CN105622087B - A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method - Google Patents
A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method Download PDFInfo
- Publication number
- CN105622087B CN105622087B CN201510997799.0A CN201510997799A CN105622087B CN 105622087 B CN105622087 B CN 105622087B CN 201510997799 A CN201510997799 A CN 201510997799A CN 105622087 B CN105622087 B CN 105622087B
- Authority
- CN
- China
- Prior art keywords
- ball milling
- voltage
- zno
- discharge capacity
- ultra
- 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.)
- Active
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
Abstract
A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method, preparing raw material includes zinc oxide ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese dioxide MnO2, chromium oxide Cr2O3, cobalt sesquioxide Co2O3, silica SiO2, silver oxide Ag2O, Ga (NO3) 3, aluminum nitrate Al (NO3) 3.Its advantage is：Leakage current is inhibited；The common addition of Al and Ga elements causes the ageing properties of the ZnO varistor of this formula making more to stablize, and eliminates the unstable shortcoming of the next varistor ageing properties of simple addition Ag ion bands.
Description
Technical field
The present invention relates to technical field of material chemistry, particularly a kind of preparation method of ceramics.
Background technology
ZnO varistor be using ZnO as primary raw material, add a small amount of Bi2O3, Sb2O3, MnO2, Cr2O3, Co2O3,
With silver glass powder etc. as auxiliary ingredients, it is prepared using ceramic sintering process.Due to its good non-linear behaviour and greatly
The advantages of discharge capacity, since 19 century 70s are found, core element of the ZnO varistor as electric system arrester
It is widely used in the overvoltage protection of electric system lightning protection and power equipment.
Particularly it is extra-high voltage system with the continuous improvement of transmission voltage grade, apparatus insulated problem becomes increasingly conspicuous, entirely
Face raising will be apparatus insulated to pay through the nose.The arrester assembled using the ZnO varistor of high gradient, low residual voltage
The dielectric level of system can be reduced, reduces the weight and volume of power transmission and transforming equipment, improves the reliability of transmission system.
The nonlinear characteristic of ZnO varistor can be divided into three regions：Low current area, middle Current Zone and high current area.
Low current area (<Prebreakdown area 10-4A/cm2) is also known as, crystal boundary shows high-impedance state in the region, and I-V curve shows as Europe
Nurse characteristic, the Ohm characteristic slope of curve in the region is bigger, then the power dissipation characteristics in leakage current region of ZnO varistor is more stable, pressure-sensitive electricity
Press U1mA also higher.Middle Current Zone is nonlinear resistance area, this zone current increased dramatically and voltage increases slow, this region
I-V characteristic is determined by ZnO crystal grain with ZnO crystal boundaries joint effect, is the workspace of varistor.High current area (>103A/
Cm2) and Ohm characteristic is become, the resistance of region ZnO crystal grain determines the height of residual voltage, while the region is put down in I-V characteristic
The position that face occurs determines the size of ZnO varistor discharge capacity.
Whether in middle Current Zone or high current area, ZnO grain resistances all affect I-V characteristic.It is pressure-sensitive to reduce ZnO
The residual voltage of resistance, it is necessary to reduce the resistivity of ZnO varistor.According to previous research show to add a certain amount of alms giver from
Son can significantly improve the resistivity of ZnO crystal grain, so as to achieve the purpose that reduce residual voltage.It is adopted mostly in actual industrial production
It is added to by the use of Al ions as donor ion in ZnO varistor material, but the addition of Al ions is usually associated with leakage electricity
The increase of stream, also results in the reduction of nonlinear factor, and the aging characteristics of ZnO varistor also become unstable.It should in industry
In, also have in a manner that ZnO and part adjunct are pre-sintered so that part mixed raw material pre-reaction, to improve pressure
The potential barrier and stability of quick material, this mode cause complex production process.At present mainly by improving the uniform journey of crystal grain
Degree so that electric current can uniform flow entire varistor valve, so as to improve the discharge capacity of ZnO varistor, but it is brilliant
The uniformity coefficient of grain is affected by sintering process and raw material mixed grinding technique etc., accomplishes that the homogenization of crystal grain is difficult
It is larger.
