CN101792316B - High-Curie-point lead-free PTCR (Positive Temperature Coefficient of Resistance) thermo-sensitive ceramic material - Google Patents
High-Curie-point lead-free PTCR (Positive Temperature Coefficient of Resistance) thermo-sensitive ceramic material Download PDFInfo
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- CN101792316B CN101792316B CN2010101021134A CN201010102113A CN101792316B CN 101792316 B CN101792316 B CN 101792316B CN 2010101021134 A CN2010101021134 A CN 2010101021134A CN 201010102113 A CN201010102113 A CN 201010102113A CN 101792316 B CN101792316 B CN 101792316B
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Abstract
The invention relates to a semi-conductive ceramic material, in particular to a thermo-sensitive ceramic resistance material which accords with the semi-conduction of a high-Curie-point (larger than 120 DEG C) lead-free ceramic material and has PTCR (Positive Temperature Coefficient of Resistance). The material comprises (Bi1/2K1/2-a/2Naa/2)Ce1-bDbO3, wherein a equals to 0-1, and b equals to 0.0005-0.005. The high-Curie-point PTCR thermo-sensitive ceramic material does not contain lead, is made of wide and rich raw materials and prevents lead of resistance components from harming the environment and human beings in the manufacture and use processes. The invention solves the technical problems of content design and material semi-conduction of the lead-free high-Curie-point PTCR thermo-sensitive ceramic material and can realize the adjustability of Curie points in a wider temperature range by adjusting the formulation of main components.
Description
Technical field
The invention belongs to a kind of semiconductor ceramic material, especially meet unleaded high curie point ferroelectric ceramic material and realize that semiconductor, preparation have the PTCR thermal sensitive ceramic material of the unleaded high curie point thermal sensitive ceramics resistance unit of positive temperature coefficient of resistance (PTCR) effect.
Background technology
The PTCR pottery is a kind of semiconductor transformation, have the electron ceramic material of positive temperature coefficient of resistance (PositiveTemperature Coefficient of Resistance).This electronic ceramics element with intelligent characteristic integrates heating and temperature control, has automatic temperature-controlled, energy-saving safe, recoverys automatically, contactless action, the flames of anger, life-span and characteristics such as grows.The product systems such as components and parts, temperature control, overcurrent protection, overheating protection, thermoinduction and temperature alarming that can be used for generating heat are widely used in automobile, electronics, communication, project of transmitting and converting electricity, air-conditioning warm-air drier engineering, less energy-consumption safety type home-use electrical equipment and fields such as demagnetization, overcurrent protection, overheating protection and temperature alarming.
Modal PTCR thermal sensitive ceramics element is ABO
3The BaTiO of type
3Sill, its Curie temperature are 120 ℃.In order to improve the working temperature of ceramic component, current is that Curie temperature moves agent, realizes that with the crystallographic site of Pb displacement Ba this type of thermal sensitive ceramics is the higher (Ba of lead tolerance to add plumbous oxide or lead-containing compounds all
1-xPb
x) TiO
3System or (Sr
1-x-yBa
yPb
x) TiO
3, wherein x or y can be between 0 to 1 value.As, the staple of Chinese invention patent ZL97100777.2 number disclosed thermistor material is: (Sr
1-x-yBa
yPb
x) Ti
zO
3+ wPbSi
nO
2n+m, x=0.1～0.9 wherein, y=0～0.9, z=0.8～1.2, w=0.001～1, m/n=0.1～10; This invention prescription and technology are can obtained performance adjustable, stability and the good PTC thermistor material of reproducibility.In addition, disclosing a kind of equation for Chinese invention patent ZL96106337.8 number is (Sr
1-xPb
x) Ti
yO
3PTC stupalith system, x=0.1～0.9 wherein, y=0.8～1.2; The semiconductor constituent content is 0.012～2mol%, and additive level is 0.2～3mol%; This invention can obtain good comprehensive properties PTC thermal sensitive ceramics resistor.
