CN100486928C - Zinc oxide press-sensitive ceramic and preparation method thereof - Google Patents
Zinc oxide press-sensitive ceramic and preparation method thereof Download PDFInfo
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- CN100486928C CN100486928C CNB2006100881480A CN200610088148A CN100486928C CN 100486928 C CN100486928 C CN 100486928C CN B2006100881480 A CNB2006100881480 A CN B2006100881480A CN 200610088148 A CN200610088148 A CN 200610088148A CN 100486928 C CN100486928 C CN 100486928C
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Abstract
The invention discloses a zinc oxide pressure-sensitive ceramic and the manufacturing method. The ceramic comprises the doping element (titanium, bismuth, tin, manganese, cobalt, aluminium, chromium, nickel, barium, barium, silver, boron, antimony)as nanometer oxide disperse phase in the oxide ceramic base. The method comprises the following steps: weighing butyl titanate, bismuth nitrate, tin nitrate, manganese nitrate, cobalt nitrate, aluminum nitrate, chromium nitrate, nickel nitrate, barium nitrate, silver nitrate, boracic acid, antimony oxide and zinc oxide power; formulating the doping original material into the mixed solution; making the nanometer doping predecessor body with carbon; mixing the predecessor body with the zinc oxide powder; getting he zinc oxide composite powder after annealing; or formulating the doping original material into alcohol mixed solution; encapsulating the zinc oxide powder with alcohol mixed solution; getting the zinc oxide composite powder after annealing; getting zinc oxide pressure-sensitive ceramic by pressing and sintering. The invention can be used for 8-100V low-pressure system.
Description
Technical field the present invention relates to a kind of voltage-sensitive ceramic and method for making, especially zinc oxide pressure-sensitive ceramic and preparation method thereof.
The background technology zinc oxide pressure-sensitive ceramic is because of having good non-linear volt-ampere characteristic; resistance value is very responsive to specific impressed voltage; so can be made into piezoresistor, have a wide range of applications in fields such as extinguish arcs, overvoltage protection, lightning-arrest and voltage stabilizations.Existing result of study and practical application to zinc oxide pressure-sensitive ceramic show that all the prescription of zinc oxide pressure-sensitive ceramic and preparation technology are determining its macroscopical electrical property, the i.e. size of gradient voltage, nonlinear factor, leakage current, through-current capability jointly.For this reason, people have done some and have attempted and various effort, attempt change by prescription and technology and realize regulation and control to its macroscopical electrical property.As a kind of " the making the method for pressure-sensitive ceramic resistor and the resistance made from present method " that discloses among the disclosed Chinese invention patent ublic specification of application CN 86102994A on October 29th, 1986 with zinc oxide.It is intended to provide a kind of zinc oxide and doping oxide of using to make the method for pressure-sensitive ceramic resistor and the resistance of producing with this method; Wherein, manufacture method is that doped element is added in the aqeous suspension of Zinc oxide powder with the aqueous solution of organic acid salt, acid, complex compound and/or the form of colloidal solution, again suspension/aqueous solution is spray dried to powder with airflow in spray-dryer, then that powder compression is in blocks, again it progressively is heated to 650 ℃, 900 ℃, 1100 to 1300 ℃, decompose to finish organism, doped element is converted into oxide compound, resolvent waves and remove and sintering process, thereby make sintered compact; Pressure-sensitive ceramic resistor is made of this sintered compact, and it is made up of the oxide compound of selecting among Co, Mn, Cr, Ni, Ba, Bi, Sb, rare earth, Al, B, Si, Ga, the Ti in zinc oxide and the doped element group.But this pressure-sensitive ceramic resistor and manufacture method all exist many weak points, and at first, the gradient voltage of pressure-sensitive ceramic resistor is more than the 200V/mm, is difficult to use it in the lp system; Secondly, be starting raw material with organic salt, complex compound, acid, ammonium salt or the alkyl fat of doped element, make the cost height of raw material, and some raw materials wherein itself are toxic substance; Once more, use the aqueous solution to mix in the manufacturing processed with the aqeous suspension of Zinc oxide powder, spraying drying then, whole process needs main equipment, and energy consumption is big, production cost is high and effect is undesirable: the component of doped element and the homogeneity that is distributed in the pressure-sensitive ceramic resistor thereof can only guarantee in micron dimension; At last, the organic decomposition and the eliminating of bringing into of mixing all carried out after the pressed compact moulding, can damage be arranged and inevitably can produce virulent waste base substrate.
In addition, though the gradient voltage that adopts different prescriptions and technology to try hard to reduce Zinc oxide pressure-sensitive ceramic material is also arranged, as once described a kind of " nanometer doped composite low-voltage zinc oxide pressure sensitive resistor and manufacture craft thereof " among the disclosed Chinese invention patent ublic specification of application CN1614720A on May 11st, 2005.Voltage dependent resistor is made of bismuthous oxide bismuth trioxide, titanium dioxide, cobaltic oxide, nickel sesquioxide, manganous carbonate, aluminum nitrate and zinc oxide, and titanium dioxide wherein is liquid phase synthetic monodisperse nano-titanium dioxide, and all the other are micron-sized powder; Manufacture craft be with the dispersed nano grade titanium dioxide in ball grinder with pure water fully miscible after, added the zinc oxide ball milling again 2 hours, add Silver Nitrate and aluminum nitrate afterwards, ball milling adds remaining composition after 1 hour again, ball milling discharging after 3 hours then, make the voltage dependent resistor powder by mist projection granulating again, sinter voltage dependent resistor at last into.Yet, this Zinc-oxide piezoresistor and manufacture craft thereof also have the following disadvantages: the one, and the pressure sensitive voltage gradient is still higher, and lower limit only is 24.2V/mm, only is applicable to the preparation of 18V and above voltage dependent resistor, can not be used for lower pressure-sensitive voltage, for example the making of the piezoresistor about 10V; The 2nd, there are the following problems in producing: the preparation of monodispersed titanium dioxide nano sol is big with the preservation difficulty on the one hand, dispersiveness in order to guarantee that titanium dioxide mixes on the other hand, TiO 2 sol needs to add respectively and mix with other adulterated powder, technology is numerous and diverse, during energy charge, the production cost height; Three are to use titanium dioxide nano sol to produce the conventional oxide hybrid system of low-voltage zinc oxide pressure sensitive resistor with respect to the common powder of whole uses, gradient voltage reduces, other performance also is optimized simultaneously, the yield rate of the low-voltage zinc oxide pressure sensitive resistor production of 18V and 22V has been brought up to 90%, effect is obvious, but the dispersion of each doped element and homogeneity question still exist in the product, and yield rate also remains further to be improved.
The summary of the invention the technical problem to be solved in the present invention is for overcoming weak point of the prior art, provide a kind of prescription rationally, can be used for lp system, prepare easy zinc oxide pressure-sensitive ceramic and preparation method thereof.
Zinc oxide pressure-sensitive ceramic comprises zinc oxide, and particularly (a) said voltage-sensitive ceramic is to be made by the raw material of following molar percentage, tetra-n-butyl titanate (C
16H
36O
4Ti) 0.4～1.2%, Bismuth trinitrate (Bi (NO
3)
35H
2O) 0.3～1.2%, nitric acid tin (Sn (NO
3)
4) 0.2～0.8%, manganous nitrate (Mn (NO
3)
2) 0.4～1%, Xiao Suangu (Co (NO
3)
26H
2O) 0.5～1.5%, aluminum nitrate (Al (NO
3)
39H
2O) 0.002～0.02%, chromium nitrate (Cr (NO
3)
39H
2O) 0.03～0.2%, nickelous nitrate (Ni (NO
3)
26H
2O) 0.03～0.2%, nitrate of baryta (Ba (NO
3)
2) 0.03～0.1%, Silver Nitrate (AgNO
3) 0.001～0.005%, boric acid (H
3BO
3) 0.02～0.05%, weisspiessglanz (Sb
2O
3) 0.01～0.08%, all the other are Zinc oxide powder; (b) said tetra-n-butyl titanate, Bismuth trinitrate, nitric acid tin, manganous nitrate, Xiao Suangu, aluminum nitrate, chromium nitrate, nickelous nitrate, nitrate of baryta, Silver Nitrate, boric acid and weisspiessglanz all are distributed in the zinc oxide ceramics matrix with nano oxide dispersion form mutually.
