CN108218420A - A kind of titanium dioxide high pressure varistor and preparation method thereof - Google Patents

A kind of titanium dioxide high pressure varistor and preparation method thereof Download PDF

Info

Publication number
CN108218420A
CN108218420A CN201710379496.1A CN201710379496A CN108218420A CN 108218420 A CN108218420 A CN 108218420A CN 201710379496 A CN201710379496 A CN 201710379496A CN 108218420 A CN108218420 A CN 108218420A
Authority
CN
China
Prior art keywords
titanium dioxide
high pressure
hours
oxide
preparation
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
Application number
CN201710379496.1A
Other languages
Chinese (zh)
Other versions
CN108218420B (en
Inventor
李文联
李杨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangyang Tte Electric Co ltd
Original Assignee
Hubei University of Arts and Science
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hubei University of Arts and Science filed Critical Hubei University of Arts and Science
Priority to CN201710379496.1A priority Critical patent/CN108218420B/en
Publication of CN108218420A publication Critical patent/CN108218420A/en
Application granted granted Critical
Publication of CN108218420B publication Critical patent/CN108218420B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B35/46—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 titanium oxides or titanates
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/115—Titanium dioxide- or titanate type
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, 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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates 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
    • C04B2235/3294—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
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
    • 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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The present invention relates to a kind of preparation method of piezoresistor, spy is related to a kind of titanium dioxide high pressure varistor and preparation method thereof.The titanium dioxide high pressure varistor of the present invention is using titanium dioxide as main material, improve the nonlinear factor and dielectric constant of piezoresistor, reduce dielectric loss, by adding zinc oxide, bismuth oxide auxiliary material, the electric potential gradient of piezoresistor is improved, and add the auxiliary materials such as titanium dioxide violent, antimony oxide, nickel protoxide, cobalt oxide, silicon carbide, chromium oxide, boron glass powder to improve the electric properties such as the square wave discharge capacity, high current tolerance, aging coefficient of piezoresistor.Titanium dioxide high pressure varistor of the present invention has the characteristics that electric potential gradient is high, sintering time is short, lower-cost.

