CN105622087A - Preparation method of large-discharge-current-capacity and low-residual-voltage voltage-sensitive ceramic used for ultrahigh voltage power transmission system - Google Patents
Preparation method of large-discharge-current-capacity and low-residual-voltage voltage-sensitive ceramic used for ultrahigh voltage power transmission system Download PDFInfo
- Publication number
- CN105622087A CN105622087A CN201510997799.0A CN201510997799A CN105622087A CN 105622087 A CN105622087 A CN 105622087A CN 201510997799 A CN201510997799 A CN 201510997799A CN 105622087 A CN105622087 A CN 105622087A
- Authority
- CN
- China
- Prior art keywords
- ball milling
- zno
- voltage
- preparation
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B2235/3267—MnO2
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3289—Noble metal oxides
- C04B2235/3291—Silver oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
The invention provides a preparation method of large-discharge-current-capacity and low-residual-voltage voltage-sensitive ceramic used for an ultrahigh voltage power transmission system. The ceramic is prepared from zinc oxide ZnO, bismuth oxide Bi2O3, antimonous oxide Sb2O3, manganese dioxide MnO2, chromic oxide Cr2O3, cobalt oxide Co2O3, silicon dioxide SiO2, silver oxide Ag2O, Ga(NO3)3 and aluminium nitrate Al(NO3)3. The method has the advantages that the leakage current is restrained, the ageing performance of a ZnO voltage-sensitive resistor manufactured according to the formula is more stable by adding elements Al and Ga together, and the defect that when only Ag ions are added, the ageing performance of the voltage-sensitive resistor is not stable is overcome.
Description
Technical field
The present invention relates to technical field of material chemistry, particularly the preparation method of a kind of pottery.
Background technology
ZnO varistor is main raw material taking ZnO, adds a small amount of Bi2O3, Sb2O3, MnO2, Cr2O3, Co2O3 and silver glass powder etc. as auxiliary composition, adopts ceramic sintering process to be prepared from. The advantage of the non-linear behaviour good due to it and big through-flow capacity, since being found the seventies in 19th century, ZnO varistor is widely used in the superpotential protection of power system lightning protection and power equipment as the core parts of power system thunder arrester.
Along with improving constantly of transmission voltage grade, being particularly extra-high voltage system, apparatus insulated problem is day by day outstanding, and raising is apparatus insulated comprehensively will pay high cost. The thunder arrester that the ZnO varistor of employing high-gradient, low residual voltage assembles can reduce the dielectric level of system, reduces the weight and volume of power transmission and transforming equipment, it is to increase the reliability of transmission of electricity system.
The non-linear character of ZnO varistor can be divided into three regions: small area analysis district, middle Current Zone and big current district. Small area analysis district (<10-4A/cm2) it is also called prebreakdown district, in this region, crystal boundary presents high resistance state, and I-V curve shows as ohm property, and the ohm property rate of curve in this region is more big, then the power dissipation characteristics in leakage current region of ZnO varistor is more stable, and pressure sensitive voltage U1mA is also more high. Middle Current Zone is nonlinear resistance district, and this zone current sharply increases and voltage increases slowly, and this region I-V characteristic is affected and determine jointly by ZnO crystal grain and ZnO crystal boundary, is the workspace of voltage dependent resistor. Big current district (>103A/cm2) turn into again ohm property, the resistance of this region ZnO crystal grain determines the height of residual voltage, the position that this region occurs in I-V characteristic plane simultaneously, it is resolved that the size of the through-flow capacity of ZnO varistor.
