CN102515742A - High potential gradient zinc oxide pressure-sensitive resistor material and preparation process thereof - Google Patents
High potential gradient zinc oxide pressure-sensitive resistor material and preparation process thereof Download PDFInfo
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Abstract
The invention relates to a high potential gradient zinc oxide pressure-sensitive resistor material and a preparation process thereof. The high potential gradient zinc oxide pressure-sensitive resistor material with uniform particle sizes is obtained by weighing a main material ZnO, a doping oxide, and a product rare earth oxide obtained by carrying out thermal decomposition on a rare earth oxalate or/and carbonate or/and hydroxide according to proportions, carrying out high energy wet grinding, drying, presintering at 200-800DEG C, carrying out high energy dry grinding, and sintering at 800-1100DEG C. The preparation process of the invention has the advantages of simplicity, low cost, environmental protection and low energy consumption, and the prepared zinc oxide pressure-sensitive resistor material can be used for preparing high quality lightning arrester products for ultrahigh electric power systems.
Description
Technical field
The present invention relates to the piezoresistive material preparing technical field, particularly, the present invention relates to a kind of high-potential gradient 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 ".
ZnO has the hexagonal system wurtzite structure; It is the superfluous non-stoichiometric n of metal N-type semiconductorN; ZnO varistor has good non-linear character and shock resistance energy absorption capability; Be widely used in the safeguard system of various electronic circuits and power equipment, as voltage stabilizing and transient overvoltage protection.Especially in the ultra-high voltage AC input transformation system, for miniaturized and the lightness that realizes arrester valve piece made, reduce manufacturing cost, the ZnO varistor of exploitation high potential gradient is a development trend.
At present; Bibliographical information has been arranged improved the research of the voltage gradient of ZnO varistor, mainly be through doped with rare-earth oxide, or reduce the voltage dependent resistor sintering temperature and reduce ZnO grain growing speed; Or the shortening soaking time reduces the grain growing time to improve the potential gradient of ZnO varistor; Yet the shortcoming of this method is variation (T Imai, the T Udagawa such as non-linear, the through-current capability of volt-ampere and aging resistance that can make voltage dependent resistor; H Ando; Et al.Development of high gradient Zinc-oxide nonlinear resistors and their application to surge arresters.IEEE Trans Power Del, 1998,13 (4): 1182～1187; With Bernik S, Macek S, Ai B.Microstructural and electrical characteristics of Y
2O
3-doped ZnO-Bi
2O
3-based varistor ceramics.J Eur Ceram Soc, 2001,21 (10-11): 1875～1878).Employing chemical methods such as Duran prepare nano-powder, and it is Zinc-oxide piezoresistor (P. Duran, the F.Capel of 2000V/mm that 900 ℃ on warp and 825 ℃ of double sinterings have prepared potential gradient; J.Tartaj; C.Moure.Effects of low-temperature annealing on the microstructure and electrical properties of doped-ZnO varistors [J] .Key Engineering Materials, 2002,206-213:1389-1392); But; There is complex process in this method, and the shortcoming that cost is high is difficult to form large-scale production.
CN 101279844A relates to a kind of Zinc oxide pressure-sensitive ceramic material and preparation method of doped with composite rare-earth oxide, function of dominant stupalith manufacturing technology field.It is characterized in that zinc oxide piezoresistive material comprises following component by mole per-cent: ZnO 95%-98% is a material of main part, MnO
2, Co
2O
3, Bi
2O
3, Cr
2O
3, Sb
2O
3Respectively be 0.1%-1.0%, composite rare-earth oxide is 0.01%-0.4%, and wherein composite rare-earth oxide is not for mixing or being mixed with Al
2O
3Sc
2O
3With rare earth oxide Y
2O
3, La
2O
3, Ce
2O
3, Er
2O
3, Dy
2O
3, Nd
2O
3In a kind of.This invention makes the potential gradient of zinc oxide pressure-sensitive ceramic bring up to 1300-1600V/mm through the rational proportion of adjustment composite rare-earth oxide, and nonlinear factor is 30-50; Leakage current is 2-20mA, and still, what this invention was adopted is the commercial rare earth oxide of directly buying; Sintering temperature is up to 900～1200 ℃; Its cost is high, and energy consumption is big, is not suitable for suitability for industrialized production.
CN 101265083A relates to a kind of Zinc oxide pressure-sensitive ceramic material and preparation method of rare earth nitrate doping, function of dominant stupalith manufacturing technology field.It is characterized in that zinc oxide piezoresistive 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 be 0.1-1.0%, rare earth nitrate is 0.01-2.0%, and wherein rare earth nitrate is nitrate salt a kind of of rare earth yttrium, praseodymium, strontium.This invention is through adopting the rare earth oxide that adds by after Yttrium trinitrate and the praseodymium nitrate decomposition; And through adjusting the reasonable doping content of rare earth nitrate; Make the microstructure of zinc oxide pressure-sensitive ceramic even, electrical property is improved, and the potential gradient of voltage-sensitive ceramic is brought up to 1000-1300V/mm; Nonlinear factor is 30-50, and leakage current is 2-20mA.Wherein, Though decompose the acquisition rare earth oxide with Yttrium trinitrate and praseodymium nitrate production cost is decreased, nitrate salt can discharge a large amount of atmospheric polluting materials such as oxynitride when decomposing, and can cause severe contamination to environment; Simultaneously; Sintering temperature in this invention will increase energy consumption up to 1200 ℃, is unfavorable for the industrialization promotion application.
Because there is following problem in existing high-potential gradient zinc oxide piezoresistive material in the preparation process: on the one hand, sintering temperature is high, and energy consumption is big; Increased production cost greatly; Be unfavorable for industrialization promotion, yet, ZnO grain growing speed reduced through reducing the voltage dependent resistor sintering temperature; Or shorten soaking time and reduce the grain growing time when improving the potential gradient of ZnO varistor, can make the volt-ampere of voltage dependent resistor non-linear, variation such as through-current capability and aging resistance; On the other hand; Relate to when adopting doped with rare-earth oxide to improve the potential gradient of Zinc-oxide piezoresistor; Most employings are purchased rare earth oxide and directly mix, and the mode that perhaps adopts nitrate of rare earth element to decompose obtains the required rare earth oxide that mixes, and these methods perhaps can increase production cost; Perhaps pollute the environment, all be unfavorable for suitability for industrialized production.
