CN102515741A - Zinc oxide varistor material and preparation method thereof - Google Patents
Zinc oxide varistor material and preparation method thereof Download PDFInfo
- Publication number
- CN102515741A CN102515741A CN2011104045402A CN201110404540A CN102515741A CN 102515741 A CN102515741 A CN 102515741A CN 2011104045402 A CN2011104045402 A CN 2011104045402A CN 201110404540 A CN201110404540 A CN 201110404540A CN 102515741 A CN102515741 A CN 102515741A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- oxide
- content
- doping
- nano
- 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.)
- Pending
Links
Abstract
The invention relates to a zinc oxide varistor material and a preparation method thereof. The method comprises steps that: micron-grade zinc oxide, nano-grade zinc oxide, doping oxide and a sintering material are mixed; the mixture is subject to high-energy wet grinding, pre-sintering, and high-energy dry-grinding, such that a novel zinc oxide varistor material is obtained; the novel zinc oxide varistor material is press-molded and sintered, such that a novel zinc oxide varistor is obtained. The novel zinc oxide varistor material provided by the invention has better non-linear coefficient, lower leak current, and lower residual voltage ratio. If the proportions of the four materials of micron-grade zinc oxide, nano-grade zinc oxide, doping oxide and the sintering material are regulated, parameters such as potential gradient and non-linear coefficient of the zinc oxide varistor can be flexibly regulated. The method is advantaged in simple preparation technology and convenient operation. With the method, low-temperature sintering of the zinc oxide varistor can be realized, and the energy consumption is low. The method is suitable for scaled productions.
Description
Technical field
The present invention relates to the piezoresistive material preparing technical field, particularly, the present invention relates to zinc oxide piezoresistive material and preparation method thereof.
Background technology
Voltage dependent resistor is to become with voltage in certain current/voltage scope internal resistance value, or says the resistance device of " resistance value is to voltage-sensitive ".English name is abbreviated as " VDR " " Voltage Dependent Resistor ", perhaps is called " Varistor ".The resistive element material of piezoresistor is a semi-conductor, so it is a kind of semiconductor resistor.A large amount of now " zinc oxide " that use are piezoresistor (ZnO), and its material of main part has dyad (Zn) and hexad oxygen (O) to constitute.So from the angle of material, zinc oxide varistor is a kind of " II-VI family oxide semiconductor ".
Zinc oxide varistor is since nineteen sixty-eight comes out; As the overvoltage protection and the surge absorbing element of circuit, equipment and components and parts, created the technological achievement of epoch-making significance by generally at electric power, electronic technology field with its superior non-linear conductive characteristic.
The preparation method of traditional Zinc-oxide piezoresistor, be mostly oxide compound with micron-sized ZnO major ingredient, Mn, Co, Cr, Bi, Sb etc. according to certain ratio weighing and ball milling, last under 1100 ℃～1500 ℃ high temperature sintering form.For example CN 101613199A relates to a kind of high-performance zinc oxide composite ceramic voltage dependent resistor material and preparation method, belongs to electronic ceramics preparation and applied technical field.Said pottery is principal phase with zinc oxide, and adopting Praseodymium trioxide is the non-linear phase of starting, and to adopt a small amount of Co, Cr, the oxide compound of Fe or W be potential gradient and non-linear toughener, and each component molar content is following: ZnO 80～95%, Pr
6O
110.01～15%, CoO 0.01～10.0%, Cr
2O
30.01～8.0%, Fe
2O
30.0～5.0%, WO
30.0～3.0%.Said material preparation method comprises " the whole grain of batch mixing → high-energy ball milling → oven dry → mixing → sieve → compression molding → sintering → quilt silver " process step successively.The piezoresistive material crystal grain of this invention is tiny, microstructure is even, and (current density is 1mA/cm to potential gradient E
2The time corresponding potential gradient value) bring up to 570～750V/mm, nonlinear factor α is 24～32, leakage current I
L(75%E current corresponding density value) is 0.0004～0.0006mA/cm
2, have good comprehensive electric property.But; For the grain boundary layer that obtains high resistance need carry out sintering under 1100 ℃～1500 ℃ high temperature, energy consumption is big, simultaneously; In the preparation process; The kind of various doping oxides and content etc. have certain limitation, and then make the various electrical properties of the final ZnO varistor that obtains receive certain restriction, lack controllability.P. Duran etc. utilizes chemical method to prepare nano powder, under 900 ℃ and 825 ℃ of double sintering temperature, prepared potential gradient and be 2000V/mm Zinc-oxide piezoresistor (Key Engineering Materials, 2002,206-213:1389-1392).But this method exists complex process, shortcoming that cost is high, is difficult to large-scale production.CN 1273424A discloses a kind of nano-TiO
2Application in the preparation ZnO varistor is earlier with nano-TiO
2Even with dispersant, and then add in the material side of people's ZnO varistor, adopt electronic ceramic process, through vibration mixing, granulating and forming, 1260 ℃ of sintering are processed ZnO varistor.Nanometer is oozed assorted ZnO varistor performance parameters and is superior to a micron TiO
2Mix, wherein, the ZnO varistor of mixed nanometer need be under 1260 ℃ hot conditions sintering, this not only can increase current consumption, and can shorten the shelf life of sintering oven, thereby has increased production cost.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of preparation method of zinc oxide piezoresistive material.Said method is through introducing the zinc oxide major ingredient of part nanometer; Nano level oxide dopant and micron order are or/and nano level agglomerated material; Adopt high-energy ball-milling process and presintering technology, finally obtain the excellent novel zinc oxide piezoresistive material of electrical property.One aspect of the present invention is because part Nano-class zinc oxide major ingredient, nano-scale oxide doping agent and micron order, greatly reduce the sintering temperature of Zinc-oxide piezoresistor or/and the introducing of nano level agglomerated material; On the other hand, zinc oxide piezoresistive material is carried out suitable presintering, effectively improved the big electric current and the little current characteristics of Zinc-oxide piezoresistor.Simultaneously, or/and the adding proportion of nano level agglomerated material can effectively be regulated and control the comprehensive electrochemical properties of Zinc-oxide piezoresistor, and simplify preparation technology, be convenient to large-scale production through the appropriate change micron order.