Whether in middle Current Zone or big current district, ZnO grain resistance all affects I-V characteristic. Reduce the residual voltage of ZnO varistor, it is necessary to reduce the resistivity of ZnO varistor. Show according to conventional research, add the resistivity that a certain amount of donor ion can significantly improve ZnO crystal grain, thus reach the object reducing residual voltage. The industrial production of reality adopt mostly Al ion add in ZnO varistor material as donor ion, but the interpolation of Al ion is often with the increase of leakage current, causing the reduction of nonlinear factor, the aging property of ZnO varistor also become unstable simultaneously. In industrial application, also there is the mode adopting ZnO and the auxiliary addition material presintering of part so that part mixing raw material pre-reaction, to improve potential barrier and the stability of pressure-sensitive material, this kind of mode makes complex manufacturing. At present mainly through improving the degree of uniformity of crystal grain, make electric current can uniform flow whole varistor valve, thus improve the through-flow capacity of ZnO varistor, but the degree of uniformity of crystal grain is relatively big by the impact of sintering process and raw material mixed grinding technique etc., accomplish that an equal change of crystal grain is difficult bigger.
Summary of the invention
It is an object of the invention to solve the problem, devise a kind of big through-flow capacity of system for ultra-high voltage transmission, the pressure-sensitive ceramic preparation of low residual voltage. Specific design scheme is:
A kind of system for ultra-high voltage transmission big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, prepare raw material and comprise zinc oxide ZnO, bismuth oxide Bi2O3, antimonous oxide Sb2O3, Manganse Dioxide MnO2, chromic oxide Cr2O3, cobalt sesquioxide Co2O3, silicon-dioxide SiO2, silver suboxide Ag2O��Ga(NO3)3, aluminum nitrate Al (NO3)3, preparation process comprises that preparation is auxiliary adds slurry, shaping, sintering, and described preparation is auxiliary to be added sauce step and comprise first ball milling, secondary ball milling, three ball millings, mist projection granulating, automatically moisture.
Respectively preparing the mol ratio between raw material is:
ZnO:Bi2O3: Sb2O3: MnO2: Cr2O3: Co2O3: SiO2: Ag2O:Ga (NO3)3: Al (NO3)3=87.5��95.8:0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0:0.1-1.0:0.1-1.0:1.0-1.5
In described first ball milling step, the composition of described first ball milling comprises Bi2O3��MnO2��Sb2O3��Co2O3��SiO2��Cr2O3, deionized water, the described first ball milling time is greater than 6h, obtains the auxiliary mixed slurry of first ball milling,
The Bi added2O3��MnO2��Cr2O3��Co2O3��SiO2The mol ratio of composition is: 0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0.
Described forming step is compression molding, it may also be useful to the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, and by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, molding time 3min.
Using high temperature circuit to complete described sintering step, in described sintering step, temperature control with time controling is:
From room temperature to 400 DEG C, heating-up time 2h;
At 400 DEG C of insulation row glue 4h;
From 400 DEG C to 1000 DEG C, heating-up time 3h;
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h;
It is incubated 3h at 1200 DEG C;
Temperature fall.
In secondary ball milling step, ZnO, PVAC polyvinylalcohol, powder powder, deionized water is added in the auxiliary mixed slurry of described first ball milling, and ball milling is mixed to and is uniformly dispersed, obtain the auxiliary mixed slurry of secondary ball milling, described in add ZnO and assist Bi in mixed slurry with first ball milling2O3Mol ratio be 87.5��95.8:0.5-2.0.
In three ball milling step, in the auxiliary mixed slurry of described secondary ball milling, add Ag2O:Ga (NO3)3: Al (NO3)3, carry out three ball millings after deionized water, the time of described three ball millings is 2h, obtains slurry, described in add Ag2O:Ga (NO3)3: Al (NO3)3The mol ratio assisting the ZnO added in mixed slurry with secondary ball milling is 0.1-1.0:0.1-1.0:0.5��1.5:87.5��95.8.
