CN101891458A - Preparation method of zinc oxide pressure-sensitive ceramic slurry and pressure-sensitive ceramic resistor material - Google Patents
Preparation method of zinc oxide pressure-sensitive ceramic slurry and pressure-sensitive ceramic resistor material Download PDFInfo
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Abstract
The invention relates to a preparation method of zinc oxide pressure-sensitive ceramic slurry and a pressure-sensitive ceramic resistor material. The preparation method comprises the following steps: weighing raw materials including main raw material ZnO and additives; adding water to proportionally prepared additives, and ball-milling for 1-4 hours; and putting the weighed ZnO, milled additives, pure water and mixing assistant into a mixing tank, quickly dispersing in a homo-mixer for 20-60 minutes, opening the valve, starting a pipeline type high-shear dispersion emulsion machine to circularly disperse for 1-3 hours, driving into a liquid storage tank, and starting a basket type mill to mill for 2-4 hours, thereby obtaining the slurry. The zinc oxide pressure-sensitive ceramic resistor material comprises the following components in percentage by mol: 93-95% of ZnO, 0.6-0.9% of Bi2O3, 0.9-1.3% of Sb2O3, 1.0-1.3% of Co2O3, 0.5-0.8% of MnCO3, 0.5-0.8% of Cr2O3, 0.5-0.8% of NiO and 1.0-1.5% of SiO2. The invention has the advantages of simple preparation procedure and high efficiency, and impurities can not be easily incorporated in the manufacturing process. The prepared slurry is even and stable and has favorable flowability.
Description
Technical field
The present invention relates to a kind of ceramic material manufacturing technology, relate in particular to a kind of preparation method of zinc oxide pressure-sensitive ceramic slurry and the zinc oxide pressure-sensitive ceramic resistive material for preparing with this method.
Background technology
The zinc oxide pressure-sensitive ceramic resistor disc has good non-linear volt-ampere characteristic and huge energy receptivity, is widely used in electric power and electronic system, is mainly used to limit current potential and absorbs the superpotential energy.It is material of main part with zinc oxide, adds multiple additives such as bismuth oxide, weisspiessglanz, makes by electronic ceramic process.
At present, through the research and development of many decades, the performance of zinc oxide pressure-sensitive ceramic resistor disc improves constantly, and Application Areas is constantly expanded, be low to moderate the microelectronic circuit of several volts and high to the system for ultra-high voltage transmission of 1,000,000 volts of voltage ranges at voltage, all be used widely.
The microstructure model of zinc oxide pressure-sensitive ceramic as shown in Figure 1, main crystalline phase comprises zinc oxide phase, rich Bi
2O
3Intergranular phase, spinel phase, have pore in addition.The ZnO main body is to be 0.001 Ω m～0.1 Ω m by resistivity, and the ZnO crystal grain 1 that is of a size of 10 μ m～30 μ m is formed, and solid solution has the elements such as Co, Mn of trace.Grain boundary layer 2 is enrichment regions of various additives, is the root that produces pressure-sensitive, in low electric field region resistivity greater than 10
8Ω m, at high electric field region, the grain boundary layer conducting.Spinel crystal grain 3 is ZnO and Sb
2O
3Composite oxides, contain impurity such as Co, Mn, Cr in addition, particle diameter is about about several micron.
Research thinks that resistor disc internal microstructure and composition are even more, pore is few more, and energy absorption capability is big more.Use the big resistor disc of through-current capability can increase protection nargin, increase the service life.Pulp preparation has directly determined the quality of the final performance of product as the critical process of zinc oxide pressure-sensitive ceramic resistor disc production.