All leaded in the foregoing invention patent formulation.Lead is a kind of toxic heavy metal element that has; In the production process of leaded PTCR thermal sensitive ceramic material; Contain lead oxides and can flow into living environment and the Nature because of a variety of causes inevitably; As clean the ball grinder behind each batch production product waste water, clean other produce with take place in waste water, calcining and the sintering process of device plumbous evaporable atmosphere be full of production plant in addition be diffused into around very large-scale physical environment, thereby cause pollution, to the particularly producer and user's healthy harm of the mankind to physical environment.In recent years; Many developed countries have begun the use of strict control products containing lead, and " about in electricinstallation, banning use of leaded some objectionable impurities instruction that waits " (the ROHS instruction) of issuing like European Union proposes clearly to forbid that leaded electronic product gets into the European market.On the other hand; Along with scientific-technical progress and The development in society and economy; The application of electronic product more and more widely also strengthens with environmental consciousnesses universal, people gradually, and environmentally friendly green product is just more and more favored, and environmentally friendly machine will be the unique selection of Future Society product.At present, the development of China PTCR industry is being faced with serious test and challenge.The exploitation of the lead-free PTCR thermal sensitive ceramic material of environment-friendly type has become an extremely urgent problem.The development of lead-free will obtain immediately society certainly and welcome, the timely application of product, replace products containing lead fully and will become inevitable.
In recent years, domestic and international many scientific research personnel and production work person have set about the exploitation and the research work of the lead-free PTCR thermal sensitive ceramic material of high curie point (greater than 120 ℃).Utilize BaTiO
3-(Bi, Na) TiO
3System is the PTCR thermal sensitive ceramic material about 170 ℃ for research object has obtained Curie temperature.Chinese patent publication number CN101013618A and CN101188156A have explained that the composition system is (Na
1/2Bi
1/2) BaTiO
3The PTC stupalith of base; With Y, La, Sb, Nb, Ta etc. is that to add element and a small amount of Sr or Ca be that element is changed in the Ba position in semiconductor; And add the Mn constituent content and account for total amount of material 0.019～0.0199mol%, this invention can realize that Curie temperature is higher than 120 ℃ thermal sensitive ceramics.Chinese patent publication number CN1426072A has explained that the composition system is (Ba
xSr
yCa
z) Ti
uO
3A kind of lead-free PTCR ceramic material, x=0.6～0.9 wherein, y=0～0.3, z=0.02～0.2, u=0.98～1.02.But the Curie temperature scope that this patent proposes can only fail to realize more high curie point at 50-120 ℃.Chinese invention patent application number 200810143548.6 has been explained a kind of based on Ce doping (Bi
0.5K
0.5) TiO
3High curie point lead-free PTCR thermal sensitive ceramics resistive material, Curie temperature can reach 250 ℃.Also there is the investigator to utilize KNbO
3The PTC ferroelectric ceramic material (Journal of Materials Research, 17 (2002) 2989) of based material research high curie point, this type material has also shown the PTC phenomenon, but performance is well below application standard.
Find out thus; Though environmentally friendly PTCR thermal sensitive ceramic material has far-reaching social effect and economic benefit; But from documents and materials and the patent of having delivered, Tc is quite few at 120～300 ℃, achievement report functional, serial thermal sensitive ceramics thermal control material with PTC.Therefore, exploitation lead-free PTCR thermal sensitive ceramic material has become a crucial problem, has great social significance and will produce very big economic benefit.
Summary of the invention
The purpose of this invention is to provide a kind of Curie-point temperature of can making greater than 120 ℃ unleaded high curie point PTCR thermal sensitive ceramics resistive material.
Unleaded high curie point pottery PTCR thermistor material of the present invention is characterized in that the principal constituent of this material consists of:
(Bi
1/2K
1/2-a/2Na
a/2)Ce
1-bD
bO
3
A=0～1 wherein, b=0.0005～0.005.D is micro-semiconductor element in the prescription principal constituent, and D contains at least a element in Sb, Nb, Ta, V, Mo, the W element, and its content accounts for total amount of material 0.05～0.5mol%.Contain Bi, K, Na, Ce metallic element in the prescription principal constituent; The semiconductor alloying element contains at least a metallic element in Sb, Nb, Ta, V, Mo, the W element.
The initial raw materials of implementation process of the present invention is selected from Bi
2O
3, K
2CO
3, Na
2CO
3, CeO
2, Sb
2O
3, Nb
2O
5, Ta
2O
5, V
2O
5Can obtain high-purity phase composite, stable performance, unleaded high curie point PTCR thermistor that safety is high by the said preparation method of the embodiment of the invention.Starting material can be selected the compounds such as oxide compound, inorganic salt or organic salt that contain at least a metallic element in Bi, K, Na, Ce metallic element in the prescription principal constituent and Sb, Nb, Ta, V, Mo, the W element for use; Material synthesis method can be selected the conventional solid-state reaction method for use, also can adopt chemical synthesis process.The detection of thermistor material characteristic of the present invention is to adopt the coated silver slurry to be electrode, the room temperature resistance of measuring sensor and resistance-temperature characteristics.Actual production can be selected other electrode materials (like aluminium electrode, In-Ga alloy electrode, nickel electrode etc.) for use.