The content of the invention
The purpose of the present invention is to solve the above problem, devise a kind of system for ultra-high voltage transmission with big discharge capacity,
Low residual voltage voltage-sensitive ceramic preparation method.Specifically designing scheme is：
A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method, preparing raw material includes oxygen
Change zinc ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese dioxide MnO2, chromium oxide Cr2O3, cobalt sesquioxide Co2O3, two
Silicon oxide sio2, silver oxide Ag2O、Ga(NO3)3, aluminum nitrate Al (NO3)3, preparation process include prepare auxiliary addition slurry, into
Type, sintering, the auxiliary addition sauce step for preparing include first ball milling, three times secondary ball milling, ball milling, mist projection granulating, automatic
It is aqueous.
The molar ratio respectively prepared 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 the first ball milling step, the ingredient of the first ball milling includes Bi2O3、MnO2、Sb2O3、Co2O3、SiO2、
Cr2O3, deionized water, the first Ball-milling Time is more than 6h, obtains first ball milling auxiliary mixed slurry,
The Bi added in2O3、MnO2、Cr2O3、Co2O3、SiO2The molar ratio of ingredient 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。
The forming step is compression molding, using hydraulic pressure tablet press machine and the cylindrical die of diameter 50mm, by drying
Particulate material compression molding after granulation, briquetting pressure 150MPa, molding time 3min.
The sintering step is completed using high temperature circuit, and in the sintering step, temperature is controlled is with time control：
From room temperature to 400 DEG C, heating-up time 2h；
Dumping 4h is kept the temperature at 400 DEG C；
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；
3h is kept the temperature at 1200 DEG C；
Temperature fall.
In secondary ball milling step, into the first ball milling auxiliary mixed slurry, addition ZnO, PVAC polyvinylalcohol, powder dissipate
Agent, deionized water, and ball milling mixing obtain secondary ball milling auxiliary mixed slurry, the addition ZnO and first ball to being uniformly dispersed
Bi in mill auxiliary mixed slurry2O3Molar ratio be 87.5~95.8：0.5-2.0.
Three times in ball milling step, aid in adding in Ag in mixed slurry to the secondary ball milling2O：Ga(NO3)3：Al(NO3)3、
Ball milling three times is carried out after deionized water, the time of the ball milling three times is 2h, obtains slurry, the addition Ag2O：Ga(NO3)3：
Al(NO3)3It is 0.1-1.0 to aid in the molar ratio of the ZnO added in mixed slurry with secondary ball milling:0.1-1.0：0.5~1.5：
87.5~95.8.
System for ultra-high voltage transmission big discharge capacity, the pressure-sensitive pottery of low residual voltage obtained by the above-mentioned technical proposal of the present invention
Porcelain preparation method, its advantage are：
Ag and Al elements are with the addition of simultaneously in ZnO and mixed slurry, the collective effect of Ag and Al ions causes high current
The grain resistance in area declines, and the residual voltage for reducing ZnO varistor is horizontal；On V-I characteristic curves, the inflection point in high current area is right
It moves, improves the ZnO varistor that this formula makes and release the ability of charge；Under the collective effect of Al and Ga ions so that this
It is formulated V-I characteristic of the ZnO varistor made in low current area more to stablize, voltage gradient is improved, nonlinear factor
Increase, compared with addition Ag ions merely, leakage current is inhibited；The common addition of Al and Ga elements is so that this formula makes
The ageing properties of ZnO varistor more stablize, eliminate varistor ageing properties that simple addition Ag ion bands come not
Stable shortcoming.
Specific embodiment
A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method, preparing raw material includes oxygen
Change zinc ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese dioxide MnO2, chromium oxide Cr2O3, cobalt sesquioxide Co2O3, two
Silicon oxide sio2, silver oxide Ag2O、Ga(NO3)3, aluminum nitrate Al (NO3)3, preparation process include prepare auxiliary addition slurry, into
Type, sintering, the auxiliary addition sauce step for preparing include first ball milling, three times secondary ball milling, ball milling, mist projection granulating, automatic
It is aqueous.
The molar ratio respectively prepared 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 the first ball milling step, the ingredient of the first ball milling includes Bi2O3、MnO2、Sb2O3、Co2O3、SiO2、
Cr2O3, deionized water, the first Ball-milling Time is more than 6h, obtains first ball milling auxiliary mixed slurry,
The Bi added in2O3、MnO2、Cr2O3、Co2O3、SiO2The molar ratio of ingredient 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。
The forming step is compression molding, using hydraulic pressure tablet press machine and the cylindrical die of diameter 50mm, by drying
Particulate material compression molding after granulation, briquetting pressure 150MPa, molding time 3min.