The pulping process of zinc oxide pressure-sensitive ceramic commonly used roughly has two kinds: a kind of is grog technology, and characteristics are at first with Bi
2O
3, Sb
2O
3Deng the additive ball milling after calcining about 850 ℃ is mixed with form slurry with ZnO etc. again after the secondary fine grinding; Another kind is the raw material technologies, characteristics be after the additive mixing and ball milling directly and ZnO etc. be mixed with form slurry.The equipment that uses in two kinds of technology has drum ball mill, agitating ball mill, calcining furnace, pulverizer, homogenizer, colloidal mill, sand mill etc. usually.The shortcoming of grog technology be operation loaded down with trivial details, easily sneak into impurity, slurry easily precipitates.In addition, all there is inefficiency in the employed equipment of tradition slurrying, disperses problems such as inhomogeneous, colloidal mill for example: its basic functional principle is the high speed shear effect, shear the relative movement that relies on two toothed surface, one of them high speed rotating, another is static, makes by the material between the flank of tooth and is subjected to great shearing force and friction, thereby realize dispersion, emulsification, homogeneous; Colloidal mill to the macrobead in the material (particle diameter is greater than 10 μ m) and hard aggregation can't be effectively broken, disperse; It is easy to wear to add its gap, adjusts difficulty, so be difficult to guarantee that paste composition reaches even in the limited time.
Practice finds that not only factor such as the size-grade distribution of raw material, particle profile is influential to slurrying, and the material performance difference of different manufacturers is also bigger, brings great effect to pulping process, therefore will choose cautiously.With ZnO is example, and median size is extremely difficult the dispersion during less than 0.4 μ m, needs a large amount of pure water and dispersion agents of using.In the pulping process, also can use some subsidiary material, comprise wedding agent and defoamer etc., mostly be organic high molecular polymer, whether its kind and consumption be suitable also very crucial to pulping process.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned traditional pulping process, a kind of preparation method of zinc oxide pressure-sensitive ceramic slurry of slurry that can uniform and stable, the good fluidity of preparation is provided.
Another object of the present invention provides a kind of zinc oxide pressure-sensitive ceramic resistive material that adopts preparation method's preparation of above-mentioned zinc oxide pressure-sensitive ceramic slurry.
The present invention realizes by following technical scheme: a kind of preparation method of zinc oxide pressure-sensitive ceramic slurry comprises the steps:
The first step: take by weighing raw material by mole per-cent, described raw material comprises main raw material ZnO and additive, and described additive comprises Bi
2O
3, Sb
2O
3, Co
2O
3, MnCO
3, Cr
2O
3, NiO and SiO
2, the molar percentage of described ZnO and additive is: ZnO:93～95%, Bi
2O
3: 0.6～0.9%, Sb
2O
3: 0.9～1.3%, Co
2O
3: 1.0～1.3%, MnCO
3: 0.5～0.8%, Cr
2O
3: 0.5～0.8%, NiO:0.5～0.8%, SiO
2: 1.0～1.5%; Described ZnO raw material particle size is 0.42～0.45 μ m, and loose density is 0.55～0.65g/cm
3, described additive raw material particle diameter is 2～5 μ m, loose density is 0.5～1.3g/cm
3
Second step: will pour in the agitating ball mill in the additive that the described ratio of the first step prepares, and add 70～90% the pure water that weight is described additive gross weight, ball milling 1～4 hour, to particle diameter less than 1.5 μ m;
The 3rd step: with the ZnO that takes by weighing in the first step, ground additive in second step, 45～55% the pure water that adds mixed aid and weight again and be described ZnO weight drops in the mixing tank, disperseed fast 20～60 minutes with homogenizer, open valve, open the pipeline high-shearing dispersion emulsifying machine, circulation disperses to squeeze into receiver after 1～3 hour, open basket shredder again, the setting rotating speed is 500～1400rpm, grinds and obtains slurry after 2～4 hours.
Described mixed aid comprises dispersion agent and defoamer, described dispersion agent is made up of tetradecyl Ammoniom-Acetate and polyoxyethylene glycol (PEG4000), the weight percent of described dispersion agent in whole slurry system is 0.2～0.4%, the weight ratio of described tetradecyl Ammoniom-Acetate and described polyoxyethylene glycol (PEG4000) is 1.8～2.2: 1, the weight percent of described defoamer in whole slurry system is 0.03～0.05%, described defoamer is made up of tributyl phosphate and water-soluble organic silicon oil, and the weight ratio of described tributyl phosphate and described water-soluble organic silicon oil is 1.6～2.0: 1.