The preparation method of zinc oxide pressure-sensitive ceramic comprises solid reaction process, and particularly it is finished according to the following steps: (a) work the tetra-n-butyl titanate (C that expects by required stoicheiometry weighing hotchpotch
16H
36O
4Ti), Bismuth trinitrate (Bi (NO
3)
35H
2O), nitric acid tin (Sn (NO
3)
4), manganous nitrate (Mn (NO
3)
2), Xiao Suangu (Co (NO
3)
26H
2O), aluminum nitrate (Al (NO
3)
39H
2O), chromium nitrate (Cr (NO
3)
39H
2O), nickelous nitrate (Ni (NO
3)
26H
2O), nitrate of baryta (Ba (NO
3)
2), Silver Nitrate (AgNO
3), boric acid (H
3BO
3), weisspiessglanz (Sb
2O
3), and Zinc oxide powder, respectively various hotchpotchs are worked to expect earlier being mixed with the aqueous solution, wherein, weisspiessglanz uses the citric acid preparation, and the mol ratio of citric acid and weisspiessglanz is 20:1～5, under stirring, mixes above-mentioned each aqueous solution again and gets mixing solutions,
Perhaps work the tetra-n-butyl titanate (C that expects by required stoicheiometry weighing hotchpotch
16H
36O
4Ti), Bismuth trinitrate (Bi (NO
3)
35H
2O), nitric acid tin (Sn (NO
3)
4), manganous nitrate (Mn (NO
3)
2), Xiao Suangu (Co (NO
3)
26H
2O), aluminum nitrate (Al (NO
3)
39H
2O), chromium nitrate (Cr (NO
3)
39H
2O), nickelous nitrate (Ni (NO
3)
26H
2O), nitrate of baryta (Ba (NO
3)
2), Silver Nitrate (AgNO
3), boric acid (H
3BO
3), weisspiessglanz (Sb
2O
3), and Zinc oxide powder, choosing hotchpotch earlier works in expecting more than one and is made into ethanolic soln, and adding dispersion agent after mixing, wherein, the cation concn of ethanolic soln is 0.02～0.1mol/L, the pH value of alcohol mixed solution is 6～7, again Zinc oxide powder is added and mix in the alcohol mixed solution and heat, the dry zinc oxide powder that gets the hotchpotch parcel, wherein, the temperature of heating is 80～95 ℃, time is 6～10 hours, and the exsiccant temperature is 90～120 ℃, time is 10～24 hours, then remaining hotchpotch is worked to expect respectively it is mixed with the aqueous solution earlier, wherein, weisspiessglanz uses the citric acid preparation, and the mol ratio of citric acid and weisspiessglanz is 20:1～5, and above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again;
(b) in mixing solutions, add citric acid and nitric acid and stirring earlier, the metal ion total concn that makes mixing solutions is 0.1～0.5mol/L, wherein, the add-on of citric acid and the mol ratio of metal ion are 1:0.3～3, the add-on of nitric acid is that to make the pH value of mixing solutions be 0.5～4, after the stirring at room at least 1 hour, add coordination agent and be stirred to dissolving, again mixed solution is filtered the back and continue to stir and be heated to the formation gel, gel is carried out drying, thermal treatment gets carbon containing doping presoma, wherein, the temperature of heating is 60～100 ℃, the exsiccant temperature is 60～120 ℃, heat treated temperature is 120～400 ℃, time is 6～12 hours
Perhaps add dispersion agent in mixing solutions, wherein, the cation concn in the mixing solutions is 0.02～0.1mol/L, after the stirring and dissolving, earlier add in the mixed solution nano carbon black and ultra-sonic dispersion, again it carried out heated and stirred to forming solid mixt, be dried then carbon containing doping presoma, wherein, nano carbon black is 5:1～2 with the total mass ratio of initial hotchpotch, and Heating temperature is 80～95 ℃, and the time is 6～10 hours, drying temperature is 90～120 ℃, and the time is 12～24 hours;
(c) the back ball milling mixed at least 1 hour with the zinc oxide powder of Zinc oxide powder or hotchpotch parcel in elder generation with carbon containing doping presoma, again with it in 400～580 ℃ of following thermal treatments 3～8 hours, afterwards, again successively ball milling at least 1 hour, in 700～850 ℃ of following thermal treatments 1～8 hour, obtain zinc oxide composite powder;
(d) earlier with the moulding of zinc oxide composite powder pressed compact, under 1200～1280 ℃, fired 2～4 hours again, make the zinc oxide low voltage varistor ceramics.
As the preparation method's of zinc oxide pressure-sensitive ceramic further improvement, the temperature of the citric acid solution that the described preparation weisspiessglanz aqueous solution is used is 50～100 ℃; The described dispersion agent that adds in the ethanolic soln that is made into is polyoxyethylene glycol PEG or PVAC polyvinylalcohol or polyacrylic acid PAA, wherein, the consumption of polyoxyethylene glycol PEG is 10～40g/L, the consumption of PVAC polyvinylalcohol is 20～40g/L, the consumption of polyacrylic acid PAA is 20～80g/L, and L is the unit liter of the cumulative volume of the ethanolic soln that is made into; The described coordination agent that adds in mixing solutions is polyoxyethylene glycol PEG or ethylene glycol or PVAC polyvinylalcohol or polyacrylic acid PAA, wherein, when coordination agent is selected polyoxyethylene glycol for use, its molecular weight is 4000～20000, with the mass ratio of citric acid be 1:0.2～0.5, when coordination agent is selected ethylene glycol for use, the mass ratio of itself and citric acid is 2:2.5～3.5, when coordination agent is selected PVAC polyvinylalcohol for use, its consumption is 20～40g/L, when coordination agent is selected polyacrylic acid PAA for use, its consumption is 20～80g/L, and L is the unit liter of the cumulative volume of mixing solutions; The described dispersion agent that adds in mixing solutions is polyoxyethylene glycol PEG or PVAC polyvinylalcohol or polyacrylic acid PAA, wherein, the consumption of polyoxyethylene glycol PEG is 10～40g/L, the consumption of PVAC polyvinylalcohol is 20～40g/L, the consumption of polyacrylic acid PAA is 20～80g/L, and L is the unit liter of the cumulative volume of mixing solutions; The frequency of ultrasonic of the nano carbon black in the described ultra-sonic dispersion mixing solutions is 10～60KHz; Described ball milling mixes on planetary ball mill and grinding for mixture being placed ball grinder, and wherein, the rotating speed of ball milling is that 200～300rad/min, time are 1～8 hour; Described pressed compact is the single shaft pressed compact, and its pressure is 120～300MPa.
