CN102324290B - Copper-electrode zinc-oxide voltage-sensitive resistor and preparation method thereof - Google Patents
Copper-electrode zinc-oxide voltage-sensitive resistor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a copper-electrode zinc-oxide voltage-sensitive resistor, which comprises the following steps of: voltage-sensitive ceramic-body manufacture, copper-electrode slurry printing, copper-electrode drying and copper-electrode sintering and permeation, wherein the copper-electrode sintering and permeation are carried out under an oxygen-free atmosphere environment by adopting a chain-belt type tunnel electric furnace as production equipment. In the invention, the copper-electrode zinc-oxide voltage-sensitive resistor with qualified performances is manufactured by replacing noble-metal silver with base-metal copper as an electrode material and using special electrode sintering and permeating processes, so that the production cost is greatly saved. The preparation method has the following advantages that: 1. the process technology is suitable for the mass production of the copper-electrode zinc-oxide voltage-sensitive resistors; 2. all the electrical performances (comprising voltage nonlinear coefficient, leakage current, through-current capacity, energy tolerance and the like) of a product produced through the process technology can reach the level equivalent to a silver-electrode product, and the requirements of clients are met; and 3. the cost of the product is much lower than that of the silver-electrode product in the same specification.
Description
Technical field
The present invention relates to the technical field of copper as the zinc oxide varistor of electrode.
Background technology
Zinc oxide varistor is a kind of take zinc oxide as main material, after mixing by semiconducting, and the semiconductive ceramic element that high temperature sintering forms under normal atmospheric environment.Widely used zinc oxide pressure-sensitive device is still the silver electrode element in the industry.This element has excellent non-linear to voltage characteristic and the ability to bear of high energy impact events, is mainly used in the fields such as household electrical appliances, communication, industrial power, illumination, automobile, plays lightning protection and overvoltage protection effect.Because silver is a kind of precious metal material, uses it as the cost that electrode material will inevitably increase product, consider that therefore other metal material substitutes silver as electrode, for example copper.With the electrode of silver paste making varistor, the atmosphere of its burning infiltration is normal atmospheric environment, and is the same with the sintering environment of voltage-sensitive ceramic matrix, so silver electrode burning infiltration technique is less on the electrical property impact of piezo-resistance.And adopt copper slurry to make the electrode of varistor, the atmosphere of its burning infiltration can not adopt normal atmospheric environment, the control of on the other hand burning infiltration temperature also can be crucial, the too high crystal boundary potential barrier that will destroy the pressure-sensitive semiconductor element, thus cause the seriously deteriorated of varistor electrical property.This technology is in the research and development state both at home and abroad, wishes to develop the zinc oxide varistor technology of alternative silver electrode.
Application number is 200310117432.2, and denomination of invention discloses a kind of annular voltage-sensitive resistor and preparation method thereof for the Chinese invention patent application of " copper electrode strontium titanates annular voltage-sensitive resistor and preparation method thereof ".This annular voltage-sensitive resistor comprises resistance ceramic substrate and the electrode more than three or three of an annular, and substrate is made by strontium titanates, and electrode is copper electrode, and is positioned on upper surface, lower surface or the lateral surface of substrate.Its preparation method comprises: the reduction of the manufacturing of porcelain base, the printing of copper slurry and oven dry, copper electrode.This application has been introduced the technique of manufactured copper electrode strontium titanates annular voltage-sensitive resistor, and the dry copper electrode that forms after copper slurry is printed onto on the ceramic substrate under blanket of nitrogen or nitrogen and hydrogen mixture atmosphere environment, reduces to copper electrode under 700～900 ℃.
Summary of the invention
The object of the present invention is to provide a kind of with copper as zinc oxide varistor of electrode and preparation method thereof.
In order to realize the foregoing invention purpose, the present invention has adopted following technical scheme: a kind of preparation method of copper-electrode zinc-oxide voltage-sensitive resistor, it is characterized in that may further comprise the steps: make voltage-sensitive ceramic body, print copper electrode slurry, copper electrode oven dry, copper electrode burning infiltration, wherein the copper electrode burning infiltration adopts chain-belt type tunnel electric furnace as production equipment, carries out under the oxygen-free atmosphere environment.