The system for ultra-high voltage transmission obtained by the technique scheme of the present invention big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, its useful effect is:
With the addition of Ag and Al element in ZnO and mixed slurry, the acting in conjunction of Ag and Al ion makes the grain resistance in big current district decline, and reduces the residual voltage level of ZnO varistor simultaneously; On V-I rational curve, the flex point in big current district moves to right, it is to increase the ZnO varistor that this formula makes is released the ability of electric charge; Under the acting in conjunction of Al and Ga ion so that the V-I characteristic of the ZnO varistor that this formula makes in small area analysis district is more stable, and voltage gradient is improved, nonlinear factor increases, and compared with simple interpolation Ag ion, leakage current is inhibited; The common interpolation of Al and Ga element makes the aging resistance of the ZnO varistor that this formula makes more stable, eliminates the simple weak point adding the voltage dependent resistor aging resistance instability that Ag ion brings.
Embodiment
A kind of system for ultra-high voltage transmission big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, prepare raw material and comprise zinc oxide ZnO, bismuth oxide Bi2O3, antimonous oxide Sb2O3, Manganse Dioxide MnO2, chromic oxide Cr2O3, cobalt sesquioxide Co2O3, silicon-dioxide SiO2, silver suboxide Ag2O��Ga(NO3)3, aluminum nitrate Al (NO3)3, preparation process comprises that preparation is auxiliary adds slurry, shaping, sintering, and described preparation is auxiliary to be added sauce step and comprise first ball milling, secondary ball milling, three ball millings, mist projection granulating, automatically moisture.
Respectively preparing the mol ratio between raw material is:
ZnO:Bi2O3: Sb2O3: MnO2: Cr2O3: Co2O3: SiO2: Ag2O:Ga (NO3)3: Al (NO3)3=87.5��95.8:0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0:0.1-1.0:0.1-1.0:1.0-1.5
In described first ball milling step, the composition of described first ball milling comprises Bi2O3��MnO2��Sb2O3��Co2O3��SiO2��Cr2O3, deionized water, the described first ball milling time is greater than 6h, obtains the auxiliary mixed slurry of first ball milling,
The Bi added2O3��MnO2��Cr2O3��Co2O3��SiO2The mol ratio of composition is: 0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0.
Described forming step is compression molding, it may also be useful to the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, and by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, molding time 3min.
Using high temperature circuit to complete described sintering step, in described sintering step, temperature control with time controling is:
From room temperature to 400 DEG C, heating-up time 2h;
At 400 DEG C of insulation row glue 4h;
From 400 DEG C to 1000 DEG C, heating-up time 3h;
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h;
It is incubated 3h at 1200 DEG C;
Temperature fall.
In secondary ball milling step, ZnO, PVAC polyvinylalcohol, powder powder, deionized water is added in the auxiliary mixed slurry of described first ball milling, and ball milling is mixed to and is uniformly dispersed, obtain the auxiliary mixed slurry of secondary ball milling, described in add ZnO and assist Bi in mixed slurry with first ball milling2O3Mol ratio be 87.5��95.8:0.5-2.0.
In three ball milling step, in the auxiliary mixed slurry of described secondary ball milling, add Ag2O:Ga (NO3)3: Al (NO3)3, carry out three ball millings after deionized water, the time of described three ball millings is 2h, obtains slurry, described in add Ag2O:Ga (NO3)3: Al (NO3)3The mol ratio assisting the ZnO added in mixed slurry with secondary ball milling is 0.1-1.0:0.1-1.0:0.5��1.5:87.5��95.8.
Embodiment one
A kind of system for ultra-high voltage transmission big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage introduced according to patent specification part of the present invention, carries out the actual preparation of high-performance ZnO based varistor.
(1) preparation of raw material:
In following ratio ZnO (87.5%), Bi2O3(2.0mol%), Sb2O3(1.5mol%), MnO2(1.0mol%), Cr2O3(1.0mol%), Co2O3(1.5mol%), SiO2, and Ag (2.0mol%)2O (1.0mol%), Ga (NO3)3(1.0mol%), Al (NO3)3(1.5mol%) initial feed is prepared.
(2) slurry preparation
1) the auxiliary addition material of ball milling:
By Bi2O3(2.0mol%), Sb2O3(1.5mol%), MnO2(1.0mol%), Cr2O3(1.0mol%), Co2O3(1.5mol%), SiO2(2.0mol%) put into the ball grinder into planetary ball mill, add appropriate deionized water, ball milling 8 hours.