Beneficial effect with respect to prior art is, one, after the hotchpotch of the employing different ingredients that repeatedly makes worked expect the zinc oxide composite powder molding blank made with zinc oxide and zinc oxide pressure-sensitive ceramic and use field emission scanning electron microscope and incidental power spectrum tester, x-ray diffractometer and laser particle size analyzer to characterize respectively, test collection of illustrative plates, X-ray diffracting spectrum and laser particle size analysis test result as can be known from the stereoscan photograph, the power spectrum that obtain, the epigranular of the powder in the base substrate, narrowly distributing does not have any coacervate.The uniform particles of zinc oxide pressure-sensitive ceramic, densification, it is to be distributed in the zinc oxide ceramics matrix with the form of nano oxide dispersion phase by doped element to constitute; They are two years old, after the hotchpotch of the employing different ingredients that repeatedly makes worked the zinc oxide pressure-sensitive ceramic made with zinc oxide of expecting and use the I-V tester of self-assembly to carry out the test of current-voltage curve, from the multi-group data that obtains as can be known, its pressure sensitive voltage gradient is 8～100V/mm, nonlinear factor α is 16～30, and leakage current is 6～30 μ A; They are three years old, preparation method's science, reasonable, and simple and convenient, effect is remarkable, solution wherein wraps up and/or contains two kinds of doping way of carbon matrix precursor mechanically mixing and can guarantee that all doped elements finally all can be distributed in the zinc oxide ceramics matrix with the particulate form of nanometer scale, thereby both prepared the zinc oxide pressure-sensitive ceramic that is applicable to lp system, solve the homogeneity of the zinc oxide pressure-sensitive ceramic preparation that is used for the low pressure system, the technical barrier of consistence difference again simultaneously, also be easy to suitability for industrialized production.The technological core of the solution pack among the preparation method be stable neutral alcohol hotchpotch mixing solutions preparation and with the mixing of Zinc oxide powder, this scheme is with respect to existing solution or the adulterated advantage of colloidal sol, and unequal problem is separated out, disperseed to the hotchpotch that solution is neutrality when having avoided acid or alkaline doping mixed solution to mix with zinc oxide and the oxide powder and zinc precursor reactant causes; In addition, alcohol is made solvent and is very easily removed, and does not have any residue, and whole process does not have toxic substance and generates, and is environmentally friendly; In addition, powder does not have reunion in the mixing process, can guarantee well that hotchpotch invests around the Zinc oxide powder with the particulate form bag of nanometer scale.The core concept of the solid carbon-contg forerunner method among the preparation method is that hotchpotch is mixed earlier with Zinc oxide powder in the mode of solid carbon-contg precursor, subsequent heat treatment makes to contain carbon matrix precursor and be transformed into doping oxide and be distributed in the zinc oxide ceramics matrix with the particulate form of nanometer scale; The advantage of this scheme is that mixing of solid carbon-contg precursor and Zinc oxide powder and subsequent treatment process can be produced on the Zinc-oxide piezoresistor equipment in existing oxide compound hybrid system and finishes easily, can realize hotchpotch and the Zinc oxide powder uniform mixing at nanoscale under the prerequisite of not changing equipment; Another advantage of this method is to make by the selection of doped element source material, solvent and coordination agent the solid carbon-contg precursor of any doped element, realizes that doped element evenly is incorporated in the zinc oxide pressure-sensitive powder with the nanoparticle form.This preparation method who the solution pack is combined utilization with solid carbon-contg forerunner method and constitute is variable flexibly, can select suitable doped forms according to the characteristic of doped element, ie in solution pack and/or solid carbon-contg forerunner method, evenly mix in the zinc oxide pressure-sensitive powder with the nanoparticle form with final realization hotchpotch, thus the preparation of realization zinc-oxide nano composite granule; They are four years old, the starting raw material that the preparation method uses is good and cheap thing and is easy to get, Zinc oxide powder wherein still is common powder, hotchpotch rises to expect and only is nitrate or acetate and the comparatively cheap organic salt of price, this has not only reduced production cost, do not have any pollutant emission again, belong to environmental protection industry; Its five, the preparation method only need use the equipment of existing preparation conventional oxidation zinc voltage-sensitive ceramic, and does not need to acquire the spray drying device of power consumption again; They are six years old, after changing the prescription among the preparation method, also can directly use it for the preparation of middle and high pressure Zinc-oxide piezoresistor, disperse with the nanometer scale that realizes hotchpotch in the compound pressure-sensitive powder preparing of middle and high this two individual system, thereby solve ubiquitous homogeneity question in the Zinc-oxide piezoresistor preparation.
As the further embodiment of beneficial effect, the one, the temperature of the citric acid solution that the configuration weisspiessglanz aqueous solution is used is selected 50～100 ℃ for use, can make the weisspiessglanz dissolved more abundant, complete; The 2nd, respectively in the ethanolic soln that is made into and the dispersion agent that in mixing solutions, adds be polyoxyethylene glycol or polyvinyl alcohol or polyacrylic acid, the coordination agent that adds in mixing solutions is polyoxyethylene glycol or ethylene glycol or polyvinyl alcohol or polyacrylic acid, make the selection of dispersion agent or coordination agent that bigger leeway be arranged, not only convenient flexibly, also be beneficial to suitability for industrialized production; The 3rd, the frequency of ultrasonic of the nano carbon black in the ultra-sonic dispersion mixing solutions adopts 10～60KHz, can make nano carbon black dispersive in mixing solutions more even.
Description of drawings is described in further detail optimal way of the present invention below in conjunction with accompanying drawing.
Fig. 1 is that the hotchpotch to the employing different ingredients that repeatedly makes works the zinc oxide composite powder molding blank made from zinc oxide of expecting and uses the Sirion 200FEG field emission scanning electron microscope (FESEM) of U.S. FEI Co. to observe one of photo of taking behind the surface topography, by seeing in the FESEM photo, powder is by nano level granulometric composition, particle all is uniform dispersed, and does not have any agglomeration;
The laser particle size analysis test result that Fig. 2 obtains after being to use the Zetasizer3000HSa laser particle size analyzer of Britain Malvern company that base substrate shown in Figure 1 is tested, wherein, X-coordinate is a particle diameter, ordinate zou is a quantity.This result shows that its median size is 683nm, and the narrowly distributing of granularity does not have the reunion greater than 1 μ m.This result is consistent with the content of the FESEM photo of base substrate, and as seen, doped element is distributed in around the Zinc oxide powder with the form of nano particle;
Fig. 3 is to use the incidental power spectrum of the Sirion 200FEG field emission scanning electron microscope of U.S. FEI Co. test (EDS) instrument that EDS that five points carry out gained after spot scan figure is as a result chosen on the surface of base substrate shown in Figure 1 arbitrarily, the basically identical as a result of the result of this figure and Fig. 1 and Fig. 2, can find out that by EDS figure the homogeneity of zinc oxide composite powder has reached nanometer scale;
Fig. 4 is that the hotchpotch to the different proportionings of the employing that repeatedly makes works the zinc oxide pressure-sensitive ceramic made from zinc oxide of expecting and uses the U.S. Sirion 200FEG of FEI Co. field emission scanning electron microscope to observe the photo of taking behind the surface topography, by photo as can be known, the particle of zinc oxide pressure-sensitive ceramic in conjunction with closely, evenly, can be realized the adjusting control of zinc oxide pressure-sensitive ceramic granular size each other by the change of prescription;
Fig. 5 uses X-ray diffraction (XRD) collection of illustrative plates that obtains after the test of Phillips X ' Pert type x-ray diffractometer respectively to Fig. 1 and zinc oxide composite powder molding blank and zinc oxide pressure-sensitive ceramic shown in Figure 4, wherein, X-coordinate is 2 θ angles, ordinate zou is a diffracted intensity, (a) figure is the XRD figure spectrum of zinc oxide composite powder molding blank, (b) figure is the XRD figure spectrum of zinc oxide pressure-sensitive ceramic, and the symbols Z in the collection of illustrative plates is that ZnO, S are Zn
2TiO
4, T is Bi
4Ti
3O
12, T
2Be Bi
12TiO
20, B is Bi
2O
3, compose constituting of zinc oxide pressure-sensitive ceramic as can be known by XRD figure;
The I-V tester that Fig. 6 is to use self-assembly works the typical current-voltage curve that obtains after the I-V test that the voltage-sensitive ceramic made with zinc oxide of expecting carries out to the hotchpotch that adopts different proportionings, among the figure from top to bottom the gradient voltage of four curve correspondences be respectively 68.6V/mm, 44V/mm, 27V/mm, 8.4V/mm, nonlinear factor α is respectively 29.3,33,26.8,24.4, and leakage current is respectively 16 μ A, 11.5 μ A, 12 μ A, 9 μ A.As seen, proportioning raw materials provided by the invention and preparation method can well realize the preparation of the zinc oxide low voltage varistor that pressure sensitive voltage 8～100V, comprehensive electrochemical properties are excellent.