The major advantage of PTCR thermal sensitive ceramics resistive material of the present invention is: 1. adopt monovalence and trivalent element (Bi, K, Na) compound as ABO
3A crystallographic site element in the type calcium titanium ore structure, Ce are B crystallographic site element; 2. K capable of using, Na constituent content move agent as Tc; 3. realize the semiconductor of lead-free ceramics material through micro-donor doping; 4. not leaded in the system component, realized the unleaded of high curie point PTCR material.
The electrical property of PTCR thermal sensitive ceramics resistive material of the present invention can be realized following parameter request:
Curie temperature scope: 165～205 ℃; Liftdrag log (R
Max/ R
Min): 3.1; Temperature coefficient of resistance: 24%/℃.
Compare with at present existing like product; Not leaded in the high curie point PTCR thermal sensitive ceramics resistive material of the present invention; And solved the technical barrier that unleaded high curie point PTCR thermal sensitive ceramics resistive material is realized semiconductor, avoided plumbous harm in such thermistor manufacturing and the use environment and human body.
Description of drawings
Fig. 1 is the resistance-temperature characteristics curve of thermal sensitive ceramics resistive material among the embodiment.
Content of the present invention combines following examples to do explanation further.Following examples just meet several instances of technology contents of the present invention, do not explain that the present invention only limits to the described content of following instance.
Embodiment
Embodiment 1
This instance is by molecular formula (Bi
1/2K
1/2-a/2Na
A/2) Ce
1-bD
bO
3+ cM prepares burden, wherein a=0, b=0.003.Initial raw materials is selected from Bi
2O
3, K
2CO
3, CeO
2, Sb
2O
3The process step of following experiment is pressed in material prepn:
1. initial feed is pressed Bi
0.5K
0.5Ce
0.997Sb
0.003O
3The prescription batching takes by weighing 72.07g Bi
2O
3, 21.36g K
2CO
3, 106.38g CeO
2, 0.275g Sb
2O
3
2. will go up the Bi that a step takes by weighing
2O
3, K
2CO
3, CeO
2And Sb
2O
3Put in the ball grinder, and added suitable zero(ppm) water, ball mill mixing 4 hours;
3. the mixed slurry that will go up step preparation places glassware, puts into the baking oven for heating drying;
4. will go up the powder that a step makes and calcine, temperature is 800 ℃, is incubated 2 hours;
5. a step synthetic powder be will go up and granulation, molding blank carried out; Base substrate is the disk type, and the disk diameter is 15 millimeters, and thickness is 3.5～4.0 millimeters;
6. will go up the base substrate that a step obtains and carry out sintering, sintering temperature is 900 ℃, is incubated 2 hours, heats up and rate of cooling is 5 ℃ of PMs; So just obtain lead-free PTC thermal sensitive ceramics resistance unit;
7. will go up after lead-free PTCR thermal sensitive ceramics resistance unit two sides that a step makes polishes, the Tu Yiyin slurry also solidifies through 550 ℃ and to make electrodes;
8. will go up lead-free PTCR thermistor element that a step makes carries out resistance-temperature characteristics and measures.
Prepared material property such as table 1 are with shown in Figure 1.
Embodiment 2
This instance is by molecular formula (Bi
1/2K
1/2-a/2Na
A/2) Ce
1-bD
bO
3+ cM prepares burden, wherein a=1, b=0.0026.Initial raw materials is selected from Bi
2O
3, Na
2CO
3, CeO
2, Sb
2O
3The process step of following experiment is pressed in material prepn:
1. initial feed is pressed Bi
0.5Na
0.5Ce
0.9974Sb
0.0026O
3The prescription batching takes by weighing 73.91g Bi
2O
3, 16.79g Na
2CO
3, 109.09g CeO
2, 0.277g Sb
2O
3
2. preparation process is 2.～8. identical with step among the embodiment 1.
Prepared material property such as table 1 are with shown in Figure 1.
