CN104844196B - Thermal sensitive ceramic material with Curie temperature - Google Patents
Thermal sensitive ceramic material with Curie temperature Download PDFInfo
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- CN104844196B CN104844196B CN201510167870.2A CN201510167870A CN104844196B CN 104844196 B CN104844196 B CN 104844196B CN 201510167870 A CN201510167870 A CN 201510167870A CN 104844196 B CN104844196 B CN 104844196B
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Abstract
The invention relates to the technical field of inorganic non-metallic materials, especially a thermal sensitive ceramic material with Curie temperature. The material is characterized by comprising the following ingredients by molar percentage: 92-99% of Ba0.398Pb0.6La0.002TiO3, 0.1-4.0% of BN, 0.01-2.8% of Bi2O3, 0.01-1.5% of MnCO3, 0.5-2% of CaTiSiO5, 0.01-2.5% of SiO2, and 0.02-1.5% of LaCrZrSiO7. Ba0.398Pb0.6La0.002TiO3, CaTiSiO5 and LaCrZrSiO7 are synthesized from conventional chemical materials by a solid phase method. The thermal sensitive ceramic material with Curie temperature has low sintering temperature, high Curie temperature and good PTC temperature-sensitive performance.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, refers in particular to the formula composition of high-curie temperature PTC thermal sensitive ceramicses；
Constituted using special formula, obtain high-curie temperature high-performance PTC thermal sensitive ceramic material, and sintering temperature be 1050 ~
1100℃；Using high-curie temperature PTC thermal sensitive ceramic materials of the invention, not only sintering temperature is low but also Curie temperature is high, together
When thermo-sensitive property it is good, it is suppressed that the volatilization of lead in high-curie temperature PTC thermal sensitive ceramics manufacture processes, meet environmental requirement, while
Reduce manufacturing cost.
Background technology
PTC-ceramic is a kind of semiconductor transformation with positive temperature coefficient（Positive Temperature
Coefficient, referred to as：PTC）Electron ceramic material；The heating of smart electronicses ceramic component collection with this characteristic and temperature
Control in one, with temperature automatically controlled, energy-saving safe, automatically recovery, contactless action, the flames of anger, life-span length the features such as；Product can
For systems such as heating element, temperature control, overcurrent protection, overtemperature protection and thermoinductions, be widely used in automobile, electronics,
Communication, project of transmitting and converting electricity, air-conditioning fan heater engineering, low energy consumption safety type home-use electrical equipment and demagnetization, overcurrent protection, overtemperature protection
Deng field.
The most frequently used PTC thermal sensitive ceramicses are BaTiO3Base ceramic material, its Curie temperature is 120 DEG C；In order to improve temperature-sensitive
The operating temperature of ceramics, moves agent, the lattice position for replacing Ba with Pb to add lead oxide or lead-containing compounds as Curie temperature
Put to realize, such product is that lead tolerance is higher（Ba, Pb）TiO3System；Lead is a kind of virose heavy metal element of tool,
（Ba, Pb）TiO3In the production process of base thermal sensitive ceramics, lead can cause the pollution to natural environment and the body to the mankind is good for
Health works the mischief；It is an approach for eliminating lead contamination to develop unleaded high-Curie-point PTC thermal sensitive ceramicses, but unleaded high-Curie-point
The performance of PTC thermal sensitive ceramicses is not ideal, it is difficult to meet application, and complicated process of preparation, high cost, existing PTC temperature-sensitives
The sintering temperature of ceramics is high, is more than 1300 DEG C, if reducing the sintering temperature of high-curie temperature PTC thermal sensitive ceramicses, will press down
The volatilization of oxygenerating lead, is also another the effective approach for eliminating lead contamination；At present, China PTC thermal sensitive ceramicses industry send out
Exhibition is faced with serious test and challenge, the exploitation of the high-curie temperature PTC thermal sensitive ceramic materials of sintering temperature and low into
One extremely urgent problem.
In recent years, both at home and abroad many scientific research personnel and production work person have set about low-temperature sintering high-curie temperature（Occupy
In temperature be more than 120 DEG C）PTC thermal sensitive ceramic materials exploitation and research work, Curie's temperature of some PTC thermal sensitive ceramic materials
Degree is high, but comprehensive thermo-sensitive property is not so good；The Curie temperature of some PTC thermal sensitive ceramic materials is too low, both of which without
Method meets actual application.