Embodiment at first makes or buys from market tetra-n-butyl titanate, Bismuth trinitrate, nitric acid tin, manganous nitrate, Xiao Suangu, aluminum nitrate, chromium nitrate, nickelous nitrate, nitrate of baryta, Silver Nitrate, boric acid, weisspiessglanz and Zinc oxide powder with ordinary method, and citric acid, ethanol, nitric acid, nano carbon black, the polyoxyethylene glycol as dispersion agent and coordination agent, polyvinyl alcohol, polyacrylic acid, ethylene glycol.Then,
Embodiment 1: finish preparation according to the following steps, a) rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 1%, Bismuth trinitrate 1.2%, nitric acid tin 0.2%, manganous nitrate 1%, Xiao Suangu 0.5%, aluminum nitrate 0.02%, chromium nitrate 0.03%, nickelous nitrate 0.2%, nitrate of baryta 0.1%, Silver Nitrate 0.001%, boric acid 0.02%, weisspiessglanz 0.01%, all the other are Zinc oxide powder.Earlier respectively various hotchpotchs are worked to expect being mixed with the aqueous solution, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 50 ℃, and the mol ratio of citric acid and weisspiessglanz is 20:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
Perhaps rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 1%, Bismuth trinitrate 1.2%, nitric acid tin 0.2%, manganous nitrate 1%, Xiao Suangu 0.5%, aluminum nitrate 0.02%, chromium nitrate 0.03%, nickelous nitrate 0.2%, nitrate of baryta 0.1%, Silver Nitrate 0.001%, boric acid 0.02%, weisspiessglanz 0.01%, all the other are Zinc oxide powder.Choose earlier hotchpotch rise in expecting one or more or all be made into ethanolic soln, and mix the back and add dispersion agent; Wherein, the cation concn of ethanolic soln is 0.02mol/L, and the pH value of alcohol mixed solution is 7, and dispersion agent is a polyoxyethylene glycol, and its consumption is 10g/L, and L is the unit liter of the cumulative volume of the ethanolic soln that is made into.Again Zinc oxide powder is added mix in the alcohol mixed solution and heat, the zinc oxide powder of dry hotchpotch parcel; Wherein, the temperature of heating is that 80 ℃, time are 10 hours, and the exsiccant temperature is that 90 ℃, time are 24 hours.Then remaining hotchpotch is worked to expect respectively it is mixed with the aqueous solution earlier, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 50 ℃, and the mol ratio of citric acid and weisspiessglanz is 20:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
B) add citric acid and nitric acid and stirring earlier in mixing solutions, the metal ion total concn that makes mixing solutions is 0.1mol/L; Wherein, the add-on of citric acid and the mol ratio of metal ion are 1:0.3, and the add-on of nitric acid is that to make the pH value of mixing solutions be 0.5.After the stirring at room 1 hour, add coordination agent and be stirred to dissolving, wherein, coordination agent is a polyoxyethylene glycol, its molecular weight is 4000, with the mass ratio of citric acid be 1:0.5.Again mixed solution is filtered the back and continues to stir and be heated to the formation gel, to gel carry out drying, thermal treatment gets carbon containing doping presoma, wherein, the temperature of heating is that 60 ℃, exsiccant temperature are that 60 ℃, heat treated temperature are that 120 ℃, time are 12 hours.
Perhaps add dispersion agent in mixing solutions, wherein, the cation concn in the mixing solutions is 0.02mol/L, and dispersion agent is a polyoxyethylene glycol, and its consumption is 10g/L.After the stirring and dissolving, add in the mixed solution nano carbon black and ultra-sonic dispersion earlier, the frequency of ultrasonic of the nano carbon black in the ultra-sonic dispersion mixing solutions is 10KHz.Again it is carried out heated and stirred to forming solid mixt.Be dried then carbon containing doping presoma, wherein, nano carbon black is 5:1 with the total mass ratio of initial hotchpotch, Heating temperature is 80 ℃, the time is 10 hours, drying temperature is 90 ℃, the time is 24 hours.
C) earlier with the zinc oxide powder of Zinc oxide powder or hotchpotch parcel with after carbon containing doping presoma mixes, place ball grinder on planetary ball mill, to mix and grinding; Wherein, the rotating speed of ball milling is that 200rad/min, time are 1 hour.Again with it in 400 ℃ of following thermal treatments 8 hours.Afterwards, be placed on the ball mill subject to the foregoing ball milling 1 hour more successively,, obtain zinc oxide composite powder in 700 ℃ of following thermal treatments 8 hours.
D) earlier with zinc oxide composite powder on the single shaft harder through the moulding of 120MPa pressure pressed compact, obtain the base substrate as Fig. 1, Fig. 3 and the middle curve of Fig. 2, Fig. 5 (a) shown in.Again it was fired under 1200 ℃ 4 hours, make as Fig. 4 and the zinc oxide low voltage varistor ceramics shown in curve among Fig. 5 (b), Fig. 6.
Embodiment 2: finish preparation according to the following steps, a) rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 1.2%, Bismuth trinitrate 1%, nitric acid tin 0.3%, manganous nitrate 0.9%, Xiao Suangu 0.8%, aluminum nitrate 0.015%, chromium nitrate 0.05%, nickelous nitrate 0.12%, nitrate of baryta 0.08%, Silver Nitrate 0.002%, boric acid 0.03%, weisspiessglanz 0.02%, all the other are Zinc oxide powder.Earlier respectively various hotchpotchs are worked to expect being mixed with the aqueous solution, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 60 ℃, and the mol ratio of citric acid and weisspiessglanz is 10:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
Perhaps rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 1.2%, Bismuth trinitrate 1%, nitric acid tin 0.3%, manganous nitrate 0.9%, Xiao Suangu 0.8%, aluminum nitrate 0.015%, chromium nitrate 0.05%, nickelous nitrate 0.12%, nitrate of baryta 0.08%, Silver Nitrate 0.002%, boric acid 0.03%, weisspiessglanz 0.02%, all the other are Zinc oxide powder.Choose earlier hotchpotch rise in expecting one or more or all be made into ethanolic soln, and mix the back and add dispersion agent; Wherein, the cation concn of ethanolic soln is 0.04mol/L, and the pH value of alcohol mixed solution is 7, and dispersion agent is a polyoxyethylene glycol, and its consumption is 20g/L, and L is the unit liter of the cumulative volume of the ethanolic soln that is made into.Again Zinc oxide powder is added mix in the alcohol mixed solution and heat, the zinc oxide powder of dry hotchpotch parcel; Wherein, the temperature of heating is that 88 ℃, time are 8 hours, and the exsiccant temperature is that 95 ℃, time are 20 hours.Then remaining hotchpotch is worked to expect respectively it is mixed with the aqueous solution earlier, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 60 ℃, and the mol ratio of citric acid and weisspiessglanz is 10:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
B) add citric acid and nitric acid and stirring earlier in mixing solutions, the metal ion total concn that makes mixing solutions is 0.2mol/L; Wherein, the add-on of citric acid and the mol ratio of metal ion are 1:0.5, and the add-on of nitric acid is that to make the pH value of mixing solutions be 1.After the stirring at room 2 hours, add coordination agent and be stirred to dissolving, wherein, coordination agent is a polyoxyethylene glycol, its molecular weight is 8000, with the mass ratio of citric acid be 1:0.4.Again mixed solution is filtered the back and continues to stir and be heated to the formation gel, to gel carry out drying, thermal treatment gets carbon containing doping presoma, wherein, the temperature of heating is that 70 ℃, exsiccant temperature are that 80 ℃, heat treated temperature are that 200 ℃, time are 11 hours.