The preparation method of said zinc oxide piezoresistive material comprises: with micron order zinc oxide, Nano-class zinc oxide, doping oxide and agglomerated material mix, high energy wet-milling then, and presintering, the high energy dry grinding obtains zinc oxide piezoresistive material.
Preferably, with carrying out sintering after the zinc oxide piezoresistive material compression moulding that makes, obtain Zinc-oxide piezoresistor.
With micron order zinc oxide, Nano-class zinc oxide and doping oxide note condiments A; Preferably; Said material A comprises by the quality percentage composition: the micron order zinc oxide content is 32～90%; The content of Nano-class zinc oxide is 5～65%, and the content of doping oxide is 0.01～15%, and the said components sum is 100%; Further preferred, said material A comprises by the quality percentage composition: the micron order zinc oxide content is 38～85%, and the content of Nano-class zinc oxide is 10～60%, and the content of doping oxide is 0.08～10%, and the said components sum is 100%; Preferred especially, said material A comprises by the quality percentage composition: the micron order zinc oxide content is 44～80%, and the content of nano level zinc oxide is 15～55%, and the content of doping oxide is 0.1～5%, and the said components sum is 100%.
Preferably, said doping oxide is B
2O
3, Fe
2O
3, SnO
2, ZrO
2, SiO
2, TiO
2, V
2O
5, WO
3, Pr
6O
11, Nb
2O
5, Y
2O
3, NiO, La
2O
3, Sb
2O
3, CeO
2, Li
2O, CuO, Al
2O
3, Co
2O
3, MnO
2, Bi
2O
3, Cr
2O
3In a kind or at least 2 kinds combination, said combination typical case but the example of non-limit have: B
2O
3, Fe
2O
3, SnO
2, ZrO
2Combination, Co
2O
3, Cr
2O
3Combination, CeO
2, Li
2O, CuO, Al
2O
3Combination, TiO
2, V
2O
5, WO
3Combination, NiO, La
2O
3, Sb
2O
3, CeO
2, Li
2The combination of O, CuO, Al
2O
3, Co
2O
3, MnO
2, Bi
2O
3, Cr
2O
3Combination etc., be preferably B especially
2O
3, Fe
2O
3, SnO
2, ZrO
2, SiO
2, TiO
2, V
2O
5, WO
3, Pr
6O
11, Nb
2O
5, Y
2O
3, NiO, La
2O
3, Sb
2O
5, CeO
2, Li
2O, CuO, Al
2O
3, Co
2O
3And Cr
2O
3In a kind or at least 2 kinds combination; Said doping oxide can obtain through commercially available, also can be prepared according to the expertise/new technology of its grasp by one of ordinary skill in the art.
Preferably, said doping oxide is the nano level doping oxide.
Preferably, said agglomerated material is a micron order or/and the nano level agglomerated material, and with said agglomerated material note condiments B, said material B is preferably ZnO, NiO, Bi
2O
3, Sb
2O
3, Co
2O
3, MnO
2, Cr
2O
3, V
2O
5, SiO
2, B
2O
3, TiO
2, ZrO
2, Ni
2O
3, Al
2O
3, Dy
2O
3, Y
2O
3In the composite oxides of combination behind high energy dry grinding, sintering of a kind or at least 2 kinds, said combination typical case but the example of non-limit comprise: the combination of ZnO, NiO, Bi
2O
3, Sb
2O
3, Co
2O
3Combination, MnO
2, Cr
2O
3, V
2O
5, SiO
2Combination, B
2O
3, TiO
2, ZrO
2, Ni
2O
3, Al
2O
3Combination, ZrO
2, Ni
2O
3, Al
2O
3, Dy
2O
3, Y
2O
3Combination, ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Dy
2O
3, B
2O
3Combination, ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Y
2O
3, V
2O
5, B
2O
3Combination etc., preferred especially, said material B is ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Dy
2O
3, Y
2O
3, V
2O
5, B
2O
3In a kind or at least 2 kinds composite oxides behind high energy dry grinding, sintering.
Various components contents can be selected according to the expertise of its grasp by one of ordinary skill in the art among the said material B.
Preferably; Said material A is 100: 1～100: 55 with the ratio of material B quality; Further preferred said material A is 100: 2～100: 45 with the ratio of material B quality; More preferably said material A is 100: 4～100: 40 with the ratio of material B quality, and preferred especially said material A is 100: 5～100: 35 with the ratio of material B quality.
Preferably, high energy ball mill is adopted in said high energy wet-milling, and the further preferred planetary high-energy ball mill that adopts especially preferably adopts the frequency conversion type planetary high-energy ball mill.