Summary of the invention
To the problems referred to above that high-potential gradient zinc oxide piezoresistive material exists in the preparation process, one of the object of the invention is to provide a kind of preparation method of high-potential gradient zinc oxide piezoresistive material.Said method is introduced high-energy ball-milling process and is made that prepared zinc oxide piezoresistive material microstructure is even; Comprehensive electrochemical properties is excellent; Adopt the oxalate of corresponding REE or/and carbonate obtains the required rare earth oxide that mixes or/and the oxyhydroxide decomposition method replaces that environment is produced the nitrate salt decomposition method of polluting; Thereby when having reduced production cost, reduced pollution to environment; Sintering is finally prepared the high-potential gradient zinc oxide piezoresistive material of low cost and excellent performance to cut down the consumption of energy under 800～1100 ℃ low temperature.
The preparation method of said high-potential gradient zinc oxide piezoresistive material may further comprise the steps:
(1) preparation rare earth oxide:, decompose the acquisition rare earth oxide with the rare-earth compound calcining;
(2) high energy wet-milling: the mixture that the said rare earth oxide mixing that ZnO, doping oxide and step (1) are made obtains carries out the high energy wet-milling, and subsequent drying obtains even exsiccant powder mix;
(3) the said powder mix presintering that step (2) is obtained obtains sintering mix;
(4) high energy dry grinding: the said sintering mix that step (3) is obtained carries out the high energy dry grinding, obtains even exsiccant powder mix;
(5) compression moulding: the said powder mix that step (4) is obtained carries out granulation, and compression moulding then obtains the base sheet;
(6) binder removal burns till: with the said base sheet intensification binder removal that step (5) obtains, and sintering, cooling obtains high-potential gradient zinc oxide piezoresistive material.
One of the object of the invention also is to provide a kind of preparation method of end electrode of high-potential gradient zinc oxide piezoresistive material; Said method is: carry out step (7) preparation end electrode afterwards in step (6): on two end faces of the said high-potential gradient zinc oxide piezoresistive material that step (6) obtains; Coat conductive coating; High temperature keeps for some time then, and cooling obtains end electrode.
One of the object of the invention also is to provide a kind of preparation method of high-potential gradient zinc oxide voltage-sensitive ceramic; Said method is: carry out step (8) grid for welding lead-in wire afterwards in step (7): grid for welding lead-in wire on the said end electrode end face that step (7) makes, the high-potential gradient zinc oxide voltage-sensitive ceramic of electrical property can be directly tested in acquisition.
Preferably, rare-earth compound described in the step (1) be REE oxalate or/and carbonate or/and oxyhydroxide, the oxalate that is preferably REE especially is or/and carbonate.
Preferably; REE described in the step (1) is a kind or at least 2 kinds combination among Sc, Y, Pr, Ce, La, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu; Said combination typical case but the instance of non-limit have: the combination of La, Nd, the combination of Eu, Gd, Tb, the combination of Sc, Y, Pr, Ce; The combination of Pm, Sm, Eu, Gd, Tb, the combination of Dy, Ho, Er, Tm, Yb and Lu etc.
Preferably; Calcining temperature is more than 300 ℃ described in the step (1); For example 301 ℃, 302 ℃, 303 ℃, 399 ℃, 400 ℃, 401 ℃, 402 ℃, 999 ℃, 1001 ℃, 1090 ℃, 1095 ℃, 1099 ℃ etc.; Further be preferably 300～1100 ℃, more preferably 350～1050 ℃, be preferably 400～1000 ℃ especially.
Preferably; Calcination time is more than the 0.5h described in the step (1); For example 0.51h, 0.52h, 0.53h, 0.55h, 0.99h, 1.01h, 1.02h, 1.05h, 1.1h, 5.9h, 11.9h, 23h, 23.5h, 23.8h, 23.9h etc. further are preferably 0.5～24h, more preferably 1～12h; More preferably 1～8h is preferably 1～6h especially.
Preferably; Heat-up rate is 1～15 ℃/min during calcining described in the step (1); For example 1 ℃/min, 1.01 ℃/min, 1.02 ℃/min, 1.05 ℃/min, 1.1 ℃/min, 1.2 ℃/min, 4.9 ℃/min, 9.9 ℃/min, 14 ℃/min, 14.5 ℃/min, 14.9 ℃/min etc.; Further be preferably 1～10 ℃/min, more preferably 1～7 ℃/min is preferably 1～5 ℃/min especially.
Preferably, doping oxide is B described in the step (2)
2O
3, Fe
2O
3, SnO, 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, ZrO
2Combination, Co
2O
3, Cr
2O
3Combination, CeO
2, Li
2O, CuO, Al
2O
3Combination, TiO
2, V
2O
5, WO
3Combination etc., further be preferably Bi
2O
3, MnO
2, Co
2O
3, Sb
2O
3, SiO
2, Cr
2O
3, a kind or at least 2 kinds combination among the NiO, be preferably Bi especially
2O
3, MnO
2, Co
2O
3, Sb
2O
3, SiO
2, Cr
2O
3Combination with NiO.
Preferably, rare earth oxide is Sc described in the step (2)
2O
3, Y
2O
3, Pr
6O
11, CeO
2, La
2O
3, Nd
2O
3, Pm
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
2O
3, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3And Lu
2O
3In a kind or at least 2 kinds combination, said combination typical case but the instance of non-limit has Tb
2O
3, Dy
2O
3Combination, Ho
2O
3, Er
2O
3, Tm
2O
3Combination, Pm
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3Combination, Sc
2O
3, Y
2O
3, Pr
6O
11, CeO
2, La
2O
3Combination, La
2O
3, Nd
2O
3, Pm
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3Combination etc.