A kind of zinc oxide pressure-sensitive ceramic resistive material comprises the material of following molar percentage, ZnO:93～95%, Bi
2O
3: 0.6～0.9%, Sb
2O
3: 0.9～1.3%, Co
2O
3: 1.0～1.3%, MnCO
3: 0.5～0.8%, Cr
2O
3: 0.5～0.8%, NiO:0.5～0.8%, SiO
2: 1.0～1.5%.
As the preferred embodiment of zinc oxide pressure-sensitive ceramic resistive material, the material of described molar percentage is ZnO:93.3～94.5%, Bi
2O
3: 0.7～0.8%, Sb
2O
3: 1.0～1.2%, Co
2O
3: 1.1～1.3%, MnCO
3: 0.6～0.7%, Cr
2O
3: 0.5～0.7%, NiO:0.6～0.7%, SiO
2: 1.0～1.5%.
As the more preferred of zinc oxide pressure-sensitive ceramic resistive material, the material of described molar percentage is ZnO:94.3%, Bi
2O
3: 0.7%, Sb
2O
3: 1.1%, Co
2O
3: 1.1%, MnCO
3: 0.6%, Cr
2O
3: 0.6%, NiO:0.6%, SiO
2: 1.0%.
As the more preferred of zinc oxide pressure-sensitive ceramic resistive material, the material of described molar percentage is ZnO:93.8%, Bi
2O
3: 0.7%, Sb
2O
3: 1.0%, Co
2O
3: 1.3%, MnCO
3: 0.6%, Cr
2O
3: 0.5%, NiO:0.6%, SiO
2: 1.5%.
As the more preferred of zinc oxide pressure-sensitive ceramic resistive material, the material of described molar percentage is ZnO:95%, Bi
2O
3: 0.6%, Sb
2O
3: 0.9%, Co
2O
3: 1.0%, MnCO
3: 0.5%, Cr
2O
3: 0.5%, NiO:0.5%, SiO
2: 1.0%.
As the more preferred of zinc oxide pressure-sensitive ceramic resistive material, the material of described molar percentage is ZnO:94.5%, Bi
2O
3: 0.6%, Sb
2O
3: 1.0%, Co
2O
3: 1.0%, MnCO
3: 0.6%, Cr
2O
3: 0.5%, NiO:0.5%, SiO
2: 1.3%.
As the more preferred of zinc oxide pressure-sensitive ceramic resistive material, the material of described molar percentage is ZnO:93.3%, Bi
2O
3: 0.8%, Sb
2O
3: 1.3%, Co
2O
3: 1.2%, MnCO
3: 0.7%, Cr
2O
3: 0.8%, NiO:0.7%, SiO
2: 1.2%.
As the more preferred of zinc oxide pressure-sensitive ceramic resistive material, the material of described molar percentage is ZnO:93%, Bi
2O
3: 0.9%, Sb
2O
3: 1.2%, Co
2O
3: 1.2%, MnCO
3: 0.8%, Cr
2O
3: 0.7%, NiO:0.8%, SiO
2: 1.4%.
Can find out by above technical scheme, the selected zinc oxide of the present invention and other additive raw material, the common ground of raw material is the purity height, particle size distribution is narrow, physicochemical property is stable, during slurrying and mixed aid do not react; In addition, the present invention's raw material operational path carries out thinning processing earlier to additive, and the present invention also adopts extraordinary organic mixed aid, makes that the preparation section of slurry is simple, efficient is high, is difficult for sneaking into impurity in the making processes, slurry easily precipitates.Uniform and stable, the good fluidity of the slurry that adopts this preparation method to make makes the zinc oxide pressure-sensitive ceramic resistive material of excellent performance again through subsequent technique.
Description of drawings
Fig. 1 is the microtexture synoptic diagram of zinc oxide pressure-sensitive ceramic;
Fig. 2 is the structural representation of the mixing system of preparation slurry of the present invention.
Embodiment
The equipment (as shown in Figure 2) that the present invention adopts is the mixing system of custom-made, comprises homogenizer 5, basket shredder 7 and pipeline high-shearing dispersion emulsifying machine 8.
