CN101188156B - Heat sensitive resistor for high Curie temperature BaTiO3 base positive temperature coefficient and its making method - Google Patents
Heat sensitive resistor for high Curie temperature BaTiO3 base positive temperature coefficient and its making method Download PDFInfo
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- CN101188156B CN101188156B CN2007101511108A CN200710151110A CN101188156B CN 101188156 B CN101188156 B CN 101188156B CN 2007101511108 A CN2007101511108 A CN 2007101511108A CN 200710151110 A CN200710151110 A CN 200710151110A CN 101188156 B CN101188156 B CN 101188156B
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- temperature coefficient
- positive temperature
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- srco
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Abstract
The invention relates to a BaTiO3 group positive temperature coefficient thermistance and a preparation method thereof, wherein, the BaTiO3 group positive temperature coefficient thermistance has highCurie temperature. The invention belongs to the electronic ceramics technique. The recombination positive temperature coefficient thermistance is composed of main materials and assistant materials. The mol ratio of TiO2 and (BaCO3+SrCO3+Bi2O3+Na2CO3) of the main materials is 1:1. The mol components of the assistant materials are that Nb2O5 is 0.0011; TiO2 is 0.01; Sb2O3 is 0.0006; MnO2 is 0.0004;SiO2is 0.005; Al2O3 is 0.0017. The preparation process comprises that materials are weighed and mixed according to the mol prescription; the mixed materials are processed with ball milling after being added with water, and preparative complex materials are made through drying and heat preservation. The preparative complex materials are again added with raw materials, and then the preparative complex materials are processed with ball milling after being added with the water, thus the positive temperature coefficient thermistance is made through drying, granulation, foliation and baking. The invention has the advantages that the process of the composite (Na0.5Bi0.5)TiO3 is simple; the made positive temperature coefficient thermistance is unleaded and environment-friendly.
Description
Technical field
The present invention relates to a kind of high-curie temperature BaTiO
3Base positive temperature coefficient thermal resistor and preparation method belong to the electronic ceramic technology.
Background technology
Curie temperature is higher than 120 ℃ BaTiO at present
3Base positive temperature coefficient thermal resistor, its material batching is introduced lead element as mobile agent (Zhou Dongxiang etc., semiconductive ceramic and application, publishing house of HUST in forming, p90), this high-temp PTC R material can cause plumbous pollution to environment aborning when discarded.
Summary of the invention
The object of the present invention is to provide a kind of high-curie temperature BaTiO
3Base positive temperature coefficient thermal resistor and preparation method, this high-curie temperature BaTiO
3The additive that base positive temperature coefficient thermal resistor is unleaded, environmentally friendly, its preparation method process is simple.
The present invention is achieved by the following technical solutions, a kind of high-curie temperature BaTiO
3Base positive temperature coefficient thermal resistor is characterized in that, this high-curie temperature BaTiO
3Base positive temperature coefficient thermal resistor is made up of main material and auxiliary material, and wherein the main material mole consists of: TiO
2: (BaCO
3+ SrCO
3+ Bi
2O
3+ Na
2CO
3) be 1: 1;
BaCO
3, SrCO
3, Bi
2O
3And Na
2CO
3Molar fraction be:
BaCO
3：0.963～0.999
SrCO
3：0～0.035
Bi
2O
3：0.0005～0.001
Na
2CO
3：0.0005～0.001；
And BaCO
3, SrCO
3, Bi
2O
3And Na
2CO
3The molar fraction sum be 1;
The auxiliary material mole consists of:
Nb
2O
5：0.0011
TiO
2：0.01
Sb
2O
3：0.0006
MnO
2：0.0004
SiO
2：0.005
Al
2O
3：0.0017。
Above-mentioned high-curie temperature BaTiO
3The base positive temperature coefficient thermal resistor preparation method is characterized in that comprising following process: press TiO
2With BaCO
3, SrCO
3Mol ratio is 1: (0.963～0.999): (0～0.035) meter takes by weighing TiO with precision for the one thousandth balance
2, BaCO
3And SrCO
3Molal weight, press Bi
2O
3, Na
2CO
3, Nb
2O
5And Sb
2O
3Mol ratio is (0.0005～0.001): (0.0005～0.001): with precision be ten thousand/balance take by weighing Bi at 0.0011: 0.0006
2O
3, Na
2CO
3, Nb
2O
5And Sb
2O
