CN101279843A - Superplastic zinc oxide pressure-sensitive ceramic material and preparation thereof - Google Patents

Superplastic zinc oxide pressure-sensitive ceramic material and preparation thereof Download PDF

Info

Publication number
CN101279843A
CN101279843A CNA2008100376584A CN200810037658A CN101279843A CN 101279843 A CN101279843 A CN 101279843A CN A2008100376584 A CNA2008100376584 A CN A2008100376584A CN 200810037658 A CN200810037658 A CN 200810037658A CN 101279843 A CN101279843 A CN 101279843A
Authority
CN
China
Prior art keywords
ceramic material
zinc oxide
ball
superplastic
functional additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2008100376584A
Other languages
Chinese (zh)
Other versions
CN101279843B (en
Inventor
施利毅
徐东
钟庆东
吴振红
巫欣欣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Shanghai for Science and Technology
Original Assignee
University of Shanghai for Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Shanghai for Science and Technology filed Critical University of Shanghai for Science and Technology
Priority to CN2008100376584A priority Critical patent/CN101279843B/en
Publication of CN101279843A publication Critical patent/CN101279843A/en
Application granted granted Critical
Publication of CN101279843B publication Critical patent/CN101279843B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention relates to a superplastic zinc oxide varistor ceramic material and a method for the production thereof, which belongs to the functional ceramic material manufacturing technique field. The ceramic material is characterized in that the zinc oxide varistor resistance material comprises the following compositions of 94 percent to 98 percent of ZnO as a main material, respectively 0.1 percent to 1.0 percent of MnO2, Co2O3, Bi2O3, Cr2O3 and Sb2O3 as a varistor functional additive, a small amount of ZrO2, Al2O3, Y2O3 and SiO2 as a superplastic functional additive by molar percentage, and all the oxides are micron-sized oxides. The varistor ceramic can be obtained by superplastic hot pressing and sintering at a temperature of between 1060 and 1200 DEG C, and the electric potential gradient can be increased to between 1500 and 1800V/mm. The varistor ceramic of the invention can be used for making high grade lightning protector products with supervoltage electric systems, thereby reducing the net hanging weight of equipment, reducing the equipment cost and enhancing the ice-snow resisting capability of the high voltage transmission network.