Following each embodiment all can make of following method, just earlier take by weighing corresponding Z nO and additive by the molar percentage among following each embodiment, the additive that takes by weighing is put into agitating ball mill, and add 70～90% the pure water that weight is described additive gross weight, ground 1～4 hour, to particle diameter less than 1.5 μ m, the ZnO that will take by weighing again, additive after the grinding, mixed aid and weight are that 45～55% pure water of described ZnO weight drops in the mixing tank 4, disperseed fast 20～60 minutes with homogenizer 5, open valve, open pipeline high-shearing dispersion emulsifying machine 8, raw material circulation dispersion was squeezed into receiver 6 after 1～3 hour, open basket shredder 7 again, the setting rotating speed is 500～1400rpm, further refinement, all raw material obtained slurry after 2～4 hours.
Among the present invention, the weight of described whole slurry system is meant: the ZnO that is taken by weighing, additive, the gross weight of the pure water of mixed aid and twice adding.
Table 1 is the physical property table of raw materials such as ZnO among the present invention.Wherein ZnO is a main raw material, and its particle diameter is 0.42～0.45 μ m, and loose density is 0.55～0.65g/cm
3, except that ZnO, other material is additive, and described additive raw material particle diameter is 2～5 μ m, and loose density is 0.5～1.3g/cm
3
The physical property of raw materials such as table 1ZnO
Take by weighing and comprise the raw material that contains following molar percentage, ZnO:95%, Bi
2O
3: 0.6%, Sb
2O
3: 0.9%, Co
2O
3: 1.0%, MnCO
3: 0.5%, Cr
2O
3: 0.5%, NiO:0.5%, SiO
2: 1.0%, wherein ZnO is a main raw material, except that ZnO, other raw material is additive.
The additive of aforementioned proportion is poured in the agitating ball mill, and is added 70% the pure water that weight is described additive gross weight, ball milling 1 hour, to particle diameter less than 1.5 μ m.
Take by weighing mixed aid, described mixed aid comprises dispersion agent and defoamer, and the weight percent that described dispersion agent and defoamer account for whole slurry system is respectively 0.2% and 0.03%.Described dispersion agent is made up of tetradecyl Ammoniom-Acetate and polyoxyethylene glycol (PEG4000), the weight ratio of described tetradecyl Ammoniom-Acetate and described polyoxyethylene glycol (PEG4000) is 1.8: 1, described defoamer is made up of tributyl phosphate and water-soluble organic silicon oil, and the weight ratio of described tributyl phosphate and described water-soluble organic silicon oil is 1.6: 1.
Additive after will grinding again, mixed aid that takes by weighing and weight are that 55% pure water of described ZnO weight drops in the mixing tank 4, open homogenizer 5, and slowly drop into the ZnO that takes by weighing, disperse 20 minutes fast with homogenizer 5 after, open valve, open pipeline high-shearing dispersion emulsifying machine 8, raw material circulation dispersion was squeezed into receiver 6 after 1 hour, open basket shredder 7, the setting rotating speed is 800rpm, obtains slurry after 3 hours.
In the present embodiment, the raw material gross weight is 100kg, and the concrete weight that each material need take by weighing is respectively: ZnO:95kg, Bi
2O
3: 0.6kg, Sb
2O
3: 0.9kg, Co
2O
3: 1.0kg, MnCO
3: 0.5kg, Cr
2O
3: 0.5kg, NiO:0.5kg, SiO
2: 1.0kg, when pouring into the additive of above-mentioned weight in the agitating ball mill, needing the weight of the pure water of adding is 3.5kg; The weight that adds the pure water in the mixing tank 4 is 52.25kg, and the gross weight of mixed aid is: 0.359kg, wherein the weight of dispersion agent and defoamer is respectively: 0.312kg, 0.047kg.Below among each embodiment, will no longer write out concrete weight, the technician can calculate occurrence according to these routine method of calculation.
Embodiment 2
Take by weighing and comprise the raw material that contains following molar percentage, ZnO:94.5%, Bi
2O
3: 0.6%, Sb
2O
3: 1.0%, Co
2O
3: 1.0%, MnCO
3: 0.6%, Cr
2O
3: 0.5%, NiO:0.5%, SiO
2: 1.3%, wherein ZnO is a main raw material, except that ZnO, other material is additive.