Perhaps add dispersion agent in mixing solutions, wherein, the cation concn in the mixing solutions is 0.04mol/L, and dispersion agent is a polyoxyethylene glycol, and its consumption is 18g/L.After the stirring and dissolving, add in the mixed solution nano carbon black and ultra-sonic dispersion earlier, the frequency of ultrasonic of the nano carbon black in the ultra-sonic dispersion mixing solutions is 20KHz.Again it is carried out heated and stirred to forming solid mixt.Be dried then carbon containing doping presoma, wherein, nano carbon black is 5:1 with the total mass ratio of initial hotchpotch, Heating temperature is 83 ℃, the time is 9 hours, drying temperature is 100 ℃, the time is 21 hours.
C) earlier with the zinc oxide powder of Zinc oxide powder or hotchpotch parcel with after carbon containing doping presoma mixes, place ball grinder on planetary ball mill, to mix and grinding; Wherein, the rotating speed of ball milling is that 220rad/min, time are 2 hours.Again with it in 440 ℃ of following thermal treatments 7 hours.Afterwards, be placed on the ball mill subject to the foregoing ball milling 2 hours more successively,, obtain zinc oxide composite powder in 750 ℃ of following thermal treatments 6 hours.
D) earlier with zinc oxide composite powder on the single shaft harder through the moulding of 160MPa pressure pressed compact, obtain the base substrate as Fig. 1, Fig. 3 and the middle curve of Fig. 2, Fig. 5 (a) shown in.Again it was fired under 1220 ℃ 3.5 hours, make as Fig. 4 and the zinc oxide low voltage varistor ceramics shown in curve among Fig. 5 (b), Fig. 6.
Embodiment 3: finish preparation according to the following steps, a) rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 0.8%, Bismuth trinitrate 0.8%, nitric acid tin 0.5%, manganous nitrate 0.7%, Xiao Suangu 1%, aluminum nitrate 0.01%, chromium nitrate 0.08%, nickelous nitrate 0.08%, nitrate of baryta 0.06%, Silver Nitrate 0.003%, boric acid 0.04%, weisspiessglanz 0.04%, all the other are Zinc oxide powder.Earlier respectively various hotchpotchs are worked to expect being mixed with the aqueous solution, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 75 ℃, and the mol ratio of citric acid and weisspiessglanz is 20:3.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
Perhaps rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 0.8%, Bismuth trinitrate 0.8%, nitric acid tin 0.5%, manganous nitrate 0.7%, Xiao Suangu 1%, aluminum nitrate 0.01%, chromium nitrate 0.08%, nickelous nitrate 0.08%, nitrate of baryta 0.06%, Silver Nitrate 0.003%, boric acid 0.04%, weisspiessglanz 0.04%, all the other are Zinc oxide powder.Choose earlier hotchpotch rise in expecting one or more or all be made into ethanolic soln, and mix the back and add dispersion agent; Wherein, the cation concn of ethanolic soln is 0.06mol/L, and the pH value of alcohol mixed solution is 6.5, and dispersion agent is a polyoxyethylene glycol, and its consumption is 25g/L, and L is the unit liter of the cumulative volume of the ethanolic soln that is made into.Again Zinc oxide powder is added mix in the alcohol mixed solution and heat, the zinc oxide powder of dry hotchpotch parcel; Wherein, the temperature of heating is that 90 ℃, time are 8 hours, and the exsiccant temperature is that 105 ℃, time are 17 hours.Then remaining hotchpotch is worked to expect respectively it is mixed with the aqueous solution earlier, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 75 ℃, and the mol ratio of citric acid and weisspiessglanz is 20:3.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
B) add citric acid and nitric acid and stirring earlier in mixing solutions, the metal ion total concn that makes mixing solutions is 0.3mol/L; Wherein, the add-on of citric acid and the mol ratio of metal ion are 1:1, and the add-on of nitric acid is that to make the pH value of mixing solutions be 2.After the stirring at room 3 hours, add coordination agent and be stirred to dissolving, wherein, coordination agent is a polyoxyethylene glycol, its molecular weight is 12000, with the mass ratio of citric acid be 1:0.35.Again mixed solution is filtered the back and continues to stir and be heated to the formation gel, to gel carry out drying, thermal treatment gets carbon containing doping presoma, wherein, the temperature of heating is that 80 ℃, exsiccant temperature are that 90 ℃, heat treated temperature are that 260 ℃, time are 9 hours.
Perhaps add dispersion agent in mixing solutions, wherein, the cation concn in the mixing solutions is 0.06mol/L, and dispersion agent is a polyoxyethylene glycol, and its consumption is 25g/L.After the stirring and dissolving, add in the mixed solution nano carbon black and ultra-sonic dispersion earlier, the frequency of ultrasonic of the nano carbon black in the ultra-sonic dispersion mixing solutions is 35KHz.Again it is carried out heated and stirred to forming solid mixt.Be dried then carbon containing doping presoma, wherein, nano carbon black is 5:1.5 with the total mass ratio of initial hotchpotch, Heating temperature is 88 ℃, the time is 8 hours, drying temperature is 105 ℃, the time is 18 hours.
C) earlier with the zinc oxide powder of Zinc oxide powder or hotchpotch parcel with after carbon containing doping presoma mixes, place ball grinder on planetary ball mill, to mix and grinding; Wherein, the rotating speed of ball milling is that 250rad/min, time are 4 hours.Again with it in 490 ℃ of following thermal treatments 5 hours.Afterwards, be placed on the ball mill subject to the foregoing ball milling 3 hours more successively,, obtain zinc oxide composite powder in 780 ℃ of following thermal treatments 4 hours.
D) earlier with zinc oxide composite powder on the single shaft harder through the moulding of 210MPa pressure pressed compact, obtain the base substrate as Fig. 1, Fig. 3 and the middle curve of Fig. 2, Fig. 5 (a) shown in.Again it was fired under 1240 ℃ 3 hours, make as Fig. 4 and the zinc oxide low voltage varistor ceramics shown in curve among Fig. 5 (b), Fig. 6.
Embodiment 4: finish preparation according to the following steps, a) rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 0.6%, Bismuth trinitrate 0.5%, nitric acid tin 0.7%, manganous nitrate 0.6%, Xiao Suangu 1.3%, aluminum nitrate 0.008%, chromium nitrate 0.12%, nickelous nitrate 0.05%, nitrate of baryta 0.05%, Silver Nitrate 0.004%, boric acid 0.04%, weisspiessglanz 0.06%, all the other are Zinc oxide powder.Earlier respectively various hotchpotchs are worked to expect being mixed with the aqueous solution, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 90 ℃, and the mol ratio of citric acid and weisspiessglanz is 5:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
Perhaps rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 0.6%, Bismuth trinitrate 0.5%, nitric acid tin 0.7%, manganous nitrate 0.6%, Xiao Suangu 1.3%, aluminum nitrate 0.008%, chromium nitrate 0.12%, nickelous nitrate 0.05%, nitrate of baryta 0.05%, Silver Nitrate 0.004%, boric acid 0.04%, weisspiessglanz 0.06%, all the other are Zinc oxide powder.Choose earlier hotchpotch rise in expecting one or more or all be made into ethanolic soln, and mix the back and add dispersion agent; Wherein, the cation concn of ethanolic soln is 0.08mol/L, and the pH value of alcohol mixed solution is 6, and dispersion agent is a polyoxyethylene glycol, and its consumption is 35g/L, and L is the unit liter of the cumulative volume of the ethanolic soln that is made into.Again Zinc oxide powder is added mix in the alcohol mixed solution and heat, the zinc oxide powder of dry hotchpotch parcel; Wherein, the temperature of heating is that 93 ℃, time are 7 hours, and the exsiccant temperature is that 110 ℃, time are 13 hours.Then remaining hotchpotch is worked to expect respectively it is mixed with the aqueous solution earlier, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 90 ℃, and the mol ratio of citric acid and weisspiessglanz is 5:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
B) add citric acid and nitric acid and stirring earlier in mixing solutions, the metal ion total concn that makes mixing solutions is 0.4mol/L; Wherein, the add-on of citric acid and the mol ratio of metal ion are 1:2, and the add-on of nitric acid is that to make the pH value of mixing solutions be 3.After the stirring at room 4 hours, add coordination agent and be stirred to dissolving, wherein, coordination agent is a polyoxyethylene glycol, its molecular weight is 16000, with the mass ratio of citric acid be 1:0.3.Again mixed solution is filtered the back and continues to stir and be heated to the formation gel, to gel carry out drying, thermal treatment gets carbon containing doping presoma, wherein, the temperature of heating is that 90 ℃, exsiccant temperature are that 110 ℃, heat treated temperature are that 330 ℃, time are 8 hours.
Perhaps add dispersion agent in mixing solutions, wherein, the cation concn in the mixing solutions is 0.08mol/L, and dispersion agent is a polyoxyethylene glycol, and its consumption is 33g/L.After the stirring and dissolving, add in the mixed solution nano carbon black and ultra-sonic dispersion earlier, the frequency of ultrasonic of the nano carbon black in the ultra-sonic dispersion mixing solutions is 50KHz.Again it is carried out heated and stirred to forming solid mixt.Be dried then carbon containing doping presoma, wherein, nano carbon black is 5:2 with the total mass ratio of initial hotchpotch, Heating temperature is 93 ℃, the time is 7 hours, drying temperature is 110 ℃, the time is 15 hours.
C) earlier with the zinc oxide powder of Zinc oxide powder or hotchpotch parcel with after carbon containing doping presoma mixes, place ball grinder on planetary ball mill, to mix and grinding; Wherein, the rotating speed of ball milling is that 280rad/min, time are 6 hours.Again with it in 550 ℃ of following thermal treatments 4 hours.Afterwards, be placed on the ball mill subject to the foregoing ball milling 4 hours more successively,, obtain zinc oxide composite powder in 810 ℃ of following thermal treatments 2 hours.
D) earlier with zinc oxide composite powder on the single shaft harder through the moulding of 260MPa pressure pressed compact, obtain the base substrate as Fig. 1, Fig. 3 and the middle curve of Fig. 2, Fig. 5 (a) shown in.Again it was fired under 1260 ℃ 2.5 hours, make as Fig. 4 and the zinc oxide low voltage varistor ceramics shown in curve among Fig. 5 (b), Fig. 6.
Embodiment 5: finish preparation according to the following steps, a) rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 0.4%, Bismuth trinitrate 0.3%, nitric acid tin 0.8%, manganous nitrate 0.4%, Xiao Suangu 1.5%, aluminum nitrate 0.002%, chromium nitrate 0.2%, nickelous nitrate 0.03%, nitrate of baryta 0.03%, Silver Nitrate 0.005%, boric acid 0.05%, weisspiessglanz 0.08%, all the other are Zinc oxide powder.Earlier respectively various hotchpotchs are worked to expect being mixed with the aqueous solution, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 100 ℃, and the mol ratio of citric acid and weisspiessglanz is 4:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
Perhaps rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 0.4%, Bismuth trinitrate 0.3%, nitric acid tin 0.8%, manganous nitrate 0.4%, Xiao Suangu 1.5%, aluminum nitrate 0.002%, chromium nitrate 0.2%, nickelous nitrate 0.03%, nitrate of baryta 0.03%, Silver Nitrate 0.005%, boric acid 0.05%, weisspiessglanz 0.08%, all the other are Zinc oxide powder.Choose earlier hotchpotch rise in expecting one or more or all be made into ethanolic soln, and mix the back and add dispersion agent; Wherein, the cation concn of ethanolic soln is 0.1mol/L, and the pH value of alcohol mixed solution is 6, and dispersion agent is a polyoxyethylene glycol, and its consumption is 40g/L, and L is the unit liter of the cumulative volume of the ethanolic soln that is made into.Again Zinc oxide powder is added mix in the alcohol mixed solution and heat, the zinc oxide powder of dry hotchpotch parcel; Wherein, the temperature of heating is that 95 ℃, time are 6 hours, and the exsiccant temperature is that 120 ℃, time are 10 hours.Then remaining hotchpotch is worked to expect respectively it is mixed with the aqueous solution earlier, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 100 ℃, and the mol ratio of citric acid and weisspiessglanz is 4:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
B) add citric acid and nitric acid and stirring earlier in mixing solutions, the metal ion total concn that makes mixing solutions is 0.5mol/L; Wherein, the add-on of citric acid and the mol ratio of metal ion are 1:3, and the add-on of nitric acid is that to make the pH value of mixing solutions be 4.After the stirring at room 5 hours, add coordination agent and be stirred to dissolving, wherein, coordination agent is a polyoxyethylene glycol, its molecular weight is 20000, with the mass ratio of citric acid be 1:0.2.Again mixed solution is filtered the back and continues to stir and be heated to the formation gel, to gel carry out drying, thermal treatment gets carbon containing doping presoma, wherein, the temperature of heating is that 100 ℃, exsiccant temperature are that 120 ℃, heat treated temperature are that 400 ℃, time are 6 hours.
Perhaps add dispersion agent in mixing solutions, wherein, the cation concn in the mixing solutions is 0.1mol/L, and dispersion agent is a polyoxyethylene glycol, and its consumption is 40g/L.After the stirring and dissolving, add in the mixed solution nano carbon black and ultra-sonic dispersion earlier, the frequency of ultrasonic of the nano carbon black in the ultra-sonic dispersion mixing solutions is 60KHz.Again it is carried out heated and stirred to forming solid mixt.Be dried then carbon containing doping presoma, wherein, nano carbon black is 5:2 with the total mass ratio of initial hotchpotch, Heating temperature is 95 ℃, the time is 6 hours, drying temperature is 120 ℃, the time is 24 hours.
C) earlier with the zinc oxide powder of Zinc oxide powder or hotchpotch parcel with after carbon containing doping presoma mixes, place ball grinder on planetary ball mill, to mix and grinding; Wherein, the rotating speed of ball milling is that 300rad/min, time are 8 hours.Again with it in 580 ℃ of following thermal treatments 8 hours.Afterwards, be placed on the ball mill subject to the foregoing ball milling 5 hours more successively,, obtain zinc oxide composite powder in 850 ℃ of following thermal treatments 1 hour.
D) earlier with zinc oxide composite powder on the single shaft harder through the moulding of 300MPa pressure pressed compact, obtain the base substrate as Fig. 1, Fig. 3 and the middle curve of Fig. 2, Fig. 5 (a) shown in.Again it was fired under 1280 ℃ 2 hours, make as Fig. 4 and the zinc oxide low voltage varistor ceramics shown in curve among Fig. 5 (b), Fig. 6.
Embodiment 6: finish preparation according to the following steps, a) rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 0.9%, Bismuth trinitrate 0.7%, nitric acid tin 0.2%, manganous nitrate 0.5%, Xiao Suangu 1%, aluminum nitrate 0.01%, chromium nitrate 0.03%, nickelous nitrate 0.03%, nitrate of baryta 0.04%, Silver Nitrate 0.001%, boric acid 0.02%, weisspiessglanz 0.01%, all the other are Zinc oxide powder.Earlier respectively various hotchpotchs are risen to expect and be mixed with ethanolic soln, wherein, Bismuth trinitrate is dissolved in ethylene glycol earlier, and is miscible with ethanol again, weisspiessglanz is dissolved in behind the citric acid (mol ratio of citric acid and weisspiessglanz is 20:1) miscible with ethanol again, then above-mentioned solution is under agitation mixed the back and adds dispersion agent; Wherein, the cation concn of ethanolic soln is 0.1mol/L, and the pH value of alcohol mixed solution is 7, and dispersion agent is a polyoxyethylene glycol, and its consumption is 20g/L, and L is the unit liter of the cumulative volume of the ethanolic soln that is made into.Again Zinc oxide powder is added mix in the alcohol mixed solution and heat, the zinc oxide powder of dry hotchpotch parcel; Wherein, the temperature of heating is that 70 ℃, time are 6 hours, and the exsiccant temperature is that 120 ℃, time are 12 hours.
B) the zinc oxide powder with the hotchpotch parcel places ball grinder to grind on planetary ball mill; Wherein, the rotating speed of ball milling is that 250rad/min, time are 8 hours.Again with it in 550 ℃ of following thermal treatments 4 hours.Afterwards, be placed on the ball mill subject to the foregoing ball milling 4 hours more successively,, obtain zinc oxide composite powder in 800 ℃ of following thermal treatments 2 hours.
C) earlier with zinc oxide composite powder on the single shaft harder through the moulding of 200MPa pressure pressed compact, obtain the base substrate as Fig. 1, Fig. 3 and the middle curve of Fig. 2, Fig. 5 (a) shown in.Again it was fired under 1250 ℃ 2.5 hours, make as Fig. 4 and the zinc oxide low voltage varistor ceramics shown in curve among Fig. 5 (b), Fig. 6.
Embodiment 7: finish preparation according to the following steps, a) rise by following molar percentage weighing hotchpotch and expect: tetra-n-butyl titanate 0.7%, Bismuth trinitrate 0.6%, nitric acid tin 0.2%, manganous nitrate 0.6%, Xiao Suangu 1%, aluminum nitrate 0.01%, chromium nitrate 0.04%, nickelous nitrate 0.04%, nitrate of baryta 0.03%, Silver Nitrate 0.002%, boric acid 0.03%, weisspiessglanz 0.01%, surplus are Zinc oxide powder.Earlier respectively various hotchpotchs are worked to expect being mixed with the aqueous solution, wherein, weisspiessglanz uses the citric acid preparation, and the temperature of the citric acid solution that the preparation weisspiessglanz aqueous solution is used is 50 ℃, and the mol ratio of citric acid and weisspiessglanz is 10:1.Above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again.
B) add citric acid and nitric acid and stirring earlier in mixing solutions, the metal ion total concn that makes mixing solutions is 0.1mol/L; Wherein, the add-on of citric acid and the mol ratio of metal ion are 2:1, and the add-on of nitric acid is that to make the pH value of mixing solutions be 1.5.After the stirring at room 1 hour, add coordination agent and be stirred to dissolving, wherein, coordination agent is a polyoxyethylene glycol, its molecular weight is 20000, with the mass ratio of citric acid be 1:0.2.Again mixed solution is filtered the back and continues to stir and be heated to the formation gel, to gel carry out drying, thermal treatment gets carbon containing doping presoma, wherein, the temperature of heating is that 60 ℃, exsiccant temperature are that 90 ℃, heat treated temperature are that 200 ℃, time are 12 hours.
Perhaps add dispersion agent in mixing solutions, wherein, the cation concn in the mixing solutions is 0.05mol/L, and dispersion agent is a polyoxyethylene glycol, and its consumption is 10g/L.After the stirring and dissolving, add in the mixed solution nano carbon black and ultra-sonic dispersion earlier, the frequency of ultrasonic of the nano carbon black in the ultra-sonic dispersion mixing solutions is 60KHz.Again it is carried out heated and stirred to forming solid mixt.Be dried then carbon containing doping presoma, wherein, nano carbon black is 5:1 with the total mass ratio of initial hotchpotch, Heating temperature is 80 ℃, the time is 10 hours, drying temperature is 120 ℃, the time is 24 hours.
C) earlier with Zinc oxide powder with after carbon containing doping presoma mixes, place ball grinder on planetary ball mill, to mix and grinding; Wherein, the rotating speed of ball milling is that 300rad/min, time are 6 hours.Again with it in 400 ℃ of following thermal treatments 8 hours.Afterwards, be placed on the ball mill subject to the foregoing ball milling 6 hours more successively,, obtain zinc oxide composite powder in 750 ℃ of following thermal treatments 6 hours.
D) earlier with zinc oxide composite powder on the single shaft harder through the moulding of 230MPa pressure pressed compact, obtain the base substrate as Fig. 1, Fig. 3 and the middle curve of Fig. 2, Fig. 5 (a) shown in.Again it was fired under 1280 ℃ 2 hours, make as Fig. 4 and the zinc oxide low voltage varistor ceramics shown in curve among Fig. 5 (b), Fig. 6.
Select polyvinyl alcohol or polyacrylic acid or ethylene glycol in dispersion agent and the coordination agent more respectively for use, wherein, the consumption of polyvinyl alcohol is 20～40g/L, polyacrylic consumption is 20～80g/L, L is the unit liter of the cumulative volume of the ethanolic soln that is made into or mixing solutions, when coordination agent is selected ethylene glycol for use, the mass ratio of itself and citric acid is 2:2.5～3.5, repeat the foregoing description 1～5, the same base substrate that obtains shown in curve among Fig. 1, Fig. 3 and Fig. 2, Fig. 5 (a), and make as Fig. 4 and the zinc oxide low voltage varistor ceramics shown in curve among Fig. 5 (b), Fig. 6.
Obviously, those skilled in the art can carry out various changes and modification to zinc oxide pressure-sensitive ceramic of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (9)
1, a kind of zinc oxide pressure-sensitive ceramic comprises zinc oxide, it is characterized in that:
(a) said voltage-sensitive ceramic is to be made by the raw material of following molar percentage, tetra-n-butyl titanate 0.4～1.2%, Bismuth trinitrate 0.3～1.2%, nitric acid tin 0.2～0.8%, manganous nitrate 0.4～1%, Xiao Suangu 0.5～1.5%, aluminum nitrate 0.002～0.02%, chromium nitrate 0.03～0.2%, nickelous nitrate 0.03～0.2%, nitrate of baryta 0.03～0.1%, Silver Nitrate 0.001～0.005%, boric acid 0.02～0.05%, weisspiessglanz 0.01～0.08%, all the other are Zinc oxide powder;
(b) said tetra-n-butyl titanate, Bismuth trinitrate, nitric acid tin, manganous nitrate, Xiao Suangu, aluminum nitrate, chromium nitrate, nickelous nitrate, nitrate of baryta, Silver Nitrate, boric acid and weisspiessglanz all are distributed in the zinc oxide ceramics matrix with nano oxide dispersion form mutually.