Description

Superplastic zinc oxide pressure-sensitive ceramic material and preparation method
Technical field
The present invention relates to a kind of superplastic zinc oxide pressure-sensitive ceramic material and preparation method, function of dominant stupalith manufacturing technology field.
Background technology
Superplasticity is a thin brilliant pottery build-in attribute at high temperature.Stupalith is hard brittle material at normal temperatures, because its structure and key, slip system is few, and dislocation produces and dyskinesia, and the tendency along boundary segregation is arranged, and it is a kind of hard brittle material in itself, produces viscous deformation at normal temperatures hardly.But some thin brilliant stupaliths can have certain plasticity under higher temperature.
Two prerequisites that produce superplasticity deformation are: stretching plastic stability does not promptly produce obvious constriction; Effectively suppress hole and boundary segregation.Crystalline material will have superplasticity by following several important requirements: (1) is because the super process of moulding is subjected to diffusion control, so experimental temperature should be enough high, so that diffusion enough soon.In the reality, experimental temperature will reach the over half of material melts temperature usually.(2) grain-size is tiny (for metallic substance, answers＜10 μ m usually; For stupalith, answer＜1 μ m usually), and want to keep stablizing fine crystalline structure, there is not or has only grain growing slightly, produce hole or the needed critical stress of boundary segregation so that make stress of fluidity be lower than.(3) it is granular that crystal grain such as has at axle, so that the generation of crystal boundary slippage.With the metallographic phase ratio, the easier acquisition fine crystalline structure of stupalith, at high temperature structure is more stable.
Thunder arrester is a kind of protection equipment that can absorb superpotential energy, over-voltage amplitude.During use thunder arrester is installed near the protected equipment, in parallel with protected equipment.The protection feature of thunder arrester is the basis of equipment for power transmission and distribution Insulation Coordination, and the thunder arrester of excellent property can be with the overvoltage Limiting in the power system to the harmless level that insulate.Improve the protective value of thunder arrester, can not only improve the serviceability of electrical power trans mission/distribution system, and can reduce the insulation of electrical installation level, thereby alleviate weight of equipment, reduce equipment cost.Zinc-Oxide Arrester is the key equipment of the anti-lightning strike and flashover fault of high pressure, supergrid and high voltage electric power equip ment, is widely used in ultra-high-tension power transmission line, city underground direct current supply line and railway network system.In order to cooperate the needs of domestic electrical network to extreme high voltage grade development, realize the miniaturization and the lightness of arrester valve piece made, reduce manufacturing cost, exploitation high potential gradient, excellent property, the ultra-high voltage thunder arrester product that reliability is high.The country of relative advanced technology, China develops slower aspect piezoresistive material, and its scale production is just development to some extent in recent years, already compares with international counterparts to have a certain distance.Annual production as companies such as PANASONIC, Siemens, U.S. Harris all surpasses hundred million, and the manufacturer of the more than one hundred million values of output in domestic seldom, has only one or two family, and product performance fall behind, for ultralow (potential gradient＜＜200V/mm) or the superelevation potential gradient (potential gradient＞＞300V/mm) voltage dependent resistor dependence on import still.And Japan and other countries has been developed the ZnO varistor sheet of potential gradient up to 400V/mm, is used for the lightning protection of 1000kV power transmission.The several large-scale electric corporation of Japan, as Toshiba, Mitsubishi, Hitachi, Fujitsu etc., all having developed potential gradient voluntarily is 300-400V/mm, discharge capacity is up to 300J/cm 3The MOA valve block.
Summary of the invention
One of purpose of the present invention provides that a kind of product performance are good, production cost is low, can be suitable for the superplastic zinc oxide pressure-sensitive ceramic material of suitability for industrialized production.
Two of purpose of the present invention provides a kind of preparation method of superplastic zinc oxide pressure-sensitive ceramic material.
For achieving the above object, the present invention is by the following technical solutions:
A kind of superplastic zinc oxide pressure-sensitive ceramic material, it is characterized in that this material comprises following component by mole per-cent: ZnO 94%-98% is a material of main part, MnO 2, Co 2O 3, Bi 2O 3, Cr 2O 3, Sb 2O 3Respectively for 0.1%-1.0% is pressure-sensitive functional additive, ZrO 20.2%-1.0%, Al 2O 30.001%-0.01%, Y 2O 30.01%-1.0%, SiO 20.01%-1.0% is the superplasticity functional additive, and above oxide compound is the micron order oxide compound.
A kind of preparation method who is used for above-mentioned superplastic zinc oxide pressure-sensitive ceramic material is characterized in that this method comprises following processing step:
1) prepare burden by following molar percentage component, ZnO 94%-98% is a material of main part, MnO 2, Co 2O 3, Bi 2O 3, Cr 2O 3, Sb 2O 3Respectively for 0.1%-1.0% is pressure-sensitive functional additive, ZrO 20.2%-1.0%, Al 2O 30.001%-0.01%, Y 2O 30.01%-1.0%, SiO 20.01%-1.0% is the superplasticity functional additive, and above oxide compound is the micron order oxide compound;
2) adopt zirconia ball, polyethylene jar, dehydrated alcohol is a ball-milling medium, zirconia ball: the batching powder: the mass ratio of dehydrated alcohol is 20: 1: 4, wet-milling 3-8h in the frequency conversion planetary ball mill, rotating speed 400-600rpm; The slurry that ball milling is good becomes dry powder at 70 ℃ of baking 24h;