Preferably; In the said mixture of step (2), the content of ZnO is 85～99% by mole per-cent, for example 85.1%, 85.2%, 85.3%, 85.5%, 91%, 94%, 98%, 98.1%, 98.8%, 98.9% etc.; Further be preferably 90～99%, be preferably 93～98.5 especially; Preferably; The content of any in the said doping oxide independently is 0.001～5%; For example 0.0011%, 0.0012%, 0.002%, 0.006%, 2.9%, 4%, 4.9%, 4.95%, 4.99% etc., further be preferably 0.005～3%, be preferably 0.01～2% especially; Preferably; The total content of said rare earth oxide is 0.001～5%; For example 0.0011%, 0.0012%, 0.002%, 0.006%, 2.9%, 4%, 4.9%, 4.95%, 4.99% etc., further be preferably 0.005～3%, be preferably 0.01～2% especially.
Preferably, ZnO is a micron order described in the step (2).
Preferably, doping oxide is a micron order described in the step (2).
Preferably, the liquid medium of high energy wet-milling is water and/or organic solvent described in the step (2), 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 mass ratio of used abrading-ball of high energy wet-milling and powder is 10: 1～25: 1 described in the step (2), further is preferably 14: 1～20: 1, is preferably 18: 1 especially.
Preferably, the volume sum of the used abrading-ball of high energy wet-milling, powder, liquid medium is no more than ball grinder volumetrical 3/4 described in the step (2), is preferably especially and is no more than ball grinder volumetrical 2/3.
Preferably, high energy wet-milling rotating speed is 200～700 rev/mins described in the step (2), further is preferably 300～600 rev/mins, is preferably 400～550 rev/mins especially.
Preferably; The high energy wet-milling time described in the step (2) is more than 2 hours; For example 2 hours, 2.1 hours, 2.3 hours, 2.5 hours, 2.9 hours, 3.1 hours, 19 hours, 19.5 hours, 24 hours, 24.9 hours, 29 hours, 29.5 hours, 29.9 hours etc.; Further be preferably 2～25 hours, more preferably 3～20 hours, be preferably 3～16 hours especially.
Preferably; Can add dispersion agent during high energy wet-milling described in the step (2); Said dispersion agent is preferably a kind or at least 2 kinds combination in ROHM, ammonium polymethacrylate, ammonium citrate, the ammonium polyacrylate; Said combination is typical but the instance of non-limit has the combination of ROHM, ammonium polymethacrylate, the combination of ammonium polymethacrylate, ammonium citrate, ammonium polyacrylate, the combination of ammonium polymethacrylate, ammonium citrate etc.; Further the add-on of preferred said dispersion agent is 0.01～10wt%, and more preferably 0.03～5wt% is preferably 0.05～3wt% especially.
Preferably, dry described in the step (2) for adopting the straight tube pneumatic drier to carry out thorough drying.
Preferably, in the step (3), before presintering, the dry mixed powder that step (2) is obtained is pressed into block, and further preferred, the block density that the dry mixed powder that step (2) is obtained is pressed into is 1.0～10.0g/cm
3, 3.0～8.0g/cm more preferably
3, be preferably 4.0～6.0g/cm especially
3
Preferably, presintering is carried out in cabinet-type electric furnace described in the step (3).
Preferably, pre-sintering temperature is 200～800 ℃ described in the step (3), more preferably 250～750 ℃, is preferably 300～680 ℃ especially.
Preferably; The presintering time described in the step (3) is more than 0.5 hour; For example 0.51 hour, 0.52 hour, 0.55 hour, 0.6 hour, 0.81 hour, 7 hours, 23 hours, 23.5 hours, 23.9 hours etc.; Further be preferably 0.8～24 hour, more preferably 1～8 hour, be preferably 1～4 hour especially.
Preferably, the dry grind mass ratio of used abrading-ball and powder of high energy described in the step (4) is 10: 1～25: 1, further is preferably 14: 1～20: 1, is preferably 18: 1 especially.
Preferably, the dry grinding of high energy described in the step (4) rotating speed is 200～700 rev/mins, further is preferably 300～600 rev/mins, is preferably 400～550 rev/mins especially.
Preferably; The high energy dry grinding time described in the step (4) is more than 0.2 hour; For example 0.2 hour, 0.21 hour, 0.22 hour, 0.23 hour, 0.29 hour, 0.31 hour, 9 hours, 9.5 hours, 24 hours, 24.9 hours, 29 hours, 29.5 hours, 29.9 hours etc.; Further be preferably 0.3～25 hour, more preferably 0.4～10 hour, be preferably 0.5～6 hour especially.
Preferably, carry out granulation after in the powder mix that step (4) obtains, adding PVA in the step (5), said PVA add-on is preferably 0.1～5% of base sheet total mass, further is preferably 0.2～3%, and more preferably 0.3～1%, be preferably 0.4% especially; Preferred said PVA adds with aqueous solution form, and further the quality percentage composition of PVA is 1～15% in the preferred said PVA aqueous solution, further is preferably 3～10% again, and more preferably 4～7%, be preferably 5% especially.
Preferably, 8～100 t hydraulic press are adopted in compression moulding described in the step (5), further are preferably 9～60 t hydraulic press, are preferably 10～50 t hydraulic press especially.
Preferably, the base sheet thickness that obtains in the step (5) is 1～5mm, further is preferably 2～3mm, is preferably 2mm especially.
Preferably, binder removal described in the step (6) burns till preferably and in chamber type electric resistance furnace, carries out.
Preferably, binder removal described in the step (6) burns till under the air atmosphere of circulation and carries out.
Preferably; Heat-up rate is more than 1 ℃/minute described in the step (6); For example 1.01 ℃/minute, 1.05 ℃/minute, 1.1 ℃/minute, 1.2 ℃/minute, 9 ℃/minute, 9.5 ℃/minute, 9.9 ℃/minute, 9.99 ℃/grade, further be preferably 1～10 ℃/minute, be preferably 1～5 ℃/minute especially.
Preferably, dump temperature is 200～800 ℃ described in the step (6), further is preferably 250～700 ℃, is preferably 300～600 ℃ especially.
Preferably; The binder removal time described in the step (6) is more than 1 hour, for example 1.1 hours, 1.2 hours, 2.1 hours, 2.2 hours, 14 hours, 14.5 hours, 14.9 hours etc., further is preferably 1.5～15 hours; More preferably 2～10 hours, be preferably 2～8 hours especially.
Preferably, sintering temperature is 800～1100 ℃ described in the step (6), further is preferably 850～1100 ℃, is preferably 900～1000 ℃ especially.
Preferably; Sintering time is more than 0.5 hour described in the step (6); For example 0.51 hour, 0.52 hour, 0.55 hour, 0.6 hour, 1.01 hours, 1.02 hours, 1.1 hours, 2 hours, 5 hours, 10 hours, 20 hours, 24 hours, 24.5 hours, 24.9 hours, 25.1 hours, 26 hours etc.; Further be preferably 1～25 hour, more preferably 1～15 hour, be preferably 1～8 hour especially.
Preferably, conductive coating described in the step (7) is the silver slurry.
Preferably; After coating conductive coating in the step (7); Heat-up rate is more than 1 ℃/minute; For example 1.01 ℃/minute, 1.02 ℃/minute, 1.05 ℃/minute, 1.1 ℃/minute, 9 ℃/minute, 9.5 ℃/minute, 9.9 ℃/minute, 10.1 ℃/grade, further be preferably 1～10 ℃/minute, be preferably 1～5 ℃/minute especially.
Preferably, high temperature is 300～1000 ℃ described in the step (7), further is preferably 400～800 ℃, is preferably 450～750 ℃ especially.
The high temperature hold-time described in the step (7) can be selected according to the expertise of its grasp by one of ordinary skill in the art; Be preferably more than 5 minutes; Further be preferably 10 minutes～10 hours, more preferably 12 minutes～5 hours, be preferably 15 minutes especially～3 hours.
Preferably, high temperature is provided by chamber type electric resistance furnace described in the step (7).
The commercially available acquisition of rare-earth compound according to the invention, ZnO and doping oxide, or prepare according to the expertise/new technology of its grasp by one of ordinary skill in the art.
Preferably, said high energy wet-milling and high energy are dry grinded used abrading-ball independently for a kind or at least 2 kinds combination in zirconium oxide balls, wolfram varbide abrading-ball, the aluminum oxide abrading-ball, are preferably zirconium oxide balls especially.
Preferably, the used high energy ball mill of said high energy wet-milling and high energy dry grinding is the frequency conversion planetary high-energy ball mill.
Preferably, said high energy wet-milling and high energy are dry grinded used ball grinder independently for a kind in tetrafluoroethylene ball grinder, ceramic ball grinder, the urethane ball grinder, are preferably the tetrafluoroethylene ball grinder especially.
One of the object of the invention also is to provide a kind of high-potential gradient zinc oxide piezoresistive material, and said high-potential gradient zinc oxide piezoresistive material is by method for preparing, its uniform microstructure, and comprehensive electrochemical properties is excellent.
One of the object of the invention also is to provide a kind of purposes that adopts the high-potential gradient zinc oxide piezoresistive material of method preparation of the present invention.
Adopt the high-potential gradient zinc oxide piezoresistive material of method preparation of the present invention to can be used for preparing the thunder arrester that the super-high power system uses.
Compared with prior art, outstanding advantage of the present invention and positively effect are following:
(1) adopt 800 ℃～1100 ℃ low-temperature sintering, with 1100 ℃～1500 ℃ traditional high temperature sintering, the present invention can significantly cut down the consumption of energy, and prolongs the work-ing life of sintering oven greatly, has reduced production cost, helps large-scale production relatively;
(2) make final zinc oxide piezoresistive material uniform microstructure through introducing high-energy ball-milling process and adding suitable dispersion agent, comprehensive electrochemical properties is excellent;
(3) the liquid slurry after the high energy wet-milling directly adopts the straight tube pneumatic drier to carry out drying; Desciccate be uniformly dispersed, non-caking powder; Avoid adopting complicated technology such as also need ball milling after traditional blast drier drying, sieve, and reduced production cost and energy consumption;
(4) mixed powder is carried out presintering; High energy dry grinding then, granulation, comparatively high temps sintering obtain the Zinc-oxide piezoresistor pottery; The microtexture homogenizing that helps the finished product can effectively reduce the final sintering temperature of sample, obtains excellent electric performance parameter more;
(5) directly do not adopt the rare earth oxide be purchased dopant material as the high-gradient zinc oxide piezoresistive material; Adopt corresponding REE oxalate or/and carbonate or/and the nitrate salt decomposition method that the oxyhydroxide decomposition method replaces environment being produced severe contamination obtains the required rare earth oxide that mixes, thereby when reducing production costs greatly, reduced pollution to environment.
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
An amount of yttrium oxalate and Sedemesis were calcined 3 hours and 4 hours at 650 ℃ and 400 ℃ respectively, and heat-up rate is 1 ℃/minute, obtains rare earth oxide Y
2O
3And CeO
2Calculate with molar content, weighing is purchased micron order ZnO 93.5%, Bi respectively
2O
31.0%, MnO
21.0%, Co
2O
31.0%, Sb
2O
32.0%, SiO
20.09%, Cr
2O
31.0%, NiO 0.01%, the product Y that simultaneously weighing is above-mentioned after fully being decomposed by yttrium oxalate and Sedemesis
2O
30.3%, CeO
20.1%, above-mentioned materials is put into the frequency conversion planetary high-energy ball mill, add an amount of ethanol and carry out the high energy wet-milling; Wherein, the quality of zirconium oxide balls and powder total amount is 18: 1, and ball, powder and alcoholic acid total amount are no more than ball grinder volumetrical 2/3; Rotating speed is 400 rev/mins, and the ball milling time is 16 hours, in mechanical milling process, adds the polyacrylic acid dispersant of 0.05wt%; Slurry behind the ball milling is carried out thorough drying by the straight tube pneumatic drier, obtain even exsiccant powder mix.
It is 4.0g/cm that above-mentioned powder mix is pressed into density
3Circular block, then in cabinet-type electric furnace in 300 ℃ of presintering 4 hours, obtain the sintering block.Put it into ball mill for dry grinding, the mass ratio that makes zirconium oxide balls and powder total amount is 18: 1, and rotating speed is 550 rev/mins, and the ball milling time is 0.5 hour, obtains even exsiccant powder mix.In this powder mix, add 8% quality percentage composition and carry out granulation for the 5%PVA aqueous solution, then, in 50 t hydraulic press pressed moulding; Obtaining thickness is the round billet sheet of 2mm; Then this round billet sheet is put into chamber type electric resistance furnace, sintering under the air atmosphere of circulation, heat-up rate is 5 ℃/minute; Be incubated binder removals 2 hours at 600 ℃, then insulation 1 hour and furnace cooling under 1000 ℃ condition.
On two end faces of the sample behind the above-mentioned sintering, coat ag paste electrode, put into chamber type electric resistance furnace; 750 ℃ of insulations 15 minutes; Cool to room temperature then with the furnace, and grid for welding goes between on its end face, the potential gradient that behind electric performance test, obtains this Zinc-oxide piezoresistor is 1280V/mm; Nonlinear factor is 56, and leakage current is 6.8 μ A.
Embodiment 2
Respectively 1000 ℃ of calcinings 1 hour, heat-up rate is 2 ℃/minute, obtains corresponding rare earth oxide La with an amount of lanthanum oxalate, praseodymium oxalate, neodymium oxalate, samaric oxalate
2O
3, Pr
6O
11, Nd
2O
3And Sm
2O
3Calculate with molar content, weighing is purchased micron order ZnO 98.5%, Bi respectively
2O
30.42%, MnO
20.02%, Co
2O
30.03%, Sb
2O
30.49%, SiO
20.01%, Cr
2O
30.02%, NiO 0.01%, the product La that simultaneously weighing is above-mentioned after fully being decomposed by the REE oxalate
2O
30.1%, Pr
6O
110.3%, Nd
2O
30.05%, Sm
2O
30.05% puts into the frequency conversion planetary high-energy ball mill with above-mentioned materials, adds an amount of ethanol and carries out the high energy wet-milling, wherein; The quality of zirconium oxide balls and powder total amount is 18: 1, and ball, powder and alcoholic acid total amount are no more than ball grinder volumetrical 2/3, and rotating speed is 550 rev/mins; The ball milling time is 3 hours; In mechanical milling process, add the ammonium polyacrylate dispersion agent of 0.3wt%, the slurry behind the ball milling is carried out thorough drying by the straight tube pneumatic drier, obtain even exsiccant powder mix.
It is 6.0g/cm that above-mentioned powder mix is pressed into density
3Circular block, then in cabinet-type electric furnace in 680 ℃ of presintering 1 hour, obtain the sintering block.Put it into ball mill for dry grinding, the mass ratio that makes zirconium oxide balls and powder total amount is 18: 1, and rotating speed is 550 rev/mins, and the ball milling time is 3 hours, obtains even exsiccant powder mix.In this powder mix, add 8% quality percentage composition and carry out granulation for the 5%PVA aqueous solution, then, in 40 t hydraulic press pressed moulding; Obtaining thickness is the round billet sheet of 2mm; Then this round billet sheet is put into chamber type electric resistance furnace, sintering under the air atmosphere of circulation, heat-up rate is 1 ℃/minute; Be incubated binder removals 8 hours at 300 ℃, then insulation 8 hours and furnace cooling under 900 ℃ condition.
On two end faces of the sample behind the above-mentioned sintering, coat ag paste electrode, put into chamber type electric resistance furnace; 450 ℃ of insulations 3 hours; Cool to room temperature then with the furnace, and grid for welding goes between on its end face, the potential gradient that behind electric performance test, obtains this Zinc-oxide piezoresistor is 860V/mm; Nonlinear factor is 41, and leakage current is 7.7 μ A.
Embodiment 3
An amount of Phosbloc, europium carbonate, scandium carbonate were calcined 2 hours at 900 ℃, 1000 ℃ and 950 ℃ respectively, and heat-up rate is 2 ℃/minute, obtains corresponding rare earth oxide La
2O
3, Eu
2O
3And Sc
2O
3Calculate with molar content, weighing is purchased micron order ZnO 95.0%, Bi respectively
2O
30.9%, MnO
20.8%, Co
2O
30.7%, Sb
2O
31.0%, SiO
20.03%, Cr
2O
30.5%, NiO 0.02%, the product La that simultaneously weighing is above-mentioned after fully being decomposed by REE carbonate
2O
30.05%, Eu
2O
30.4%, Sc
2O
30.6% puts into the frequency conversion planetary high-energy ball mill with above-mentioned materials, adds an amount of ethanol and carries out the high energy wet-milling, wherein; The quality of zirconium oxide balls and powder total amount is 18: 1, and ball, powder and alcoholic acid total amount are no more than ball grinder volumetrical 2/3, and rotating speed is 500 rev/mins; The ball milling time is 8 hours; In mechanical milling process, add the ammonium citrate dispersion agent of 0.2wt%, the slurry behind the ball milling is carried out thorough drying by the straight tube pneumatic drier, obtain even exsiccant powder mix.
It is 5.0g/cm that above-mentioned powder mix is pressed into density
3Circular block, then in cabinet-type electric furnace in 500 ℃ of presintering 3 hours, obtain the sintering block.Put it into ball mill for dry grinding, the mass ratio that makes zirconium oxide balls and powder total amount is 18: 1, and rotating speed is 450 rev/mins, and the ball milling time is 2 hours, obtains even exsiccant powder mix.In this powder mix, add 8% quality percentage composition and carry out granulation for the 5%PVA aqueous solution, then, in 30 t hydraulic press pressed moulding; Obtaining thickness is the round billet sheet of 2mm; Then this round billet sheet is put into chamber type electric resistance furnace, sintering under the air atmosphere of circulation, heat-up rate is 3 ℃/minute; Be incubated binder removals 4 hours at 500 ℃, then insulation 5 hours and furnace cooling under 950 ℃ condition.