2) adding the ZnO of (87.5mol%) in auxiliary mixed slurry after ball milling, add PVA, dispersion agent and appropriate deionized water, by all mixing raw material mixing and ball milling to being uniformly dispersed.
3) silver, aluminium plus gallium ion is added
In the ZnO mixed and auxiliary addition material, add Ag2O (1.0mol%), Ga (NO3)3(1.0mol%), Al (NO3)3(1.5mol%), ball milling is continued 2 hours, after mist projection granulating, moisture.
(3) shaping
The powder obtained in previous step is sprayed, after automatically moisture, adopts tabletting molding process. Using the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, 3 minutes dwell times.
(4) sinter
With high-temperature electric resistance furnace sintered body in closed atmosphere, actual temp and period are as follows:
From room temperature to 400 DEG C, 2 hours heating-up times;
Glue are arranged 4 hours 400 DEG C of insulations;
From 400 DEG C to 1000 DEG C, 3 hours heating-up times;
From 1000 DEG C to 1200 DEG C, 1.5 hours heating-up times;
It is incubated 3 hours at 1200 DEG C;
Temperature fall.
The sample of the ZnO varistor prepared is carried out every performance test. Its residual voltage ratio is that the through-flow capacity of 1.47,2ms square wave reaches 535J/cm3. In addition, leakage current is less than 1 �� A/cm2, nonlinear factor is greater than 70. Its performance has met industrial application requirement.
Embodiment two
A kind of system for ultra-high voltage transmission big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage introduced according to patent specification part of the present invention, carries out the actual preparation of high-performance ZnO based varistor.
(1) preparation of raw material:
In following ratio ZnO (95.8mol%), Bi2O3(0.5mol%), Sb2O3(0.5mol%), MnO2(0.5mol%), Cr2O3(0.5mol%), Co2O3(0.5mol%), SiO2, and Ag (1.0mol%)2O (0.1mol%), Ga (NO3)3(0.1mol%), Al (NO3)3(0.5mol%) initial feed is prepared.
(2) slurry preparation
1) the auxiliary addition material of ball milling:
By Bi2O3(0.5mol%), Sb2O3(0.5mol%), MnO2(0.5mol%), Cr2O3(0.5mol%), Co2O3(0.5mol%), SiO2(1.0mol%) put into the ball grinder into planetary ball mill, add appropriate deionized water, ball milling more than 6 hours.
2) adding the ZnO of (87.5��95.8mol%) in auxiliary mixed slurry after ball milling, add PVA, dispersion agent and appropriate deionized water, by all mixing raw material mixing and ball milling to being uniformly dispersed.
3) silver, aluminium plus gallium ion is added
In the ZnO mixed and auxiliary addition material, add Ag2O (0.1��1.0mol%), Ga (NO3)3(0.1��1.0mol%), Al (NO3)3(0.5��1.5mol%), continues ball milling 2 hours, after mist projection granulating, moisture.
(3) shaping
The powder obtained in previous step is sprayed, after automatically moisture, adopts tabletting molding process. Using the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, 3 minutes dwell times.
(4) sinter
With high-temperature electric resistance furnace sintered body in closed atmosphere, actual temp and period are as follows:
From room temperature to 400 DEG C, 2 hours heating-up times;
Glue are arranged 4 hours 400 DEG C of insulations;
From 400 DEG C to 1000 DEG C, 3 hours heating-up times;
From 1000 DEG C to 1200 DEG C, 1.5 hours heating-up times;
It is incubated 3 hours at 1200 DEG C;
Temperature fall.
The sample of the ZnO varistor prepared is carried out every performance test. Its residual voltage ratio is that the through-flow capacity of 1.49,2ms square wave reaches 508J/cm3. In addition, leakage current is less than 1 �� A/cm2, nonlinear factor is greater than 70. Its performance has met industrial application requirement.