3) adopt zirconia ball, polyethylene jar, the 1-3h that in the frequency conversion planetary ball mill, dry grinds, rotating speed 400-600rpm, zirconia ball: the powder quality ratio is 20: 1; Press forming behind the dry grinding back powder interpolation 2%PVA;
4) base substrate of press forming is warming up to 500-600 ℃ with 5 ℃/min in resistance furnace, is incubated 2h, furnace cooling in the air atmosphere; Pretreated base substrate places the tipping of super plastic compression to apply precompression in putting, and is warming up to 900-1200 ℃ of super plastic compression jointing temp and in the super strain rate 10 of moulding with 5 ℃/min -4-10 -2s -1Surpass through the 3-5min short period of time down and mould hot pressed sintering, be incubated 2-3h again in 1060-1200 ℃ of air atmosphere, furnace cooling promptly gets superplastic zinc oxide pressure-sensitive ceramic material.
The present invention is by adjusting pressure-sensitive functional additive MnO 2, Co 2O 3, Bi 2O 3, Cr 2O 3, Sb 2O 3With superplasticity functional additive ZrO 2, Al 2O 3, Y 2O 3, SiO 2Rational proportion, superplasticity ZnO pressure-sensitive ceramic material in conjunction with preparation method's preparation, it super moulded hot pressed sintering and obtains voltage-sensitive ceramic at 1060-1200 ℃, product has the excellent comprehensive performance, the density high porosity is low, and homogeneous microstructure does not have obvious coacervate, and potential gradient can be brought up to 1500-1800V/mm, nonlinear factor is 30-50, and leakage current is 2-20 μ A.Voltage-sensitive ceramic of the present invention can be used for making the high-quality thunder arrester product of ultrahigh voltage power system.
Embodiment
After now embodiments of the invention being described in.
Embodiment 1
(1) weighing is ZnO 95.445% in molar ratio respectively, MnO 20.5%, Co 2O 30.5%, Bi 2O 30.5%, Cr 2O 30.5%, Sb 2O 31.0%, ZrO 21.0%, Al 2O 30.005%, Y 2O 30.05%, SiO 20.5%, prepare burden.
(2) adopt zirconia ball, polyethylene jar, dehydrated alcohol is a ball-milling medium, wet-milling 5h in the frequency conversion planetary ball mill, and rotating speed 500rpm, ball: powder: the mass ratio of dehydrated alcohol is 20: 1: 4.
(3) slurry that ball milling is good becomes dry powder at 70 ℃ of baking 24h.
(4) adopt zirconia ball, polyethylene jar, the 3h that in the frequency conversion planetary ball mill, dry grinds, rotating speed 600rpm, ball: the powder mass ratio is 20: 1.
(5) press forming behind the dry grinding back powder interpolation 2%PVA.
(6) base substrate of press forming is warming up to 500 ℃ with 5 ℃/min in resistance furnace, is incubated 2h, furnace cooling in the air atmosphere.
(7) pretreated base substrate places the tipping of super plastic compression to apply precompression in putting, and is warming up to 1100 ℃ of super plastic compression jointing temps and in the super strain rate 10 of moulding with 5 ℃/min -4-10 -2s -1Surpass through the 3-5min short period of time down and mould hot pressed sintering, in 1100 ℃ of air atmospheres, be incubated 2h again, furnace cooling.
The Zinc-oxide piezoresistor of present embodiment made is through performance test, and potential gradient reaches 1800V/mm, leakage current 2 μ A, and nonlinear factor is 46.
Embodiment 2
(1) weighing is ZnO 95.49% in molar ratio respectively, MnO 20.5%, Co 2O 30.8%, Bi 2O 30.7%, Cr 2O 30.5%, Sb 2O 31.0%, ZrO 20.475%, Al 2O 30.01%, Y 2O 30.025%, SiO 20.5%, prepare burden.
(2) adopt zirconia ball, polyethylene jar, dehydrated alcohol is a ball-milling medium, wet-milling 5h in the frequency conversion planetary ball mill, and rotating speed 600rpm, ball: powder: the mass ratio of dehydrated alcohol is 20: 1: 4.
(3) slurry that ball milling is good becomes dry powder at 70 ℃ of baking 24h.
(4) adopt zirconia ball, polyethylene jar, the 2h that in the frequency conversion planetary ball mill, dry grinds, rotating speed 500rpm, ball: the powder mass ratio is 20: 1.
(5) press forming behind the dry grinding back powder interpolation 2%PVA.
(6) base substrate of press forming is warming up to 500 ℃ with 5 ℃/min in resistance furnace, is incubated 2h, furnace cooling in the air atmosphere.
(7) pretreated base substrate places the tipping of super plastic compression to apply precompression in putting, and is warming up to 1060 ℃ of super plastic compression jointing temps and in the super strain rate 10 of moulding with 5 ℃/min -4-10 -2s -1Surpass through the 3-5min short period of time down and mould hot pressed sintering, in 1060 ℃ of air atmospheres, be incubated 2.5h again, furnace cooling.
The Zinc-oxide piezoresistor of present embodiment made is through performance test, and potential gradient reaches 1600V/mm, leakage current 5 μ A, and nonlinear factor is 40.
Embodiment 3
(1) weighing is ZnO 95.29% in molar ratio respectively, MnO 20.5%, Co 2O 30.8%, Bi 2O 30.7%, Cr 2O 30.5%, Sb 2O 31.0%, ZrO 20.38%, Al 2O 30.01%, Y 2O 30.02%, SiO 20.8%, prepare burden.
(2) adopt zirconia ball, polyethylene jar, dehydrated alcohol is a ball-milling medium, wet-milling 5h in the frequency conversion planetary ball mill, and rotating speed 500rpm, ball: powder: the mass ratio of dehydrated alcohol is 20: 1: 4.
(3) slurry that ball milling is good becomes dry powder at 70 ℃ of baking 24h.
(4) adopt zirconia ball, polyethylene jar, the 2h that in the frequency conversion planetary ball mill, dry grinds, rotating speed 500rpm, ball: the powder mass ratio is 20: 1.
(5) press forming behind the dry grinding back powder interpolation 2%PVA.
(6) base substrate of press forming is warming up to 500 ℃ with 5 ℃/min in resistance furnace, is incubated 2h, furnace cooling in the air atmosphere.
(7) pretreated base substrate places the tipping of super plastic compression to apply precompression in putting, and is warming up to 1200 ℃ of super plastic compression jointing temps and in the super strain rate 10 of moulding with 5 ℃/min -4-10 -2s -1Surpass through the 3-5min short period of time down and mould hot pressed sintering, in 1200 ℃ of air atmospheres, be incubated 3h again, furnace cooling.
The Zinc-oxide piezoresistor of present embodiment made is through performance test, and potential gradient reaches 1500V/mm, leakage current 15 μ A, and nonlinear factor is 35.