Described oxygen-free atmosphere is to realize by the high pure nitrogen that passes into high pure nitrogen to burner hearth or contain the denier air.
The import of described chain-belt type continuous tunnel furnace and outlet are provided with densely covered pore, pass into high pure nitrogen to described pore, form gas curtain, completely cut off entering of extraneous air.
The throughput of described gas curtain is 10～200L/min.
The burner hearth of described chain-belt type tunnel electric furnace is disposed with import gas curtain district, some sections heating zones, high-temperature region, cooling area and outlet gas curtain districts, in heating zone, pass into the high-purity nitrogen that is mixed with micro-air, wherein the mixed proportion of oxygen is controlled at 50～500ppm, the interval that temperature is higher, the ratio of oxygen is less.
The temperature of described high temperature section is 500～600 ℃, and constant temperature time is 1～10 minute, and this high-temperature region passes into the High Purity Nitrogen of 99.999% purity, and Control for Oxygen Content is at≤20ppm.
Described cooling area passes into the High Purity Nitrogen of 99.999% purity, and Control for Oxygen Content is at≤20ppm, and adopts water cooling equipment to lower the temperature, and the temperature of the product of coming out of the stove is lower than 60 ℃.
Described print copper electrode slurry is to adopt 200～250 purpose nylon mesh to print electrode, and obtaining thickness is the copper electrode layer of 5-10 μ m.
Described copper electrode oven dry is carried out under the normal atmospheric environment, and the temperature of oven dry is 100-200 ℃, and the time cycle is 5～15 minutes.
A kind of copper-electrode zinc-oxide voltage-sensitive resistor that makes according to above-mentioned preparation method.
The present invention substitutes noble silver as electrode material with copper base metal, uses special electrode burning infiltration technique, produces the qualified copper-electrode zinc-oxide voltage-sensitive resistor of performance, has saved greatly production cost.The present invention has the following advantages: 1, this technology is fit to the production in enormous quantities of copper-electrode zinc-oxide voltage-sensitive resistor.2, the product of this technology production, every electrical property (comprising voltage nonlinearity, leakage current, discharge capacity, energy tolerance etc.) all can reach the level suitable with the silver electrode product, meets customer need.2, product cost is more much lower than the silver electrode product of same size.
Description of drawings
Fig. 1 is the structural representation of copper electrode voltage-sensitive ceramic body.
Wherein, 1 voltage-sensitive ceramic body, 2 copper electrodes
Embodiment
This example is the 20K821 specification copper electrode Zinc-oxide piezoresistor production technology of φ 20mm for diameter dimension, and its step is as follows:
Make the voltage-sensitive ceramic body by traditional pressure sensitive electrical resistance sintering technique first, then stamp the copper content of 8-10 μ m thickness at 70%-75% with 200 order silk screens at the voltage-sensitive ceramic body, the burning infiltration temperature is 520-600 ℃ Zinc-oxide piezoresistor special low temperature copper slurry (can buy from the market), then use general chain-belt type drying oven, under the normal atmospheric environment, use maximum temperature to be 150-200 ℃, the oven dry cycle is that 5-10 minute technique is dried.Then, after installing with screen cloth, put into the chain-belt type nitrogen atmosphere protection tunnel electric furnace of zinc oxide varistor special use, for example adopting the model of Xin Baohua electronic equipment company design is the continuous tunnel furnace of BHTDL-100, middle burning infiltration copper electrode.The technological parameter of burning infiltration process is as shown in table 1 below:
Table 1
Whole burning infiltration process must be carried out under the atmosphere of anaerobic almost.By the pore that import and the outlet of continuous tunnel furnace are gathered, the ejection high pure nitrogen forms gas curtain, and the atmosphere of an anaerobic is brought up in entering of isolated extraneous air for burner hearth.The big or small use traffic meter control of gas curtain.In burner hearth, utilizing pipeline is that each warm area section is carried satisfactory high pure nitrogen or contained the gaseous mixture of denier air.It is 200～450 ℃ heating zone in temperature, in order more advantageously to drain the organic substances such as solvent in the copper slurry and adhesive, the High Purity Nitrogen that passes into is mixed with micro-air, and wherein the mixed proportion of oxygen is controlled at 50～500ppm, the interval that temperature is higher, the ratio of oxygen is less.For the high-temperature region, the highest copper electrode burning infiltration temperature of Zinc-oxide piezoresistor is 500～600 ℃, and constant temperature time is 1～10 minute, and this warm area section must pass into the High Purity Nitrogen of 99.999% purity, and Control for Oxygen Content is at≤20ppm.The setting of temperature and time is depending on the different and to some extent difference of the size of piezo-resistance.Cooling area passes into the High Purity Nitrogen of 99.999% purity, and Control for Oxygen Content is at≤20ppm.Use water-cooled cooling near the place of outlet, be lower than 60 ℃ with the temperature of the product of guaranteeing to come out of the stove.Coming out of the stove rear product will be 20～30 ℃ of room temperature, humidity≤60%, the environment lower seal deposit.
The 20K821 specification copper electrode Zinc-oxide piezoresistor product that uses above-mentioned explained hereafter to go out, its pressure sensitive voltage is 740～900v, non linear coefficient α 〉=50, leakage current≤3 μ A, the electrode solderability is good, 8/20 μ s discharge capacity and 2ms energy tolerance performance reach the level of same size silver electrode varistor, and production cost is saved more than 50%.
This example may further comprise the steps for diameter dimension is the 10K471 specification copper electrode Zinc-oxide piezoresistor production technology of φ 10mm:
Make the voltage-sensitive ceramic body by traditional pressure sensitive electrical resistance sintering technique first, then stamp the copper content of 8-10 μ m thickness at 70%-75% with 200 order silk screens at the voltage-sensitive ceramic body, the burning infiltration temperature is 520-600 ℃ Zinc-oxide piezoresistor special low temperature copper slurry (can buy from the market), then use general chain-belt type drying oven, under the normal atmospheric environment, use maximum temperature to be 150-200 ℃, the oven dry cycle is that 5-10 minute technique is dried.Then, after installing with screen cloth, put into the chain-belt type nitrogen atmosphere protection tunnel electric furnace burning infiltration copper electrode of zinc oxide varistor special use.The technological parameter of burning infiltration process is as follows:
Whole burning infiltration process is carried out under the atmosphere of anaerobic almost.Can adopt the atmosphere identical with embodiment 1.
The 10K471 specification copper electrode Zinc-oxide piezoresistor product that uses above-mentioned explained hereafter to go out, its pressure sensitive voltage is 430～5100v, non linear coefficient α 〉=50, leakage current≤3 μ A, the electrode solderability is good, 8/20 μ s discharge capacity and 2ms energy tolerance performance reach the level of same size silver electrode varistor, and production cost is saved more than 50%.
Embodiment 3
This example may further comprise the steps for diameter dimension is the 7K271 specification copper electrode Zinc-oxide piezoresistor production technology of φ 7mm:
Make the voltage-sensitive ceramic body by traditional pressure sensitive electrical resistance sintering technique first, then stamp the copper content of 8-10 μ m thickness at 70%-75% with 200 order silk screens at the voltage-sensitive ceramic body, the burning infiltration temperature is 520-600 ℃ Zinc-oxide piezoresistor special low temperature copper slurry (can buy from the market), then use general chain-belt type drying oven, under the normal atmospheric environment, use maximum temperature to be 150-200 ℃, the oven dry cycle is that 5-10 minute technique is dried.Then, after installing with screen cloth, put into the chain-belt type nitrogen atmosphere protection tunnel electric furnace burning infiltration copper electrode of zinc oxide varistor special use.The technological parameter of burning infiltration process is as follows:
Whole burning infiltration process is carried out under the atmosphere of anaerobic almost.Can adopt the atmosphere identical with embodiment 1.
The 7K271 specification copper electrode Zinc-oxide piezoresistor product that uses above-mentioned explained hereafter to go out, its pressure sensitive voltage is 243～297v, non linear coefficient α 〉=48, leakage current≤3 μ A, the electrode solderability is good, 8/20 μ s discharge capacity and 2ms energy tolerance performance reach the level of same size silver electrode varistor, and production cost is saved more than 50%.
Claims (9)
1. the preparation method of a copper-electrode zinc-oxide voltage-sensitive resistor, it is characterized in that may further comprise the steps: make voltage-sensitive ceramic body, print copper electrode slurry, copper electrode oven dry, copper electrode burning infiltration, wherein the copper electrode burning infiltration adopts chain-belt type tunnel electric furnace as production equipment, carry out under the oxygen-free atmosphere environment, described oxygen-free atmosphere is to realize by the high pure nitrogen that passes into high pure nitrogen to burner hearth or contain the denier air; The burner hearth of described chain-belt type tunnel electric furnace is disposed with import gas curtain district, some sections heating zones, high-temperature region, cooling area and outlet gas curtain districts, and the temperature of described high temperature section is 500～600 ℃, and constant temperature time is 1～10 minute.
2. preparation method according to claim 1 is characterized in that: the import of described chain-belt type continuous tunnel furnace and outlet are provided with densely covered pore, pass into high pure nitrogen to described pore, form gas curtain, the entering of isolated extraneous air.
3. preparation method according to claim 2, it is characterized in that: the throughput of described gas curtain is 10～200L/min.
4. preparation method according to claim 1, it is characterized in that: pass into the high-purity nitrogen that is mixed with micro-air in heating zone, wherein the mixed proportion of oxygen is controlled at 50～500ppm, the interval that temperature is higher, the ratio of oxygen is less.
5. preparation method according to claim 4, it is characterized in that: this high-temperature region passes into the High Purity Nitrogen of 99.999% purity, and Control for Oxygen Content is at≤20ppm.
6. preparation method according to claim 4, it is characterized in that: described cooling area passes into the High Purity Nitrogen of 99.999% purity, and Control for Oxygen Content is at≤20ppm, and adopts water cooling equipment to lower the temperature, and the temperature of the product of coming out of the stove is lower than 60 ℃.
7. preparation method according to claim 1 is characterized in that: described print copper electrode slurry is to adopt 200～250 purpose nylon mesh to print electrode, and obtaining thickness is the copper electrode layer of 5-10 μ m.
8. preparation method according to claim 1 is characterized in that: described copper electrode oven dry is carried out under the normal atmospheric environment, and the temperature of oven dry is 100-200 ℃, and the time cycle is 5～15 minutes.
9. a copper-electrode zinc-oxide voltage-sensitive resistor is characterized in that: comprise the voltage-sensitive ceramic body, be printed with copper electrode paste on the voltage-sensitive ceramic body, and process prepares copper-electrode zinc-oxide voltage-sensitive resistor such as the arbitrary preparation method of claim 1～8.
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| CN103319170B (en) * | 2013-06-14 | 2014-07-16 | 广东风华高新科技股份有限公司 | Annular piezoresistor ceramic and preparation method thereof, and annular piezoresistor and preparation method thereof |
| CN203733541U (en) | 2013-12-24 | 2014-07-23 | 爱普科斯公司 | Rheostat device |
| CN104319043B (en) * | 2014-10-10 | 2017-05-03 | 广州新莱福磁电有限公司 | Manufacturing method of negative-temperature-coefficient thermistor chip electrode |
| CN104835606B (en) * | 2015-04-03 | 2017-10-10 | 兴勤（常州）电子有限公司 | electronic component multilayer alloy electrode and preparation method thereof |
| CN109920580B (en) * | 2019-03-13 | 2020-04-14 | 昆明理工大学 | Preparation process and application of copper conductor slurry for zinc oxide piezoresistor |
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