CN101891464B - High temperature thermistor and manufacturing method thereof - Google Patents
High temperature thermistor and manufacturing method thereof Download PDFInfo
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- CN101891464B CN101891464B CN 201010221601 CN201010221601A CN101891464B CN 101891464 B CN101891464 B CN 101891464B CN 201010221601 CN201010221601 CN 201010221601 CN 201010221601 A CN201010221601 A CN 201010221601A CN 101891464 B CN101891464 B CN 101891464B
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Abstract
The invention relates to a high temperature thermistor and a manufacturing method thereof. The high temperature thermistor is formed by barium titanate, lead titanate, calcium titanate, strontium titanate, semi-conducting elements, silicon oxide, titanium oxide, alumina, manganese dioxide and magnesium oxide, wherein the semi-conducting elements are one or more of niobium oxide, yttrium oxide and antimony oxide. The manufacturing method is characterized by adding water to barium titanate, lead titanate and the like in a ball mill and finely grinding the mixture, discharging and drying the ground mixture, presintering the ground mixture for 2h, grinding the ground mixture in the ball mill, adding PVA adhesive solution, pelleting the mixture, forming the mixture through pressing by a tablet press, sintering the formed material to obtain semi-conducting ceramics, carrying out grinding and spraying the Al electrode, thus obtaining the product. The sintering potential barrier is increased in the sintering process by adding the Mg element, thus ensuring the grains to be fine and uniform and the voltage resistance to be high. The ceramic structure is denser by replacing Ba with Mg, thus being capable of blocking ionic migration in the abominable atmosphere and improving the stability in the strongly abominable atmosphere. The high temperature thermistor can withstand 500V voltage under extremely low oxygen partial pressure by being assembled in a sealed Al pipe.
Description
Technical field
The present invention relates to a kind of high-temperature thermistor and method of manufacture thereof.
Background technology
Because Global climate change trend, weather environmental protection subject under discussion is suggested.Compare the wire spiral heating element, reliable, energy-conservation because of using posistor safety, so in the warm-air drier heating unit, use at present.
At present the posistor that uses of warm-air drier with (Pb, Ba) TiO3 is a principal crystalline phase, through lead displacement barium, its switch temperature is at 200-300 ℃.The method of manufacture of this posistor is to use ball mill or disperse ball mill mixing, through press filtration, light-burned ball milling; Add the tackiness agent granulating and forming again; In air, after sintering pottery under 1200-1400 ℃, the coating electrode forms thermistor chip then.Its grain size is not easy controlled, and compactness is lower, under severe environment, loses efficacy easily.
Owing to consider the security of this type warm-air drier; Heat generating components is sealed among the Al pipe; In ME, also need use organic glue, the heating thermistor chip is in thermal extremes and the extremely low state of oxygen pressure during energising, so high to the reliability requirement of thermistor.The thermistor chip security of domestic production at present is unsatisfactory.
Summary of the invention
The objective of the invention is to above-mentioned present situation, it is high to aim to provide a kind of proof voltage ability, and ceramic structure is fine and close, can hinder ion migration, can press high-temperature thermistor and the method for manufacture thereof that can stablize use under the extremely low state at thermal extremes and oxygen.
The implementation of the object of the invention is that high-temperature thermistor is with 50-85%mol barium titanate, 2-39mol lead titanate, 1-7mol calcium titanate; The 1-10mol strontium titanate is a staple, contains 0.12-0.13mol semiconductor element, glass substance: the 1-2mol silicon oxide; The 1mol titanium oxide, the 0.2mol aluminum oxide receives the main classes material: 0.08%mol Manganse Dioxide; 0.09mol Natural manganese dioxide, wherein the semiconductor element is one or more in niobium oxides, yttrium oxide, the weisspiessglanz.
The method of manufacture of high-temperature thermistor is got 2-39mol lead titanate, 1-7mol calcium titanate, and the 1-10mol strontium titanate is a staple, contains 0.12-0.13mol semiconductor element, 1-2mol silicon oxide; 1mol titanium oxide, 0.2mol aluminum oxide, 0.08mol Manganse Dioxide and 0.09mol Natural manganese dioxide add the water mixing in ball mill levigate, and discharging is dry; 1050 ℃ of pre-burnings 2 hours, and broken in ball mill again, and adding powder weight ratio is 8% PVA binder solution; The tabletting machine moulding is passed through in granulation, and becomes the semiconductor pottery in 30 minutes at 1290 ℃ of sintering; Through abrasive disc, spray Al electrode gets the high-temperature thermistor product.
The present invention has increased sintering potential barrier through adding the Mg element in sintering process, make crystal grain tiny evenly, has improved the proof voltage ability; Because Ba
2+Radius 1.42, and Mg
2+Radius be 0.72, through the position of Mg displacement Ba, make ceramic structure fine and close more, in abominable atmosphere, can hinder ion migration, can press extremely low state to stablize use down at thermal extremes and oxygen.Be assemblied in the Al pipe of sealing, under the extremely low severe environment of oxygen partial pressure, it is withstand voltage to stand 500V.
Embodiment
High-temperature thermistor of the present invention is by barium titanate, lead titanate, calcium titanate, strontium titanate, semiconductor element, silicon oxide, and titanium oxide, titanium oxide, aluminum oxide, Manganse Dioxide and Natural manganese dioxide are formed.The semiconductor element is one or more in niobium oxides, yttrium oxide and the weisspiessglanz.
Method of manufacture is that above-mentioned barium titanate, lead titanate etc. are added water mill in ball mill thin, and discharging is dry, and is light-burned 2 hours, broken in the ball mill; Add the PVA binder solution, granulation, the tabletting machine moulding, burning till is that semiconductor is ceramic; Through abrasive disc, spray Al electrode gets product.
Enumerate the specific embodiment of the invention below:
Example 1, get 85mol barium titanate, 7mol lead titanate, 7mol calcium titanate, 1mol strontium titanate, 0.13mol niobium oxides, 2.1mol silicon oxide, 1mol titanium oxide, 0.2mol aluminum oxide, 0.08mol Manganse Dioxide and 0.01mol Natural manganese dioxide add water and mix levigate in ball mill; Discharging is dry, 1050 ℃ light-burned 2 hours, and broken in ball mill again; Adding powder weight ratio is 8% PVA binder solution, and granulation is through the tabletting machine moulding; And became the semiconductor pottery in 30 minutes at 1290 ℃ of sintering; Through abrasive disc, spray Al electrode gets 32 * 12 * 2.4mm thermistor chip product.
Example 2, get 85mol barium titanate, 7%mol lead titanate, 6mol calcium titanate, 2mol strontium titanate, 0.13%mol niobium oxides, 2.1%mol silicon oxide, 1%mol titanium oxide, 0.2%mol aluminum oxide, 0.08%mol Manganse Dioxide and 0.04%mol Natural manganese dioxide add water and mix levigate in ball mill; Discharging is dry, 1050 ℃ light-burned 2 hours, and broken in ball mill again; Adding powder weight ratio is 8% PVA binder solution, and granulation is through the tabletting machine moulding; And became the semiconductor pottery in 30 minutes at 1290 ℃ of sintering; Through abrasive disc, spray Al electrode gets 32 * 12 * 2.4mm thermistor chip product.
Example 3, get 85mol barium titanate, 7mol lead titanate, 5mol calcium titanate, 3mol strontium titanate, 0.13mol niobium oxides, 2.1mol silicon oxide, 1mol titanium oxide, 0.2mol aluminum oxide, 0.08mol Manganse Dioxide and 0.09mol Natural manganese dioxide add water and mix levigate in ball mill; Discharging is dry, 1050 ℃ light-burned 2 hours, and broken in ball mill again; The PVA binder solution of adding 8%, granulation is through the tabletting machine moulding; And became the semiconductor pottery in 30 minutes at 1290 ℃ of sintering; Through abrasive disc, spray Al electrode gets 32 * 12 * 2.4mm thermistor chip product.
Comparative example 1, get 85mol barium titanate, 7mol lead titanate, 7mol calcium titanate, 1mol strontium titanate, 0.13mol niobium oxides, 2.1mol silicon oxide, 1mol titanium oxide, 0.2mol aluminum oxide, 0.08mol Manganse Dioxide add water and mix levigate in ball mill; Discharging is dry, 1050 ℃ light-burned 2 hours, and broken in ball mill again; The PVA binder solution of adding 8%, granulation is through the tabletting machine moulding; And became the semiconductor pottery in 30 minutes at 1290 ℃ of sintering; Through abrasive disc, spray Al electrode gets 32 * 12 * 2.4mm thermistor chip product.
With routine 1-example 3 making methods, the semiconductor element is used the 0.12%mol weisspiessglanz instead, gets routine 4-example 6
Comparative example 2, get 57mol barium titanate, 35mol lead titanate, 3mol calcium titanate, 5mol strontium titanate, 0.12mol weisspiessglanz, 2.1mol silicon oxide, 1mol titanium oxide, 0.2mol aluminum oxide, 0.08mol Manganse Dioxide add water and mix levigate in ball mill; Discharging is dry, 1050 ℃ light-burned 2 hours, and broken in ball mill again; Adding powder weight ratio is 8% PVA binder solution, and granulation is through the tabletting machine moulding; And became the semiconductor pottery in 30 minutes at 1290 ℃ of sintering; Through abrasive disc, spray Al electrode gets 32 * 12 * 2.4mm thermistor chip product.
With routine 1-example 3 making methods, the semiconductor element is used the 0.15%mol yttrium oxide instead, gets routine 7-example 9
Comparative example 3, get 50mol barium titanate, 39mol lead titanate, 1mol calcium titanate, 10mol strontium titanate, 0.15mol yttrium oxide, 2.1mol silicon oxide, 1mol titanium oxide, 0.2mol aluminum oxide, 0.08mol Manganse Dioxide add water and mix levigate in ball mill; Discharging is dry, 1050 ℃ light-burned 2 hours, and broken in ball mill again; Adding powder weight ratio is 8% PVA binder solution, and granulation is through the tabletting machine moulding; And became the semiconductor pottery in 30 minutes at 1290 ℃ of sintering; Through abrasive disc, spray Al electrode gets 32 * 12 * 2.4mm thermistor chip product.
The applicant's use-case 1-example 9 has been done constituent content and performance comparison test with existing comparative example 1-comparative example 3 (getting 32 * 12 * 2.4mm thermistor chip product with traditional method), and test-results sees the following form:
Visible from last table, through the posistor that the present invention makes, under severe environment, the proof voltage ability has strengthened greatly, thereby has improved safety.
Claims (1)
1. high-temperature thermistor is characterized in that getting 50-85mol barium titanate, 2-39mol lead titanate, 1-7mol calcium titanate, 1-10mol strontium titanate, 0.12-0.13mol semiconductor element, 1-2mol silicon oxide, the 1mol titanium oxide with following method preparation; 0.2mol aluminum oxide, 0.08mol Manganse Dioxide and 0.09mol Natural manganese dioxide add the water mixing in ball mill levigate, discharging was dry, 1050 ℃ of pre-burnings 2 hours; And broken in ball mill again, the PVA binder solution of adding powder weight 8%, granulation; Pass through the tabletting machine moulding, and became the semiconductor pottery in 30 minutes, through abrasive disc at 1290 ℃ of sintering; Spray Al electrode gets the high-temperature thermistor product
Wherein silicon oxide, titanium oxide, aluminum oxide are glass substance, and Manganse Dioxide, Natural manganese dioxide are for receiving the main classes material, and the semiconductor element is one or more in niobium oxides, yttrium oxide, the weisspiessglanz.
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| CN102617133B (en) * | 2012-03-26 | 2013-10-16 | 常熟市林芝电子有限责任公司 | Thermal sensitive ceramic material and high-voltage-resistant thermistor prepared by using thermal sensitive ceramic material and preparation method |
| CN102603291A (en) * | 2012-03-26 | 2012-07-25 | 常熟市林芝电子有限责任公司 | Thermosensitive ceramic material, thermosensitive resistor made from thermosensitive ceramic material and used for starting refrigerator, and preparation method |
| CN102617132A (en) * | 2012-03-26 | 2012-08-01 | 常熟市林芝电子有限责任公司 | Thermal sensitive ceramic material, thermistor made of thermal sensitive ceramic material and used for yarn heating, and thermistor production method |
| CN102617134A (en) * | 2012-03-26 | 2012-08-01 | 常熟市林芝电子有限责任公司 | Thermal sensitive ceramic material, thermal resistor made of thermal sensitive ceramic material and used for heating, and manufacture method for thermal resistor |
| CN102603290A (en) * | 2012-03-26 | 2012-07-25 | 常熟市林芝电子有限责任公司 | Thermal sensitive ceramic material, thermistor therefrom for battery protection and manufacture method |
| CN102617136A (en) * | 2012-03-26 | 2012-08-01 | 常熟市林芝电子有限责任公司 | Thermosensitive ceramic material and electromobile thermosensitive resistor made of thermosensitive ceramic material and manufacturing method of thermosensitive resistor |
| CN107056279B (en) * | 2017-03-23 | 2018-06-05 | 汕尾比亚迪实业有限公司 | Single donor doping positive temperature coefficient thermal sensitive ceramic and preparation method thereof |
| CN107631820A (en) * | 2017-09-25 | 2018-01-26 | 南京航伽电子科技有限公司 | A kind of pressure transmitter being suitable under low temperature environment |
| CN108727055A (en) * | 2018-06-27 | 2018-11-02 | 佛山市南海蜂窝电子制品有限公司 | A kind of PTC ceramic honey combs heating element and preparation method thereof |
| CN110467455B (en) * | 2019-08-20 | 2022-02-08 | 威海市科博乐汽车电子有限公司 | Preparation method of positive temperature coefficient thermistor for electric automobile |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1237949A (en) * | 1996-11-20 | 1999-12-08 | 株式会社村田制作所 | Barium titanate-base semiconducting ceramic composition |
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| US7230817B2 (en) * | 2005-04-15 | 2007-06-12 | Ferro Corporation | Y5V dielectric composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237949A (en) * | 1996-11-20 | 1999-12-08 | 株式会社村田制作所 | Barium titanate-base semiconducting ceramic composition |
Non-Patent Citations (2)
| Title |
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| 唐功本.稀土高温热敏电阻及其应用.《传感器技术》.1987,(第3期),第42-43页，第48页. * |
| 赵俊英等.介电温度稳定型钛酸钡基陶瓷的研究进展.《材料导报》.2008,第22卷(第11期),第21-25页. * |
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