On two end faces of the sample behind the above-mentioned sintering, coat ag paste electrode, put into chamber type electric resistance furnace; 600 ℃ of insulations 1 hour; Cool to room temperature then with the furnace, and grid for welding goes between on its end face, the potential gradient that behind electric performance test, obtains this Zinc-oxide piezoresistor is 1100V/mm; Nonlinear factor is 37, and leakage current is 3.8 μ A.
Embodiment 4
An amount of yttrium oxalate, oxalic acid terbium, praseodymium oxalate were calcined 3 hours at 650 ℃, 900 ℃ and 900 ℃ respectively, and heat-up rate is 3 ℃/minute, obtains corresponding rare earth oxide Y
2O
3, Tb
2O
3And Pr
6O
11Calculate with molar content, weighing is purchased micron order ZnO 96.0%, Bi respectively
2O
30.8%, MnO
20.6%, Co
2O
30.7%, Sb
2O
30.1%, SiO
20.01%, Cr
2O
30.5%, NiO 0.01%, the product Y that simultaneously weighing is above-mentioned after fully being decomposed by the REE oxalate
2O
30.6%, Tb
2O
30.3%, Pr
6O
110.38% puts into the frequency conversion planetary high-energy ball mill with above-mentioned materials, adds an amount of ethanol and carries out the high energy wet-milling, wherein; The quality of zirconium oxide balls and powder total amount is 18: 1, and ball, powder and alcoholic acid total amount are no more than ball grinder volumetrical 2/3, and rotating speed is 520 rev/mins; The ball milling time is 7 hours; In mechanical milling process, add the ammonium polymethacrylate dispersion agent of 0.18wt%, the slurry behind the ball milling is carried out thorough drying by the straight tube pneumatic drier, obtain even exsiccant powder mix.
It is 5.5g/cm that above-mentioned powder mix is pressed into density
3Circular block, then in cabinet-type electric furnace in 550 ℃ of presintering 2 hours, obtain the sintering block.Put it into ball mill for dry grinding, the mass ratio that makes zirconium oxide balls and powder total amount is 18: 1, and rotating speed is 480 rev/mins, and the ball milling time is 2 hours, obtains even exsiccant powder mix.Follow-up granulation, binder removal, sintering are with embodiment 1
On two end faces of the sample behind the above-mentioned sintering, coat ag paste electrode, put into chamber type electric resistance furnace; 680 ℃ of insulations 30 minutes; Cool to room temperature then with the furnace, and grid for welding goes between on its end face, the potential gradient that behind electric performance test, obtains this Zinc-oxide piezoresistor is 1320V/mm; Nonlinear factor is 45, and leakage current is 5.4 μ A.
Embodiment 5
An amount of carbonic acid holmium, gadolinium carbonate, praseodymium carbonate, scandium carbonate, hydroxide lutetium were calcined 3 hours at 1000 ℃, 1000 ℃, 1000 ℃, 950 ℃ and 1000 ℃ respectively, and heat-up rate is 3 ℃/minute, obtains corresponding rare earth oxide Ho
2O
3, Gd
2O
3, Pr
6O
11, Sc
2O
3And Lu
2O
3Calculate with molar content, weighing is purchased micron order ZnO 99.0%, Y respectively
2O
30.01%, MnO
20.1%, Co
2O
30.2%, TiO
20.001%, SiO
20.01%, Cr
2O
30.5%, Li
2O 0.008%, the product Ho that simultaneously weighing is above-mentioned after fully being decomposed by REE carbonate and oxyhydroxide
2O
30.01%, Gd
2O
30.03%, Pr
6O
110.05%, Sc
2O
30.07%, Lu
2O
30.011% puts into the frequency conversion planetary high-energy ball mill with above-mentioned materials; Add proper amount of acetone and alcoholic acid mixture and carry out the high energy wet-milling, wherein, the quality of wolfram varbide abrading-ball and powder total amount is 10: 1; The total amount of ball, powder and liquid medium is no more than ball grinder volumetrical 3/4; Rotating speed is 200 rev/mins, and the ball milling time is 25 hours, in mechanical milling process, adds the ammonium polymethacrylate dispersion agent of 10wt%; Slurry behind the ball milling is carried out thorough drying by the straight tube pneumatic drier, obtain even exsiccant powder mix.
It is 10g/cm that above-mentioned powder mix is pressed into density
3Circular block, then in cabinet-type electric furnace in 200 ℃ of presintering 24 hours, obtain the sintering block.Put it into ball mill for dry grinding, the mass ratio that makes wolfram varbide abrading-ball and powder total amount is 10: 1, and rotating speed is 200 rev/mins, and the ball milling time is 25 hours, obtains even exsiccant powder mix.In this powder mix, add 33% quality percentage composition and carry out granulation for the 15%PVA aqueous solution, then, in 100 t hydraulic press pressed moulding; Obtaining thickness is the round billet sheet of 1mm; Then this round billet sheet is put into chamber type electric resistance furnace, sintering under the air atmosphere of circulation, heat-up rate is 10 ℃/minute; Be incubated binder removals 1 hour at 800 ℃, then insulation 0.5 hour and furnace cooling under 1100 ℃ condition.
On two end faces of the sample behind the above-mentioned sintering, coat ag paste electrode, put into chamber type electric resistance furnace; 300 ℃ of insulations 10 hours; Cool to room temperature then with the furnace, and grid for welding goes between on its end face, the potential gradient that behind electric performance test, obtains this Zinc-oxide piezoresistor is 967V/mm; Nonlinear factor is 39, and leakage current is 6.1 μ A.
Embodiment 6
An amount of erbium hydroxide, thulium hydroxide, Ytterbium trihydroxide were calcined 0.5 hour at 1000 ℃, 1000 ℃ and 1100 ℃ respectively, and heat-up rate is 15 ℃/minute, obtains corresponding rare earth oxide Er
2O
3, Tm
2O
3And Yb
2O
3Calculate with molar content, weighing is purchased micron order ZnO 85%, ZrO respectively
20.2%, MnO
20.3%, Co
2O
35%, TiO
20.2%, V
2O
54.8%, Cr
2O
31.67%, the product Er that simultaneously weighing is above-mentioned after fully being decomposed by rare earth element hydroxide
2O
30.001%, Tm
2O
32%, Yb
2O
30.829% puts into the frequency conversion planetary high-energy ball mill with above-mentioned materials, adds The addition of C Cl
4Carry out the high energy wet-milling with the alcoholic acid mixture, wherein, the quality of aluminum oxide abrading-ball and powder total amount is 25: 1; The total amount of ball, powder and liquid medium is no more than ball grinder volumetrical 2/3; Rotating speed is 700 rev/mins, and the ball milling time is 2 hours, in mechanical milling process, adds the ammonium polymethacrylate dispersion agent of 0.01wt%; Slurry behind the ball milling is carried out thorough drying by the straight tube pneumatic drier, obtain even exsiccant powder mix.
It is 1.0g/cm that above-mentioned powder mix is pressed into density
3Circular block, then in cabinet-type electric furnace in 800 ℃ of presintering 0.5 hour, obtain the sintering block.Put it into ball mill for dry grinding, the mass ratio that makes aluminum oxide abrading-ball and powder total amount is 25: 1, and rotating speed is 700 rev/mins, and the ball milling time is 0.2 hour, obtains even exsiccant powder mix.In this powder mix, add 10% quality percentage composition and carry out granulation for the 1%PVA aqueous solution, then, in 8 t hydraulic press pressed moulding; Obtaining thickness is the round billet sheet of 5mm; Then this round billet sheet is put into chamber type electric resistance furnace, sintering under the air atmosphere of circulation, heat-up rate is 2 ℃/minute; Be incubated binder removals 15 hours at 200 ℃, then insulation 25 hours and furnace cooling under 800 ℃ condition.
On two end faces of the sample behind the above-mentioned sintering, coat ag paste electrode, put into chamber type electric resistance furnace; 1000 ℃ of insulations 5 minutes; Cool to room temperature then with the furnace, and grid for welding goes between on its end face, the potential gradient that behind electric performance test, obtains this Zinc-oxide piezoresistor is 895V/mm; Nonlinear factor is 46, and leakage current is 7.2 μ A.
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 high-potential gradient zinc oxide piezoresistive material is characterized in that, said method comprising the steps of:
(1) preparation rare earth oxide:, decompose the acquisition rare earth oxide with the rare-earth compound calcining;
(2) high energy wet-milling: the mixture that the said rare earth oxide mixing that ZnO, doping oxide and step (1) are made obtains carries out the high energy wet-milling, and subsequent drying obtains even exsiccant powder mix;
(3) the said powder mix presintering that step (2) is obtained obtains sintering mix;
(4) high energy dry grinding: the said sintering mix that step (3) is obtained carries out the high energy dry grinding, obtains even exsiccant powder mix;
(5) compression moulding: the said powder mix that step (4) is obtained carries out granulation, and compression moulding then obtains the base sheet;
(6) binder removal burns till: with the said base sheet intensification binder removal that step (5) obtains, and sintering, cooling obtains high-potential gradient zinc oxide piezoresistive material.
2. the preparation method of a high-potential gradient zinc oxide piezoresistive material end electrode; It is characterized in that; Said method is: carry out step (7) afterwards in the said step of claim (1) (6): on two end faces of the said high-potential gradient zinc oxide piezoresistive material that step (6) obtains, coat conductive coating, high temperature keeps for some time then; Cooling obtains end electrode.
3. the preparation method of a high-potential gradient zinc oxide voltage-sensitive ceramic; It is characterized in that; Said method comprises: carry out step (8) grid for welding lead-in wire afterwards in the said step of claim (2) (7): grid for welding lead-in wire on the said end electrode end face that step (7) makes, the high-potential gradient zinc oxide voltage-sensitive ceramic of electrical property can be directly tested in acquisition.
4. like each described method of claim 1-3, it is characterized in that, rare-earth compound described in the step (1) be preferably REE oxalate or/and carbonate or/and oxyhydroxide, the oxalate that is preferably REE especially is or/and carbonate;
Preferably, REE described in the step (1) is a kind or at least 2 kinds combination among Sc, Y, Pr, Ce, La, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu;
Preferably, calcining temperature is more than 300 ℃ described in the step (1), further is preferably 300～1100 ℃, more preferably 350～1050 ℃, is preferably 400～1000 ℃ especially;
Preferably, calcination time is more than the 0.5h described in the step (1), further is preferably 0.5～24h, 1～12h more preferably, and more preferably 1～8h is preferably 1～6h especially;
Preferably, heat-up rate is 1～15 ℃/min during calcining described in the step (1), further is preferably 1～10 ℃/min, and more preferably 1～7 ℃/min is preferably 1～5 ℃/min especially.
5. like each described method of claim 1-3, it is characterized in that doping oxide is preferably B described in the step (2)
2O
3, Fe
2O
3, SnO, 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, further be preferably Bi
2O
3, MnO
2, Co
2O
3, Sb
2O
3, SiO
2, Cr
2O
3, a kind or at least 2 kinds combination among the NiO, be preferably Bi especially
2O
3, MnO
2, Co
2O
3, Sb
2O
3, SiO
2, Cr
2O
3Combination with NiO;
Preferably, rare earth oxide is Sc described in the step (2)
2O
3, Y
2O
3, Pr
6O
11, CeO
2, La
2O
3, Nd
2O
3, Pm
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
2O
3, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3And Lu
2O
3In a kind or at least 2 kinds combination;
Preferably, in the mixture, the content of ZnO is 85～99% by mole per-cent, further is preferably 90～99%, is preferably 93～98.5 especially described in the step (2); Preferably, the content of any in the said doping oxide independently is 0.001～5%, further is preferably 0.005～3%, is preferably 0.01～2% especially; Preferably, the total content of said rare earth oxide is 0.001～5%, further is preferably 0.005～3%, is preferably 0.01～2% especially;
Preferably, ZnO is a micron order described in the step (2);
Preferably, doping oxide is a micron order described in the step (2);
Preferably, the liquid medium of high energy wet-milling is water and/or organic solvent described in the step (2), 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.