Description

A kind of titanium dioxide high pressure varistor and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of piezoresistor, spy be related to a kind of titanium dioxide high pressure varistor and Preparation method.
Background technology
At present, common piezoresistor is mostly zinc oxide varistor on the market, and zinc oxide varistor is A kind of nonlinear device is the core devices for making arrester, but performance parameter is more difficult to control during production, and production technology is more multiple It is miscellaneous, while the sintering time of production process is longer, manufacture cost is also higher.
Titanium dioxide piezoresistor dielectric with higher nonlinear factor, superelevation compared with Zinc-oxide piezoresistor Constant, relatively low dielectric loss.But existing formula and manufacturing process, make titanium dioxide piezoresistor electric potential gradient compared with Low, generally less than 200V/mm is thus not suitable for making high pressure（High-potential gracient）Piezoresistor.
Invention content
The purpose of the present invention is to provide a kind of preparation method of titanium dioxide high pressure varistor, by with titanium dioxide Titanium is main material, improves the nonlinear factor and dielectric constant of piezoresistor, reduces dielectric loss, by add zinc oxide, Bismuth oxide auxiliary material, improves the electric potential gradient of piezoresistor, and adds violent titanium dioxide, antimony oxide, nickel protoxide, oxidation The auxiliary materials such as cobalt, silicon carbide, chromium oxide, boron glass powder improve the square wave discharge capacity of piezoresistor, high current tolerance, old Change the electric properties such as coefficient.
The technical scheme is that：A kind of preparation method of titanium dioxide high pressure varistor, it is characterised in that：Packet Include following steps：
Step 1: by titanium dioxide 75-79.1%, zinc oxide 10-14.1%, bismuth oxide 2.2-2.226%, the violent 0.3- of titanium dioxide 0.369%, antimony oxide 0.5-0.569%, nickel protoxide 2.1-2.133%, cobalt oxide 1.2-1.268%, silicon carbide 1.2- 1.263%, chromium oxide 0.4-0.439%, boron glass powder 3-3.2% mixing, the titanium dioxide and zinc oxide use nano powder Material, nanopowder grain size concentrate below 100nm；
Step 2: the mixture to step 1 is ground, the pasty material after grinding is screened；
Step 3: the step of pressure spray drying granulation：Using pressure atomizer by the pressure of diaphragm pump by step 2 Pasty material after separation is atomized into fine droplets, it is then dried through carrying out heat exchange with hot wind, 90 μm of grain size average out to is made ~115 μm of hollow ball-shape, the fine particle that residual moisture is less than 0.5%；
Step 4: two-way floating pressurizes the step of compression moulding：Upper and lower ends are pressurizeed during punching press, toward intermediate compression；
Step 5: the step of sintering：Temperature is risen to 800 DEG C in 1.5 to 2.5 hours under room temperature, then slowly heats up 2 hours extremely Temperature is made to rise to 1300 DEG C -1350 DEG C within 2.5 hours, in 1300 DEG C of -1350 DEG C of temperature range inside holdings 2 hours, then slow cooling 2 Hour made temperature be down to about 900 DEG C to 2.5 hours, then natural fast cooling is to room temperature.
According to the preparation method of titanium dioxide high pressure varistor as described above, it is characterised in that：It further includes to burning The end surfaces up and down of ceramic product after system are ground processing, make its surface smooth, then carry out coating aluminium or silver electrode, painting The step of insulated paint, detection.
According to the preparation method of titanium dioxide high pressure varistor as described above, it is characterised in that：It, will in step 2 Material more than 60 mesh is isolated.
According to the preparation method of titanium dioxide high pressure varistor as described above, it is characterised in that：In step 2, adopt The mixture of step 1 is ground 4-5 hours with vertical mixing ball-milling method.
A kind of titanium dioxide high pressure varistor, it is characterised in that：It the ratio of each component is according to weight percent：Two Titanium oxide 75-79.1%, zinc oxide 10-14.1%, bismuth oxide 2.2-2.226%, the violent 0.3-0.369% of titanium dioxide, antimony oxide 0.5-0.569%, nickel protoxide 2.1-2.133%, cobalt oxide 1.2-1.268%, silicon carbide 1.2-1.263%, chromium oxide 0.4- 0.439%, boron glass powder 3-3.2%.
According to titanium dioxide high pressure varistor as described above, it is characterised in that：Titanium dioxide high voltage varistor Device for diameter range 20mm-80mm, thickness range 10mm-50mm cylinder.
According to titanium dioxide high pressure varistor as described above, it is characterised in that：Its manufacturing process includes following step Suddenly：Step 1: the titanium dioxide and zinc oxide, using nanopowder, nanopowder grain size concentrates on 100nm hereinafter, and will Each component mixing；
Step 2: the mixture to step 1 is ground, the pasty material after grinding is screened；
Step 3: the step of pressure spray drying granulation：Using pressure atomizer by the pressure of diaphragm pump by step 2 Pasty material after separation is atomized into fine droplets, is then dried through carrying out heat exchange with hot wind, 90 μm of grain size average out to is made ~115 μm of hollow ball-shape, the fine particle that residual moisture is less than 0.5%；
Step 4: two-way floating pressurizes the step of compression moulding：Upper and lower ends are pressurizeed during punching press, toward intermediate compression；
Step 5: the step of sintering：Temperature is risen to 800 DEG C in 1.5 to 2.5 hours under room temperature, then slowly heats up 2 hours extremely Temperature is made to rise to 1300 DEG C -1350 DEG C within 2.5 hours, in 1300 DEG C of -1350 DEG C of temperature range inside holdings 2 hours, then slow cooling 2 Hour made temperature be down to about 900 DEG C to 2.5 hours, then natural fast cooling is to room temperature.
According to the preparation method of titanium dioxide high pressure varistor as described above, it is characterised in that：It, will in step 2 Material more than 60 mesh is isolated.