2, the preparation method of zinc oxide pressure-sensitive ceramic according to claim 1 comprises solid reaction process, it is characterized in that finishing according to the following steps:
(a) work the tetra-n-butyl titanate of expecting, Bismuth trinitrate, nitric acid tin, manganous nitrate, Xiao Suangu, aluminum nitrate, chromium nitrate, nickelous nitrate, nitrate of baryta, Silver Nitrate, boric acid and weisspiessglanz by required stoicheiometry weighing hotchpotch, and Zinc oxide powder, earlier respectively various hotchpotchs are risen to expect and be mixed with the aqueous solution, wherein, weisspiessglanz uses the citric acid preparation, the mol ratio of citric acid and weisspiessglanz is 20:1～5, and above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again
Perhaps work the tetra-n-butyl titanate of expecting by required stoicheiometry weighing hotchpotch, Bismuth trinitrate, nitric acid tin, manganous nitrate, Xiao Suangu, aluminum nitrate, chromium nitrate, nickelous nitrate, nitrate of baryta, Silver Nitrate, boric acid and weisspiessglanz, and Zinc oxide powder, choosing hotchpotch earlier works in expecting more than one and is made into alcohol mixed solution, and adding dispersion agent after mixing, wherein, the cation concn of alcohol mixed solution is 0.02～0.1mol/L, the pH value of alcohol mixed solution is 6～7, again Zinc oxide powder is added and mix in the alcohol mixed solution and heat, the dry zinc oxide powder that gets the hotchpotch parcel, wherein, the temperature of heating is 80～95 ℃, time is 6～10 hours, the exsiccant temperature is 90～120 ℃, time is 10～24 hours, then remaining hotchpotch is risen to expect and respectively it is mixed with the aqueous solution earlier, wherein, weisspiessglanz uses the citric acid preparation, and the mol ratio of citric acid and weisspiessglanz is 20:1～5, and above-mentioned each aqueous solution of mixing gets mixing solutions in stirring down again;
(b) in mixing solutions, add citric acid and nitric acid and stirring earlier, the metal ion total concn that makes mixing solutions is 0.1～0.5mol/L, wherein, the add-on of citric acid and the mol ratio of metal ion are 1:0.3～3, the add-on of nitric acid is that to make the pH value of mixing solutions be 0.5～4, after the stirring at room at least 1 hour, add coordination agent and be stirred to dissolving, again mixed solution is filtered the back and continue to stir and be heated to the formation gel, gel is carried out drying, thermal treatment gets carbon containing doping presoma, wherein, the temperature of heating is 60～100 ℃, the exsiccant temperature is 60～120 ℃, heat treated temperature is 120～400 ℃, time is 6～12 hours
Perhaps add dispersion agent in mixing solutions, wherein, the cation concn in the mixing solutions is 0.02～0.1mol/L, after the stirring and dissolving, earlier add in the mixed solution nano carbon black and ultra-sonic dispersion, again it carried out heated and stirred to forming solid mixt, be dried then carbon containing doping presoma, wherein, nano carbon black is 5:1～2 with the total mass ratio of initial hotchpotch, and Heating temperature is 80～95 ℃, and the time is 6～10 hours, drying temperature is 90～120 ℃, and the time is 12～24 hours;
(c) the back ball milling mixed at least 1 hour with the zinc oxide powder of Zinc oxide powder or hotchpotch parcel in elder generation with carbon containing doping presoma, again with it in 400～580 ℃ of following thermal treatments 3～8 hours, afterwards, again successively ball milling at least 1 hour, in 700～850 ℃ of following thermal treatments 1～8 hour, obtain zinc oxide composite powder;
(d) earlier with the moulding of zinc oxide composite powder pressed compact, under 1200～1280 ℃, fired 2～4 hours again, make the zinc oxide low voltage varistor ceramics.
3, the preparation method of zinc oxide pressure-sensitive ceramic according to claim 2, the temperature that it is characterized in that preparing the used citric acid solution of the weisspiessglanz aqueous solution is 50～100 ℃.
4, the preparation method of zinc oxide pressure-sensitive ceramic according to claim 2, it is characterized in that the dispersion agent that adds is polyoxyethylene glycol or polyvinyl alcohol or polyacrylic acid in the ethanolic soln that is made into, wherein, the consumption of polyoxyethylene glycol is 10～40g/L, the consumption of polyvinyl alcohol is 20～40g/L, polyacrylic consumption is 20～80g/L, and L is the unit liter of the cumulative volume of the ethanolic soln that is made into.
5, the preparation method of zinc oxide pressure-sensitive ceramic according to claim 2, it is characterized in that the coordination agent that adds is polyoxyethylene glycol or ethylene glycol or polyvinyl alcohol or polyacrylic acid in mixing solutions, wherein, when coordination agent is selected polyoxyethylene glycol for use, its molecular weight is 4000～20000, with the mass ratio of citric acid be 1: 0.2～0.5, when coordination agent is selected ethylene glycol for use, the mass ratio of itself and citric acid is 2:2.5～3.5, when coordination agent is selected polyvinyl alcohol for use, its consumption is 20～40g/L, when coordination agent was selected polyacrylic acid for use, its consumption was 20～80g/L, and L is the unit liter of the cumulative volume of mixing solutions.
6, the preparation method of zinc oxide pressure-sensitive ceramic according to claim 2, it is characterized in that the dispersion agent that adds is polyoxyethylene glycol or polyvinyl alcohol or polyacrylic acid in mixing solutions, wherein, the consumption of polyoxyethylene glycol is 10～40g/L, the consumption of polyvinyl alcohol is 20～40g/L, polyacrylic consumption is 20～80g/L, and L is the unit liter of the cumulative volume of mixing solutions.
7, the preparation method of zinc oxide pressure-sensitive ceramic according to claim 2, the frequency of ultrasonic that it is characterized in that the nano carbon black in the ultra-sonic dispersion mixing solutions is 10～60KHz.
8, the preparation method of zinc oxide pressure-sensitive ceramic according to claim 2, it is characterized in that ball milling is to place ball grinder to mix and grinding mixture on planetary ball mill, wherein, the rotating speed of ball milling is that 200～300rad/min, time are 1～8 hour.
9, the preparation method of zinc oxide pressure-sensitive ceramic according to claim 2 is characterized in that pressed compact is the single shaft pressed compact, and its pressure is 120～300MPa.
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| CN101565163B (en) * | 2009-04-10 | 2010-12-08 | 黑龙江科技学院 | Preparation method of Zn2.33Sb0.67O4 in-situ growth material coated with ZnO fiber heterostructure |
| CN101792307B (en) * | 2010-03-30 | 2013-04-17 | 中国科学院上海硅酸盐研究所 | Preparation method of zinc oxide varistor ceramic composite powder |
| CN101891458B (en) * | 2010-07-08 | 2012-08-22 | 深圳Abb银星避雷器有限公司 | Preparation method of zinc oxide pressure-sensitive ceramic slurry and pressure-sensitive ceramic resistor material |
| CN103011800A (en) * | 2012-12-27 | 2013-04-03 | 青岛艾德森能源科技有限公司 | Preparation method of zinc oxide resistor |
| CN111718192B (en) | 2012-12-27 | 2023-07-21 | 东莞令特电子有限公司 | Varistor based on zinc oxide and method for manufacturing same |
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| CN108329023B (en) * | 2018-03-05 | 2021-03-30 | 国网湖南省电力有限公司 | Preparation method of zinc oxide based nano composite powder resistance card |
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| CN111548142B (en) * | 2020-04-16 | 2021-10-08 | 华南理工大学 | Heat preservation device for microwave sintering and method for microwave sintering of zinc oxide pressure-sensitive ceramic |
| CN112851332A (en) * | 2021-01-30 | 2021-05-28 | 西安电子科技大学 | Method for preparing high-voltage gradient zinc oxide piezoresistor by doping coating method |
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