Preferably, the liquid medium that said high energy wet-milling is adopted is water and/or organic solvent, further is preferably water, C
1-C
5Alcohols, C
3-C
71 kind or at least 2 kinds combination in ketone, halogenated alkane, the aromatics, more preferably water, ethanol, acetone, CCl
4, a kind or at least 2 kinds combination in the toluene, said combination typical case but the example of non-limit have: water makes up the combination of acetone and toluene, acetone, CCl with alcoholic acid
4, toluene combination etc., be preferably ethanol especially.
Preferably, the slurry after the high energy wet-milling is carried out carrying out presintering after the drying, preferred especially said drying is a thorough drying in vacuum drying oven.
Preferably, box-type furnace is adopted in said presintering.
Preferably; Said pre-sintering temperature is 300～750 ℃, for example 301 ℃, 302 ℃, 305 ℃, 401 ℃, 598 ℃, 599 ℃, 740 ℃, 745 ℃, 749 ℃ etc., further is preferably 300～700 ℃; More preferably 350～650 ℃, be preferably 400～600 ℃ especially.
Preferably; The said presintering time is more than 0.5 hour; For example 0.51 hour, 0.55 hour, 0.99 hour, 1.1 hours, 1.99 hours, 4.5 hours, 4.9 hours, 4.95 hours, 4.99 hours, 5 hours etc.; Further be preferably 0.7～5 hour, more preferably 0.9～3 hour, be preferably 1～2 hour especially.
Preferably, high energy ball mill is adopted in said high energy dry grinding, and the further preferred planetary high-energy ball mill that adopts especially preferably adopts the frequency conversion type planetary high-energy ball mill.
Said high energy wet-milling and high energy dry grinding are the technology of affiliated known, can select appropriate condition according to the expertise of its grasp by one of ordinary skill in the art, to obtain nano level, the uniform zinc oxide piezoresistive material of particle diameter.
Preferably; After zinc oxide piezoresistive material compression moulding, sintering temperature is 780～1200 ℃, for example 781 ℃, 782 ℃, 783 ℃, 785 ℃, 851 ℃, 1099 ℃, 1195 ℃, 1199 ℃ etc.; Further be preferably 820～1150 ℃, be preferably 850～1100 ℃ especially.
Preferably; After zinc oxide piezoresistive material compression moulding; Sintering time is more than 0.5 hour, for example 0.51 hour, 0.52 hour, 0.55 hour, 1.05 hours, 1.1 hours, 1.2 hours, 5.9 little+time, 11 hours, 11.5 hours, 11.9 hours, 11.99 hours etc., further be preferably 0.7～12 hour; More preferably 0.8～8 hour, be preferably 1～6 hour especially.
One of the object of the invention also is to provide a kind of zinc oxide piezoresistive material.
Said zinc oxide piezoresistive material is by method for preparing of the present invention; Effectively improve nanometer zinc oxide, various nano level doping oxide and micron order or/and the uniform microstructure property of the dispersing uniformity of nano level agglomerated material and zinc oxide pressure-sensitive ceramic the time; Can effectively improve the big electric current and the little current characteristics of Zinc-oxide piezoresistor; And effectively reduce the residual voltage ratio of Zinc-oxide piezoresistor, reduced leakage current.
Said zinc oxide piezoresistive material, its component comprises: micron order zinc oxide, Nano-class zinc oxide, doping oxide and agglomerated material.
With micron order zinc oxide, Nano-class zinc oxide and doping oxide note condiments A; Preferably; Said material A comprises by the quality percentage composition: the micron order zinc oxide content is 32～90%; The content of Nano-class zinc oxide is 5～65%, and the content of doping oxide is 0.01～15%, and the said components sum is 100%; Further preferred, said material A comprises by the quality percentage composition: the micron order zinc oxide content is 38～85%, and the content of Nano-class zinc oxide is 10～60%, and the content of doping oxide is 0.08～10%, and the said components sum is 100%; Preferred especially, said material A comprises by the quality percentage composition: the micron order zinc oxide content is 44～80%, and the content of nano level zinc oxide is 15～55%, and the content of doping oxide is 0.1～5%, and the said components sum is 100%.
Preferably, said doping oxide is B
2O
3, Fe
2O
3, SnO
2, ZrO
2, SiO
2, TiO
2, V
2O
5, WO
3, Pr
6O
11, Nb
2O
5, Y
2O
3, NiO, La
2O
3, Sb
2O
3, CeO
2, Li
2O, CuO, Al
2O
3, Co
2O
3, MnO
2, Bi
2O
3, Cr
2O
3In a kind or at least 2 kinds combination, said combination typical case but the example of non-limit have: B
2O
3, Fe
2O
3, SnO
2, ZrO
2Combination, Co
2O
3, Cr
2O
3Combination, CeO
2, Li
2O, CuO, Al
2O
3Combination, TiO
2, V
2O
5, WO
3Combination, NiO, La
2O
3, Sb
2O
3, CeO
2, Li
2The combination of O, CuO, Al
2O
3, Co
2O
3, MnO
2, Bi
2O
3, Cr
2O
3Combination etc., be preferably B especially
2O
3, Fe
2O
3, SnO
2, ZrO
2, SiO
2, TiO
2, V
2O
5, WO
3, Pr
6O
11, Nb
2O
5, Y
2O
3, NiO, La
2O
3, Sb
2O
5, CeO
2, Li
2O, CuO, Al
2O
3, Co
2O
3And Cr
2O
3In a kind or at least 2 kinds combination; Said doping oxide can obtain through commercially available, also can be prepared according to the expertise/new technology of its grasp by one of ordinary skill in the art.