6. like each described method of claim 1-5, it is characterized in that, the mass ratio of used abrading-ball of high energy wet-milling and powder described in the step (2) is preferably 10: 1～and 25: 1, further be preferably 14: 1～20: 1, be preferably 18: 1 especially;
Preferably, the volume sum of the used abrading-ball of high energy wet-milling, powder, liquid medium is no more than ball grinder volumetrical 3/4 described in the step (2), is preferably especially and is no more than ball grinder volumetrical 2/3;
Preferably, high energy wet-milling rotating speed is 200～700 rev/mins described in the step (2), further is preferably 300～600 rev/mins, is preferably 400～550 rev/mins especially;
Preferably, the high energy wet-milling time described in the step (2) is more than 2 hours, further is preferably 2～25 hours, more preferably 3～20 hours, is preferably 3～16 hours especially;
Preferably; Can add dispersion agent during high energy wet-milling described in the step (2); Said dispersion agent is preferably a kind or at least 2 kinds combination in ROHM, ammonium polymethacrylate, ammonium citrate, the ammonium polyacrylate; Further the add-on of preferred said dispersion agent is 0.01～10wt%, and more preferably 0.03～5wt% is preferably 0.05～3wt% especially;
Preferably, dry described in the step (2) for adopting the straight tube pneumatic drier to carry out thorough drying.
7. like each described method of claim 1-3, it is characterized in that, in the step (3); Before presintering; The dry mixed powder that preferably step (2) is obtained is pressed into block, and further preferred, the block density that the dry mixed powder that step (2) is obtained is pressed into is 1.0～10.0g/cm
3, 3.0～8.0g/cm more preferably
3, be preferably 4.0～6.0g/cm especially
3
Preferably, presintering is carried out in cabinet-type electric furnace described in the step (3);
Preferably, pre-sintering temperature is 200～800 ℃ described in the step (3), more preferably 250～750 ℃, is preferably 300～680 ℃ especially;
Preferably, the presintering time described in the step (3) is more than 0.5 hour, further is preferably 0.8～24 hour, more preferably 1～8 hour, is preferably 1～4 hour especially;
Preferably, the dry grind mass ratio of used abrading-ball and powder of high energy described in the step (4) is 10: 1～25: 1, further is preferably 14: 1～20: 1, is preferably 18: 1 especially;
Preferably, the dry grinding of high energy described in the step (4) rotating speed is 200～700 rev/mins, further is preferably 300～600 rev/mins, is preferably 400～550 rev/mins especially;
Preferably, the high energy dry grinding time described in the step (4) is more than 0.2 hour, further is preferably 0.3～25 hour, more preferably 0.4～10 hour, is preferably 0.5～6 hour especially.
8. like each described method of claim 1-3; It is characterized in that; In the powder mix that step (4) obtains, carry out granulation behind the preferred adding PVA in the step (5), said PVA add-on is preferably 0.1～5% of base sheet total mass, further is preferably 0.2～3%; More preferably 0.3～1%, be preferably 0.4% especially; Preferred said PVA adds with aqueous solution form, and further the quality percentage composition of PVA is 1～15% in the preferred said PVA aqueous solution, further is preferably 3～10% again, and more preferably 4～7%, be preferably 5% especially;
Preferably, 8～100 t hydraulic press are adopted in compression moulding described in the step (5), further are preferably 9～60 t hydraulic press, are preferably 10～50 t hydraulic press especially;
Preferably, the base sheet thickness that obtains in the step (5) is 1～5mm, further is preferably 2～3mm, is preferably 2mm especially;
Preferably, binder removal described in the step (6) burns till preferably and in chamber type electric resistance furnace, carries out;
Preferably, binder removal described in the step (6) burns till under the air atmosphere of circulation and carries out;
Preferably, heat-up rate is more than 1 ℃/minute described in the step (6), further is preferably 1～10 ℃/minute, is preferably 1～5 ℃/minute especially;
Preferably, dump temperature is 200～800 ℃ described in the step (6), further is preferably 250～700 ℃, is preferably 300～600 ℃ especially;
Preferably, the binder removal time described in the step (6) is more than 1 hour, further is preferably 1.5～15 hours, more preferably 2～10 hours, is preferably 2～8 hours especially;
Preferably, sintering temperature is 800～1100 ℃ described in the step (6), further is preferably 850～1100 ℃, is preferably 900～1000 ℃ especially;
Preferably, sintering time is more than 0.5 hour described in the step (6), further is preferably 1～25 hour, more preferably 1～15 hour, is preferably 1～8 hour especially.
9. like each described method of claim 1-8, it is characterized in that conductive coating described in the step (7) is preferably the silver slurry;
Preferably, coat conductive coating in the step (7) after, heat-up rate is more than 1 ℃/minute, further is preferably 1～10 ℃/minute, is preferably 1～5 ℃/minute especially;
Preferably, high temperature is 300～1000 ℃ described in the step (7), further is preferably 400～800 ℃, is preferably 450～750 ℃ especially;
Preferably, the high temperature hold-time described in the step (7) is more than 5 minutes, further is preferably 10 minutes～10 hours, more preferably 12 minutes～5 hours, is preferably 15 minutes especially～3 hours;
Preferably, high temperature is provided by chamber type electric resistance furnace described in the step (7);
Preferably, said high energy wet-milling and high energy are dry grinded used abrading-ball independently for a kind or at least 2 kinds combination in zirconium oxide balls, wolfram varbide abrading-ball, the aluminum oxide abrading-ball, are preferably zirconium oxide balls especially;
Preferably, the used high energy ball mill of said high energy wet-milling and high energy dry grinding is the frequency conversion planetary high-energy ball mill;
Preferably, said high energy wet-milling and high energy are dry grinded used ball grinder independently for a kind in tetrafluoroethylene ball grinder, ceramic ball grinder, the urethane ball grinder, are preferably the tetrafluoroethylene ball grinder especially.
10. the purposes of the high-potential gradient zinc oxide piezoresistive material of the method for claim 1 preparation is characterized in that said high-potential gradient zinc oxide piezoresistive material can be used for preparing the thunder arrester that the super-high power system uses.
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