3Molal weight, the material that is taken by weighing is mixed, be to add ball mill at 1: 1: 2 to carry out ball milling 3～24 hours by the mass ratio of compound and abrading-ball, deionized water then, the slip behind the mix grinding is placed baking oven 110～120 ℃ of oven dry, the oven dry material is incubated 2～4 hours down at 1000～1100 ℃ and carries out the synthetic in advance pre-synthesis material that makes again; Press MnO
2, SiO
2, TiO
2And Al
2O
3Mol ratio be 0.0004: 0.005: 0.01: 0.0017, be that ten thousand/balance takes by weighing MnO with precision
2, SiO
2, TiO
2And Al
2O
3Molal weight, to take by weighing in the pre-synthesis material of material adding and get batching entirely, by full batching and abrading-ball, the mass ratio of deionized water is that 1: 1: 2 adding ball mill carried out ball milling 4～24 hours, the complete wear material is dried under 110～120 ℃ of conditions, by the oven dry after the complete wear material quality 5～8%, adding mass concentration to the complete wear material is that the adhesive of 5% polyvinyl alcohol water solution carries out granulation, the granulation material is by 40 mesh sieves, the granulation material with 300～500MPa compacting in flakes, it is on the aluminium oxide backing plate of bedding and padding that sample in blocks is placed on the titanium dioxide zirconium powder, separate with the titanium dioxide zirconium powder in flakes, put into high-temperature electric resistance furnace then, the control programming rate is warming up under 1200 ℃～1350 ℃ conditions and burnt till 0.2～4 hour, wherein at 150 ℃ at 350～450 ℃/h, 250 ℃ and 350 ℃ respectively are incubated 20 minutes.Burn till the back sample with the stove cool to room temperature.After the zirconium dioxide bedding and padding removing of burning till on the ceramics of back, on ceramics two planes, evenly apply the metal ohmic contact electrode slurry, 450～610 ℃ of following burning infiltrations 8～15 minutes, make high-curie temperature BaTiO
3Base positive temperature coefficient thermal resistor.
Outstanding advantage of the present invention is to adopt to add Na
2CO
3And Bi
2O
3Adjust and raising BaTiO
3The Curie temperature of base positive temperature coefficient thermal resistor ceramic material (＞120 ℃), the BaTiO of realization high-curie temperature
3Base positive temperature coefficient thermal resistor ceramic material unleaded; Simultaneously can save synthetic (Na
0.5Bi
0.5) TiO
3Technology has been simplified technology.
Embodiment
Mol ratio by prescription takes by weighing 0.916molBaCO with the one thousandth balance
3, 0.08molSrCO
3, 1molTiO
2Molal weight, use ten thousand/balance to take by weighing 0.002molBi again
2O
3, 0.002molNa
2CO
3, 0.0011molNb
2O
5And 0.0006molSb
2O
3Molal weight, by batching: abrading-ball: the mass ratio of deionized water=1: 1: 2 will be prepared burden wet ball grinding 12h hour.Slip behind the mix grinding places baking oven 120 ℃ of oven dry.To dry material insulation under 1050 ℃ then carried out synthetic in advance in 2 hours.In pre-synthesis material according to the mol ratio of prescription, with precision be ten thousand/ balance allocate 0.0004molMnO into
2, 0.005molSiO
2, 0.0017molAl
2O
3, 0.01molTiO
2Molal weight, with batching: abrading-ball: the mass ratio of deionized water=1: 1: 2 carried out wet ball grinding 24 hours.The ball milling material is dried under 120 ℃ of conditions, is that 5～8% concentration is that 5% polyvinyl alcohol water solution is that adhesive joins in the oven dry material and carries out granulation with mass percent, and the granulation material is by 40 mesh sieves.Under 350MPa pressure, the granulation material is pressed into Φ 10mm * 3mm disk sample.Sample after the moulding is placed on the aluminium oxide backing plate that the titanium dioxide zirconium powder is bedding and padding, separate with the titanium dioxide zirconium powder between matrix band and sheet, put into high-temperature electric resistance furnace then, the control programming rate is 400 ℃/h, intensification reaches under 1250 ℃ of conditions burns till 2h, wherein respectively is incubated 20 minutes at 150 ℃, 250 ℃ and 350 ℃ in temperature-rise period.After burning till, sample is with the stove cool to room temperature.After the zirconium dioxide bedding and padding removing of burning till on the ceramics of back, on ceramics two planes, evenly apply the ohmic contact silver electrode paste, 450 ℃ of following burning infiltrations 10 minutes, make BaTiO of the present invention
3The base positive temperature coefficient thermal resistor sample.The measurement result of sample is: Curie temperature T
cBe 175 ℃, lift-drag ratio is 10
4, room temperature resistivity ρ is 12 Ω .cm.