Preferably, said agglomerated material is a micron order or/and the nano level agglomerated material, and with said agglomerated material note condiments B, said material B is preferably ZnO, NiO, Bi
2O
3, Sb
2O
3, Co
2O
3, MnO
2, Cr
2O
3, V
2O
5, SiO
2, B
2O
3, TiO
2, ZrO
2, Ni
2O
3, Al
2O
3, Dy
2O
3, Y
2O
3In the composite oxides of combination behind high energy dry grinding, sintering of a kind or at least 2 kinds, said combination typical case but the example of non-limit comprise: the combination of ZnO, NiO, Bi
2O
3, Sb
2O
3, Co
2O
3Combination, MnO
2, Cr
2O
3, V
2O
5, SiO
2Combination, B
2O
3, TiO
2, ZrO
2, Ni
2O
3, Al
2O
3Combination, ZrO
2, Ni
2O
3, Al
2O
3, Dy
2O
3, Y
2O
3Combination, ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Dy
2O
3, B
2O
3Combination, ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Y
2O
3, V
2O
5, B
2O
3Combination etc., preferred especially, said material B is ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Dy
2O
3, Y
2O
3, V
2O
5, B
2O
3In a kind or at least 2 kinds composite oxides behind high energy dry grinding, sintering.
Preferably; Said material A is 100: 1～100: 55 with the ratio of material B quality; Further preferred said material A is 100: 2～100: 45 with the ratio of material B quality; More preferably said material A is 100: 4～100: 40 with the ratio of material B quality, and preferred especially said material A is 100: 5～100: 35 with the ratio of material B quality.
Preferably, said doping oxide is the nano level doping oxide.
Compared with prior art, the present invention has the following advantages:
(1) the present invention or/and the introducing of nano level agglomerated material, greatly reduces the sintering temperature of Zinc-oxide piezoresistor through introducing part nanometer zinc oxide major ingredient, nano-scale oxide doping agent and micron order;
(2) compare with traditional Zinc-oxide piezoresistor preparation method; Zinc oxide piezoresistive material is carried out suitable presintering; Carrying out the high energy dry grinding then; Effectively improving nanometer zinc oxide, various nano level doping oxide and micron order or/and in the uniform microstructure property of the dispersing uniformity of nano level agglomerated material and zinc oxide pressure-sensitive ceramic, can effectively improve the big electric current and the little current characteristics of Zinc-oxide piezoresistor;
(3) through the appropriate change micron order or/and the adding proportion of nano level agglomerated material, can effectively regulate and control the comprehensive electrochemical properties of Zinc-oxide piezoresistor, parameter such as potential gradient, nonlinear factor for example, and simplified preparation technology is convenient to large-scale production;
(4) preparation technology of the present invention is simple, and is easy to operate, when having reduced production cost, has more excellent nonlinear factor, effectively reduces the residual voltage ratio of Zinc-oxide piezoresistor, reduced leakage current.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
Get an amount of micron order ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Dy
2O
3And B
2O
3Carry out the high energy dry grinding be followed successively by 8%, 27%, 7.5%, 7.09%, 6.2%, 23%, 0.01%, 0.3%, 0.9% and 20% ratio weighing according to weight percentage after,, obtain agglomerated material B1 then 400 ℃ of presintering 2 hours.
The percentage composition of weighing quality in proportion is respectively 44.9% micron order ZnO, 50.1% nano level ZnO and 5% nano level Pr
6O
11Main base material A 1, the agglomerated material B1 that weighing is an amount of, the mass ratio that makes A1 and B1 is 100: 5, will in A1 and B1, add absolute ethyl alcohol, in the frequency conversion planetary ball mill, carries out high-energy ball milling, then thorough drying in vacuum drying oven.Dried powder in 400 ℃ of presintering 2 hours, carries out the high energy dry grinding then in the frequency conversion type planetary high-energy ball mill in box-type furnace, obtain novel zinc oxide piezoresistive material.
Above-mentioned with after the novel zinc oxide piezoresistive material compression moulding, 850 ℃ of sintering 6 hours, obtain novel Zinc-oxide piezoresistor.Know that through electric performance test the potential gradient of this novel Zinc-oxide piezoresistor is 336V/mm, nonlinear factor is 22, leakage current 9.5 μ A.
Embodiment 2
Get an amount of micron order ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, V
2O
5, Y
2O
3And B
2O
3Carry out the high energy dry grinding be followed successively by 8%, 26.8%, 4%, 8%, 4%, 23%, 0.02%, 0.08%, 7%, 0.1% and 19% ratio weighing according to weight percentage after,, obtain agglomerated material B2 then 600 ℃ of presintering 1 hour.
The percentage composition of weighing quality in proportion is respectively 80% micron order ZnO, 18.05% nano level ZnO, 1.85% nano level Sb
2O
5With 0.1% nano level MnO
2Main base material A 2, the agglomerated material B2 that weighing is an amount of, the mass ratio that makes A1 and B1 is 100: 10, will in A2 and B2, add absolute ethyl alcohol, in the frequency conversion planetary ball mill, carries out high-energy ball milling, then thorough drying in vacuum drying oven.Dried powder in 600 ℃ of presintering 1 hour, carries out the high energy dry grinding then in the frequency conversion type planetary high-energy ball mill in box-type furnace, obtain novel zinc oxide piezoresistive material.
