CN1046052C - Oxidate semi-conductor thermosensitive resistance and mfg. method thereof - Google Patents
Oxidate semi-conductor thermosensitive resistance and mfg. method thereof Download PDFInfo
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- CN1046052C CN1046052C CN96122180A CN96122180A CN1046052C CN 1046052 C CN1046052 C CN 1046052C CN 96122180 A CN96122180 A CN 96122180A CN 96122180 A CN96122180 A CN 96122180A CN 1046052 C CN1046052 C CN 1046052C
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Abstract
The present invention relates to an oxide semi-conductor thermo-sensitive resistor and a manufacture method thereof. The present invention mainly takes nitrates or acetates of Co, Mn and Ni as raw materials, material powder is prepared by a liquid phase coprecipitation method, emulsifier OP is added for cleaning, and the powder is prepared after decomposition, grinding and presintering. The thermo-sensitive resistor is a lead wire type with both ends sealed by glass and has the characteristics of small size, high stability, high reliability, etc., and the thermo-sensitive resistor is suitable for temperature measurement and control and circuit compensation. The electric parameter index of products can reach a level of similar Japanese products, and therefore, the present invention replaces import products.
Description
The present invention relates to a kind of manufacture method of oxidate semi-condcutor thermo-sensitive resistance device
Oxidate semi-condcutor thermo-sensitive resistance of the present invention is glass capsulation two ends wire types, has little, the good stability of volume, and characteristics such as reliability height are applicable to refrigerator, the measurement of air-conditioning equitemperature, control and line build-out.The product of the existing same spline structure of Japan, same parameter comes out, but such device of China relies on import substantially, costs an arm and a leg.
In general, the semiconductor temperature-sensitive material of performance of the same race, because its manufacture craft difference, Main Ingredients and Appearance and ratio thereof also have than big-difference.Japan adopts nitrate heat of mixing decomposition method to prepare powder body material, and its electrical parameter is: B25/50=3470 ± 1%, R25 ℃=2.0-6.0K Ω.Domestic preparation oxide heat sensitive material normally adopts oxide mixed grinding method.The present invention is through for many years exploration, research, and adopting the nitrate or the acetate of cobalt, manganese, nickel is raw material, and with liquid-phase coprecipitation powder process body, its ratio and technology have marked difference.The parameter index of products obtained therefrom all reaches external like product index.
The object of the invention is, the manufacture method of oxidate semi-condcutor thermo-sensitive resistance device of development is that nitrate or the acetate with cobalt, manganese, nickel is raw material, adopt liquid-phase coprecipitation to prepare the material powder, adding polyoxyethylene nonylphenol ether cleans, then powder is decomposed, grind, presintering, carry out preforming, isostatic cool pressing, high temperature sintering again and make, its electrical parameter index of this products obtained therefrom all reaches Japanese like product level, thereby has substituted the situation of like product dependence import.
The manufacture method of oxidate semi-condcutor thermo-sensitive resistance device of the present invention, it mainly is that this thermistor is that nitrate or acetate with cobalt, manganese, nickel is raw material, adopt liquid-phase coprecipitation to prepare the material powder, then powder decomposed, add after the grinding, presintering polyoxyethylene nonylphenol ether and clean and make, raw material each component proportioning is (molar percentage %) cobalt 30-40, manganese 35-45, nickel 15-20; Oxidate semi-condcutor thermo-sensitive resistance of the present invention and manufacture method thereof, the nitrate or the acetate that are pure to analyze (molar percentage %) cobalt 30-40, manganese 35-45, nickel 15-20 are raw material, adopt liquid-phase coprecipitation to prepare the powder precipitated liquid, precipitated liquid is cobalt, the manganese of concentration 1N, the salting liquid of nickel, under violent stirring, evenly add precipitation reagent in the precipitated liquid, in precipitated liquid, add polyoxyethylene nonylphenol ether then, precipitation adds that deionized water cleans and solution is carried out sonicated after finishing repeatedly, oven dry, levigate, presintering; Precipitation reagent concentration is the ammonium bicarbonate soln of 1.5-2N, and the addition of precipitation reagent is 2-2.5 times (Capacity Ratio) of precipitated liquid; The addition 1% (weight) of polyoxyethylene nonylphenol ether is after the material oven dry is levigate, earlier at 400-500 ℃ of thermal decomposition 5-10 hour; Carry out presintering at 650-800 ℃ again through after grinding, carry out isostatic cool pressing after material is pre-formed as φ 50mm left and right sides cylinder, pressure is 2.0-3.5T/cm
2Then 1180-1200 ℃ of sintering 2 hours, the lifting temperature is controlled at 1-1.5 ℃/minute, cut into slices again, two sides blackening AgPd electrode, scribing, be chip, and then glass envelope technology glass is pressed in the chip employing sealed, temperature is controlled in the 650-700 ℃ of scope, and the glass envelope time was controlled in 25 minutes.
The manufacture method of oxidate semi-condcutor thermo-sensitive resistance device of the present invention has original solution in the following areas:
(1) when adopting liquid-phase coprecipitation to prepare powder, too high as the pH value of solution, the sediment of some element can produce complexing and dissolve; PH value is low excessively, some element can not precipitate again fully, and pH value is a parameter that is difficult to accurately control in chemical reaction, this certainly will cause the powder element ratio and the original formulation that are settled out variant, and each technology all is difficult to repetition, and the present invention takes strict control precipitated liquid and the concentration of precipitation reagent and the ratio of measuring between the two, and precipitation reagent evenly slowly adds, the temperature of precipitated liquid is controlled in the 30-40 ℃ of scope all the time, thereby reaches the purpose of control powder element ratio.
(2) to make powder thinner because of liquid-phase coprecipitation, the powder surface activity is big, reunites further this reunion of aggravation of a large amount of anionic existence in the precipitated liquid especially easily, cause granularity big, inhomogeneous, the consistency of material is very poor, and the present invention adds emulsifying agent in precipitated liquid, reduce the surface activity of powder, add deionized water with sediment and clean repeatedly, carry out sonicated simultaneously, destroy the reunion of powder.Before pre-burning, introduce thermal decomposition process, decompose the back powder is ground.
(3) traditional quick resistance of pearl body heat or thick-film thermistor, because material behavior is inhomogeneous, the temperature-sensitive chip size is inconsistent, the influence of factors such as electrode effect, packaging technology causes the inconsistent of component parameters.The present invention introduces the cold isostatic compaction technology, adopts section, scribing process, has guaranteed that product has higher consistency.
(4) thermistor that adopts the present invention to produce, its chip size should be at V=a * a * d, 0.70＜a＜0.5mm; 0.20 in＜d＜0.30mm scope, be convenient to the operation of glass packaging technology, its electrical parameter B25/50=3470 ± 1%, R25 ℃=2.0-6.0K Ω.
Embodiment 1:
Use commercially available analysis pure by cobalt nitrate 30%, manganese nitrate 45%, nickel nitrate 205% (mol ratio) as proportion of raw material weighing 2mol, be mixed with the precipitated liquid that concentration is 1N, solution temperature is at 30-40 ℃.
Use the pure carbonic hydroammonium 6mol of commercially available analysis as precipitation reagent, be mixed with the precipitant solution that concentration is 2N, solution temperature is controlled at 30-40 ℃;
Add the emulsifier op-10 of 1% weight in precipitated liquid, and in vigorous stirring the speed of precipitation reagent by 50-100ml/ minute is evenly added, till adding, precipitation process is finished;
To have sedimentary solution and place Ultrasound Instrument to handle 10 minutes, and carry out suction filtration, and add the 3000ml deionized water again, temperature is at 30-40 ℃, stirring-sonicated-suction filtration, and this process is 3-5 time repeatedly, dries levigate;
Powder was 400 ℃ of thermal decompositions 6 hours, and is levigate, 800 ℃ of pre-burnings 3 hours, levigate then, and the powder preparing process finishes;
Carry out isostatic cool pressing after pressed by powder being become the cylinder of φ 50mm, pressure is 2.0-3.5T/cm
2Then 1180 ℃ of sintering 2 hours, the lifting temperature is controlled at 1-1.5 ℃/minute, use slicing machine, the cylinder that sintering is intact is cut into disk, two sides blackening AgPd electrode, divide electrode chip again into, chip is pressed glass envelope technology glass envelope, temperature is controlled in 650 ℃ of scopes again, and the glass envelope time was controlled in 25 minutes.
The quick resistance electrical parameter of gained pearl body heat B25/50=3470 ± 1%, R25 ℃=2.0-6.0K Ω
Embodiment 2:
Use commercially available analysis pure by cobalt nitrate 40%, manganese nitrate 42%, nickel nitrate 15% (mol ratio) as proportion of raw material weighing 2mol, be mixed with the precipitated liquid that concentration is 1N, solution temperature is at 30-40 ℃.
Use the pure carbonic hydroammonium 6mol of commercially available analysis as precipitation reagent, be mixed with the precipitant solution that concentration is 1.5N, solution temperature is controlled at 30-40 ℃;
Add the emulsifier op-10 of 1% weight in precipitated liquid, and in vigorous stirring the speed of precipitation reagent by 50-100ml/ minute is evenly added, till adding, precipitation process is finished;
To have sedimentary solution and place Ultrasound Instrument to handle 10 minutes, and carry out suction filtration, and add the 3000ml deionized water again, temperature is at 30-40 ℃, stirring-sonicated-suction filtration, and this process is 3-5 time repeatedly, dries levigate;
Powder was 500 ℃ of thermal decompositions 10 hours, and is levigate, 800 ℃ of pre-burnings 3 hours, levigate then, and the powder preparing process finishes;
Carry out isostatic cool pressing after pressed by powder being become the cylinder of φ 50mm, pressure is 2.0-3.5T/cm
2Then 1200 ℃ of sintering 2 hours, the lifting temperature is controlled at 1-1.5 ℃/minute, use slicing machine, the cylinder that sintering is intact is cut into disk, two sides blackening AgPd electrode, divide electrode chip again into, chip is pressed glass envelope technology glass envelope, temperature is controlled in 700 ℃ of scopes again, and the glass envelope time was controlled in 25 minutes
The quick resistance electrical parameter of gained pearl body heat B25/50=3470 ± 1%, R25 ℃=2.0-6.0K Ω
Embodiment 3:
Use commercially available analysis pure by cobalt nitrate 35%, manganese acetate 40%, nickel nitrate 18% (mol ratio) as proportion of raw material weighing 2mol, be mixed with the precipitated liquid that concentration is 1N, solution temperature is at 30-40 ℃.
Use the pure carbonic hydroammonium 6mol of commercially available analysis as precipitation reagent, be mixed with the precipitant solution that concentration is 2N, solution temperature is controlled at 30-40 ℃;
Add the emulsifier op-10 of 1N weight in precipitated liquid, and in vigorous stirring the speed of precipitation reagent by 50-100ml/ minute is evenly added, till adding, precipitation process is finished;
To have sedimentary solution and place Ultrasound Instrument to handle 10 minutes, and carry out suction filtration, and add the 3000ml deionized water again, temperature is at 30-40 ℃, stirring-sonicated-suction filtration, and this process is 3-5 time repeatedly, dries levigate;
Powder was 400 ℃ of thermal decompositions 5 hours, and is levigate, 800 ℃ of pre-burnings 3 hours, levigate then, and the powder preparing process finishes;
Carry out isostatic cool pressing after pressed by powder being become the cylinder of φ 50mm, pressure is 2.0-3.5T/cm
2Then 1180 ℃ of sintering 2 hours, the lifting temperature is controlled at 1-1.5 ℃/minute, use slicing machine, the cylinder that sintering is intact is cut into disk, two sides blackening AgPd electrode, divide electrode chip again into, chip is pressed glass envelope technology glass envelope, temperature is controlled in 680 ℃ of scopes again, and the glass envelope time was controlled in 25 minutes
The quick resistance electrical parameter of gained pearl body heat B25/50=3470 ± 1%, R25 ℃=2.0-6.0K Ω
Embodiment 4:
Use commercially available analysis pure by cobalt acetate 40%, manganese acetate 38%, nickel nitrate 17% (mol ratio) as proportion of raw material weighing 2mol, be mixed with the precipitated liquid that concentration is 1N, solution temperature is at 30-40 ℃.
Use the pure carbonic hydroammonium 6mol of commercially available analysis as precipitation reagent, be mixed with the precipitant solution that concentration is 2N, solution temperature is controlled at 30-40 ℃;
Add the emulsifier op-10 of 1% weight in precipitated liquid, and in vigorous stirring the speed of precipitation reagent by 50-100ml/ minute is evenly added, till adding, precipitation process is finished;
To have sedimentary solution and place Ultrasound Instrument to handle 10 minutes, and carry out suction filtration, and add the 3000ml deionized water again, temperature is at 30-40 ℃, stirring-sonicated-suction filtration, and this process is 3-5 time repeatedly, dries levigate;
Powder was 500 ℃ of thermal decompositions 6 hours, and is levigate, 750 ℃ of pre-burnings 3 hours, levigate then, and the powder preparing process finishes;
Carry out isostatic cool pressing after pressed by powder being become the cylinder of φ 50mm, pressure is 2.0-3.5T/cm
2Then 1200 ℃ of sintering 2 hours, the lifting temperature is controlled at 1-1.5 ℃/minute, use slicing machine, the cylinder that sintering is intact is cut into disk, two sides blackening AgPd electrode, divide electrode chip again into, chip is pressed glass envelope technology glass envelope, temperature is controlled in 700 ℃ of scopes again, and the glass envelope time was controlled in 25 minutes
The quick resistance electrical parameter of gained pearl body heat B25/50=3470 ± 1%, R25 ℃=2.0-6.0K Ω
Claims (4)
1, a kind of manufacture method of oxidate semi-condcutor thermo-sensitive resistance device, it is characterized in that, this thermistor is to be raw material with the nitrate of cobalt, manganese, nickel or acetate, adopt liquid-phase coprecipitation to prepare the material powder, add polyoxyethylene nonylphenol ether and enter cleaning, then powder is decomposed, grinding, pre-burning, carry out preforming again, isostatic cool pressing high humidity sintering is made; Raw material each component proportioning is (molar percentage %)
Cobalt 30-40 manganese 35-45 nickel 15-20
2, a kind of manufacture method of type oxidate semi-condcutor thermo-sensitive resistance device, it is characterized in that, this manufacture method is: pure to analyze (molar percentage %) cobalt 30-40, manganese 35-45, the nitrate of nickel 15-20 or acetate are raw material, adopt liquid-phase coprecipitation to prepare the precipitated liquid of material powder, precipitated liquid is the cobalt of concentration 1N, manganese, nickel salt solution, under violent stirring, evenly add precipitation reagent in the precipitated liquid, in precipitated liquid, add polyoxyethylene nonylphenol ether then, after finishing, anti-shallow lake adds repeatedly that deionized water cleans and solution is carried out sonicated, oven dry, levigate, presintering.
According to the manufacture method of the described oxidate semi-condcutor thermo-sensitive resistance device of claim 2, it is characterized in that 3, precipitation reagent concentration is the ammonium bicarbonate soln of 1.5-2N, the addition of precipitation reagent is 2-2.5 times (Capacity Ratio) of precipitated liquid.
4, the manufacture method of oxidate semi-condcutor thermo-sensitive resistance device according to claim 2, it is characterized in that, the addition 1% (weight) of polyoxyethylene nonylphenol ether, material oven dry, levigate after, earlier at 400-500 ℃ of thermal decomposition 5-10 hour, carry out presintering at 650-800 ℃ again through after grinding, carry out isostatic cool pressing after material is pre-formed as φ 50mm left and right sides cylinder, pressure is 2.0-3.5T/cm
2Then 1180-1200 ℃ of sintering 2 hours, warming and cooling rate is controlled at 1-1.5 ℃/minute, cut into slices again, two sides blackening AgPd electrode, scribing, be chip, and then glass envelope technology glass is pressed in the chip employing sealed, temperature is controlled in the 650-700 ℃ of scope, and the glass envelope time was controlled in 25 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96122180A CN1046052C (en) | 1996-12-14 | 1996-12-14 | Oxidate semi-conductor thermosensitive resistance and mfg. method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96122180A CN1046052C (en) | 1996-12-14 | 1996-12-14 | Oxidate semi-conductor thermosensitive resistance and mfg. method thereof |
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| Publication Number | Publication Date |
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| CN1185634A CN1185634A (en) | 1998-06-24 |
| CN1046052C true CN1046052C (en) | 1999-10-27 |
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| CN96122180A Expired - Fee Related CN1046052C (en) | 1996-12-14 | 1996-12-14 | Oxidate semi-conductor thermosensitive resistance and mfg. method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1332404C (en) * | 2004-09-02 | 2007-08-15 | 中国科学院新疆理化技术研究所 | Negative temperature coefficient thermosensitive resistance material and its producing method |
| CN1332405C (en) * | 2004-09-02 | 2007-08-15 | 中国科学院新疆理化技术研究所 | Negative temperature coefficient thermosensitive resistance material and its producing method |
| CN100443631C (en) * | 2006-08-17 | 2008-12-17 | 中国科学院上海技术物理研究所 | Preparation method of manganese-cobalt-nickel thin film heat-sensitive material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102991A (en) * | 1985-04-01 | 1987-01-17 | 中国科学院新疆物理研究所 | high-temperature thermistor with high reproducibility |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102991A (en) * | 1985-04-01 | 1987-01-17 | 中国科学院新疆物理研究所 | high-temperature thermistor with high reproducibility |
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| CN1185634A (en) | 1998-06-24 |
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