According to the preparation method of titanium dioxide high pressure varistor as described above, it is characterised in that：In step 2, adopt The mixture of step 1 is ground 4-5 hours with vertical mixing ball-milling method.
The beneficial effects of the invention are as follows：First, electric potential gradient is high, allow the resistor of the present invention as the pressure-sensitive electricity of high pressure Hinder device；Second is that sintering time is short, cost is relatively low；Third, improve the square wave discharge capacity of piezoresistor, high current tolerance, The electric properties such as aging coefficient.
Description of the drawings
Fig. 1 is sintering temperature curve figure.
Specific embodiment
Technical scheme of the present invention is described further below.
The formula of titanium dioxide high pressure varistor of the present invention is according to the proportioning of weight percent：Titanium dioxide 75- 79.1%, zinc oxide 10-14.1%, bismuth oxide 2.2-2.226%, titanium dioxide violent 0.3-0.369%, antimony oxide 0.5- 0.569%, nickel protoxide 2.1-2.133%, cobalt oxide 1.2-1.268%, silicon carbide 1.2-1.263%, chromium oxide 0.4-0.439%, Boron glass powder 3-3.2%.The titanium dioxide high pressure varistor of the present invention is by using titanium dioxide as main material, improving pressure-sensitive The nonlinear factor and dielectric constant of resistor reduce dielectric loss, by adding zinc oxide, bismuth oxide auxiliary material, improve pressure-sensitive The electric potential gradient of resistor, and add that titanium dioxide is violent, antimony oxide, nickel protoxide, cobalt oxide, silicon carbide, chromium oxide, boron glass The auxiliary materials such as glass powder improve the electric properties such as the square wave discharge capacity, high current tolerance, aging coefficient of piezoresistor.
The preparation method of the titanium dioxide high pressure varistor of the present invention is to include the following steps：
Step 1: by titanium dioxide 75-79.1%, zinc oxide 10-14.1%, bismuth oxide 2.2-2.226%, the violent 0.3- of titanium dioxide 0.369%, antimony oxide 0.5-0.569%, nickel protoxide 2.1-2.133%, cobalt oxide 1.2-1.268%, silicon carbide 1.2- 1.263%, chromium oxide 0.4-0.439%, boron glass powder 3-3.2% mixing, titanium dioxide and zinc oxide are preferably with receiving in this step Rice flour material, nanopowder grain size concentrate on 100nm hereinafter, using made of titanium dioxide and zinc oxide of the grain size less than 100nm Resistor, evenly, 2ms square waves discharge capacity reaches more than 3000A to microstructure, and 4/10 μ s high current tolerances are more than 100kA.Other auxiliary material raw materials use common powder, through dry vibration（4-6h）And sieving（150-200 mesh）It is disposable after processing It adds in and is uniformly mixed.
Step 2: the mixture of step 1 is ground 4-5 hours using vertical mixing ball-milling method, to the slurry after grinding Shape material is screened, and the material that will be greater than 60 mesh is isolated, and the substance isolated can re-grind or as waste disposal.
Step 3: the step of pressure spray drying granulation：It will be walked by the pressure of diaphragm pump using pressure atomizer It is rapid two separation after pasty material be atomized into fine droplets, significantly increase surface area, through with hot wind carry out sufficient heat exchange and Rapid draing afterwards, so as to which the hollow ball-shape of 90~115 μm of grain size average out to be made, residual moisture be tiny of less than 0.5% Grain, the material particles generated after step 3 manufacture are small, and water content is low, is easy to subsequent step in this way by material compression moulding.
Step 4: two-way floating pressurizes the step of compression moulding：Upper and lower ends are pressurizeed during punching press, toward intermediate compression, mesh Be that compacting is uniform, this step is compressed to routine techniques.The material of step 3 can be pressed by this step according to actual demand Various sizes of piezoresistive wafer, piezoresistive wafer after molding can be that diameter range exists in 20mm-80mm, thickness range The cylinder of 10mm-50mm.
Step 5: under atmospheric air atmosphere, the product of compression moulding is burnt at 1300 DEG C -1350 DEG C of maximum temperature Knot, sintering time about 8 hours make it be fired into ceramics, and sintering process and temperature are：It will be warm in 1.5 to 2.5 hours under room temperature Degree rises to about 800 DEG C, then slowly heating makes temperature rise to 1300 DEG C -1350 DEG C in 2 hours to 2.5 hours, at 1300 DEG C -1350 DEG C Temperature range inside holding 2 hours, then slow cooling make temperature be down to about 900 DEG C, then natural fast cooling for 2 hours to 2.5 hours To room temperature.Specific sintering temperature curve is shown in attached drawing 1.Slow heating and slow temperature-fall period in this step can prevent from bursting, Insulating process can ensure the formation of internal grain, and can improve the property indices of resistor.
Step 6: the end surfaces up and down to the ceramic product after firing are ground processing, make its surface smooth, Ran Houjin Row coating aluminium or silver electrode apply the technological processes such as insulated paint, detection, the processing mode of step 6 and existing processing mode one Sample.
The beneficial effects of the present invention are：The titanium dioxide high pressure pressure formed by above-mentioned formula and manufacturing process Sensitive resistor has higher nonlinear factor（Nonlinear factor >=13）, superelevation dielectric constant（Dielectric constant >= 160000）, relatively low dielectric loss（Dielectric loss≤0.32）Higher electric potential gradient（Electric potential gradient >=400V/mm）, make Titanium dioxide can be applicable to the manufacturing field of high pressure varistor.And preparation process is simple, and production cost is low.Meanwhile this Invention is also short with sintering time, and sintering time is can be controlled in eight hours or so, and the burning of conventional zinc oxide varistor It is more than 20 hours to tie the time, so as to reduce the manufacture cost of product of the present invention.