Above-mentioned with after the novel zinc oxide piezoresistive material compression moulding, 1100 ℃ of sintering 1 hour, obtain novel Zinc-oxide piezoresistor.Know that through electric performance test the potential gradient of this novel Zinc-oxide piezoresistor is 826V/mm, nonlinear factor is 35, leakage current 1.2 μ A.
Embodiment 3
Preparation agglomerated material B1, method is with embodiment 1.The percentage composition of weighing quality in proportion is respectively 65% micron order ZnO, 32% nano level ZnO and 3% nano level SnO
2Main base material A 3, the agglomerated material B1 that weighing is an amount of, the mass ratio that makes A3 and B1 is 100: 35, will in A3 and B1, add absolute ethyl alcohol, in the frequency conversion planetary ball mill, carries out high-energy ball milling, then thorough drying in vacuum drying oven.Dried powder in 500 ℃ of presintering 1.5 hours, carries out the high energy dry grinding then in the frequency conversion type planetary high-energy ball mill in box-type furnace, obtain novel zinc oxide piezoresistive material.
Above-mentioned with after the novel zinc oxide piezoresistive material compression moulding, 950 ℃ of sintering 2 hours, obtain novel Zinc-oxide piezoresistor.Know that through electric performance test the potential gradient of this novel Zinc-oxide piezoresistor is 582V/mm, nonlinear factor is 23, leakage current 8.9 μ A.
Embodiment 4
Get an amount of micron order ZnO, Bi
2O
3, Sb
2O
3, ZrO
2, Ni
2O
3, Al
2O
3, Dy
2O
3, SiO
2, MnO
2, Co
2O
3And B
2O
3Carry out the high energy dry grinding be followed successively by 7%, 25%, 8%, 0.05%, 0.03%, 0.01%, 0.5%, 22.01%, 7%, 8% and 22.4% ratio weighing according to weight percentage after,, obtain agglomerated material B4 then 300 ℃ of presintering 5 hours.
The percentage composition of weighing quality in proportion is respectively 32% micron order ZnO, 65% nano level ZnO and 1.6% nano level SiO
2, 0.55% nano level TiO
2, 0.85% nano level V
2O
5Main base material A 4, the agglomerated material B4 that weighing is an amount of, the mass ratio that makes A4 and B4 is 100: 1, will in A4 and B4, add acetone and alcoholic acid mixture, in the frequency conversion planetary ball mill, carries out high-energy ball milling, then thorough drying in vacuum drying oven.Dried powder in 300 ℃ of presintering 5 hours, carries out the high energy dry grinding then in the frequency conversion type planetary high-energy ball mill in box-type furnace, obtain zinc oxide piezoresistive material.
Above-mentioned with after the zinc oxide piezoresistive material compression moulding, 1200 ℃ of sintering 0.5 hour, obtain Zinc-oxide piezoresistor.Know that through electric performance test the potential gradient of this Zinc-oxide piezoresistor is 382V/mm, nonlinear factor is 21, leakage current 9.2 μ A.
Embodiment 5
Get proper amount of nano level ZnO, NiO, Bi
2O
3, Sb
2O
3, ZrO
2, Ni
2O
3, Cr
2O
3, Co
2O
3, TiO
2, Dy
2O
3, SiO
2And B
2O
3Carry out the high energy dry grinding be followed successively by 8%, 0.05%, 28%, 5%, 0.1%, 0.2%, 6%, 7%, 0.01%, 0.3%, 23.34 and 22% ratio weighing according to weight percentage after; 750 ℃ of presintering 0.5 hour, obtain agglomerated material B5 then.
The percentage composition of weighing quality in proportion is respectively 90% micron order ZnO, 5% nano level ZnO and 1% nano level La
2O
3, 3% nano level Sb
2O
3, 0.5% nano level CeO
2, 0.5% nano level MnO
2Main base material A 5, the agglomerated material B5 that weighing is an amount of, the mass ratio that makes A5 and B5 is 100: 55, will in A5 and B5, add ethanol and CCl
4Mixed solution, in the frequency conversion planetary ball mill, carry out high-energy ball milling, then thorough drying in vacuum drying oven.Dried powder in 750 ℃ of presintering 0.5 hour, carries out the high energy dry grinding then in the frequency conversion type planetary high-energy ball mill in box-type furnace, obtain zinc oxide piezoresistive material.
Above-mentioned with after the zinc oxide piezoresistive material compression moulding, 780 ℃ of sintering 12 hours, obtain Zinc-oxide piezoresistor.Know that through electric performance test the potential gradient of this Zinc-oxide piezoresistor is 455V/mm, nonlinear factor is 26, leakage current 6.8 μ A.
Can find out from above-mentioned all embodiment, as long as the proportioning that guarantees various parameters in the preparation process can obtain novel zinc oxide piezoresistive material of the present invention in the listed scope of claim.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the preparation method of a zinc oxide piezoresistive material is characterized in that, said method; Comprise: with micron order zinc oxide, Nano-class zinc oxide, doping oxide and agglomerated material mix, high energy wet-milling then; Presintering, the high energy dry grinding obtains zinc oxide piezoresistive material.
2. the method for claim 1 is characterized in that, with carrying out sintering after the zinc oxide piezoresistive material compression moulding that makes, obtains Zinc-oxide piezoresistor.
3. according to claim 1 or claim 2 method; It is characterized in that; With micron order zinc oxide, Nano-class zinc oxide and doping oxide note condiments A, said material A preferably includes by the quality percentage composition: the micron order zinc oxide content is 32～90%, and the content of Nano-class zinc oxide is 5～65%; The content of doping oxide is 0.01～15%, and the said components sum is 100%;
Further preferred, said material A comprises by the quality percentage composition: the micron order zinc oxide content is 38～85%, and the content of Nano-class zinc oxide is 10～60%, and the content of doping oxide is 0.08～10%, and the said components sum is 100%;
Preferred especially, said material A comprises by the quality percentage composition: the micron order zinc oxide content is 44～80%, and the content of nano level zinc oxide is 15～55%, and the content of doping oxide is 0.1～5%, and the said components sum is 100%.
4. like each described method of claim 1-3, it is characterized in that said doping oxide is preferably B
2O
3, Fe
2O
3, SnO
2, ZrO
2, SiO
2, TiO
2, V
2O
5, WO
3, Pr
6O
11, Nb
2O
5, Y
2O
3, NiO, La
2O
3, Sb
2O
3, CeO
2, Li
2O, CuO, Al
2O
3, Co
2O
3, MnO
2, Bi
2O
3, Cr
2O
3In a kind or at least 2 kinds combination, be preferably B especially
2O
3, Fe
2O
3, SnO
2, ZrO
2, SiO
2, TiO
2, V
2O
5, WO
3, Pr
6O
11, Nb
2O
5, Y
2O
3, NiO, La
2O
3, Sb
2O
5, CeO
2, Li
2O, CuO, Al
2O
3, Co
2O
3And Cr
2O
3In a kind or at least 2 kinds combination;
Preferably, said agglomerated material is a micron order or/and the nano level agglomerated material, and with said agglomerated material note condiments B, said material B is preferably ZnO, NiO, Bi
2O
3, Sb
2O
3, Co
2O
3, MnO
2, Cr
2O
3, V
2O
5, SiO
2, B
2O
3, TiO
2, ZrO
2, Ni
2O
3, Al
2O
3, Dy
2O
3, Y
2O
3In the composite oxides of combination behind high energy dry grinding, sintering of a kind or at least 2 kinds, preferred especially, said material B is ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Dy
2O
3, Y
2O
3, V
2O
5, B
2O
3In a kind or at least 2 kinds composite oxides behind high energy dry grinding, sintering;
Preferably; Said material A is 100: 1～100: 55 with the ratio of material B quality; Further preferred said material A is 100: 2～100: 45 with the ratio of material B quality; More preferably said material A is 100: 4～100: 40 with the ratio of material B quality, and preferred especially said material A is 100: 5～100: 35 with the ratio of material B quality;
Preferably, said doping oxide is the nano level doping oxide.
5. according to claim 1 or claim 2 method is characterized in that high energy ball mill is preferably adopted in said high energy wet-milling, and the further preferred planetary high-energy ball mill that adopts especially preferably adopts the frequency conversion type planetary high-energy ball mill;
Preferably, the liquid medium that said high energy wet-milling is adopted is water and/or organic solvent, further is preferably water, C
1-C
5Alcohols, C
3-C
71 kind or at least 2 kinds combination in ketone, halogenated alkane, the aromatics, more preferably water, ethanol, acetone, CCl
4, a kind or at least 2 kinds combination in the toluene, be preferably ethanol especially;
Preferably, the slurry after the high energy wet-milling is carried out carrying out presintering after the drying, preferred especially said drying is a thorough drying in vacuum drying oven.
6. like each described method of claim 1-5, it is characterized in that box-type furnace is adopted in said presintering;
Preferably, said pre-sintering temperature is 300～750 ℃, further is preferably 300～700 ℃, more preferably 350～650 ℃, is preferably 400～600 ℃ especially;
Preferably, the said presintering time is more than 0.5 hour, further is preferably 0.7～5 hour, more preferably 0.9～3 hour, is preferably 1～2 hour especially;
Preferably, high energy ball mill is adopted in said high energy dry grinding, and the further preferred planetary high-energy ball mill that adopts especially preferably adopts the frequency conversion type planetary high-energy ball mill.
7. like each described method of claim 1-6, it is characterized in that after zinc oxide piezoresistive material compression moulding, sintering temperature is 780～1200 ℃, further is preferably 820～1150 ℃, is preferably 850～1100 ℃ especially;
Preferably, after zinc oxide piezoresistive material compression moulding, sintering time is more than 0.5 hour, further is preferably 0.7～12 hour, more preferably 0.8～8 hour, is preferably 1～6 hour especially.
8. a zinc oxide piezoresistive material is characterized in that, the component of said zinc oxide piezoresistive material comprises: micron order zinc oxide, Nano-class zinc oxide, doping oxide and agglomerated material.
9. zinc oxide piezoresistive material as claimed in claim 8 is characterized in that, said zinc oxide piezoresistive material is by each said method preparation of claim 1-7;
With micron order zinc oxide, Nano-class zinc oxide and doping oxide note condiments A; Preferably; Said material A comprises by the quality percentage composition: the micron order zinc oxide content is 32～90%; The content of Nano-class zinc oxide is 5～65%, and the content of doping oxide is 0.01～15%, and the said components sum is 100%;
Further preferred, said material A comprises by the quality percentage composition: the micron order zinc oxide content is 38～85%, and the content of Nano-class zinc oxide is 10～60%, and the content of doping oxide is 0.08～10%, and the said components sum is 100%;
Preferred especially, said material A comprises by the quality percentage composition: the micron order zinc oxide content is 44～80%, and the content of nano level zinc oxide is 15～55%, and the content of doping oxide is 0.1～5%, and the said components sum is 100%.
10. like claim 8 or 9 described zinc oxide piezoresistive materials, it is characterized in that said doping oxide is B
2O
3, Fe
2O
3, SnO
2, ZrO
2, SiO
2, TiO
2, V
2O
5, WO
3, Pr
6O
11, Nb
2O
5, Y
2O
3, NiO, La
2O
3, Sb
2O
3, CeO
2, Li
2O, CuO, Al
2O
3, Co
2O
3, MnO
2, Bi
2O
3, Cr
2O
3In a kind or at least 2 kinds combination, be preferably B especially
2O
3, Fe
2O
3, SnO
2, ZrO
2, SiO
2, TiO
2, V
2O
5, WO
3, Pr
6O
11, Nb
2O
5, Y
2O
3, NiO, La
2O
3, Sb
2O
5, CeO
2, Li
2O, CuO, Al
2O
3, Co
2O
3And Cr
2O
3In a kind or at least 2 kinds combination;
Preferably, said agglomerated material is a micron order or/and the nano level agglomerated material, and with said agglomerated material note condiments B, said material B is preferably ZnO, NiO, Bi
2O
3, Sb
2O
3, Co
2O
3, MnO
2, Cr
2O
3, V
2O
5, SiO
2, B
2O
3, TiO
2, ZrO
2, Ni
2O
3, Al
2O
3, Dy
2O
3, Y
2O
3In the composite oxides of combination behind high energy dry grinding, sintering of a kind or at least 2 kinds, preferred especially, said material B is ZnO, Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3, SiO
2, Al
2O
3, TiO
2, Dy
2O
3, Y
2O
3, V
2O
5, B
2O
3In a kind or at least 2 kinds composite oxides behind high energy dry grinding, sintering;
Preferably; Said material A is 100: 1～100: 55 with the ratio of material B quality; Further preferred said material A is 100: 2～100: 45 with the ratio of material B quality; More preferably said material A is 100: 4～100: 40 with the ratio of material B quality, and preferred especially said material A is 100: 5～100: 35 with the ratio of material B quality;
Preferably, said doping oxide is the nano level doping oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104045402A CN102515741A (en) | 2011-12-07 | 2011-12-07 | Zinc oxide varistor material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104045402A CN102515741A (en) | 2011-12-07 | 2011-12-07 | Zinc oxide varistor material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102515741A true CN102515741A (en) | 2012-06-27 |
Family
ID=46286885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104045402A Pending CN102515741A (en) | 2011-12-07 | 2011-12-07 | Zinc oxide varistor material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102515741A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030390A (en) * | 2012-12-28 | 2013-04-10 | 深圳顺络电子股份有限公司 | Zinc oxide piezoresistor material and preparation method |
| CN104478428A (en) * | 2014-11-21 | 2015-04-01 | 四川大学 | Zinc oxide piezoresistor material with high electric potential gradient |
| CN104671772A (en) * | 2013-12-03 | 2015-06-03 | 辽宁法库陶瓷工程技术研究中心 | Zinc oxide piezoresistor composite powder prepared by means of modified nanometer doping |
| CN105272205A (en) * | 2015-10-12 | 2016-01-27 | 中国科学院上海硅酸盐研究所 | Low-temperature sintering zinc oxide varistor material and preparation method thereof |
| CN105294096A (en) * | 2015-10-16 | 2016-02-03 | 中国科学院上海硅酸盐研究所 | Low-resistance zinc oxide ceramic material and preparation material thereof |
| CN107244909A (en) * | 2017-05-10 | 2017-10-13 | 蚌埠市嘉实机电设备制造有限公司 | A kind of low-pressure high-energy Zinc-oxide piezoresistor |
| CN108484157A (en) * | 2018-05-23 | 2018-09-04 | 赵娟 | TiO2The preparation method of base voltage sensitive resistor material |
| CN108558389A (en) * | 2018-05-04 | 2018-09-21 | 南阳中祥电力电子有限公司 | A kind of Novel piezoresistor piece resistive formation slurry and preparation method thereof |
| CN108675783A (en) * | 2018-05-24 | 2018-10-19 | 江苏时瑞电子科技有限公司 | A kind of material and preparation method thereof for zinc oxide varistor |
| CN113105229A (en) * | 2021-03-29 | 2021-07-13 | 国网湖南省电力有限公司 | Zinc oxide resistance card and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1832059A (en) * | 2006-04-17 | 2006-09-13 | 广东省佛山科星电子有限公司 | Method for preparing nano-added zinc oxide varistor |
| CN101604566A (en) * | 2009-07-21 | 2009-12-16 | 中国地质大学（北京） | Zinc oxide piezoresistive material and preparation method that a kind of suitable electrical appliances with low surge voltage uses |
| CN101613199A (en) * | 2009-07-21 | 2009-12-30 | 中国地质大学（北京） | A kind of high-performance zinc oxide composite ceramic voltage dependent resistor material and preparation method |
-
2011
- 2011-12-07 CN CN2011104045402A patent/CN102515741A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1832059A (en) * | 2006-04-17 | 2006-09-13 | 广东省佛山科星电子有限公司 | Method for preparing nano-added zinc oxide varistor |
| CN101604566A (en) * | 2009-07-21 | 2009-12-16 | 中国地质大学（北京） | Zinc oxide piezoresistive material and preparation method that a kind of suitable electrical appliances with low surge voltage uses |