Take by weighing mixed aid, described mixed aid comprises dispersion agent and defoamer, and the weight percent that described dispersion agent and defoamer account for whole slurry system is respectively 0.25% and 0.04%.Described dispersion agent is made up of tetradecyl Ammoniom-Acetate and polyoxyethylene glycol (PEG4000), the weight ratio of described tetradecyl Ammoniom-Acetate and described polyoxyethylene glycol (PEG4000) is 1.9: 1, and described defoamer is that 1.7: 1 tributyl phosphate and water-soluble organic silicon oil are formed by weight ratio.
The additive of aforementioned proportion is poured in the agitating ball mill, and is added 90% the pure water that weight is described additive gross weight, ball milling 4 hours, to particle diameter less than 1.5 μ m.
Additive after will grinding again, mixed aid that takes by weighing and weight are that 45% pure water of described ZnO weight drops in the mixing tank 4, open homogenizer 5, slowly drop into the ZnO that takes by weighing, disperse 30 minutes fast with homogenizer 5 after, open valve, open pipeline high-shearing dispersion emulsifying machine 8, raw material circulation dispersion was squeezed into receiver 6 after 1.5 hours, open basket shredder 7, the setting rotating speed is 700rpm, obtains slurry after 3.5 hours.
Embodiment 3
Take by weighing and comprise the raw material that contains following molar percentage, ZnO:94.3%, Bi
2O
3: 0.7%, Sb
2O
3: 1.1%, Co
2O
3: 1.1%, MnCO
3: 0.6%, Cr
2O
3: 0.6%, NiO:0.6%, SiO
2: 1.0%, wherein ZnO is a main raw material, except that ZnO, other material is additive.
Take by weighing mixed aid, described mixed aid comprises dispersion agent and defoamer, and the weight percent that described dispersion agent and defoamer account for whole slurry system is respectively 0.3% and 0.04%.Described dispersion agent is made up of tetradecyl Ammoniom-Acetate and polyoxyethylene glycol (PEG4000), the weight ratio of described tetradecyl Ammoniom-Acetate and described polyoxyethylene glycol (PEG4000) is 2.0: 1, and described defoamer is that 1.8: 1 tributyl phosphate and water-soluble organic silicon oil are formed by weight ratio.
The additive of aforementioned proportion is poured in the agitating ball mill, and is added 80% the pure water that weight is described additive gross weight, ball milling 2 hours, to particle diameter less than 1.5 μ m.
Additive after will grinding again, mixed aid that takes by weighing and weight are that 50% pure water of described ZnO weight drops in the mixing tank 4, open homogenizer 5, slowly drop into the ZnO that takes by weighing, disperse 45 minutes fast with homogenizer 5 after, open valve, open pipeline high-shearing dispersion emulsifying machine 8, raw material circulation dispersion was squeezed into receiver 6 after 2 hours, open basket shredder 7, the setting rotating speed is 500rpm, obtains slurry after 4 hours.
Embodiment 4
Take by weighing and comprise the raw material that contains following molar percentage, ZnO:93.8%, Bi
2O
3: 0.7%, Sb
2O
3: 1.0%, Co
2O
3: 1.3%, MnCO
3: 0.6%, Cr
2O
3: 0.5%, NiO:0.6%, SiO
2: 1.5%, wherein ZnO is a main raw material, except that ZnO, other material is additive.
Take by weighing mixed aid, described mixed aid comprises dispersion agent and defoamer, and the weight percent that described dispersion agent and defoamer account for whole slurry system is respectively 0.4% and 0.05%.Described dispersion agent is made up of tetradecyl Ammoniom-Acetate and polyoxyethylene glycol (PEG4000), the weight ratio of described tetradecyl Ammoniom-Acetate and described polyoxyethylene glycol (PEG4000) is 2.1: 1, and described defoamer is that 1.9: 1 tributyl phosphate and water-soluble organic silicon oil are formed by weight ratio.
The additive of aforementioned proportion is poured in the agitating ball mill, and is added 75% the pure water that weight is described additive gross weight, ball milling 3 hours, to particle diameter less than 1.5 μ m.
Additive after will grinding again, mixed aid that takes by weighing and weight are that 50% pure water of described ZnO weight drops in the mixing tank 4, open homogenizer 5, slowly drop into the ZnO that takes by weighing, disperse 50 minutes fast with homogenizer 5 after, open valve, open pipeline high-shearing dispersion emulsifying machine 8, raw material circulation dispersion was squeezed into receiver 6 after 2.5 hours, open basket shredder 7, the setting rotating speed is 1000rpm, obtains slurry after 2.5 hours.
Embodiment 5
Take by weighing and comprise the raw material that contains following molar percentage, ZnO:ZnO:93.3%, Bi
2O
3: 0.8%, Sb
2O
3: 1.3%, Co
2O
3: 1.2%, MnCO
3: 0.7%, Cr
2O
3: 0.8%, NiO:0.7%, SiO
2: 1.2%, wherein ZnO is a main raw material, except that ZnO, other material is additive.
Take by weighing mixed aid, described mixed aid comprises dispersion agent and defoamer, and the weight percent that described dispersion agent and defoamer account for whole slurry system is respectively 0.2% and 0.05%.Described dispersion agent is made up of tetradecyl Ammoniom-Acetate and polyoxyethylene glycol (PEG4000), the weight ratio of described tetradecyl Ammoniom-Acetate and described polyoxyethylene glycol (PEG4000) is 2.2: 1, and described defoamer is that 2.0: 1 tributyl phosphate and water-soluble organic silicon oil are formed by weight ratio.
The additive of aforementioned proportion is poured in the agitating ball mill, and is added 85% the pure water that weight is described additive gross weight, ball milling 4 hours, to particle diameter less than 1.5 μ m.
Additive after will grinding again, mixed aid that takes by weighing and weight are that 48% pure water of described ZnO weight drops in the mixing tank 4, open homogenizer 5, slowly drop into the ZnO that takes by weighing, disperse 60 minutes fast with homogenizer 5 after, open valve, open pipeline high-shearing dispersion emulsifying machine 8, the slurry circulation disperses to squeeze into receiver 6 after 3 hours, opens basket shredder 7, the setting rotating speed is 1400rpm, obtains slurry after 2 hours.
Embodiment 6
Take by weighing and comprise the raw material that contains following molar percentage, ZnO:93%, Bi
2O
3: 0.9%, Sb
2O
3: 1.2%, Co
2O
3: 1.2%, MnCO
3: 0.8%, Cr
2O
3: 0.7%, NiO:0.8%, SiO
2: 1.4%, wherein ZnO is a main raw material, except that ZnO, other material is additive.
Take by weighing mixed aid, described mixed aid comprises dispersion agent and defoamer, and the weight percent that described dispersion agent and defoamer account for whole slurry system is respectively 0.4% and 0.04%.Described dispersion agent is made up of tetradecyl Ammoniom-Acetate and polyoxyethylene glycol (PEG4000), the weight ratio of described tetradecyl Ammoniom-Acetate and described polyoxyethylene glycol (PEG4000) is 2.0: 1, and described defoamer is that 2.0: 1 tributyl phosphate and water-soluble organic silicon oil are formed by weight ratio.
The additive of aforementioned proportion is poured in the agitating ball mill, and is added 70% the pure water that weight is described additive gross weight, ball milling 3 hours, to particle diameter less than 1.5 μ m.
Additive after will grinding again, mixed aid that takes by weighing and weight are that 52% pure water of described ZnO weight drops in the mixing tank 4, open homogenizer 5, slowly drop into the ZnO that takes by weighing, disperse 60 minutes fast with homogenizer 5 after, open valve, open pipeline high-shearing dispersion emulsifying machine 8, the slurry circulation disperses to squeeze into receiver 6 after 3 hours, opens basket shredder 7, the setting rotating speed is 1200rpm, obtains slurry after 2.5 hours.
Send into the drying tower granulation through surge pump again by the slurry that the various embodiments described above are prepared; Adopt three kinds of specification zinc oxide pressure-sensitive ceramic resistive materials of bidirectional hydraulic machine compacting, through binder removal, operation such as burn till and make resistor disc, the finished product specification is Φ 35 * 24, Φ 53 * 24, Φ 86 * 24.
Table 2 is the results that tested by the GB11032-2000 standard by the resistor disc of the resistor disc of embodiment 2 and embodiment 4 preparations and the preparation of traditional pulping process method.
Table 2ZnO resistor disc performance comparison
The made resistor disc performance of the slurry that the visible the present invention of listed correlation data makes from table 2 significantly improves than the traditional resistor sheet, the square wave through-current capability improves more than 40%, big electric current tolerance improves more than 30%, this shows that new pulping process has improved multicomponent mixture blended homogeneity and stability, and microtexture is good, the resistor disc of excellent thereby can produce.
Claims (10)
1. the preparation method of a zinc oxide pressure-sensitive ceramic slurry is characterized in that, comprises the steps:
The first step: take by weighing raw material by mole per-cent, described raw material comprises main raw material ZnO and additive, and described additive comprises Bi
2O
3, Sb
2O
3, Co
2O
3, MnCO
3, Cr
2O
3, NiO and SiO
2, the molar percentage of described ZnO and additive is: ZnO:93～95%, Bi
2O
3: 0.6～0.9%, Sb
2O
3: 0.9～1.3%, Co
2O
3: 1.0～1.3%, MnCO
3: 0.5～0.8%, Cr
2O
3: 0.5～0.8%, NiO:0.5～0.8%, SiO
2: 1.0～1.5%; Described ZnO raw material particle size is 0.42～0.45 μ m, and loose density is 0.55～0.65g/cm
3, described additive raw material particle diameter is 2～5 μ m, loose density is 0.5～1.3g/cm
3
Second step: will pour in the agitating ball mill in the additive that the described ratio of the first step prepares, and add 70～90% the pure water that weight is described additive gross weight, ball milling 1～4 hour, to particle diameter less than 1.5 μ m;
The 3rd step: with the ZnO that takes by weighing in the first step, ground additive in second step, 45～55% the pure water that adds mixed aid and weight again and be described ZnO weight drops in the mixing tank, disperseed fast 20～60 minutes with homogenizer, open valve, open the pipeline high-shearing dispersion emulsifying machine, circulation disperses to squeeze into receiver after 1～3 hour, open basket shredder again, the setting rotating speed is 500～1400rpm, grinds and obtains slurry after 2～4 hours.
2. the preparation method of zinc oxide pressure-sensitive ceramic slurry according to claim 1, it is characterized in that: described mixed aid comprises dispersion agent and defoamer, the weight percent of described dispersion agent in whole slurry system is 0.2～0.4%, described dispersion agent is made up of tetradecyl Ammoniom-Acetate and polyoxyethylene glycol (PEG4000), the weight ratio of described tetradecyl Ammoniom-Acetate and described polyoxyethylene glycol (PEG4000) is 1.8～2.2: 1, the weight percent of described defoamer in whole slurry system is 0.03～0.05%, described defoamer is made up of tributyl phosphate and water-soluble organic silicon oil, and the weight ratio of described tributyl phosphate and described water-soluble organic silicon oil is 1.6～2.0: 1.
3. a zinc oxide pressure-sensitive ceramic resistive material is characterized in that, comprises the material of following molar percentage, ZnO:93～95%, Bi
2O
3: 0.6～0.9%, Sb
2O
3: 0.9～1.3%, Co
2O
3: 1.0～1.3%, MnCO
3: 0.5～0.8%, Cr
2O
3: 0.5～0.8%, NiO:0.5～0.8%, SiO
2: 1.0～1.5%.
4. zinc oxide pressure-sensitive ceramic resistive material according to claim 3 is characterized in that, the material of described molar percentage is ZnO:93.3～94.5%, Bi
2O
3: 0.7～0.8%, Sb
2O
3: 1.0～1.2%, Co
2O
3: 1.1～1.3%, MnCO
3: 0.6～0.7%, Cr
2O
3: 0.5～0.7%, NiO:0.6～0.7%, SiO
2: 1.0～1.5%.
5. zinc oxide pressure-sensitive ceramic resistive material according to claim 3 is characterized in that: the material of described molar percentage is ZnO:94.3%, Bi
2O
3: 0.7%, Sb
2O
3: 1.1%, Co
2O
3: 1.1%, MnCO
3: 0.6%, Cr
2O
3: 0.6%, NiO:0.6%, SiO
2: 1.0%.
6. zinc oxide pressure-sensitive ceramic resistive material according to claim 3 is characterized in that: the material of described molar percentage is ZnO:93.8%, Bi
2O
3: 0.7%, Sb
2O
3: 1.0%, Co
2O
3: 1.3%, MnCO
3: 0.6%, Cr
2O
3: 0.5%, NiO:0.6%, SiO
2: 1.5%.
7. zinc oxide pressure-sensitive ceramic resistive material according to claim 3 is characterized in that: the material of described molar percentage is ZnO:95%, Bi
2O
3: 0.6%, Sb
2O
3: 0.9%, Co
2O
3: 1.0%, MnCO
3: 0.5%, Cr
2O
3: 0.5%, NiO:0.5%, SiO
2: 1.0%.
8. zinc oxide pressure-sensitive ceramic resistive material according to claim 3 is characterized in that: the material of described molar percentage is ZnO:94.5%, Bi
2O
3: 0.6%, Sb
2O
3: 1.0%, Co
2O
3: 1.0%, MnCO
3: 0.6%, Cr
2O
3: 0.5%, NiO:0.5%, SiO
2: 1.3%.
9. zinc oxide pressure-sensitive ceramic resistive material according to claim 3 is characterized in that: the material of described molar percentage is ZnO:93.3%, Bi
2O
3: 0.8%, Sb
2O
3: 1.3%, Co
2O
3: 1.2%, MnCO
3: 0.7%, Cr
2O
3: 0.8%, NiO:0.7%, SiO
2: 1.2%.
10. zinc oxide pressure-sensitive ceramic resistive material according to claim 3 is characterized in that: the material of described molar percentage is ZnO:93%, Bi
2O
3: 0.9%, Sb
2O
3: 1.2%, Co
2O
3: 1.2%, MnCO
3: 0.8%, Cr
2O
3: 0.7%, NiO:0.8%, SiO
2: 1.4%.
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| CN102220109A (en) * | 2011-04-25 | 2011-10-19 | 苏州晶讯科技股份有限公司 | Preparation method of sizing applied to electrostatic devices |
| CN102617126A (en) * | 2012-03-31 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Low-temperature sintered zinc oxide voltage dependent resistance material and preparation method thereof |
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| CN102617126A (en) * | 2012-03-31 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Low-temperature sintered zinc oxide voltage dependent resistance material and preparation method thereof |
| CN103496970A (en) * | 2013-09-29 | 2014-01-08 | 陈锐群 | Voltage-sensitive ceramic material and preparation method thereof |
| CN105272205A (en) * | 2015-10-12 | 2016-01-27 | 中国科学院上海硅酸盐研究所 | Low-temperature sintering zinc oxide varistor material and preparation method thereof |
| CN106518049A (en) * | 2016-09-23 | 2017-03-22 | 清华大学 | Manufacturing process for improving voltage gradient of zinc-oxide voltage-sensitive ceramics |
| CN108751978A (en) * | 2018-06-19 | 2018-11-06 | 承德伏安电工有限公司 | The preparation method of zinc oxide pressure-sensitive ceramic resistor disc |
| CN109940752A (en) * | 2019-04-02 | 2019-06-28 | 东莞市琅菱机械有限公司 | A kind of electron ceramic material production system and technique |
| CN109940752B (en) * | 2019-04-02 | 2024-04-19 | 东莞市琅菱机械有限公司 | Electronic ceramic material production system and process |
| CN110698208A (en) * | 2019-08-22 | 2020-01-17 | 江门江益磁材有限公司 | Ferrite slurry and preparation method thereof |
| CN114315340A (en) * | 2022-01-05 | 2022-04-12 | 西安交通大学 | High-nonlinearity ZnO-based polycrystalline ceramic and preparation method and application thereof |
| CN114315340B (en) * | 2022-01-05 | 2023-03-07 | 西安交通大学 | High-nonlinearity ZnO-based polycrystalline ceramic and preparation method and application thereof |
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