Claims (9)

1. a kind of preparation method of titanium dioxide high pressure varistor, it is characterised in that：Include the following steps：
Step 1: by titanium dioxide 75-79.1%, zinc oxide 10-14.1%, bismuth oxide 2.2-2.226%, the violent 0.3- of titanium dioxide 0.369%, antimony oxide 0.5-0.569%, nickel protoxide 2.1-2.133%, cobalt oxide 1.2-1.268%, silicon carbide 1.2- 1.263%, chromium oxide 0.4-0.439%, boron glass powder 3-3.2% mixing, the titanium dioxide and zinc oxide use nano powder Material, nanopowder grain size concentrate below 100nm；
Step 2: the mixture to step 1 is ground, the pasty material after grinding is screened；
Step 3: the step of pressure spray drying granulation：Using pressure atomizer by the pressure of diaphragm pump by step 2 Pasty material after separation is atomized into fine droplets, is then dried through carrying out heat exchange with hot wind, 90 μm of grain size average out to is made ~115 μm of hollow ball-shape, the fine particle that residual moisture is less than 0.5%；
Step 4: two-way floating pressurizes the step of compression moulding：Upper and lower ends are pressurizeed during punching press, toward intermediate compression；
Step 5: the step of sintering：Temperature is risen to 800 DEG C in 1.5 to 2.5 hours under room temperature, then slowly heats up 2 hours extremely Temperature is made to rise to 1300 DEG C -1350 DEG C within 2.5 hours, in 1300 DEG C of -1350 DEG C of temperature range inside holdings 2 hours, then slow cooling 2 Hour made temperature be down to about 900 DEG C to 2.5 hours, then natural fast cooling is to room temperature.
2. the preparation method of titanium dioxide high pressure varistor according to claim 1, it is characterised in that：It further includes pair The end surfaces up and down of ceramic product after firing are ground processing, make its surface smooth, then carry out coating aluminium or silver electrode, The step of applying insulated paint, detection.
3. the preparation method of titanium dioxide high pressure varistor according to claim 1, it is characterised in that：Step 2 In, the material that will be greater than 60 mesh is isolated.
4. the preparation method of titanium dioxide high pressure varistor according to claim 1, it is characterised in that：Step 2 In, the mixture of step 1 is ground 4-5 hours using vertical mixing ball-milling method.
5. a kind of titanium dioxide high pressure varistor, it is characterised in that：It the ratio of each component is according to weight percent：Dioxy Change titanium 75-79.1%, zinc oxide 10-14.1%, bismuth oxide 2.2-2.226%, the violent 0.3-0.369% of titanium dioxide, antimony oxide 0.5-0.569%, nickel protoxide 2.1-2.133%, cobalt oxide 1.2-1.268%, silicon carbide 1.2-1.263%, chromium oxide 0.4- 0.439%, boron glass powder 3-3.2%.
6. titanium dioxide high pressure varistor according to claim 5, it is characterised in that：The pressure-sensitive electricity of titanium dioxide high pressure Hinder device for diameter range 20mm-80mm, thickness range 10mm-50mm cylinder.
7. titanium dioxide high pressure varistor according to claim 5, it is characterised in that：Its manufacturing process includes following Step：Step 1: the titanium dioxide and zinc oxide, using nanopowder, nanopowder grain size concentrates on 100nm hereinafter, simultaneously By each component mixing；
Step 2: the mixture to step 1 is ground, the pasty material after grinding is screened；
Step 3: the step of pressure spray drying granulation：Using pressure atomizer by the pressure of diaphragm pump by step 2 Pasty material after separation is atomized into fine droplets, through, into heat exchange is divided then to dry, 90 μm of grain size average out to being made with hot wind ~115 μm of hollow ball-shape, the fine particle that residual moisture is less than 0.5%；
Step 4: two-way floating pressurizes the step of compression moulding：Upper and lower ends are pressurizeed during punching press, toward intermediate compression；
Step 5: the step of sintering：Temperature is risen to 800 DEG C in 1.5 to 2.5 hours under room temperature, then slowly heats up 2 hours extremely Temperature is made to rise to 1300 DEG C -1350 DEG C within 2.5 hours, in 1300 DEG C of -1350 DEG C of temperature range inside holdings 2 hours, then slow cooling 2 Hour made temperature be down to about 900 DEG C to 2.5 hours, then natural fast cooling is to room temperature.
8. the preparation method of titanium dioxide high pressure varistor according to claim 5, it is characterised in that：Step 2 In, the material that will be greater than 60 mesh is isolated.
9. the preparation method of titanium dioxide high pressure varistor according to claim 5, it is characterised in that：Step 2 In, the mixture of step 1 is ground 4-5 hours using vertical mixing ball-milling method.
CN201710379496.1A 2017-05-25 2017-05-25 Titanium dioxide high-voltage piezoresistor and preparation method thereof Active CN108218420B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710379496.1A CN108218420B (en) 2017-05-25 2017-05-25 Titanium dioxide high-voltage piezoresistor and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710379496.1A CN108218420B (en) 2017-05-25 2017-05-25 Titanium dioxide high-voltage piezoresistor and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108218420A true CN108218420A (en) 2018-06-29
CN108218420B CN108218420B (en) 2020-11-20