Claims (2)

1. superplastic zinc oxide pressure-sensitive ceramic material, it is characterized in that this material comprises following component by mole per-cent: ZnO 94%-98% is a material of main part, MnO 2, Co 2O 3, Bi 2O 3, Cr 2O 3, Sb 2O 3Respectively for 0.1%-1.0% is pressure-sensitive functional additive, ZrO 20.2%-1.0%, Al 2O 30.001%-0.01%, Y 2O 30.01%-1.0%, SiO 20.01%-1.0% is the superplasticity functional additive, and above oxide compound is the micron order oxide compound.
2. preparation method who is used for the described superplastic zinc oxide pressure-sensitive ceramic material of claim 1 is characterized in that this method comprises following processing step:
1) prepare burden by following molar percentage component, ZnO 94%-98% is a material of main part, MnO 2, Co 2O 3, Bi 2O 3, Cr 2O 3, Sb 2O 3Respectively for 0.1%-1.0% is pressure-sensitive functional additive, ZrO 20.2%-1.0%, Al 2O 30.001%-0.01%, Y 2O 30.01%-1.0%, SiO 20.01%-1.0% is the superplasticity functional additive, and above oxide compound is the micron order oxide compound;
2) adopt zirconia ball, polyethylene jar, dehydrated alcohol is a ball-milling medium, zirconia ball: the batching powder: the mass ratio of dehydrated alcohol is 20: 1: 4, wet-milling 3-8h in the frequency conversion planetary ball mill, rotating speed 400-600rpm; The slurry that ball milling is good becomes dry powder at 70 ℃ of baking 24h;
3) adopt zirconia ball, polyethylene jar, the 1-3h that in the frequency conversion planetary ball mill, dry grinds, rotating speed 400-600rpm, zirconia ball: the powder quality ratio is 20: 1; Press forming behind the dry grinding back powder interpolation 2%PVA;
4) base substrate of press forming is warming up to 500-600 ℃ with 5 ℃/min in resistance furnace, is incubated 2h, furnace cooling in the air atmosphere; Pretreated base substrate places the tipping of super plastic compression to apply precompression in putting, and is warming up to 900-1200 ℃ of super plastic compression jointing temp and in the super strain rate 10 of moulding with 5 ℃/min -4-10 -2s -1Surpass through the 3-5min short period of time down and mould hot pressed sintering, be incubated 2-3h again in 1060-1200 ℃ of air atmosphere, furnace cooling promptly gets superplastic zinc oxide pressure-sensitive ceramic material.
CN2008100376584A 2008-05-20 2008-05-20 Superplastic zinc oxide pressure-sensitive ceramic material and preparation thereof Active CN101279843B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008100376584A CN101279843B (en) 2008-05-20 2008-05-20 Superplastic zinc oxide pressure-sensitive ceramic material and preparation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008100376584A CN101279843B (en) 2008-05-20 2008-05-20 Superplastic zinc oxide pressure-sensitive ceramic material and preparation thereof

Publications (2)

Publication Number Publication Date
CN101279843A true CN101279843A (en) 2008-10-08
CN101279843B CN101279843B (en) 2011-12-21

Family

ID=40012543

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008100376584A Active CN101279843B (en) 2008-05-20 2008-05-20 Superplastic zinc oxide pressure-sensitive ceramic material and preparation thereof

Country Status (1)