The content of the invention
It is an object of the invention to provide a kind of high-curie temperature PTC thermal sensitive ceramicses formula composition.
Described high-curie temperature PTC thermal sensitive ceramicses, its formula constituent calculates according to molar percentage and is：
Ba0.398Pb0.6La0.002TiO392 ~ 99%, BN 0.1 ~ 4.0%, Bi2O30.01 ~ 2.8%, MnCO3 0.01 ~ 1.5%, CaTiSiO5
0.5~2%, SiO20.01 ~ 2.5%, LaCrZrSiO7 0.02~1.5%；Wherein Ba0.398Pb0.6 La0.002TiO3、CaTiSiO5、
LaCrZrSiO7Conventional chemical raw material is respectively adopted with Solid phase synthesis.
The object of the present invention is achieved like this：
The present invention is used using the preparation technology of conventional PTC thermal sensitive ceramicses initially with the chemical raw material using routine
Solid phase synthesis Ba0. 398Pb0.6 La0.002TiO3、CaTiSiO5、LaCrZrSiO7, then by formula dispensing, by batch ball milling
It is pulverized and mixed, after being dried, adds adhesive granulation, re-compacted into green sheet, then dumping and sintering, warm and natural
After cooling, PTC thermal sensitive ceramicses are obtained, then Top electrode, test performance.
The formula of above-mentioned high-curie temperature PTC thermal sensitive ceramicses is constituted preferably with following two kinds of schemes（Molar percentage）：
（1）Ba0. 398Pb0.6 La0.002TiO394 ~ 98%, BN 0.1 ~ 3.0%, Bi2O30.01 ~ 2.5%, MnCO3 0.01
~ 1.5%, CaTiSiO5 0.8~2%, SiO20.01 ~ 1.8%, LaCrZrSiO7 0.02~1.5%；Wherein Ba0.398Pb0.6
La0.002TiO3, CaTiSiO5, LaCrZrSiO7Chemical raw material is adopted with Solid phase synthesis.
（2）Ba0. 398Pb0.6 La0.002TiO395 ~ 98%, BN 0.1 ~ 2.5%, Bi2O30.01 ~ 2.0%, MnCO3 0.01
~ 1.3%, CaTiSiO5 1.0~1.5%, SiO20.01 ~ 1.5%, LaCrZrSiO7 0.02~1.5%；Wherein
Ba0.398Pb0.6La0.002TiO3、CaTiSiO5、LaCrZrSiO7Conventional chemical raw material is adopted with Solid phase synthesis.
The present invention compared with prior art, has the advantage that：
1st, the sintering temperature of the high-curie temperature PTC thermal sensitive ceramicses of this patent is low, and sintering temperature is 1050 ~ 1100 DEG C, this
Sample can substantially reduce the cost of high-curie temperature PTC thermal sensitive ceramicses, suppress the volatilization of lead, environmentally safe.
2nd, the high-curie temperature PTC thermal sensitive ceramicses Curie temperature of this patent is high, can reach 350 DEG C；Room temperature resistivity is low；
Lift-drag ratio is high, lg (Rmax/Rmin) more than 4.0 can be reached；Temperature-coefficient of electrical resistance (α) is big, can reach 23%/DEG C or so.
3rd, the high-curie temperature PTC thermal sensitive ceramicses of this patent prepare work using conventional solid phase method PTC thermal sensitive ceramicses
Skill can be prepared, it is easy to produce.
Specific embodiment
Presently in connection with embodiment, the invention will be further described.
The formula of this patent is as follows（Molar percentage）：Ba0.398Pb0.6La0.002TiO392 ~ 99%, BN 0.1 ~ 4.0%,
Bi2O30.01 ~ 2.8%, MnCO3 0.01 ~ 1.5%, CaTiSiO5 0.5~2%, SiO20.01 ~ 2.5%, LaCrZrSiO7 0.02~
1.5%, wherein Ba0.398Pb0.6 La 0.002TiO3, CaTiSiO5, LaCrZrSiO7The chemical raw material of routine is adopted with solid phase method conjunction
Into.
Ba0. 398Pb0.6La0.002TiO3Preparation process it is as follows：By BaCO3、PbO、La2O3And TiO2With 0.398：0.6：
0.001：The material mixed grinding of 1 molar ratio is mixed, and compound is placed in corundum crucible and is incubated at 1100 DEG C ~ 1150 DEG C
Prepare Ba within 120 minutes0.398Pb0.6 La 0.002TiO3, grind after cooling until 200 mesh sieves can be crossed, it is standby.
CaTiSiO5Preparation process it is as follows：By conventional chemical raw material CaCO3、TiO2、SiO2By 1：1：1 mol ratio is matched somebody with somebody
Material, is put in alumina crucible after ground and mixed is uniform and is incubated 120 minutes in 1200 ~ 1250 DEG C, solid state reaction kinetics
CaTiSiO5, ground 200 mesh sieve, standby after cooling.
LaCrZrSiO7Preparation process it is as follows：By La2O3、Cr2O3、ZrO2And SiO2With 1/2：1/2： 1：1 mol ratio
The material mixed grinding of example is mixed, and compound is placed in corundum crucible and preparation in 120 minutes is incubated at 1200 DEG C ~ 1250 DEG C
LaCrZrSiO7, ground 200 mesh sieve, standby after cooling.
Table 1 provides two groups of embodiments, 6 formulas of the present invention, and the primary raw material of two groups of embodiments, 6 formulas is warm using PTC
Quick ceramics raw material, in the preparation initially with conventional chemical raw material Solid phase synthesis Ba0.398Pb0.6La0.002TiO3、
CaTiSiO5、LaCrZrSiO7, then by formula dispensing, the material distilled water for preparing or deionized water are adopted into planetary ball mill
Ball milling mixing, material:Ball:Mass ratio=1 of water:3:0.6 ~ 1.0, ball milling dries to obtain dry mash, in dry mash after 4 ~ 8 hours
Addition accounts for the concentration of its weight 8 ~ 10% for the poly-vinyl alcohol solution of 10wt.%, is granulated, it is mixed after cross 40 mesh sieves, then 20 ~
Dry-pressing is carried out under 30Mpa pressure into green sheet, then insulation carries out dumping and burning in 1 ~ 3 hour in the case where temperature is for 1050 ~ 1100 DEG C
Knot, then insulation carries out silver ink firing for 10 minutes at 520 ~ 550 DEG C, forms silver electrode；Actual production can also select other electrode materials
Material, such as aluminium electrode, then solder taul is encapsulated, that is, obtain high-curie temperature PTC sensitive ceramic resistor devices, testing element
Room temperature resistance and resistance-temperature characteristics, obtain room temperature resistivity, Curie temperature, temperature-coefficient of electrical resistance (α) and lift-drag ratio (lg
(Rmax/Rmin)), the performance of above-mentioned each formula sample is listed in table 2.
From table 2 it can be seen that prepared high-curie temperature PTC thermal sensitive ceramicses Curie temperature is high, 345 ~ 355 can be reached
℃；Room temperature resistivity is low, is 91.8 ~ 100.1 Ω cm；Lift-drag ratio（lg(Rmax/Rmin)）Height, can reach more than 4.3, be
4.3~5.1；Temperature-coefficient of electrical resistance（α）Greatly, 22.3 ~ 24% can be reached/DEG C.
The formula of the embodiments of the invention of table 1 totally 6 samples
Note：BPLT represents Ba0.398Pb0.6 La0.002TiO3
The embodiment of table 2 is respectively filled a prescription the performance of sample
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (7)
1. a kind of high-curie temperature PTC thermal sensitive ceramic materials, it is characterised in that：Its formula constituent is calculated according to molar percentage
For：Ba0.398Pb0.6La0.002TiO392～99%, BN 0.1～4.0%, Bi2O30.01～2.8%, MnCO30.01～
1.5%, CaTiSiO50.5～2%, SiO20.01～2.5%, LaCrZrSiO70.02～1.5%；Wherein
Ba0.398Pb0.6La0.002TiO3、CaTiSiO5、LaCrZrSiO7Conventional chemical raw material is respectively adopted with Solid phase synthesis；Preparation side
Method is as follows：Initially with conventional chemical raw material Solid phase synthesis Ba0.398Pb0.6La0.002TiO3、CaTiSiO5、
LaCrZrSiO7, then by formula dispensing, the material distilled water for preparing or deionized water are adopted into planetary ball mill ball milling mixing,
Material:Ball:Mass ratio=1 of water:3:0.6～1.0, ball milling dries to obtain dry mash after 4～8 hours, adds in dry mash and accounts for it
The concentration of weight 8～10% is the poly-vinyl alcohol solution of 10wt.%, is granulated, it is mixed after cross 40 mesh sieves, then 20～
Dry-pressing is carried out under 30Mpa pressure into green sheet, then temperature be at 1050～1100 DEG C insulation carry out within 1～3 hour dumping and
Sintering, then insulation carries out silver ink firing for 10 minutes at 520～550 DEG C, forms silver electrode；Again solder taul, is encapsulated, that is, obtain height
Curie temperature PTC sensitive ceramic resistor devices.
2. a kind of high-curie temperature PTC thermal sensitive ceramic materials according to claim 1, it is characterised in that：Its formula constituent
Calculate according to molar percentage and be：Ba0.398Pb0.6La0.002TiO394～98%, BN 0.1～3.0%, Bi2O30.01～
2.5%, MnCO30.01～1.5%, CaTiSiO50.8～2%, SiO20.01～1.8%, LaCrZrSiO70.02～
1.5%.
3. a kind of high-curie temperature PTC thermal sensitive ceramic materials according to claim 1, it is characterised in that：Its formula constituent
Calculate according to molar percentage and be：Ba0.398Pb0.6La0.002TiO395～98%, BN 0.1～2.5%, Bi2O30.01～
2.0%, MnCO30.01～1.3%, CaTiSiO51.0～1.5%, SiO20.01～1.5%, LaCrZrSiO70.02～
1.5%.
4. a kind of high-curie temperature PTC thermal sensitive ceramic materials according to claim 1, it is characterised in that
Ba0.398Pb0.6La0.002TiO3Preparation process it is as follows：By BaCO3、PbO、La2O3And TiO2With 0.398：0.6：0.001：1
The material mixed grinding of molar ratio is mixed, and compound is placed in corundum crucible the 120 minutes systems that are incubated at 1100 DEG C～1150 DEG C
Standby Ba0.398Pb0.6La0.002TiO3, grind after cooling until 200 mesh sieves can be crossed, it is standby.
5. a kind of high-curie temperature PTC thermal sensitive ceramic materials according to claim 1, it is characterised in that CaTiSiO5System
Standby process is as follows：By conventional chemical raw material CaCO3、TiO2、SiO2By 1：1：1 molar ratio ingredient, is put into after ground and mixed is uniform
120 minutes are incubated in 1200～1250 DEG C in alumina crucible, solid state reaction kinetics CaTiSiO5, ground 200 mesh after cooling
Sieve, it is standby.
6. a kind of high-curie temperature PTC thermal sensitive ceramic materials according to claim 1, it is characterised in that LaCrZrSiO7's
Preparation process is as follows：By La2O3、Cr2O3、ZrO2And SiO2With 1/2：1/2：1：The material mixed grinding of 1 molar ratio is mixed, and is mixed
Close material and be placed in corundum crucible 120 minutes preparation LaCrZrSiO of insulation at 1200 DEG C～1250 DEG C7, ground 200 after cooling
Mesh sieve, it is standby.
7. a kind of high-curie temperature PTC thermal sensitive ceramic materials according to claim 1, it is characterised in that：Prepared height
Curie temperature PTC thermal sensitive ceramicses Curie temperature is high, reaches 345～355 DEG C；Room temperature resistivity is low, is 91.8～100.1 Ω
cm；Lift-drag ratio (lg (Rmax/Rmin)) high, more than 4.3 are reached, it is 4.3～5.1；Temperature-coefficient of electrical resistance (α) is big, reach 22.3～
24%/DEG C.
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| CN113651612A (en) * | 2021-08-13 | 2021-11-16 | 湖州南木纳米科技有限公司 | Barium titanate PTC thermal sensitive ceramic material and application thereof in lithium battery |
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| CN102745985B (en) * | 2012-07-26 | 2014-07-02 | 陕西科技大学 | High-curie-point lead-free PTC (Positive Temperature Coefficient) ceramic material and preparation method thereof |
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Effective date of registration: 20170630 Address after: 514021 large pond head town, Dapu County, Dapu County, Guangdong, Meizhou Patentee after: Meizhou Datong Electronic Technology Co., Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: Jiangsu University |
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