Embodiment 3
This instance is by molecular formula (Bi
1/2K
1/2-a/2Na
A/2) Ce
1-bD
bO
3+ cM prepares burden, wherein a=0.4, b=0.003.Initial raw materials is selected from Bi
2O
3, K
2CO
3, Na
2CO
3, CeO
2, Sb
2O
3The process step of following experiment is pressed in material prepn:
1. initial feed is pressed Bi
0.5K
0.3Na
0.5Ce
0.997Sb
0.003O
3The prescription batching takes by weighing 36.54g Bi
2O
3, 6.5g K
2CO
3, 3.31g Na
2CO
3, 53.72g CeO
2, 0.136g Sb
2O
3
2. preparation process is 2.～8. identical with step among the embodiment 1.
Prepared material property such as table 1 are with shown in Figure 1.
Table 1 embodiment material performance index
| Sequence number | Room temperature resistance (k Ω) | Curie temperature (℃) | Side reaction coefficient (%/℃) | Liftdrag log (R max/R min) |
| Embodiment 1 | 1.21 | 204.5 | 24.8 | 3.11 |
| Embodiment 2 | 0.82 | 165.5 | 13.8 | 2.55 |
| Embodiment 3 | 5.11 | 184.5 | 18.7 | 2.46 |
Claims (2)
1. the lead-free PTCR thermal sensitive ceramic material of a high curie point is characterized in that the composition of material consists of: (Bi
1/2K
1/2-a/2Na
A/2) Ce
1-bD
bO
3, a=0～1 wherein, b=0.0005～0.005, D is micro-semiconductor element, is at least a element in Sb, Nb, Ta, V, Mo, the W element, its content accounts for 0.05～0.5mol% of total amount of material.
2. the lead-free PTCR thermal sensitive ceramic material of high curie point according to claim 1 is characterized in that: (the Bi that forms the lead-free PTCR material
1/2K
1/2-a/2Na
A/2) Ce
1-bD
bO
3In, starting material are oxide compound, inorganic salt or the organic salt compounds that contain these elements.
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|---|---|---|---|
| CN2010101021134A CN101792316B (en) | 2010-01-28 | 2010-01-28 | High-Curie-point lead-free PTCR (Positive Temperature Coefficient of Resistance) thermo-sensitive ceramic material |
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|---|---|---|---|
| CN2010101021134A CN101792316B (en) | 2010-01-28 | 2010-01-28 | High-Curie-point lead-free PTCR (Positive Temperature Coefficient of Resistance) thermo-sensitive ceramic material |
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| CN101792316B true CN101792316B (en) | 2012-06-27 |
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|---|---|---|---|---|
| CN102503403A (en) * | 2011-10-14 | 2012-06-20 | 中南大学 | Lead-free PTCR (Positive Temperature Coefficient of Resistance) thermal sensitive ceramic resistance material with Curie point larger than 120 DEG C |
| CN103922741A (en) * | 2014-03-24 | 2014-07-16 | 上海大学 | CeO2 system PTCR thermal sensitive ceramic material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524792A (en) * | 2003-02-28 | 2004-09-01 | 新加坡纳米材料科技有限公司 | Method for preparing crystalline state perovskite compounds powder |
| CN1814570A (en) * | 2005-02-01 | 2006-08-09 | 四川大学 | Bi.Na.K.Li Ag titanate series lead-free piezoelectric ceramics |
| CN1974472A (en) * | 2001-08-28 | 2007-06-06 | Tdk株式会社 | Composition for thin-film capacitive device, insulating film, thin-film capacitive device, and capacitor |
| CN101412625A (en) * | 2008-11-10 | 2009-04-22 | 中南大学 | High-curie point lead-free PTC thermal sensitive ceramic resistor material |
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2010
- 2010-01-28 CN CN2010101021134A patent/CN101792316B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974472A (en) * | 2001-08-28 | 2007-06-06 | Tdk株式会社 | Composition for thin-film capacitive device, insulating film, thin-film capacitive device, and capacitor |
| CN1524792A (en) * | 2003-02-28 | 2004-09-01 | 新加坡纳米材料科技有限公司 | Method for preparing crystalline state perovskite compounds powder |
| CN1814570A (en) * | 2005-02-01 | 2006-08-09 | 四川大学 | Bi.Na.K.Li Ag titanate series lead-free piezoelectric ceramics |
| CN101412625A (en) * | 2008-11-10 | 2009-04-22 | 中南大学 | High-curie point lead-free PTC thermal sensitive ceramic resistor material |
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