Technique scheme only embodies the optimal technical scheme of technical solution of the present invention, and some variations that wherein some part may be made by those skilled in the art all embody the principle of the present invention, belong within protection scope of the present invention.
Claims (7)
1. a system for ultra-high voltage transmission big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, it is characterized in that, prepare raw material and comprise zinc oxide ZnO, bismuth oxide Bi2O3, antimonous oxide Sb2O3, Manganse Dioxide MnO2, chromic oxide Cr2O3, cobalt sesquioxide Co2O3, silicon-dioxide SiO2, silver suboxide Ag2O, Ga (NO3) 3, aluminum nitrate Al (NO3) 3, preparation process comprises that preparation is auxiliary adds slurry, shaping, sintering, and described preparation is auxiliary to be added sauce step and comprise first ball milling, secondary ball milling, three ball millings, mist projection granulating, automatically moisture.
2.According to claimSystem for ultra-high voltage transmission described in 1 big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, it is characterised in that, respectively preparing the mol ratio between raw material is:
ZnO:Bi2O3:Sb2O3:MnO2:Cr2O3:Co2O3:SiO2:Ag2O:Ga (NO3) 3:Al (NO3) 3=87.5��95.8:0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0:0.1-1.0:0.1-1.0:1.0-1.5.
3.According to claimSystem for ultra-high voltage transmission described in 1 big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, it is characterized in that, in described first ball milling step, the composition of described first ball milling comprises Bi2O3, MnO2, Sb2O3, Co2O3, SiO2, Cr2O3, deionized water, the described first ball milling time is greater than 6h, obtain the auxiliary mixed slurry of first ball milling
The mol ratio of Bi2O3, MnO2, Cr2O3, Co2O3, SiO2 composition added is: 0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0.
4.According to claimSystem for ultra-high voltage transmission described in 1 big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, it is characterized in that, described forming step is compression molding, use the cylindrical die of hydraulic pressure tabletting machine and diameter 50mm, by the particulate material compression molding after drying-granulating, forming pressure is 150MPa, molding time 3min.
5.According to claimSystem for ultra-high voltage transmission described in 1 big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, it is characterised in that, it may also be useful to high temperature circuit completes described sintering step, and in described sintering step, temperature control with time controling is:
From room temperature to 400 DEG C, heating-up time 2h;
At 400 DEG C of insulation row glue 4h;
From 400 DEG C to 1000 DEG C, heating-up time 3h;
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h;
It is incubated 3h at 1200 DEG C;
Temperature fall.
6.According to claimSystem for ultra-high voltage transmission described in 3 big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, it is characterized in that, in secondary ball milling step, ZnO, PVAC polyvinylalcohol, powder powder, deionized water is added in the auxiliary mixed slurry of described first ball milling, and ball milling is mixed to and is uniformly dispersed, obtain the auxiliary mixed slurry of secondary ball milling, described in add ZnO and assist the mol ratio of Bi2O3 in mixed slurry to be 87.5��95.8:0.5-2.0 with first ball milling.