Claims (2)
1. high-curie temperature BaTiO
3Base positive temperature coefficient thermal resistor is characterized in that, this high-curie temperature BaTiO
3Base positive temperature coefficient thermal resistor is made up of main material and auxiliary material, and wherein the main material mole consists of: TiO
2:
(BaCO
3+ SrCO
3+ Bi
2O
3+ Na
2CO
3) be 1: 1;
BaCO
3, SrCO
3, Bi
2O
3And Na
2CO
3Molar fraction be:
BaCO
3：0.963～0.999
SrCO
3：0～0.035
Bi
2O
3：0.0005～0.001
Na
2CO
3：0.0005～0.001；
And BaCO
3, SrCO
3, Bi
2O
3And Na
2CO
3The molar fraction sum be 1;
The auxiliary material mole consists of:
Nb
2O
5：0.0011，
TiO
2：0.01，
Sb
2O
3：0.0006，
MnO
2：0.0004，
SiO
2：0.005，
Al
2O
3：0.0017。
2. one kind prepares the described high-curie temperature BaTiO of claim 1
3The base positive temperature coefficient thermal resistor method is characterized in that comprising following process: press TiO
2With BaCO
3, SrCO
3Mol ratio is 1: (0.963～0.999): (0～0.035) meter takes by weighing TiO with precision for the one thousandth balance
2, BaCO
3And SrCO
3Molal weight, press Bi
2O
3, Na
2CO
3, Nb
2O
5And Sb
2O
3Mol ratio is (0.0005～0.001): (0.0005～0.001): with precision be ten thousand/balance take by weighing Bi at 0.0011: 0.0006
2O
3, Na
2CO
3, Nb
2O
5And Sb
2O
3Molal weight, the material that is taken by weighing is mixed, be to add ball mill at 1: 1: 2 to carry out ball milling 3～24 hours by the mass ratio of compound and abrading-ball, deionized water then, the slip behind the mix grinding is placed baking oven 110～120 ℃ of oven dry, the oven dry material is incubated 2～4 hours down at 1000～1100 ℃ and carries out the synthetic in advance pre-synthesis material that makes again; Press MnO
2, SiO
2, TiO
2And Al
2O
3Mol ratio be 0.0004: 0.005: 0.01: 0.0017, be that ten thousand/balance takes by weighing MnO with precision
2, SiO
2, TiO
2And Al
2O
3Molal weight, to take by weighing in the pre-synthesis material of material adding and get batching entirely, by full batching and abrading-ball, the mass ratio of deionized water is that 1: 1: 2 adding ball mill carried out ball milling 4～24 hours, the complete wear material is dried under 110～120 ℃ of conditions, by the oven dry after the complete wear material quality 5～8%, adding mass concentration to the complete wear material is that the adhesive of 5% polyvinyl alcohol water solution carries out granulation, the granulation material is by 40 mesh sieves, the granulation material with 300～500MPa compacting in flakes, it is on the aluminium oxide backing plate of bedding and padding that sample in blocks is placed on the titanium dioxide zirconium powder, separate with the titanium dioxide zirconium powder in flakes, put into high-temperature electric resistance furnace then, the control programming rate is at 350～450 ℃/h, be warming up under 1200 ℃～1350 ℃ conditions and burnt till 0.2～4 hour, wherein at 150 ℃, 250 ℃ and 350 ℃ respectively are incubated 20 minutes, burn till the back sample with the stove cool to room temperature, after the zirconium dioxide bedding and padding removing of burning till on the ceramics of back, on ceramics two planes, evenly apply the metal ohmic contact electrode slurry, 450～610 ℃ of following burning infiltrations 8～15 minutes, make high-curie temperature BaTiO
3Base positive temperature coefficient thermal resistor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101511108A CN101188156B (en) | 2007-12-20 | 2007-12-20 | Heat sensitive resistor for high Curie temperature BaTiO3 base positive temperature coefficient and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101511108A CN101188156B (en) | 2007-12-20 | 2007-12-20 | Heat sensitive resistor for high Curie temperature BaTiO3 base positive temperature coefficient and its making method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101188156A CN101188156A (en) | 2008-05-28 |
| CN101188156B true CN101188156B (en) | 2010-06-02 |
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ID=39480483
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101511108A Expired - Fee Related CN101188156B (en) | 2007-12-20 | 2007-12-20 | Heat sensitive resistor for high Curie temperature BaTiO3 base positive temperature coefficient and its making method |
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|---|---|---|---|---|
| CN101429020B (en) * | 2008-11-26 | 2011-11-23 | 丹东国通电子元件有限公司 | Method for producing positive temperature coefficient thermistor for surge suppressor |
| CN101880161B (en) * | 2010-05-28 | 2012-10-17 | 廖园富 | High-lift-to-drag-ratio ceramic thermistor and preparation method thereof |
| CN101838143B (en) * | 2010-06-01 | 2012-06-27 | 陕西科技大学 | Bi0.5Na0.5TiO3/Ba1-xCaxTiO3-based PTC thermal sensitive ceramic material and preparation method thereof |
| CN102924078A (en) * | 2012-10-22 | 2013-02-13 | 天津大学 | BCTZ-based perovskite system multi-component lead-free piezoelectric ceramic and preparation method thereof |
| CN102976747A (en) * | 2012-12-04 | 2013-03-20 | 广西新未来信息产业股份有限公司 | Lithium niobate doped barium titanate based positive temperature coefficient resistance material and preparation method thereof |
| CN103030391A (en) * | 2012-12-10 | 2013-04-10 | 广西新未来信息产业股份有限公司 | Bismuth titanate modified barium titanate base positive temperature coefficient resistance material and fabrication method thereof |
| CN103936411B (en) * | 2014-04-03 | 2016-08-17 | 天津大学 | Use the method that annealing method prepares ultra-wide temperature stable type barium phthalate base dielectric material |
| CN103936410B (en) * | 2014-04-03 | 2015-12-02 | 天津大学 | Manganous carbonate doped high temperature stable form barium phthalate base dielectric material |
| CN104016675B (en) * | 2014-06-20 | 2016-05-04 | 电子科技大学 | BaTiO3Base PTC ceramic powder, slice heat sensitive resistor and preparation method thereof |
| CN104402431A (en) * | 2014-11-27 | 2015-03-11 | 天津鑫华智联新型材料科技有限公司 | BaTiO3high-Curie-temperature PTC ceramic material |
| CN107082637A (en) * | 2017-05-08 | 2017-08-22 | 句容市博远电子有限公司 | A kind of semistor and preparation method thereof |
| CN107010944A (en) * | 2017-05-08 | 2017-08-04 | 句容市博远电子有限公司 | A kind of PTC thermistor and preparation method thereof |
| CN108695430B (en) * | 2018-04-20 | 2022-04-22 | 张发华 | High-performance piezoelectric sensor element and preparation process thereof |
| CN112608145A (en) * | 2020-11-25 | 2021-04-06 | 无锡市惠丰电子有限公司 | Preparation method of lead-free piezoelectric ceramic material |
| CN114524672A (en) * | 2022-03-15 | 2022-05-24 | 天津瑞肯新型材料科技有限公司 | Lead-free high-Curie-temperature positive temperature coefficient thermistor material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5272122A (en) * | 1991-09-18 | 1993-12-21 | Ngk Spark Plug Company, Ltd. | BaO-xTiO2 dielectric ceramic composition |
-
2007
- 2007-12-20 CN CN2007101511108A patent/CN101188156B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5272122A (en) * | 1991-09-18 | 1993-12-21 | Ngk Spark Plug Company, Ltd. | BaO-xTiO2 dielectric ceramic composition |
Non-Patent Citations (8)
| Title |
|---|
| 侯育冬 等.(Na0.5Bi0.5)TiO3基无铅压电陶瓷研究进展.材料导报16 4.2002,16(4),41-43. |
| 侯育冬等.(Na0.5Bi0.5)TiO3基无铅压电陶瓷研究进展.材料导报16 4.2002,16(4),41-43. * |
| 刘芳，曲远方.含Ni量对Ni/BaTiO3基复合PTC材料的影响.压电与声光29 4.2007,29(4),426. |
| 刘芳,曲远方.含Ni量对Ni/BaTiO3基复合PTC材料的影响.压电与声光29 4.2007,29(4),426. * |
| 唐斌 等.钛酸钡陶瓷中居里点移动规律与机理研究进展.真空科学与技术学报28 2.2007,28(2),120-125. |
| 唐斌等.钛酸钡陶瓷中居里点移动规律与机理研究进展.真空科学与技术学报28 2.2007,28(2),120-125. * |
| 陈志武.BNT-BT和BNT-BKT基无铅压电陶瓷研究进展.材料导报20 1.2006,20(1),14. |
| 陈志武.BNT-BT和BNT-BKT基无铅压电陶瓷研究进展.材料导报20 1.2006,20(1),14. * |
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