The sintering step is completed using high temperature circuit, and in the sintering step, temperature is controlled is with time control：
From room temperature to 400 DEG C, heating-up time 2h；
Dumping 4h is kept the temperature at 400 DEG C；
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；
3h is kept the temperature at 1200 DEG C；
Temperature fall.
In secondary ball milling step, into the first ball milling auxiliary mixed slurry, addition ZnO, PVAC polyvinylalcohol, powder dissipate
Agent, deionized water, and ball milling mixing obtain secondary ball milling auxiliary mixed slurry, the addition ZnO and first ball to being uniformly dispersed
Bi in mill auxiliary mixed slurry2O3Molar ratio be 87.5~95.8：0.5-2.0.
Three times in ball milling step, aid in adding in Ag in mixed slurry to the secondary ball milling2O：Ga(NO3)3：Al(NO3)3、
Ball milling three times is carried out after deionized water, the time of the ball milling three times is 2h, obtains slurry, the addition Ag2O：Ga(NO3)3：
Al(NO3)3It is 0.1-1.0 to aid in the molar ratio of the ZnO added in mixed slurry with secondary ball milling:0.1-1.0：0.5~1.5：
87.5~95.8.
Embodiment one
According to a kind of system for ultra-high voltage transmission big discharge capacity, the low residual voltage pressure of patent specification introduction of the present invention
Quick ceramic preparation carries out the actual preparation of high-performance ZnO based varistor.
(1) raw material is prepared：
ZnO (87.5%), Bi in the following proportions2O3(2.0mol%), Sb2O3(1.5mol%), MnO2(1.0mol%),
Cr2O3(1.0mol%), Co2O3(1.5mol%), SiO2(2.0mol%) and Ag2O (1.0mol%), Ga (NO3)3
(1.0mol%), Al (NO3)3(1.5mol%) prepares initial feed.
(2) prepared by slurry
1) ball milling adjunct：
By Bi2O3(2.0mol%), Sb2O3(1.5mol%), MnO2(1.0mol%), Cr2O3(1.0mol%), Co2O3
(1.5mol%), SiO2(2.0mol%) is put into the ball grinder of planetary ball mill, adds in suitable deionized water, ball milling
8 hours.
2) ZnO of (87.5mol%) is added in auxiliary mixed slurry after ball milling, adds PVA, dispersant and suitable
Deionized water, by all mixed raw material mixing and ball millings until being uniformly dispersed.
3) addition silver, aluminium plus gallium ion
In uniformly mixed ZnO and adjunct, Ag is added2O (1.0mol%), Ga (NO3)3(1.0mol%), Al
(NO3)3(1.5mol%), it is aqueous after mist projection granulating when continuation ball milling 2 is small.
(3) it is molded
The powder obtained in previous step is sprayed, it is automatic it is aqueous after, using tabletting molding process.Use hydraulic pressure tabletting
The cylindrical die of machine and diameter 50mm, by the particulate material compression molding after drying-granulating, briquetting pressure 150MPa, pressurize
3 minutes time.
(4) it is sintered
With high-temperature electric resistance furnace, sintered body, actual temp and control time are as follows in closed atmosphere：
From room temperature to 400 DEG C, when the heating-up time 2 is small；
When 400 DEG C of heat preservation dumpings 4 are small；
From 400 DEG C to 1000 DEG C, when the heating-up time 3 is small；
From 1000 DEG C to 1200 DEG C, when the heating-up time 1.5 is small；
When 1200 DEG C of heat preservations 3 are small；
Temperature fall.
The sample of ZnO varistor to being prepared carries out properties test.Its residual voltage ratio is 1.47,2ms square waves
Discharge capacity reaches 535J/cm3.In addition, leakage current is less than 1 μ A/cm2, nonlinear factor is more than 70.Its performance is
Meet commercial Application requirement.
Embodiment two
According to a kind of system for ultra-high voltage transmission big discharge capacity, the low residual voltage pressure of patent specification introduction of the present invention
Quick ceramic preparation carries out the actual preparation of high-performance ZnO based varistor.
