CN101402523A - Complex-phase NTC thermal sensitive ceramic and method of manufacturing the same - Google Patents
Complex-phase NTC thermal sensitive ceramic and method of manufacturing the same Download PDFInfo
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- CN101402523A CN101402523A CNA2008100738725A CN200810073872A CN101402523A CN 101402523 A CN101402523 A CN 101402523A CN A2008100738725 A CNA2008100738725 A CN A2008100738725A CN 200810073872 A CN200810073872 A CN 200810073872A CN 101402523 A CN101402523 A CN 101402523A
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- complex phase
- thermal sensitive
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- sensitive ceramic
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Abstract
The invention discloses a complex phase NTC heat sensitive ceramic material and a method for preparing the same. The method comprises the following steps: using BaCO3, SnO2 and Bi2O3 as main raw materials, synthesizing BaSnO3 and BaBiO3 blanks through solid phase in advance, mixing and ball-milling the BaSnO3 and the BaBiO3 blanks secondarily or secondarily ball-milling the mixed blanks after doping micro Sb2O3 and oxides of rare earth elements into the mixed blanks, adopting an ordinary ceramic preparation process, and sintering the mixed blanks to be formed at a temperature of between 1,100 and 1,300 DEG C. Performance tests show that the B value of the complex phase NTC heat sensitive ceramic can reach more than 5,000K, and the resistivity at room temperature can be reduced to 200 omega.m. The complex phase NTC heat sensitive ceramic material has the advantages of simple preparation process, small material loss, and lower cost, and the obtained products can be used in the aspects of temperature measurement, temperature control, automatic gain adjustment, temperature compensation and the like.
Description
Technical field
The present invention relates to the NTC thermal sensitive ceramics, specifically is a kind of complex phase NTC thermal sensitive ceramics and preparation method thereof.
Background technology
NTCR (Negative Temperature Coefficient Thermistor) is a negative temperature coefficient thermistor spare, and its resistance reduces with the rising of temperature.The NTC thermistor generally is to make with the transition metal oxide semiconductor ceramic material, and resistivity is index and reduces along with the rising of temperature, is ideal temperature sensing modulator material.NTC thermal sensitive ceramic material kind is numerous, can be divided into oxide based and non-oxide system according to forming, and structure can be spinel type, perovskite typed, fluorite type, rutile-type etc.The main application of NTC thermal sensitive ceramics has temperature compensation, suppresses surge current, temperature detection and automatic gain adjustment etc.
But for the transition group metallic oxide system, become semiconductive ceramic in order to make it, generally will be at 1300 ℃ or higher sintering temperature, thereby have following shortcoming: energy consumption be big, and the kiln maintenance cost is high and damage easily.And transition group metallic oxide such as Cu, the Ni in traditional NTC thermal sensitive ceramics in the raw material, Co and rare earth oxide are lower at occurring in nature content, and cost of development is higher, and correspondence has improved the cost of NTC thermal sensitive ceramics.Therefore need the relatively low semiconductive ceramic of a kind of cost of agglomerating at a lower temperature as an alternative.
Summary of the invention
The objective of the invention is for overcoming the deficiencies in the prior art, have higher material constant B value simultaneously and than low room temperature resistivity, and cost is low, the simple complex phase NTC of technology thermal sensitive ceramics and preparation method thereof and provide a kind of.
Realize that technical scheme of the present invention is:
It is with BaCO
3, SnO
2And Bi
2O
3Be main raw material, synthetic respectively BaSnO with perovskite structure
3And BaBiO
3Compound, sintering after ball milling mixes forms the complex phase semiconductive ceramic, and its composition can be used general formula 100BaSnO
3-xBaBiO
3Represent that wherein x represents molar fraction, 0＜x≤100.
Its preparation technology is:
1. with SnO
2With BaCO
3For raw material is pressed chemical formula BaSnO
3Stoichiometric ratio is carried out proportioning, and wet ball grinding mixes it then, and oven dry is after 2 hours synthetic BaSnO of 1300 ℃ of insulations
3Blank.
2. with Bi
2O
3With BaCO
3For raw material is pressed chemical formula BaBiO
3Stoichiometric ratio is carried out proportioning, and wet ball grinding mixes it then, and oven dry is after 8 hours synthetic BaBiO of 800 ℃ of insulations
3Blank.
3.BaSnO
3And BaBiO
3Ceramic batch is pressed 100BaSnO
3-xBaBiO
3The ratio batching is mixed back secondary ball milling oven dry; Also can be at BaSnO
3And BaBiO
3Doping micro-antimony and rare earth oxide in the hybrid ceramic blank mix back secondary ball milling oven dry.Mixing or non-doping 100BaSnO
3-xBaBiO
3It is dry-pressing formed to add the PVA binding agent in the hybrid ceramic blank, discharges binding agent in 2 hours 600 ℃ of insulations, 1100～1300 ℃ of sintering 2～5 hours, cools to room temperature at last with the furnace again.Ceramic plate is two-sided by silver electrode.
This preparation method can be by adjusting BaSnO
3With BaBiO
3Mol ratio, hotchpotch molar content and sintering process regulate and control the electric property of this material system.
Novel complex phase NTC thermal sensitive ceramic material of the present invention has good thermo-sensitive property.Performance test shows that this thermal sensitive ceramics B value can reach more than the 5000K, and room temperature resistivity can be reduced to 200 Ω m, realize the characteristic of thermistor element low-resistance, high B value, can adopt traditional ceramics technology of preparing and industrial raw material to obtain, preparation technology is simple, stable, has practicality.
Description of drawings
Product ρ-T curve in Fig. 1 embodiment of the invention 1.
Product ρ-T curve in Fig. 2 embodiment of the invention 2.
Product ρ-T curve in Fig. 3 embodiment of the invention 3.
Embodiment
Embodiment 1:
With SnO
2With BaCO
3For raw material is pressed chemical formula BaSnO
3Carrying out proportioning, is the medium wet-milling with the dehydrated alcohol, and oven dry is after 2 hours synthetic BaSnO of 1300 ℃ of insulations
3Ceramic batch.
With Bi
2O
3With BaCO
3For raw material is pressed chemical formula BaBiO
3Carrying out proportioning, is the medium wet-milling with the dehydrated alcohol, and oven dry is after 8 hours synthetic BaBiO of 800 ℃ of insulations
3Ceramic batch.
BaSnO
3, BaBiO
3Ceramic batch is pressed 100BaSnO
3-30BaBiO
3The ratio batching, the secondary ball milling oven dry, the PVA solution that adds 3% concentration then is as binding agent, under 100MPa pressure, be pressed into diameter 18mm, the disk of thickness 1～1.4mm, temperature rise rate with 150 ℃/h was discharged binding agent in 2 hours 600 ℃ of insulations, and the temperature rise rate with 300 ℃/h is incubated 5 hours at 1200 ℃ again, cools to room temperature at last with the furnace.Ceramic plate is two-sided by silver electrode.
Performance test shows, room temperature resistivity ρ
25Be 200 Ω m, B
25/85Value is 4600K.Related data as shown in Figure 1.
Embodiment 2:
With SnO
2With BaCO
3For raw material is pressed chemical formula BaSnO
3Carrying out proportioning, is the medium wet-milling with the dehydrated alcohol, and oven dry is after 2 hours synthetic BaSnO of 1300 ℃ of insulations
3Ceramic batch.
With Bi
2O
3With BaCO
3For raw material is pressed chemical formula BaBiO
3Carrying out proportioning, is the medium wet-milling with the dehydrated alcohol, and oven dry is after 8 hours synthetic BaBiO of 800 ℃ of insulations
3Ceramic batch.
BaSnO
3, BaBiO
3Ceramic batch is pressed 100BaSnO
3-90BaBiO
3The ratio batching, the secondary ball milling oven dry, the PVA solution that adds 3% concentration then is as binding agent, under 100MPa pressure, be pressed into diameter 18mm, the disk of thickness 1～1.4mm, temperature rise rate with 150 ℃/h was discharged binding agent in 2 hours 600 ℃ of insulations, and the temperature rise rate with 300 ℃/h is incubated 2 hours at 1100 ℃ again, cools to room temperature at last with the furnace.Ceramic plate is two-sided by silver electrode.
Performance test shows, room temperature resistivity ρ
25Be 330 Ω m, B
25/85Value is 3400K.Related data as shown in Figure 2.
Embodiment 3:
With SnO
2With BaCO
3For raw material is pressed chemical formula BaSnO
3Carrying out proportioning, is the medium wet-milling with the dehydrated alcohol, and oven dry is after 2 hours synthetic BaSnO of 1300 ℃ of insulations
3Ceramic batch.
With Bi
2O
3With BaCO
3For raw material is pressed chemical formula BaBiO
3Carrying out proportioning, is the medium wet-milling with the dehydrated alcohol, and oven dry is after 2 hours synthetic BaBiO of 800 ℃ of insulations
3Ceramic batch.
BaSnO
3, BaBiO
3Ceramic batch is pressed 100BaSnO
3-30BaBiO
3The ratio batching adds 5at% (with respect to 100BaSnO
3-30BaBiO
3Total amount) Sb
2O
3The secondary ball milling oven dry, the PVA solution that adds 3% concentration then is as binding agent, under 100MPa pressure, be pressed into diameter 18mm, the disk of thickness 1～1.4mm, temperature rise rate with 150 ℃/h was discharged binding agent in 2 hours 600 ℃ of insulations, temperature rise rate with 300 ℃/h is incubated 2 hours at 1100 ℃ again, cools to room temperature at last with the furnace.Ceramic plate is two-sided by silver electrode.
Performance test shows, room temperature resistivity ρ
25Be 1900 Ω m, B
25/85Value is 5300K.Related data as shown in Figure 3.
Claims (3)
1, a kind of preparation method of complex phase NTC thermal sensitive ceramic material is characterized in that: comprise the steps:
(1) starting material is pressed BaCO
3: SnO
2=1: 1 molar ratio ingredient, wet ball grinding mixes it then, and oven dry synthesizes BaSnO
3Blank;
(2) starting material are pressed BaCO
3: Bi
2O
3=2: 1 molar ratio ingredient, wet ball grinding mixes it then, and oven dry synthesizes BaBiO
3Blank;
(3) ceramic batch that (1), (2) are obtained is by 100BaSnO
3-xBaBiO
3, 0＜x≤100 wherein, batching secondary ball milling; Or the ceramic batch that (1), (2) are obtained is by 100BaSnO
3-xBaBiO
3Add a small amount of hotchpotch secondary ball milling oven dry after (0＜x≤100) proportioning, preparation technology makes BaSnO by traditional ceramics
3/ BaBiO
3Complex phase NTC thermal sensitive ceramic material.
2, preparation method according to claim 1 is characterized in that: the hotchpotch described in the step (3) is micro-antimony and rare earth element.
3, a kind of complex phase NTC thermal sensitive ceramic material is characterized in that: with the complex phase NTC thermal sensitive ceramics product of the described preparation method's preparation of claim 1, it forms general formula is 100BaSnO
3-xBaBiO
3, wherein x represents molar fraction, 0＜x≤100.
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|---|---|---|---|
| CN2008100738725A CN101402523B (en) | 2008-10-31 | 2008-10-31 | Complex-phase NTC thermal sensitive ceramic and method of manufacturing the same |
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|---|---|---|---|
| CN2008100738725A CN101402523B (en) | 2008-10-31 | 2008-10-31 | Complex-phase NTC thermal sensitive ceramic and method of manufacturing the same |
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| Publication Number | Publication Date |
|---|---|
| CN101402523A true CN101402523A (en) | 2009-04-08 |
| CN101402523B CN101402523B (en) | 2012-07-25 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101826377A (en) * | 2010-03-31 | 2010-09-08 | 桂林电子科技大学 | Thick film thermistor slurry, preparation method thereof and thick film thermistor |
| CN105037991A (en) * | 2015-09-06 | 2015-11-11 | 安徽工业大学 | Bismuthic acid barium nanorod electronic packaging material |
| CN109251015A (en) * | 2018-11-09 | 2019-01-22 | 济南大学 | A kind of novel low-loss monocline microwave-medium ceramics and preparation method |
| CN110372335A (en) * | 2019-06-19 | 2019-10-25 | 山东格仑特电动科技有限公司 | A kind of manganese nickel aluminium cobalt-based NTC thermistor material and preparation method thereof |
-
2008
- 2008-10-31 CN CN2008100738725A patent/CN101402523B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101826377A (en) * | 2010-03-31 | 2010-09-08 | 桂林电子科技大学 | Thick film thermistor slurry, preparation method thereof and thick film thermistor |
| CN105037991A (en) * | 2015-09-06 | 2015-11-11 | 安徽工业大学 | Bismuthic acid barium nanorod electronic packaging material |
| CN105037991B (en) * | 2015-09-06 | 2017-07-04 | 安徽工业大学 | A kind of bismuthic acid barium nanometer rods electronic package material |
| CN109251015A (en) * | 2018-11-09 | 2019-01-22 | 济南大学 | A kind of novel low-loss monocline microwave-medium ceramics and preparation method |
| CN110372335A (en) * | 2019-06-19 | 2019-10-25 | 山东格仑特电动科技有限公司 | A kind of manganese nickel aluminium cobalt-based NTC thermistor material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101402523B (en) | 2012-07-25 |
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