7.According to claimSystem for ultra-high voltage transmission described in 6 big through-flow capacity, the pressure-sensitive ceramic preparation of low residual voltage, it is characterized in that, in three ball milling step, three ball millings are carried out after adding Ag2O:Ga (NO3) 3:Al (NO3) 3, deionized water in the auxiliary mixed slurry of described secondary ball milling, the time of described three ball millings is 2h, obtain slurry, described in add in Ag2O:Ga (NO3) 3:Al (NO3) 3 and the auxiliary mixed slurry of secondary ball milling the ZnO added mol ratio be 0.1-1.0:0.1-1.0:0.5��1.5:87.5��95.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510997799.0A CN105622087B (en) | 2015-12-25 | 2015-12-25 | A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510997799.0A CN105622087B (en) | 2015-12-25 | 2015-12-25 | A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105622087A true CN105622087A (en) | 2016-06-01 |
| CN105622087B CN105622087B (en) | 2018-05-18 |
Family
ID=56037485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510997799.0A Active CN105622087B (en) | 2015-12-25 | 2015-12-25 | A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105622087B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689700A (en) * | 2018-06-27 | 2018-10-23 | 合肥同佑电子科技有限公司 | A kind of pressure-sensitive ceramic material of high pass current capacity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003709A (en) * | 2014-06-10 | 2014-08-27 | 湖北文理学院 | Zinc oxide-based pressure-sensitive ceramic material for lightning arrester as well as preparation method and application of material |
-
2015
- 2015-12-25 CN CN201510997799.0A patent/CN105622087B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003709A (en) * | 2014-06-10 | 2014-08-27 | 湖北文理学院 | Zinc oxide-based pressure-sensitive ceramic material for lightning arrester as well as preparation method and application of material |
Non-Patent Citations (1)
| Title |
|---|
| 魏乔苑等: ""氧化锡压敏电阻特性分析"", 《高电压技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689700A (en) * | 2018-06-27 | 2018-10-23 | 合肥同佑电子科技有限公司 | A kind of pressure-sensitive ceramic material of high pass current capacity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105622087B (en) | 2018-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105645948B (en) | A kind of preparation method of high-voltage gradient, low Leakage Current varistor ceramics materials | |
| CN101700976B (en) | Formula of non-linear resistor for high voltage surge arrester and manufacturing method thereof | |
| CN105016721B (en) | Method for preparing ZnO varistor ceramic by co-doping aluminum ions, gallium ions and yttrium ions | |
| CN105622086B (en) | The method for preparing high gradient zinc oxide piezoresistor ceramic | |
| CN104944935A (en) | ZnO varister ceramic and preparation method thereof | |
| CN102476949A (en) | Method for preparing electrical property-controllable zinc oxide (ZnO) piezoresistor material at low temperature | |
| CN105859279A (en) | Novel process method for preparing zinc oxide piezoresistor ceramic with excellent properties | |
| CN103021608A (en) | High-gradient and high-capacity zinc oxide voltage dependent resistor disc and fabrication method thereof | |
| CN101503292A (en) | Formula of direct current zinc oxide resistance chip | |
| CN105481363A (en) | Large-discharge-current-capacity low-residual-voltage high-gradient zinc oxide piezoresistor ceramic | |
| CN108546111A (en) | A kind of zinc oxide piezoresistor ceramic and preparation method thereof of high-voltage gradient, low residual voltage, low Leakage Current | |
| CN107021751A (en) | A kind of high-potential gracient arrester zinc oxide piezoresistor ceramic | |
| CN105884345A (en) | High-voltage-gradient, low-residual-voltage and low-leakage-current ceramic and preparing method thereof | |
| CN105601268A (en) | Formula of zinc oxide piezoresistor ceramic with favorable comprehensive electrical performance | |
| CN105622087A (en) | Preparation method of large-discharge-current-capacity and low-residual-voltage voltage-sensitive ceramic used for ultrahigh voltage power transmission system | |
| CN110423110B (en) | Ultrahigh nonlinear ZnO-Bi2O3Base pressure sensitive ceramic and preparation method thereof | |
| CN109704752B (en) | SnO (stannic oxide)2Piezoresistor and preparation method thereof | |
| CN110922182A (en) | Preparation method of high-gradient low-leakage-current ceramic | |
| CN105565801A (en) | Preparation method of high-gradient and large-discharge-current-capacity voltage-sensitive ceramics for ultra-high-voltage power transmission system | |
| CN103910524A (en) | Rare earth oxide-modified stannic oxide varistor material and preparation method thereof | |
| CN106946560B (en) | Y3+、Sn4+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof | |
| CN105565800A (en) | Preparation method for voltage-sensitive ceramics used for ultrahigh-voltage power transmission system and having excellent comprehensive electrical performance | |
| CN106892657B (en) | In3+、Sn4+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof | |
| CN106946561B (en) | Y3+、Nb5+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof | |
| Gromov et al. | Preparation of high-voltage ZnO varistor ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |