CN114133236A - Preparation method of zinc oxide piezoresistor based on chemical precipitation method - Google Patents

Preparation method of zinc oxide piezoresistor based on chemical precipitation method Download PDF

Info

Publication number
CN114133236A
CN114133236A CN202111468009.1A CN202111468009A CN114133236A CN 114133236 A CN114133236 A CN 114133236A CN 202111468009 A CN202111468009 A CN 202111468009A CN 114133236 A CN114133236 A CN 114133236A
Authority
CN
China
Prior art keywords
powder
zinc oxide
preparation
chemical precipitation
temperature
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.)
Pending
Application number
CN202111468009.1A
Other languages
Chinese (zh)
Inventor
董曼玲
程思远
张科
郭磊
张洋
姚伟
郭培
王超凡
张小旋
赵贤根
何俊佳
许贺军
赵明
鲁永
郭洁
刘文凤
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.)
Huazhong University of Science and Technology
State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
Original Assignee
Huazhong University of Science and Technology
State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
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 Huazhong University of Science and Technology, State Grid Corp of China SGCC, Electric Power Research Institute of State Grid Henan Electric Power Co Ltd filed Critical Huazhong University of Science and Technology
Priority to CN202111468009.1A priority Critical patent/CN114133236A/en
Publication of CN114133236A publication Critical patent/CN114133236A/en
Pending legal-status Critical Current

Links

Images

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
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/28—Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals
    • H01C17/288—Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals by thin film techniques
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/30—Apparatus or processes specially adapted for manufacturing resistors adapted for baking
    • 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
    • H01C7/112—ZnO 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
    • C04B2235/3294—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • 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)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a preparation method of a zinc oxide piezoresistor based on a chemical precipitation method, which comprises the following steps: s1, dissolving the weighed raw materials by using ethylene glycol to form a mixed solution, dripping NaOH solution into the mixed solution to obtain a precipitate, filtering the precipitate, and washing; s2, drying the precipitate in a dryer, grinding the dried precipitate, and sieving the ground precipitate with a 60-mesh sieve; s3, adding a polyvinyl alcohol aqueous solution into the precipitate, mixing, drying, grinding, sieving with a 60-mesh sieve, and granulating; s4, spraying deionized water into the granulated powder, shaking up, standing and tabletting; s5, sintering the pressed sheet, and cooling to room temperature to obtain a sample; s6, finely grinding the sample, placing the sample in an ultrasonic cleaning machine for ultrasonic cleaning, and drying; and S7, coating a gold electrode on the surface of the dried sample to obtain the zinc oxide piezoresistor. The preparation method effectively realizes the uniform mixing of the ZnO powder and the doped metal oxide, so that the ZnO piezoresistor has more uniform microstructure in microscopic grains and more excellent electrical property, and can meet the development requirement of an extra-high voltage power grid.

Description

Preparation method of zinc oxide piezoresistor based on chemical precipitation method
Technical Field
The invention belongs to the technical field of electronic ceramic device preparation, and particularly relates to a preparation method of a zinc oxide piezoresistor based on a chemical precipitation method.
Background
The ZnO varistor is a functional ceramic material which is sintered by taking ZnO powder as a main material and doping a small amount of various metal oxides, and has the advantages of high nonlinear index, high transient energy absorption capacity, low price of raw materials and the like. The ZnO varistor can keep very small conductivity or dielectric constant under the action of a low electric field, is equivalent to an insulating material, shows very large conductivity and dielectric constant under the action of a high electric field, avoids high partial pressure of protected insulating equipment, and realizes effective modulation on uneven distribution of a space electric field. The arrester manufactured based on the ZnO varistor is widely applied to the aspects of transient overvoltage protection, contact arc extinction, voltage stabilization and the like of power systems of various voltage levels, and protects electrical equipment from being damaged by various overvoltages.
With the continuous improvement of the voltage grade of the domestic ultrahigh voltage transmission line, the overvoltage problem of the power system is increasingly prominent, the overvoltage needs to be effectively limited to protect the insulation of high-voltage equipment from being damaged, and further, the more severe requirements on the performance of the ZnO piezoresistor are provided. According to the traditional ceramic formula and the traditional ceramic process, ZnO original powder and various metal oxides needing to be doped are subjected to ball milling and mixing in a physical mode, the voltage-dependent voltage gradient of the prepared ZnO piezoresistor is only about 220V/mm, if the ZnO piezoresistor is used for an extra-high voltage arrester, the height, the volume and the weight of the arrester are greatly increased, the production and transportation are not facilitated, particularly, the potential distribution uniformity of the arrester is difficult to control, and the requirements of the development of a current power system on the ZnO piezoresistor cannot be met.
At present, the performance optimization and improvement effect of ZnO voltage dependent resistor by changing the doping formula and adjusting the traditional preparation processIf the voltage is limited, the effective regulation and control of the ZnO voltage-sensitive resistance is difficult to realize. For example, chinese patent publication No. CN105585316A discloses a method for preparing a ZnO varistor, which specifically comprises the following steps: mixing Mn (CH)3COO)2·4H2O、CO(NO3)2·6H2O、Cr(NO3)3·9H2O and Al (NO)3)3·9H2Mixing O and the like to obtain sol; aging, placing in an oven to prepare dry gel, and then firing to obtain composite nano additive powder; according to 83 percent of ZnO and 3.2 percent of Sb2O3And 13.8 percent of the composite nano additive is added, and the mixture is placed in a ball milling tank for ball milling and drying to obtain powder for the ZnO piezoresistor; using w (PVA) as 6% adhesive, according to m (PVA): granulating with m (powder) of 15%, pressing into a blank sheet, sintering to obtain the ZnO varistor. According to the method, two processes of doping and sintering temperature in the preparation process of the ZnO varistor are improved, and although the uniformity of the microstructure of the ZnO varistor is improved to a certain extent, the ZnO varistor prepared by the method is low in electrical performance and cannot be suitable for an extra-high voltage arrester.
Based on the background, the influence of various properties of a ZnO compound matrix or filler on the overall nonlinear characteristic of the compound is researched, the effective regulation and control of the nonlinear performance of the ZnO piezoresistor are realized by a new means, and the ZnO piezoresistor with high gradient, high flow capacity, high reliability and excellent aging resistance is further prepared.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a preparation method of a zinc oxide piezoresistor based on a chemical precipitation method. The preparation method effectively realizes the uniform mixing of the ZnO original powder and the metal oxide to be doped, so that the performance of the sintered piezoresistor in a microscopic grain structure and a grain boundary is more uniform, and more excellent electrical performance is obtained, thereby meeting the development requirement of an extra-high voltage power grid.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a zinc oxide piezoresistor based on a chemical precipitation method comprises the following steps:
(1) weighing raw materials: weighing the raw materials by using an electronic balance for later use;
(2) chemical precipitation and mixing: keeping the total volume of the reaction solution to be 800ml unchanged, dissolving the raw materials weighed in the step (1) by using a proper amount of glycol to form a mixed solution, and heating while stirring; then dissolving a certain amount of NaOH in a proper amount of deionized water, dripping the NaOH into the mixed solution at a certain speed until the pH value in the mixed solution is maintained at 9-10, reacting for 2 hours, precipitating and filtering, and then washing precipitates with deionized water for several times to obtain mixed slurry for later use;
(3) drying and sieving: placing the mixed slurry washed in the step (2) in an enamel tray, then placing the enamel tray in a blast drier for drying, placing the powder into a mortar for full grinding after complete drying, and sieving the powder by a 60-mesh sieve;
(4) and (3) granulation: adding the powder with the mass fraction of 2% and a polyvinyl alcohol aqueous solution with the mass concentration of 3% into the powder sieved in the step (3), then uniformly stirring and mixing, drying, and grinding again through a 60-mesh screen for granulation;
(5) tabletting: spraying a proper amount of deionized water into the powder granulated in the step (4), shaking the powder uniformly, standing the powder containing water for 6 hours, and pressing the powder into a wafer by using a tablet press;
(6) and (3) sintering: putting the wafer powder pressed in the step (5) into a high-temperature sintering furnace for presintering and sintering, and cooling to room temperature after sintering to obtain a sample for later use;
(7) ultrasonic cleaning: firstly, carrying out coarse grinding on the surface of the sample obtained in the step (6) by using a water grinding disc, then carrying out fine grinding by using abrasive paper, finally placing the fine-ground sample in absolute ethyl alcohol, placing the absolute ethyl alcohol into an ultrasonic cleaning machine, carrying out ultrasonic cleaning for 10min, and drying the sample for later use after the ultrasonic cleaning is finished;
(8) spraying gold: and (4) coating a gold electrode on the surface of the sample dried in the step (7) by using a coating instrument to obtain the zinc oxide piezoresistor.
Further, the raw materials in the step (1) comprise the following components in mole fraction: 86.36% ZnO, 11.42% Bi (NO)3)3·5H2O、0.6％Co(NO3)2·6H2O、0.02％Cr(NO3)3·9H2O、0.49％Mn((NO3)·4H2O、0.36％Ni((NO3)2·6H2O and 0.75% SbCl3。
Further, the volume ratio of the ethylene glycol to the deionized water in the step (2) is 1.9:1-2.1: 1.
Further, the temperature for stirring and heating in the step (2) is 80-90 ℃.
Further, the drying temperature of the forced air dryer in the step (3) is 65-70 ℃, and the drying time is 1-2 h.
Further, the conditions of the sheet pressing molding in the step (5) are as follows: the tabletting pressure is 12-15MPa, and the tabletting pressure maintaining time is 20-25 s.
Further, the diameter of the wafer pressed in the step (5) is 12-15 mm, and the thickness of the wafer is 1.5-2.0 mm.
Further, the pre-sintering temperature in the step (6) is 600-.
Further, the specific method for sintering in the step (6) is as follows: firstly, the temperature in the high-temperature sintering furnace is increased to 900 ℃ at the heating rate of 2 ℃/min, then the temperature in the high-temperature sintering furnace is increased to 1050 ℃ at the heating rate of 1 ℃/min from 900 ℃, the heat preservation time is 2-2.5h, and the high-temperature sintering furnace is cooled to the room temperature along with the furnace.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) the invention adopts a chemical precipitation method to mix ZnO original powder with metal oxide (such as Bi) required to be doped2O3、Sb2O3、MnO2、Cr2O3And Co2O3) The volume ratio of the added glycol to the deionized water in the chemical precipitation method is strictly controlled to ensure that the mixture is dopedThe metal ions can be deposited on the surfaces of ZnO particles to form a layer of film, and the film is coprecipitated with ZnO to form powder, so that the metal ions can be rapidly diffused to the surfaces of crystal grains and form a Bi-rich phase during sintering, the performance of the crystal grains is more stable, impurity ions in crystal boundaries are reduced, the particle size distribution of a ZnO sample is concentrated, the surface energy of the particles is larger, the electrical performance of the ZnO varistor is further improved, the voltage gradient is improved by 42%, and the nonlinear coefficient is improved by 1.3 times.
(2) The sintering temperature in the preparation method is obviously lower than that of the traditional solid phase synthesis process, the energy consumption is reduced, and the preparation method has the advantages of simple process, easy control and low cost.
Drawings
FIG. 1 is a process flow diagram of the manufacturing process of the present invention;
FIG. 2 is a graph showing the grain size distribution of a ZnO sample prepared by the chemical precipitation method of the present invention;
fig. 3 is a graph of grain size distribution of ZnO samples prepared by a conventional method.
Detailed Description
The invention is further described below with reference to the figures and examples.
Example 1
A preparation method of a zinc oxide piezoresistor based on a chemical precipitation method comprises the following steps:
(1) weighing raw materials: the method comprises the following steps of weighing various components of the raw materials by adopting an electronic balance scale with the precision of 0.001 g: 86.36g ZnO, 11.42g Bi (NO)3)3·5H2O、0.6g Co(NO3)2·6H2O、0.02g Cr(NO3)3·9H2O、0.49g Mn((NO3)·4H2O、0.36g Ni((NO3)2·6H2O and 0.75g of SbCl3；
(2) Chemical precipitation and mixing: keeping the total volume of the reaction solution to be 800ml unchanged, dissolving the raw materials weighed in the step (1) by using 533.3ml of ethylene glycol to form a mixed solution, continuously stirring by using a magnetic stirrer, and simultaneously heating to 90 ℃; then, 266.6ml of deionized water is used for dissolving 5g of NaOH, the NaOH solution is dripped into the mixed solution according to a certain speed until the pH value in the mixed solution is maintained at 10, precipitation filtration is carried out after 2 hours of reaction, and then deionized water is used for washing precipitates for a plurality of times to obtain mixed slurry for later use;
(3) drying and sieving: placing the mixed slurry washed in the step (2) in an enamel tray, then placing the tray in a DHG-9146A type electric heating constant-temperature air blast dryer for drying at the temperature of 70 ℃ for 1h, placing the powder in a mortar for full grinding after the powder is completely dried, and sieving the powder by a 60-mesh sieve;
(4) and (3) granulation: adding the powder with the mass fraction of 2% and a polyvinyl alcohol aqueous solution with the mass concentration of 3% into the powder sieved in the step (3), then uniformly stirring and mixing, drying, and grinding again through a 60-mesh screen for granulation;
(5) tabletting: spraying deionized water for 5-6 times to the powder granulated in the step (4), shaking the powder uniformly, standing the powder containing water for 6 hours, pressing the powder into a wafer by using a DY-30 table type automatic tablet press, wherein the pressure in the tabletting process is 15MPa, the pressure maintaining time is 20s, the diameter of the pressed sample wafer is 12mm, and the thickness of the pressed sample wafer is 2.0 mm;
(6) and (3) sintering: putting the wafer powder pressed in the step (5) into a high-temperature sintering furnace for pre-sintering, setting the pre-sintering temperature of the high-temperature sintering furnace to be 600 ℃, preserving heat for 2 hours, and cooling along with the furnace; then adopting a high-temperature sintering furnace with the same type as the presintering furnace, setting the heating rate to be 2 ℃/min, heating the temperature of the high-temperature sintering furnace to 900 ℃, then heating the temperature of the high-temperature sintering furnace to 1000 ℃ from 900 ℃ at the heating rate of 1 ℃/min, preserving the heat for 2.5 hours at 1000 ℃, and cooling the sintered powder to room temperature along with the furnace to obtain a sample for later use;
(7) ultrasonic cleaning: firstly, carrying out coarse grinding on the surface of the sample obtained in the step (6) by using a water grinding disc, then carrying out fine grinding by using sand paper, finally placing the fine-ground sample in absolute ethyl alcohol, carrying out ultrasonic cleaning for 10min by using an ultrasonic cleaning machine with the model of KQ-300DE, and fully drying for later use after the ultrasonic cleaning is finished;
(8) spraying gold: and (4) coating a gold electrode on the surface of the sample dried in the step (7) by using a Q150RPLUS series coating machine to obtain the zinc oxide piezoresistor.
Example 2
A preparation method of a zinc oxide piezoresistor based on a chemical precipitation method comprises the following steps:
(1) weighing raw materials: the method comprises the following steps of weighing various components of the raw materials by adopting an electronic balance scale with the precision of 0.001 g: 86.36g ZnO, 11.42g Bi (NO)3)3·5H2O、0.6g Co(NO3)2·6H2O、0.02g Cr(NO3)3·9H2O、0.49g Mn((NO3)·4H2O、0.36g Ni((NO3)2·6H2O and 0.75g of SbCl3；
(2) Chemical precipitation and mixing: keeping the total volume of the reaction solution to be 800ml unchanged, dissolving the raw materials weighed in the step (1) by using 524.1ml of ethylene glycol to form a mixed solution, continuously stirring by using a magnetic stirrer, and simultaneously heating to 80 ℃; then 275.9ml of deionized water is used for dissolving 5g of NaOH, the NaOH solution is dripped into the mixed solution according to a certain speed until the pH value in the mixed solution is maintained at 9, precipitation filtration is carried out after 2-hour reaction, and then the precipitate is washed by the deionized water for a plurality of times, so as to obtain mixed slurry for later use;
(3) drying and sieving: placing the mixed slurry washed in the step (2) in an enamel tray, then placing the tray in a DHG-9146A type electric heating constant-temperature air blast dryer for drying at the temperature of 65 ℃ for 2 hours, placing the completely dried powder in a mortar for fully grinding, and sieving by a 60-mesh sieve;
(4) and (3) granulation: adding the powder with the mass fraction of 2% and a polyvinyl alcohol aqueous solution with the mass concentration of 3% into the powder sieved in the step (3), then uniformly stirring and mixing, drying, and grinding again through a 60-mesh screen for granulation;
(5) tabletting: spraying deionized water for 5-6 times to the powder granulated in the step (4), shaking the powder uniformly, standing the powder containing water for 6 hours, pressing the powder into a wafer by using a DY-30 table type automatic tablet press, wherein the pressure in the tabletting process is 12MPa, the pressure maintaining time is 25s, the diameter of the pressed sample wafer is 15mm, and the thickness of the pressed sample wafer is 1.5 mm;
(6) and (3) sintering: putting the wafer powder pressed in the step (5) into a high-temperature sintering furnace for pre-sintering, setting the pre-sintering temperature of the high-temperature sintering furnace to be 600 ℃, preserving heat for 2.5 hours, and cooling along with the furnace; then, a high-temperature sintering furnace of the same type as the presintering furnace is adopted, the temperature rise rate is set to be 2 ℃/min, the temperature of the high-temperature sintering furnace is increased to 900 ℃, then the temperature of the high-temperature sintering furnace is increased to 1020 ℃ from 900 ℃ at the temperature rise rate of 1 ℃/min, the temperature is kept for 2.3 hours at 1020 ℃, and the sintered powder is cooled to the room temperature along with the furnace to obtain a sample for later use;
(7) ultrasonic cleaning: firstly, carrying out coarse grinding on the surface of the sample obtained in the step (6) by using a water grinding disc, then carrying out fine grinding by using sand paper, finally placing the fine-ground sample in absolute ethyl alcohol, carrying out ultrasonic cleaning for 10min by using an ultrasonic cleaning machine with the model of KQ-300DE, and fully drying for later use after the ultrasonic cleaning is finished;
(8) spraying gold: and (4) coating a gold electrode on the surface of the sample dried in the step (7) by using a Q150RPLUS series coating machine to obtain the zinc oxide piezoresistor.
Example 3
(1) Weighing raw materials: the method comprises the following steps of weighing various components of the raw materials by adopting an electronic balance scale with the precision of 0.001 g: 86.36g ZnO, 11.42g Bi (NO)3)3·5H2O、0.6g Co(NO3)2·6H2O、0.02g Cr(NO3)3·9H2O、0.49g Mn((NO3)·4H2O、0.36g Ni((NO3)2·6H2O and 0.75g of SbCl3；
(2) Chemical precipitation and mixing: keeping the total volume of the reaction solution to be 800ml unchanged, dissolving the raw materials weighed in the step (1) by using 541.9ml of ethylene glycol to form a mixed solution, continuously stirring by using a magnetic stirrer, and simultaneously heating to 85 ℃; then dissolving 5g of NaOH by using 258.1ml of deionized water, dripping the NaOH solution into the mixed solution at a certain speed until the pH value in the mixed solution is maintained at 9.5, reacting for 2 hours, then performing precipitation filtration, and then washing the precipitate for several times by using the deionized water to obtain mixed slurry for later use;
(3) drying and sieving: placing the mixed slurry washed in the step (2) in an enamel tray, then placing the tray in a DHG-9146A type electric heating constant-temperature air blast dryer for drying at the temperature of 68 ℃ for 1.5h, placing the powder in a mortar for full grinding after the powder is completely dried, and sieving the powder by a 60-mesh sieve;
(4) and (3) granulation: adding the powder with the mass fraction of 2% and a polyvinyl alcohol aqueous solution with the mass concentration of 3% into the powder sieved in the step (3), then uniformly stirring and mixing, drying, and grinding again through a 60-mesh screen for granulation;
(5) tabletting: spraying deionized water for 5-6 times to the powder granulated in the step (4), shaking the powder uniformly, standing the powder containing water for 6 hours, pressing the powder into a wafer by using a DY-30 table type automatic tablet press, wherein the pressure in the tabletting process is 14MPa, the pressure maintaining time is 23s, the diameter of the pressed sample wafer is 13mm, and the thickness of the pressed sample wafer is 1.7 mm;
(6) and (3) sintering: putting the wafer powder pressed in the step (5) into a high-temperature sintering furnace for pre-sintering, setting the pre-sintering temperature of the high-temperature sintering furnace to be 625 ℃, preserving heat for 2.2 hours, and cooling along with the furnace; then, a high-temperature sintering furnace of the same type as the presintering furnace is adopted, the temperature rise rate is set to be 2 ℃/min, the temperature of the high-temperature sintering furnace is increased to 900 ℃, then the temperature of the high-temperature sintering furnace is increased to 1050 ℃ from 900 ℃ at the temperature rise rate of 1 ℃/min, the temperature is kept for 2 hours at 1050 ℃, and the sintered powder is cooled to room temperature along with the furnace to obtain a sample for later use;
(7) ultrasonic cleaning: firstly, carrying out coarse grinding on the surface of the sample obtained in the step (6) by using a water grinding disc, then carrying out fine grinding by using sand paper, finally placing the fine-ground sample in absolute ethyl alcohol, carrying out ultrasonic cleaning for 10min by using an ultrasonic cleaning machine with the model of KQ-300DE, and fully drying for later use after the ultrasonic cleaning is finished;
(8) spraying gold: and (4) coating a gold electrode on the surface of the sample dried in the step (7) by using a Q150RPLUS series coating machine to obtain the zinc oxide piezoresistor.
Comparative example
A preparation method of a ZnO varistor, namely a traditional solid phase method, is completely the same as the preparation method of the ZnO varistor in the embodiment 1 except that the raw material mixing mode of the step (2) is different. The raw material mixing method of step (2) in this comparative example specifically includes: and grinding and mixing the ZnO original powder and other metal compounds needing to be doped by adopting a ball mill to obtain a ZnO mixed material.
The grain size distribution diagrams of the ZnO doped powder samples prepared by the preparation method of the invention (taking example 1 as an example) and the traditional solid-phase preparation method of the comparative example are respectively shown in FIG. 2 and FIG. 3. As can be seen from the comparison between fig. 2 and fig. 3, the grain size of the ZnO-doped powder sample prepared in example 1 of the present invention is 3.23 μm, and the grain size of the ZnO-doped powder sample prepared in the comparative example by the conventional solid phase method is 4.39 μm, which shows that the grain distribution of the ZnO-doped powder sample prepared by the method of the present invention is concentrated, and the grain size is also small, so that the grain microstructures of the ZnO original powder and the metal oxide to be doped are more uniform, and the grain boundary performance of the ZnO-doped powder sample and the electrical performance of the ZnO varistor device are improved.
The ZnO varistor devices prepared in examples 1 to 3 and comparative example were tested for electrical properties, including potential gradient E1mANon-linear coefficient alpha and leakage current density JLThe specific test results are shown in table 1.
Figure BDA0003392338150000111
As can be seen from the data in Table 1, the ZnO varistor prepared by the preparation method of the invention has the potential gradient E1mANon-linear coefficient alpha and leakage current density JLThe electrical properties of the ZnO varistor in all aspects are superior to those of the ZnO varistor prepared by the traditional method in the comparative example; from the electrical property parameters of the ZnO piezoresistors prepared in examples 1-3 of the present invention, the electrical property of the ZnO piezoresistor prepared in example 1 is better than that of examples 2 and 3, which shows that by controlling the volume ratio of the ethylene glycol to the deionized water to 2:1 in the chemical precipitation process, metal doped metal ions can be better deposited on the surfaces of ZnO particles, so that the ZnO particles are coprecipitated to form doped mixed powder, the target temperature during sintering is controlled at 1000 ℃, so that the doped metal ions can be better and rapidly diffused to the surfaces of ZnO grains to form a metal ion-rich phase, such as a Bi phase, the obtained ZnO grains have more stable properties, and grain boundaries have more stable propertiesThe impurity ions are reduced, the ZnO crystal grains are more concentrated in distribution, and the ZnO crystal grains are smaller in size, so that the sintered ZnO varistor is more excellent in electrical property.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. A preparation method of a zinc oxide piezoresistor based on a chemical precipitation method is characterized by comprising the following steps:
(1) weighing raw materials: weighing the raw materials by using an electronic balance for later use;
(2) chemical precipitation and mixing: keeping the total volume of the reaction solution to be 800ml unchanged, dissolving the raw materials weighed in the step (1) by using a proper amount of glycol to form a mixed solution, and heating while stirring; then dissolving a certain amount of NaOH in a proper amount of deionized water, dripping the NaOH into the mixed solution at a certain speed until the pH value in the mixed solution is maintained at 9-10, reacting for 2 hours, precipitating and filtering, and then washing precipitates with deionized water for several times to obtain mixed slurry for later use;
(3) drying and sieving: placing the mixed slurry washed in the step (2) in an enamel tray, then placing the enamel tray in a blast drier for drying, placing the powder into a mortar for full grinding after complete drying, and sieving the powder by a 60-mesh sieve;
(4) and (3) granulation: adding the powder with the mass fraction of 2% and a polyvinyl alcohol aqueous solution with the mass concentration of 3% into the powder sieved in the step (3), then uniformly stirring and mixing, drying, and grinding again through a 60-mesh screen for granulation;
(5) tabletting: spraying a proper amount of deionized water into the powder granulated in the step (4), shaking the powder uniformly, standing the powder containing water for 6 hours, and pressing the powder into a wafer by using a tablet press;
(6) and (3) sintering: putting the wafer powder pressed in the step (5) into a high-temperature sintering furnace for presintering and sintering, and cooling to room temperature after sintering to obtain a sample for later use;
(7) ultrasonic cleaning: firstly, carrying out coarse grinding on the surface of the sample obtained in the step (6) by using a water grinding disc, then carrying out fine grinding by using abrasive paper, finally placing the fine-ground sample in absolute ethyl alcohol, placing the absolute ethyl alcohol into an ultrasonic cleaning machine, carrying out ultrasonic cleaning for 10min, and drying the sample for later use after the ultrasonic cleaning is finished;
(8) spraying gold: and (4) coating a gold electrode on the surface of the sample dried in the step (7) by using a coating instrument to obtain the zinc oxide piezoresistor.
2. The preparation method of the zinc oxide varistor based on the chemical precipitation method according to claim 1, wherein the raw materials in step (1) comprise the following components in mole fraction: 86.36% ZnO, 11.42% Bi (NO)3)3·5H2O、0.6％Co(NO3)2·6H2O、0.02％Cr(NO3)3·9H2O、0.49％Mn((NO3)·4H2O、0.36％Ni((NO3)2·6H2O and 0.75% SbCl3。
3. The preparation method of the zinc oxide piezoresistor based on the chemical precipitation method according to claim 1, wherein the volume ratio of the ethylene glycol to the deionized water in the step (2) is 1.9:1-2.1: 1.
4. The preparation method of the zinc oxide varistor based on the chemical precipitation method according to claim 1, wherein the temperature of stirring and heating in step (2) is 80-90 ℃.
5. The preparation method of the zinc oxide piezoresistor based on the chemical precipitation method according to claim 1, wherein the drying temperature of the blast dryer in the step (3) is 65-70 ℃, and the drying time is 1-2 h.
6. The preparation method of the zinc oxide varistor based on the chemical precipitation method according to claim 1, wherein the conditions for sheet pressing in the step (5) are as follows: the tabletting pressure is 12-15MPa, and the tabletting pressure maintaining time is 20-25 s.
7. The preparation method of the zinc oxide piezoresistor based on the chemical precipitation method as claimed in claim 1, wherein the diameter of the wafer pressed in the step (5) is 12-15 mm, and the thickness of the wafer is 1.5-2.0 mm.
8. The preparation method of the zinc oxide varistor based on the chemical precipitation method as claimed in claim 1, wherein the pre-sintering temperature in step (6) is 600-.
9. The preparation method of the zinc oxide varistor based on the chemical precipitation method according to claim 1, wherein the sintering method in step (6) is as follows: firstly, the temperature in the high-temperature sintering furnace is increased to 900 ℃ at the heating rate of 2 ℃/min, then the temperature in the high-temperature sintering furnace is increased to 1050 ℃ at the heating rate of 1 ℃/min from 900 ℃, the heat preservation time is 2-2.5h, and the high-temperature sintering furnace is cooled to the room temperature along with the furnace.
CN202111468009.1A 2021-12-03 2021-12-03 Preparation method of zinc oxide piezoresistor based on chemical precipitation method Pending CN114133236A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111468009.1A CN114133236A (en) 2021-12-03 2021-12-03 Preparation method of zinc oxide piezoresistor based on chemical precipitation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111468009.1A CN114133236A (en) 2021-12-03 2021-12-03 Preparation method of zinc oxide piezoresistor based on chemical precipitation method

Publications (1)

Publication Number Publication Date
CN114133236A true CN114133236A (en) 2022-03-04

Family

ID=80387752

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111468009.1A Pending CN114133236A (en) 2021-12-03 2021-12-03 Preparation method of zinc oxide piezoresistor based on chemical precipitation method

Country Status (1)

Country Link
CN (1) CN114133236A (en)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101246769A (en) * 2007-02-15 2008-08-20 雷慧绪 Preparation of zinc oxide piezoresistor composite powder and compound additive agent powder
CN103951415A (en) * 2014-04-01 2014-07-30 西安电子科技大学 High-voltage-gradient zinc oxide pressure-sensitive resistor and making method thereof
CN104193320A (en) * 2014-09-03 2014-12-10 中国科学院新疆理化技术研究所 Nano-ZnO varistor composite powder material and preparation method thereof
CN104591726A (en) * 2014-12-29 2015-05-06 广西新未来信息产业股份有限公司 High-potential gradient zinc oxide voltage piezo-resistor material and preparation method thereof
CN104671771A (en) * 2013-12-03 2015-06-03 辽宁法库陶瓷工程技术研究中心 High voltage gradient zinc oxide based varistor material and preparation method thereof
CN104944935A (en) * 2015-06-08 2015-09-30 华中科技大学 ZnO varister ceramic and preparation method thereof
CN105585316A (en) * 2014-10-31 2016-05-18 陕西盛迈石油有限公司 Preparation method of ZnO pressure-sensitive resistor
CN107021751A (en) * 2017-04-10 2017-08-08 湖北工业大学 A kind of high-potential gracient arrester zinc oxide piezoresistor ceramic
CN107935583A (en) * 2017-11-25 2018-04-20 黑龙江科技大学 A kind of manufacture method of varistor
US20200223761A1 (en) * 2017-02-14 2020-07-16 Tdk Electronics Ag Lead-Free High-Insulating Ceramic Coating Zinc Oxide Arrester Valve and Preparation Method Thereof
CN112125660A (en) * 2020-08-31 2020-12-25 西安交通大学 Zinc oxide polyether-ether-ketone piezoresistor and preparation method thereof
CN112851332A (en) * 2021-01-30 2021-05-28 西安电子科技大学 Method for preparing high-voltage gradient zinc oxide piezoresistor by doping coating method
CN113149634A (en) * 2021-04-25 2021-07-23 国网湖南省电力有限公司 Preparation method of zinc oxide resistance card

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101246769A (en) * 2007-02-15 2008-08-20 雷慧绪 Preparation of zinc oxide piezoresistor composite powder and compound additive agent powder
CN104671771A (en) * 2013-12-03 2015-06-03 辽宁法库陶瓷工程技术研究中心 High voltage gradient zinc oxide based varistor material and preparation method thereof
CN103951415A (en) * 2014-04-01 2014-07-30 西安电子科技大学 High-voltage-gradient zinc oxide pressure-sensitive resistor and making method thereof
CN104193320A (en) * 2014-09-03 2014-12-10 中国科学院新疆理化技术研究所 Nano-ZnO varistor composite powder material and preparation method thereof
CN105585316A (en) * 2014-10-31 2016-05-18 陕西盛迈石油有限公司 Preparation method of ZnO pressure-sensitive resistor
CN104591726A (en) * 2014-12-29 2015-05-06 广西新未来信息产业股份有限公司 High-potential gradient zinc oxide voltage piezo-resistor material and preparation method thereof
CN104944935A (en) * 2015-06-08 2015-09-30 华中科技大学 ZnO varister ceramic and preparation method thereof
US20200223761A1 (en) * 2017-02-14 2020-07-16 Tdk Electronics Ag Lead-Free High-Insulating Ceramic Coating Zinc Oxide Arrester Valve and Preparation Method Thereof
CN107021751A (en) * 2017-04-10 2017-08-08 湖北工业大学 A kind of high-potential gracient arrester zinc oxide piezoresistor ceramic
CN107935583A (en) * 2017-11-25 2018-04-20 黑龙江科技大学 A kind of manufacture method of varistor
CN112125660A (en) * 2020-08-31 2020-12-25 西安交通大学 Zinc oxide polyether-ether-ketone piezoresistor and preparation method thereof
CN112851332A (en) * 2021-01-30 2021-05-28 西安电子科技大学 Method for preparing high-voltage gradient zinc oxide piezoresistor by doping coating method
CN113149634A (en) * 2021-04-25 2021-07-23 国网湖南省电力有限公司 Preparation method of zinc oxide resistance card

Similar Documents

Publication Publication Date Title
CN110272275B (en) Zinc oxide resistance card and preparation method thereof
CN101531507B (en) High energy type zinc oxide piezoresistor composite powder and method for manufacturing piezoresistor
CN103021608A (en) High-gradient and high-capacity zinc oxide voltage dependent resistor disc and fabrication method thereof
CN104591726A (en) High-potential gradient zinc oxide voltage piezo-resistor material and preparation method thereof
CN111508676B (en) Small-size distribution network annular zinc oxide resistance card and preparation method thereof
CN101613199A (en) A kind of high-performance zinc oxide composite ceramic voltage dependent resistor material and preparation method
EP2194541B1 (en) Current-voltage non-linear resistor and method of manufacture thereof
CN104557016B (en) A kind of Zinc oxide pressure-sensitive ceramic material of high non-linearity frit doping
CN105645948A (en) Preparation method of high-voltage gradient and low-leakage current pressure-sensitive resistor ceramic material
CN103787653A (en) Preparation method of carbon-modified CaCu3Ti4O12 high dielectric material
CN115536367A (en) High-resistance low-B-value thermistor ceramic body, preparation method and thermistor
CN1163465A (en) Pressure sensitive nonlinear resistor, method for producing pressure sensitive nonlinear resistor and lighting arrester
WO2024125118A1 (en) Oxide target and preparation method therefor
CN110423110B (en) Ultrahigh nonlinear ZnO-Bi2O3Base pressure sensitive ceramic and preparation method thereof
CN110078494B (en) Zinc oxide resistance card and preparation method thereof
CA2034106C (en) Process for fabricating doped zinc oxide microspheres
CN114133236A (en) Preparation method of zinc oxide piezoresistor based on chemical precipitation method
CN110922182A (en) Preparation method of high-gradient low-leakage-current ceramic
CN105523759A (en) Temperature-sensitive ceramic resistor and preparation method thereof
CN108975903A (en) A kind of Zinc oxide pressure-sensitive resistor raw material and preparation method thereof
CN114373591A (en) Resistance card, preparation process thereof and zinc oxide lightning arrester
CN108863344B (en) Preparation process of high-performance ZnO pressure-sensitive ceramic
CN102543333B (en) Non-linear resistor disc and manufacturing method thereof
CN110655400A (en) Zinc oxide varistor ceramic material with large through-flow capacity, preparation method thereof and preparation method of resistor thereof
CN113979740B (en) Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, piezoresistor and preparation method thereof, and resistor element

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