| CN101613199A (en) * | 2009-07-21 | 2009-12-30 | 中国地质大学（北京） | A kind of high-performance zinc oxide composite ceramic voltage dependent resistor material and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 柯磊等: "高电位梯度ZnO压敏电阻的高压稳压性能研究", 《功能材料》 * |
| 齐国权等: "高能球磨对Pr6O11和Y2O3掺杂ZnO压敏电阻微观结构和电学性能的影响", 《中国陶瓷工业》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030390A (en) * | 2012-12-28 | 2013-04-10 | 深圳顺络电子股份有限公司 | Zinc oxide piezoresistor material and preparation method |
| CN104671772A (en) * | 2013-12-03 | 2015-06-03 | 辽宁法库陶瓷工程技术研究中心 | Zinc oxide piezoresistor composite powder prepared by means of modified nanometer doping |
| CN104478428A (en) * | 2014-11-21 | 2015-04-01 | 四川大学 | Zinc oxide piezoresistor material with high electric potential gradient |
| CN105272205A (en) * | 2015-10-12 | 2016-01-27 | 中国科学院上海硅酸盐研究所 | Low-temperature sintering zinc oxide varistor material and preparation method thereof |
| CN105294096A (en) * | 2015-10-16 | 2016-02-03 | 中国科学院上海硅酸盐研究所 | Low-resistance zinc oxide ceramic material and preparation material thereof |
| CN105294096B (en) * | 2015-10-16 | 2018-03-09 | 中国科学院上海硅酸盐研究所 | A kind of low resistance zinc oxide ceramics material and preparation method thereof |
| CN107244909A (en) * | 2017-05-10 | 2017-10-13 | 蚌埠市嘉实机电设备制造有限公司 | A kind of low-pressure high-energy Zinc-oxide piezoresistor |
| CN108558389A (en) * | 2018-05-04 | 2018-09-21 | 南阳中祥电力电子有限公司 | A kind of Novel piezoresistor piece resistive formation slurry and preparation method thereof |
| CN108484157A (en) * | 2018-05-23 | 2018-09-04 | 赵娟 | TiO2The preparation method of base voltage sensitive resistor material |
| CN108675783A (en) * | 2018-05-24 | 2018-10-19 | 江苏时瑞电子科技有限公司 | A kind of material and preparation method thereof for zinc oxide varistor |
| CN113105229A (en) * | 2021-03-29 | 2021-07-13 | 国网湖南省电力有限公司 | Zinc oxide resistance card and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102515741A (en) | Zinc oxide varistor material and preparation method thereof | |
| CN102476949A (en) | Method for preparing electrical property-controllable zinc oxide (ZnO) piezoresistor material at low temperature | |
| CN101604566B (en) | Zinc oxide piezoresistive material used for electrical appliances with low surge voltage and preparation method thereof | |
| CN101613199B (en) | High-performance zinc oxide composite ceramic voltage dependent resistor material and preparation method | |
| CN102515742A (en) | High potential gradient zinc oxide pressure-sensitive resistor material and preparation process thereof | |
| CN102390992B (en) | Resistance card for direct-current lightning arrester and production process thereof | |
| CN104591726A (en) | High-potential gradient zinc oxide voltage piezo-resistor material and preparation method thereof | |
| CN105645948B (en) | A kind of preparation method of high-voltage gradient, low Leakage Current varistor ceramics materials | |
| CN102643086B (en) | Stannic oxide based piezoresistor material and preparation method thereof | |
| CN103030390A (en) | Zinc oxide piezoresistor material and preparation method | |
| CN101702358B (en) | High voltage varistor and preparation method thereof | |
| CN101279844A (en) | Zinc oxide pressure-sensitive ceramic material doped with composite rare-earth oxide | |
| CN105859279A (en) | Novel process method for preparing zinc oxide piezoresistor ceramic with excellent properties | |
| CN101880158A (en) | IVB-family element modified CaCu3Ti4O12-based pressure-sensitive material and preparation method thereof | |
| CN109574653A (en) | A kind of high non-linearity, low-leakage current piezoresistive wafer and preparation method thereof | |
| CN101284730A (en) | Non-bismuth additive ZnO Low-voltage Varistor Ceramics and method for making same | |
| CN104557016B (en) | A kind of Zinc oxide pressure-sensitive ceramic material of high non-linearity frit doping | |
| CN105272205A (en) | Low-temperature sintering zinc oxide varistor material and preparation method thereof | |
| JPH1012407A (en) | Voltage non-linear resistor, manufacture of voltage non-linear resistor, and lighting arrester | |
| CN110423110B (en) | Ultrahigh nonlinear ZnO-Bi2O3Base pressure sensitive ceramic 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 | |
| CN102030522A (en) | Low-equilibrium temperature ZnO-Bi2O3 series voltage-sensitive ceramic dielectric | |
| JP5337073B2 (en) | Current-voltage nonlinear resistor and method for manufacturing the same | |
| CN101286393B (en) | Stratified structure low-voltage ZnO piezoresistor preparation method | |
| CN105565801A (en) | Preparation method of high-gradient and large-discharge-current-capacity voltage-sensitive ceramics for ultra-high-voltage power transmission system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120627 |