Country Link
CN (1) CN101279843B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101823874A (en) * 2010-04-01 2010-09-08 江苏大学 High-nonlinearity rare earth oxide-doped zinc oxide voltage-sensitive ceramic material
CN101891458A (en) * 2010-07-08 2010-11-24 深圳市银星电气股份有限公司 Preparation method of zinc oxide pressure-sensitive ceramic slurry and pressure-sensitive ceramic resistor material
CN102260073A (en) * 2011-04-28 2011-11-30 江苏大学 Zinc-oxide-based low-voltage voltage-sensitive ceramic thin film material and preparation method thereof
CN101531506B (en) * 2009-04-23 2011-11-30 山东大学 Antimony silicate-modified high gradient zinc oxide pressure sensitive material
CN107082635A (en) * 2017-04-24 2017-08-22 新昌县恩喜电器有限公司 A kind of low piezoresistor of residual voltage ratio and its application

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531506B (en) * 2009-04-23 2011-11-30 山东大学 Antimony silicate-modified high gradient zinc oxide pressure sensitive material
CN101823874A (en) * 2010-04-01 2010-09-08 江苏大学 High-nonlinearity rare earth oxide-doped zinc oxide voltage-sensitive ceramic material
CN101891458A (en) * 2010-07-08 2010-11-24 深圳市银星电气股份有限公司 Preparation method of zinc oxide pressure-sensitive ceramic slurry and pressure-sensitive ceramic resistor material
CN101891458B (en) * 2010-07-08 2012-08-22 深圳Abb银星避雷器有限公司 Preparation method of zinc oxide pressure-sensitive ceramic slurry and pressure-sensitive ceramic resistor material
CN102260073A (en) * 2011-04-28 2011-11-30 江苏大学 Zinc-oxide-based low-voltage voltage-sensitive ceramic thin film material and preparation method thereof
CN107082635A (en) * 2017-04-24 2017-08-22 新昌县恩喜电器有限公司 A kind of low piezoresistor of residual voltage ratio and its application
CN107082635B (en) * 2017-04-24 2020-02-18 新昌县恩喜电器有限公司 Piezoresistor with low residual voltage ratio and application thereof

Also Published As

Publication number Publication date
CN101279843B (en) 2011-12-21

Similar Documents

Publication Publication Date Title
CN101333104A (en) Zinc oxide voltage-sensitive ceramic materials doped by superplasticity nanometer oxide and preparation method
CN101279843B (en) Superplastic zinc oxide pressure-sensitive ceramic material and preparation thereof
CN101383208B (en) Preparation of high voltage gradient zinc oxide varistor valve
CN101279844A (en) Zinc oxide pressure-sensitive ceramic material doped with composite rare-earth oxide
CN100485827C (en) Method for preparing high-potential gradient zinc oxide piezoresistance by low-temperature sintering
CN102557610A (en) High-potential-gradient zinc oxide varistor, and making method and application thereof
CN104616850B (en) A kind of preparation method of zinc oxide/epoxy resin composite pressure-sensitive resistance
CN104944935A (en) ZnO varister ceramic and preparation method thereof
CN101786874A (en) Process method for preparing low residual voltage ZnO varistor ceramic
CN102515741A (en) Zinc oxide varistor material and preparation method thereof
CN101823874A (en) High-nonlinearity rare earth oxide-doped zinc oxide voltage-sensitive ceramic material
CN105645948A (en) Preparation method of high-voltage gradient and low-leakage current pressure-sensitive resistor ceramic material
CN105016721A (en) Method for preparation of ZnO varistor ceramic by common doping of aluminum, gallium and yttrium ions
CN103080237A (en) Composition having non-linear current-voltage characteristics
CN105622086A (en) Method for preparing high-gradient zinc oxide voltage dependent resistor ceramic
CN105859279A (en) Novel process method for preparing zinc oxide piezoresistor ceramic with excellent properties
CN108546111A (en) A kind of zinc oxide piezoresistor ceramic and preparation method thereof of high-voltage gradient, low residual voltage, low Leakage Current
CN110423110B (en) Ultrahigh nonlinear ZnO-Bi2O3Base pressure sensitive ceramic and preparation method thereof
CN104557016A (en) High-nonlinearity frit doped zinc oxide voltage-sensitive ceramic material
CN101265083A (en) Rare earth nitrate doping zinc oxide pressure-sensitive ceramic material and preparation method thereof
CN111233461A (en) High surge current withstanding SnO2Method for preparing varistor ceramic
CN111161932B (en) Lightning-protection annular zinc oxide resistance card for power distribution network and preparation method thereof
CN101823875B (en) Zinc oxide varistor material suitable for being used by electrical appliance working in high-tension inrush current and preparation method thereof
JP4282243B2 (en) Non-linear resistor
CN102503582A (en) Preparation method of inorganic-organic composite insulation coating resistant to large current impact

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant