CN107244909A - A kind of low-pressure high-energy Zinc-oxide piezoresistor - Google Patents

A kind of low-pressure high-energy Zinc-oxide piezoresistor Download PDF

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CN107244909A
CN107244909A CN201710324476.4A CN201710324476A CN107244909A CN 107244909 A CN107244909 A CN 107244909A CN 201710324476 A CN201710324476 A CN 201710324476A CN 107244909 A CN107244909 A CN 107244909A
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oxide
zinc
low
pressure high
piezoresistor
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赵大鹏
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Bengbu Harvest Electromechanical Equipment Manufacturing Co Ltd
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Bengbu Harvest Electromechanical Equipment Manufacturing Co Ltd
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    • 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
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • 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
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    • 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
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
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    • 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
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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Abstract

The invention belongs to Zinc-oxide piezoresistor preparing technical field, and in particular to a kind of low-pressure high-energy Zinc-oxide piezoresistor, be made using ceramic process, and the element material includes following raw material：Zinc oxide, silicon boron glass, bismuth oxide, niobium pentaoxide, tin oxide, copper carbonate.The present invention has advantages below compared with prior art：Silicon boron glass melting temperature is low in the present invention, far below sintering temperature, its liquid phase in sintering process is set sufficiently to infiltrate zinc oxide grain, increase crystallite dimension, distribution is more uniform, effectively improves the microstructure of Zinc-oxide piezoresistor, piezo-resistance grain growth can also be promoted simultaneously, make zinc oxide that there is preferable sintering character at 950 DEG C, reduce the electric potential gradient of piezo-resistance, improve nonlinear characteristic；A kind of low-pressure high-energy Zinc-oxide piezoresistor is provided.

Description

A kind of low-pressure high-energy Zinc-oxide piezoresistor
Technical field
The invention belongs to Zinc-oxide piezoresistor preparing technical field, and in particular to a kind of low-pressure high-energy zinc oxide pressure-sensitive electricity Resistance.
Background technology
Zinc oxide varistor have concurrently technique it is simple, with low cost, it is easy to use the advantages of, be applied widely, The piezoresistor of early stage is mainly used in various electric equipments and arrester as overvoltage protection and Surge suppression, and now pressure-sensitive Resistor is widely used in the protection of auto industry, communication apparatus, railway signal, micromachine and various electronic components, makes The conventional method of piezo-resistance low pressure is original paper thickness is thinned, after component thickness is thinned, not only the mechanical strength drop of element It is low, and discharge capacity reduction, therefore, how to prepare low-pressure high-energy piezoresistor, it is desirable to the pressure sensitive voltage value of unit thickness It is low, while leakage current small piezoresistor into the problem of needing to solve now.
The content of the invention
The purpose of the present invention is reduced for the mechanical strength of existing element, and discharge capacity the problem of reduce there is provided A kind of low-pressure high-energy Zinc-oxide piezoresistor.
The present invention is achieved by the following technical solutions：A kind of low-pressure high-energy Zinc-oxide piezoresistor, utilizes potter Skill is made, and the element material includes the raw material of following parts by weight：92.4-92.8 parts of zinc oxide, 3.6-4.2 parts of silicon boron glass, 0.45-0.62 parts of bismuth oxide, 0.35-0.42 parts of niobium pentaoxide, 0.05-0.08 parts of tin oxide, copper carbonate 0.08-0.14 Part；
Wherein, the preparation method of the silicon boron glass is as follows：By arsenic oxide arsenoxide, tin oxide, lead oxide, silica, boric acid, erbium oxide By weight 18:13:28:25:34:4 are well mixed, and 650 DEG C are warming up to using programming rate as 4-6 DEG C/min, are incubated 2.5-3 Hour, then with programming rate 8-10 DEG C/min be continuously heating to after 950 DEG C, be incubated 1-1.5 hours, then in distilled water Quenching, takes out after drying, grinding, crosses 360 mesh sieves and produces.
As further improvement of these options, using ceramic technoloigcal process raw cook, raw cook is then placed in high temperature furnace In, it is warming up to 4 DEG C/min programming rate after 800 DEG C, is incubated 40 minutes, is then continuously heating to 1170 with the programming rate After DEG C, 30 minutes are incubated, 750 DEG C is cooled to, cools to room temperature with the furnace, finally by surface silver electrode.
As further improvement of these options, the specification of the raw cook is φ 16.5mm × 2mm.
As further improvement of these options, each material purity is not less than 99%.
As further improvement of these options, the glass transition temperature of the silicon boron glass is 364 DEG C, recrystallization temperature For 402 DEG C, melting temperature is 673 DEG C.
The present invention has advantages below compared with prior art：Silicon boron glass melting temperature is low in the present invention, far below sintering Temperature, enables its liquid phase in sintering process sufficiently to infiltrate zinc oxide grain, increases crystallite dimension, and distribution is more uniform, The microstructure of Zinc-oxide piezoresistor effectively is improved, while piezo-resistance grain growth can also be promoted, zinc oxide is existed 950 DEG C have preferable sintering character, reduce the electric potential gradient of piezo-resistance, improve nonlinear characteristic；Silicon boron glass The scientific matching of addition and other raw materials, the grain growth kinetics index that can make Zinc-oxide piezoresistor is 2.13 or so, Activation can be 142.6kJ/mol, compared with existing silicon boron glass, and grain growth kinetics index and activation can be all smaller, therefore The growth result of crystal grain can be promoted while sintering temperature is reduced, there is provided a kind of low-pressure high-energy for enhancing nonlinear characteristic performance Zinc-oxide piezoresistor.
Embodiment
Embodiment 1
A kind of low-pressure high-energy Zinc-oxide piezoresistor, is made using ceramic process, and the element material includes following parts by weight Raw material：92.4-92.8 parts of zinc oxide, 3.6-4.2 parts of silicon boron glass, 0.45-0.62 parts of bismuth oxide, niobium pentaoxide 0.35-0.42 parts, 0.05-0.08 parts of tin oxide, 0.08-0.14 parts of copper carbonate；
Wherein, the preparation method of the silicon boron glass is as follows：By arsenic oxide arsenoxide, tin oxide, lead oxide, silica, boric acid, erbium oxide By weight 18:13:28:25:34:4 are well mixed, and 650 DEG C are warming up to using programming rate as 4-6 DEG C/min, are incubated 2.5-3 Hour, then with programming rate 8-10 DEG C/min be continuously heating to after 950 DEG C, be incubated 1-1.5 hours, then in distilled water Quenching, takes out after drying, grinding, crosses 360 mesh sieves and produces.
Wherein, using ceramic technoloigcal process raw cook, then raw cook is placed in high temperature furnace, with 4 DEG C/min programming rate It is warming up to after 800 DEG C, is incubated 40 minutes, is then continuously heating to the programming rate after 1170 DEG C, is incubated 30 minutes, is cooled to 750 DEG C, room temperature is cooled to the furnace, finally by surface silver electrode；The specification of the raw cook is φ 16.5mm × 2mm.
Wherein, the glass transition temperature of the silicon boron glass is 364 DEG C, and recrystallization temperature is 402 DEG C, and melting temperature is 673 ℃。
The composition of in element material raw material is adjusted respectively, raw material proportioning can shadow in the present invention for each raw material Ring piezoresistor electrical property；Selecting existing silicon boron glass to replace silicon boron glass in the present invention, as a control group, now, detection is worked as When sintering temperature is 950 DEG C, its grain growth kinetics index is about 4.27, and activation can about 308.2kJ/mol；When sintering temperature Spend for 1200 DEG C when, its grain growth kinetics index is about 2.96, activation can be about 185.4kJ/mol, by the present invention Grain growth performance comparision understands that the average crystal grain growth kinetics index of piezo-resistance and activation can be smaller in the present invention, say Bright its can incorporate oxidisability crystal grain well under the conditions of relative low temperature, so as to improve piezo-resistance microstructure, improve Nonlinear characteristic, leakage current reduces, and pressure-sensitive electric field rises, that is, obtains a kind of low-pressure high-energy Zinc-oxide piezoresistor.

Claims (5)

1. a kind of low-pressure high-energy Zinc-oxide piezoresistor, is made using ceramic process, it is characterised in that the element material includes The raw material of following parts by weight：92.4-92.8 parts of zinc oxide, 3.6-4.2 parts of silicon boron glass, 0.45-0.62 parts of bismuth oxide, five Aoxidize 0.35-0.42 parts of two niobium, 0.05-0.08 parts of tin oxide, 0.08-0.14 parts of copper carbonate；
Wherein, the preparation method of the silicon boron glass is as follows：By arsenic oxide arsenoxide, tin oxide, lead oxide, silica, boric acid, erbium oxide By weight 18:13:28:25:34:4 are well mixed, and 650 DEG C are warming up to using programming rate as 4-6 DEG C/min, are incubated 2.5-3 Hour, then with programming rate 8-10 DEG C/min be continuously heating to after 950 DEG C, be incubated 1-1.5 hours, then in distilled water Quenching, takes out after drying, grinding, crosses 360 mesh sieves and produces.
2. a kind of low-pressure high-energy Zinc-oxide piezoresistor as claimed in claim 1, it is characterised in that utilize ceramic technoloigcal process life Raw cook, is then placed in high temperature furnace by piece, is warming up to 4 DEG C/min programming rate after 800 DEG C, be incubated 40 minutes, then with The programming rate is continuously heating to after 1170 DEG C, is incubated 30 minutes, is cooled to 750 DEG C, room temperature is cooled to the furnace, finally by surface Silver electrode.
3. a kind of low-pressure high-energy Zinc-oxide piezoresistor as claimed in claim 2, it is characterised in that the specification of the raw cook is φ 16.5mm×2mm。
4. a kind of low-pressure high-energy Zinc-oxide piezoresistor as claimed in claim 2, it is characterised in that each material purity is not low In 99%.
5. a kind of low-pressure high-energy Zinc-oxide piezoresistor as claimed in claim 1, it is characterised in that the glass of the silicon boron glass Conversion temperature is 364 DEG C, and recrystallization temperature is 402 DEG C, and melting temperature is 673 DEG C.
CN201710324476.4A 2017-05-10 2017-05-10 A kind of low-pressure high-energy Zinc-oxide piezoresistor Pending CN107244909A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111462970A (en) * 2020-04-08 2020-07-28 湖南省湘电试研技术有限公司 Lightning-protection annular zinc oxide resistance card for distribution network and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101630553A (en) * 2009-07-17 2010-01-20 立昌先进科技股份有限公司 Preparation method of zinc oxide varister
CN102515741A (en) * 2011-12-07 2012-06-27 中国科学院过程工程研究所 Zinc oxide varistor material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101630553A (en) * 2009-07-17 2010-01-20 立昌先进科技股份有限公司 Preparation method of zinc oxide varister
CN102515741A (en) * 2011-12-07 2012-06-27 中国科学院过程工程研究所 Zinc oxide varistor material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
万帅等: "铋硼玻璃掺杂对ZnO-Bi2O3-TiO2系压敏电阻性能影响", 《无机材料学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111462970A (en) * 2020-04-08 2020-07-28 湖南省湘电试研技术有限公司 Lightning-protection annular zinc oxide resistance card for distribution network and preparation method thereof

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Application publication date: 20171013