Family

ID=62656598

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710379496.1A Active CN108218420B (en) 2017-05-25 2017-05-25 Titanium dioxide high-voltage piezoresistor and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108218420B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108947521A (en) * 2018-09-20 2018-12-07 华蓥市职业教育培训中心 A kind of preparation method of piezoresistive material

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60107804A (en) * 1983-11-17 1985-06-13 松下電器産業株式会社 Voltage dependent nonlinear resistor porcelain composition
JPS6243110A (en) * 1985-08-21 1987-02-25 太陽誘電株式会社 Ceramic composition for varistor
JP2000243608A (en) * 1999-02-18 2000-09-08 Atsushi Iga Zinc oxide varistor and manufacture thereof
CN101714439A (en) * 2009-12-22 2010-05-26 中国科学院宁波材料技术与工程研究所 Zinc oxide resistance piece and preparation method thereof
CN102515742A (en) * 2011-12-15 2012-06-27 中国科学院过程工程研究所 High potential gradient zinc oxide pressure-sensitive resistor material and preparation process thereof
CN102584210A (en) * 2012-02-07 2012-07-18 上海海事大学 Preparation method for high-voltage TiO2 ring varistor
CN104051100A (en) * 2014-06-23 2014-09-17 中国地质大学（北京） Titanium oxide multilayer thin film varistor and preparation method for same
CN104557016A (en) * 2013-10-18 2015-04-29 湖北文理学院 High-nonlinearity frit doped zinc oxide voltage-sensitive ceramic material
CN106495685A (en) * 2016-09-19 2017-03-15 昆明理工大学 A kind of TiO2The preparation method of voltage-sensitive ceramic

