell times.
(4) sinter
With high-temperature electric resistance furnace sintered body in closed atmosphere, actual temp and the period as follows:
From room temperature to 400 DEG C, 2 hours heating-up times;
Binder removals 4 hours are incubated at 400 DEG C;
From 400 DEG C to 1000 DEG C, 3 hours heating-up times;
From 1000 DEG C to 1200 DEG C, 1.5 hours heating-up times;
1200 DEG C of insulations 3 hours;
Temperature fall.
Properties test is carried out to the sample of the ZnO varistor prepared.Its residual voltage ratio is that 1.49,2ms square wave discharge capacity reaches 508J/cm 3, breakdown voltage gradient average 463V/mm, in addition, leakage current is less than 1 μ A/cm 2, nonlinear factor is greater than 70.Its performance has met industrial application requirement.
Technique scheme only embodies the optimal technical scheme of technical solution of the present invention, and those skilled in the art all embody principle of the present invention to some variations that wherein some part may be made, and belong within protection scope of the present invention.

Claims (8)

1. a large discharge capacity, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, it is characterized in that, system component comprises zinc oxide ZnO, bismuth oxide Bi2O3, antimonous oxide Sb2O3, Manganse Dioxide MnO2, chromic oxide Cr2O3, cobalt sesquioxide Co2O3, silicon-dioxide SiO2, nitre silver suboxide Ag2O, gallium nitrate Ga (NO3) 3, Yttrium trinitrate Y (NO3) 3.
2. according to claimthe large discharge capacity of one described in 1, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, is characterized in that, the mol ratio between each system component is:
ZnO：Bi2O3：Sb2O3：MnO2：Cr2O3：Co2O3：SiO2：Ag2O：Ga(NO3)3：Y(NO3)3＝87.5～95.8:0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0:0.1-1.0:0.1-1.0：1.0-1.5。
3. the preparation method of a large discharge capacity, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, it is characterized in that, preparation process comprises that preparation is auxiliary adds slurry, shaping, sintering, and described preparation is auxiliary to be added sauce step and comprise first ball milling, secondary ball milling, three ball millings, mist projection granulating, automatically moisture.
4. according to claimthe preparation method of the large discharge capacity described in 3, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, it is characterized in that, in described first ball milling step, the composition of described first ball milling comprises Bi2O3, MnO2, Sb2O3, Co2O3, SiO2, Cr2O3, deionized water, described first Ball-milling Time is greater than 6h, obtain first ball milling and assist mixed slurry
The mol ratio of Bi2O3, MnO2, Cr2O3, Co2O3, SiO2 composition added is: 0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0.
5. according to claimthe preparation method of the large discharge capacity described in 3, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, it is characterized in that, described forming step is compression molding, use the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, molding time 3min.
6. according to claimthe preparation method of the large discharge capacity described in 3, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, is characterized in that, uses high temperature circuit to complete described sintering step, and in described sintering step, temperature controls and time controling is:
From room temperature to 400 DEG C, heating-up time 2h;
At 400 DEG C of insulation binder removal 4h;
From 400 DEG C to 1000 DEG C, heating-up time 3h;
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h;
At 1200 DEG C of insulation 3h;
Temperature fall.
7. according to claimthe preparation method of the large discharge capacity described in 4, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, it is characterized in that, in secondary ball milling step, assist in mixed slurry to described first ball milling and add ZnO, PVAC polyvinylalcohol, pulvis, deionized water, and ball milling is mixed to and is uniformly dispersed, obtain secondary ball milling and assist mixed slurry, described in add ZnO and first ball milling assists the mol ratio of Bi2O3 in mixed slurry to be 87.5 ~ 95.8:0.5-2.0.
8. according to claimthe preparation method of the large discharge capacity described in 7, low residual voltage, high-gradient zinc oxide piezoresistor ceramic, it is characterized in that, in three ball milling step, to described secondary ball milling assist in mixed slurry add Ag2O:Ga (NO3) 3:Y (NO3) 3, deionized water after carry out three ball millings, the time of described three ball millings is 2h, obtain slurry, described in add Ag2O:Ga (NO3) 3:Y (NO3) 3 and assist the mol ratio of the ZnO added in mixed slurry to be 0.1-1.0:0.1-1.0:0.5 ~ 1.5:87.5 ~ 95.8 with secondary ball milling.
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CN106278239A (en) * 2016-08-11 2017-01-04 广西新未来信息产业股份有限公司 A kind of superelevation gradient zinc oxide piezoresistive and preparation method thereof
CN106892658A (en) * 2017-04-13 2017-06-27 贵州大学 In3+、Ga3+Compound donor doping ZnO voltage-sensitive ceramics and preparation method
CN106904959A (en) * 2017-04-13 2017-06-30 贵州大学 Y3+、Ga3+Compound donor doping ZnO voltage-sensitive ceramics and preparation method
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CN106278239A (en) * 2016-08-11 2017-01-04 广西新未来信息产业股份有限公司 A kind of superelevation gradient zinc oxide piezoresistive and preparation method thereof
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CN106904959A (en) * 2017-04-13 2017-06-30 贵州大学 Y3+、Ga3+Compound donor doping ZnO voltage-sensitive ceramics and preparation method
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