(1) raw material is prepared：
ZnO (95.8mol%), Bi in the following proportions2O3(0.5mol%), Sb2O3(0.5mol%), MnO2
(0.5mol%), Cr2O3(0.5mol%), Co2O3(0.5mol%), SiO2(1.0mol%) and Ag2O (0.1mol%), Ga
(NO3)3(0.1mol%), Al (NO3)3(0.5mol%) prepares initial feed.
(2) prepared by slurry
1) ball milling adjunct：
By Bi2O3(0.5mol%), Sb2O3(0.5mol%), MnO2(0.5mol%), Cr2O3(0.5mol%), Co2O3
(0.5mol%), SiO2(1.0mol%) is put into the ball grinder of planetary ball mill, adds in suitable deionized water, ball milling
6 more than hour.
2) in auxiliary mixed slurry after ball milling add in (87.5~95.8mol%) ZnO, add PVA, dispersant and
Suitable deionized water, by all mixed raw material mixing and ball millings until being uniformly dispersed.
3) addition silver, aluminium plus gallium ion
In uniformly mixed ZnO and adjunct, Ag is added2O (0.1~1.0mol%), Ga (NO3)3(0.1~
1.0mol%), Al (NO3)3(0.5~1.5mol%), it is aqueous after mist projection granulating when continuation ball milling 2 is small.
(3) it is molded
The powder obtained in previous step is sprayed, it is automatic it is aqueous after, using tabletting molding process.Use hydraulic pressure tabletting
The cylindrical die of machine and diameter 50mm, by the particulate material compression molding after drying-granulating, briquetting pressure 150MPa, pressurize
3 minutes time.
(4) it is sintered
With high-temperature electric resistance furnace, sintered body, actual temp and control time are as follows in closed atmosphere：
From room temperature to 400 DEG C, when the heating-up time 2 is small；
When 400 DEG C of heat preservation dumpings 4 are small；
From 400 DEG C to 1000 DEG C, when the heating-up time 3 is small；
From 1000 DEG C to 1200 DEG C, when the heating-up time 1.5 is small；
When 1200 DEG C of heat preservations 3 are small；
Temperature fall.
The sample of ZnO varistor to being prepared carries out properties test.Its residual voltage ratio is 1.49,2ms square waves
Discharge capacity reaches 508J/cm3.In addition, leakage current is less than 1 μ A/cm2, nonlinear factor is more than 70.Its performance is
Meet commercial Application requirement.
Above-mentioned technical proposal only embodies the optimal technical scheme of technical solution of the present invention, those skilled in the art
The principle of the present invention is embodied to some variations that some of which part may be made, belongs to the scope of protection of the present invention it
It is interior.
Claims (5)
1. a kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method, which is characterized in that prepare former
Material includes zinc oxide ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese dioxide MnO2, chromium oxide Cr2O3, cobalt sesquioxide
Co2O3, silica SiO2, silver oxide Ag2O、Ga(NO3)3, aluminum nitrate Al (NO3)3, preparation process, which includes preparing, aids in addition slurry
Material, shaping, sintering, the preparation auxiliary addition slurry stage includes first ball milling, secondary ball milling, ball milling, spraying are made three times
It is grain, automatic aqueous,
The molar ratio respectively prepared 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 the first ball milling step, the ingredient of the first ball milling includes Bi2O3、MnO2、Sb2O3、Co2O3、SiO2、Cr2O3, go
Ionized water, the first Ball-milling Time are more than 6h, obtain first ball milling auxiliary mixed slurry,
The Bi added in2O3、MnO2、Cr2O3、Co2O3、SiO2The molar ratio of ingredient 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。
2. according to system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method described in claim 1,
It is characterized in that, the forming step is compression molding, it, will be dry using hydraulic pressure tablet press machine and the cylindrical die of diameter 50mm
Particulate material compression molding after dry granulation, briquetting pressure 150MPa, molding time 3mi n.
3. according to system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method described in claim 1,
It is characterized in that, completing the sintering step using high temperature circuit, in the sintering step, temperature is controlled is with time control：
From room temperature to 400 DEG C, heating-up time 2h；
Dumping 4h is kept the temperature at 400 DEG C；
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；
3h is kept the temperature at 1200 DEG C；
Temperature fall.
4. according to system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method described in claim 1,
It is characterized in that, in secondary ball milling step, ZnO, PVAC polyvinylalcohol, powder are added in into the first ball milling auxiliary mixed slurry
Powder, deionized water, and ball milling mixing is to being uniformly dispersed, obtain secondary ball milling auxiliary mixed slurry, the addition ZnO with it is first
Bi in ball milling auxiliary mixed slurry2O3Molar ratio be 87.5~95.8：0.5-2.0.
5. according to system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method described in claim 4,
It is characterized in that, three times in ball milling step, aid in adding in Ag in mixed slurry to the secondary ball milling2O：Ga(NO3)3：Al
(NO3)3, ball milling three times is carried out after deionized water, the time of the ball milling three times is 2h, obtains slurry, the addition Ag2O：Ga
(NO3)3：Al(NO3)3It is 0.1-1.0 to aid in the molar ratio of the ZnO added in mixed slurry with secondary ball milling: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 CN105622087A (en) | 2016-06-01 |
| CN105622087B true 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) |
Families Citing this family (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 |
|---|
| "氧化锡压敏电阻特性分析";魏乔苑等;《高电压技术》;20110331;第37卷(第3期);第629～633页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105622087A (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105645948B (en) | A kind of preparation method of high-voltage gradient, low Leakage Current varistor ceramics materials | |
| CN105622086B (en) | The method for preparing high gradient zinc oxide piezoresistor ceramic | |
| CN105481363B (en) | A kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic | |
| CN105016721B (en) | Method for preparing ZnO varistor ceramic by co-doping aluminum ions, gallium ions and yttrium ions | |
| CN101337810B (en) | (MgZnCa)TiO3 microwave ceramic dielectric material and method for preparing same | |
| CN105859279A (en) | Novel process method for preparing zinc oxide piezoresistor ceramic with excellent properties | |
| CN102476949A (en) | Method for preparing electrical property-controllable zinc oxide (ZnO) piezoresistor material at low temperature | |
| CN103021608A (en) | High-gradient and high-capacity zinc oxide voltage dependent resistor disc and fabrication method thereof | |
| CN108546111A (en) | A kind of zinc oxide piezoresistor ceramic and preparation method thereof of high-voltage gradient, low residual voltage, low Leakage Current | |
| CN105601268B (en) | The preparation method of the zinc oxide piezoresistor ceramic of Universal electric function admirable | |
| CN105884345A (en) | High-voltage-gradient, low-residual-voltage and low-leakage-current ceramic and preparing method thereof | |
| CN107021751A (en) | A kind of high-potential gracient arrester zinc oxide piezoresistor ceramic | |
| CN105622087B (en) | A kind of system for ultra-high voltage transmission big discharge capacity, low residual voltage voltage-sensitive ceramic preparation method | |
| CN108439972A (en) | The excellent low residual voltage direct current varistor preparation method of ageing properties | |
| CN109704752B (en) | SnO (stannic oxide)2Piezoresistor and preparation method thereof | |
| CN105565801A (en) | Preparation method of high-gradient and large-discharge-current-capacity voltage-sensitive ceramics for ultra-high-voltage power transmission system | |
| CN102030522A (en) | Low-equilibrium temperature ZnO-Bi2O3 series voltage-sensitive ceramic dielectric | |
| Gromov et al. | Preparation of high-voltage ZnO varistor ceramics | |
| CN112094115A (en) | Manganese-zinc ferrite material with ultrahigh magnetic conductivity and preparation method thereof | |
| CN106653259A (en) | Preparation method of low residual voltage direct-current varistor with good aging properties | |
| CN105565800A (en) | Preparation method for voltage-sensitive ceramics used for ultrahigh-voltage power transmission system and having excellent comprehensive electrical performance | |
| CN106946561B (en) | Y3+、Nb5+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof | |
| CN116655368B (en) | Preparation method of resistor disc capable of improving high-current impact resistance | |
| CN110942875B (en) | Charge-loading-bin-capacity ceramic semiconductor device and method for manufacturing the same | |
| CN113603476B (en) | Preparation method and electrochemical test of multi-point electrode zinc oxide pressure-sensitive ceramic |
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 |