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60107804A (en) * 1983-11-17 1985-06-13 松下電器産業株式会社 Voltage dependent nonlinear resistor porcelain composition
JPS6243110A (en) * 1985-08-21 1987-02-25 太陽誘電株式会社 Ceramic composition for varistor
JP2000243608A (en) * 1999-02-18 2000-09-08 Atsushi Iga Zinc oxide varistor and manufacture thereof
CN101714439A (en) * 2009-12-22 2010-05-26 中国科学院宁波材料技术与工程研究所 Zinc oxide resistance piece and preparation method thereof
CN102515742A (en) * 2011-12-15 2012-06-27 中国科学院过程工程研究所 High potential gradient zinc oxide pressure-sensitive resistor material and preparation process thereof
CN102584210A (en) * 2012-02-07 2012-07-18 上海海事大学 Preparation method for high-voltage TiO2 ring varistor
CN104557016A (en) * 2013-10-18 2015-04-29 湖北文理学院 High-nonlinearity frit doped zinc oxide voltage-sensitive ceramic material
CN104051100A (en) * 2014-06-23 2014-09-17 中国地质大学（北京） Titanium oxide multilayer thin film varistor and preparation method for same
CN106495685A (en) * 2016-09-19 2017-03-15 昆明理工大学 A kind of TiO2The preparation method of voltage-sensitive ceramic

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108947521A (en) * 2018-09-20 2018-12-07 华蓥市职业教育培训中心 A kind of preparation method of piezoresistive material

Also Published As

Publication number Publication date
CN108218420B (en) 2020-11-20

Similar Documents

Publication Publication Date Title
CN106376107B (en) High-power silicon nitride ceramic heating plate and manufacturing method of high-power silicon nitride ceramic heating plate with soft inside and hard outside
CN105174972B (en) A kind of preparation method of glass/ceramic nano composite material
CN108329033A (en) Liquid-phase sintering multichannel silicon carbide ceramics membrane component and preparation method thereof
KR20170058048A (en) Forming Method of MgAl2O4 Spinel
CN101747078B (en) Making method for sintering high-purity silicon carbide honeycomb ceramics by using nanometer silicon carbide as auxiliary
CN108218420A (en) A kind of titanium dioxide high pressure varistor and preparation method thereof
CN105174936B (en) Production process of zinc oxide resistance chip with high electric potential gradient and strong through-current capability
CN104926301B (en) Piezoelectric device
CN104240876B (en) Nonlinear resistor
CN105541319A (en) Microwave dielectric ceramic material with medium-high dielectric constant and preparation method thereof
CN105565805A (en) Composite ceramic material preparation method
CN102260074A (en) High-temperature negative temperature coefficient (NTC) material and preparation method thereof
CN101913857A (en) Method for preparing high-gradient, high-dielectric and low-loss pressure-sensitive material
CN112335001B (en) Ceramic material, varistor and method for producing the ceramic material and varistor
CN114195490A (en) Preparation method of ceramic resistor, ceramic resistor and electronic circuit device
CN116655368B (en) Preparation method of resistor disc capable of improving high-current impact resistance
CN106116573A (en) A kind of pulse power capacitor device antiferroelectric ceramics powder body and preparation method thereof
CN1313609A (en) Oxidized magnetic material, sheet components therewith and production thereof
CN104722751A (en) Flaky platinum powder, and preparation method and application thereof
CN113999001B (en) Burning bearing plate and preparation method and application thereof
JP3210063B2 (en) Power resistor
JP2942027B2 (en) Method of manufacturing voltage non-linear resistor
JP2001284039A (en) Manufacturing method of simple furnace and sintered body
JPH048921B2 (en)
JPH0253924B2 (en)

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Li Yang

Inventor after: Li Wenlian

Inventor before: Li Wenlian

Inventor before: Li Yang

GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20220601

Address after: 441200 intersection of national highway 316 and Qianjin Road, west suburb of Zaoyang City, Xiangyang City, Hubei Province

Patentee after: XIANGYANG TTE ELECTRIC CO.,LTD.

Address before: 441053 Luzhong Road, Xiangcheng District, Xiangfan, Hubei Province, No. 296

Patentee before: HUBEI University OF ARTS AND SCIENCE