CN114678177A - Composite positive temperature coefficient thermistor material and preparation method thereof - Google Patents
Composite positive temperature coefficient thermistor material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a positive temperature coefficient thermistor composite material and a preparation method thereof. The prepared BaTiO is added3And (3) immersing the porous ceramic chip of the positive temperature coefficient thermistor into a mixed solution of hydrochloric acid, aniline and ammonium persulfate, stirring for 2-12 h, taking out the porous ceramic chip immersed into the mixed solution after stirring, standing for 2-20 h, washing with deionized water, drying, and grinding off a polyaniline film on the surface to prepare the positive temperature coefficient thermistor composite material sheet. Preparing ohmic contact electrodes on upper and lower parallel planes of positive temperature coefficient thermistor composite material sheet for electrifyingAnd testing resistance and resistance temperature characteristics. The positive temperature coefficient thermistor composite material provided by the invention has the advantages that the room temperature resistivity is obviously reduced, and the lift-to-drag ratio is higher. The application field and range of the positive temperature coefficient thermistor material are expanded.
Description
Technical Field
The invention belongs to a positive temperature coefficient thermistor material, which is widely applied to the fields of electronic products, microelectronic products, household appliances, wearable products, medical appliances, automobiles, military products, instruments, mechanical and electrical appliance control and the like.
Background
At present, the room temperature resistivity of the existing barium titanate-based series positive temperature coefficient thermistor ceramic material is higher, so that the application of the material is greatly limited. Generally made by adding metal or high molecular/conductive materialThe room temperature resistivity of the prepared composite material can be reduced, but the process conditions are complex, and the prepared composite positive temperature coefficient thermistor has high cost and poor performance and cannot meet the requirements of a large number of applications, such as the following papers and patents: [ Zeming He, Jan Ma, Qu Yuanfang, Wangcheng. A structural model of Cr/(Ba, Pb) TiO)3positive temperature coefficient composites[J]Journal of Materials science, Materials in electronics 2000,11(3): 235-; effect of Li Xiao Lei, Qu Yuan, Xuting, sintering and heat treatment process on Ni/PTC ceramic composite material performance [ J]Silicate report 2001.3: 50-54](ii) a The patent "Ni/graphite/BaTiO 3-based composite PTC thermistor and preparation method", Tianjin university, application date: 2008-11-24; the patent "a positive temperature coefficient thermoplasticity thermistor composite material and its preparation method", the university school of zhongshan of electronic technology, application date: 2019-06-26. At present, the reduction of the room temperature resistivity of the ceramic material of the positive temperature coefficient thermistor and the maintenance of a good lift-to-drag ratio are still the key subjects of the research field, so as to promote the wider application of the positive temperature coefficient thermistor element in the fields of lower working voltage, such as electronics, microelectronics, household appliances, wearable products, aerospace, military industry, instruments and meters, automatic control and the like.
Disclosure of Invention
The invention aims to combine polyaniline with good conductivity and BaTiO3The composite material with lower room temperature resistivity and good lift-drag ratio characteristic is prepared based on the compounding of the positive temperature coefficient thermistor ceramic material, and a better foundation is laid for the wider application field of the positive temperature coefficient thermistor.
The invention is BaTiO to be prepared3The base positive temperature coefficient thermistor porous ceramic material is compounded with polyaniline to prepare the composite positive temperature coefficient thermistor composite material. The prepared BaTiO is added3The base positive temperature coefficient thermistor porous ceramic sheet is immersed into the prepared hydrochloric acid, aniline and ammonium persulfate solution, and the conductive polyaniline generated by the reaction in the preparation process stays in the BaTiO as low resistance phase3The present invention is compounded on the grain boundary of the porous ceramic of the thermistor with the base positive temperature coefficientThe room temperature resistivity of the material is obviously reduced, and the material has better lift-drag ratio characteristics.
The technical scheme of the invention is as follows:
BaTiO3The composition and molar ratio formula of the base positive temperature coefficient thermistor porous ceramic material are as follows:
BaCO3:0.6100～1.0000；
SrCO3:0～0.3100；
Pb3O4:0～0.0250；
TiO2：(1.0060～1.0120)；
Sb2O3：(0.0003～0.0007)；
Nb2O5：(0.0001～0.0011)；
MnO2：(0.0003～0.0005)；
Al2O3：(0.0001～0.0010)；
SiO2：(0.0001～0.0010)。
the invention relates to a composite positive temperature coefficient thermistor material and a preparation method thereof, comprising the following steps:
1) mixing (0.6100-1.0000) BaCO3、(0～0.3100)SrCO3、(0～0.0250)Pb3O4、(1.0060～1.0120)TiO2、(0.0003～0.0007)Sb2O3、(0.0001～0.0011)Nb2O5The materials are prepared according to the molar ratio, deionized water and alumina balls, zirconia balls or agate balls are taken as ball milling media, and the materials are as follows: deionized water: wet-grinding a ball-milling medium (1-1.5) to (2-3) to (3.5-4.5) in a ball mill with an alumina lining or a polyurethane lining for 4-24 h, drying a ball grinding material in drying equipment at 110-120 ℃, placing the dried material in an alumina crucible, placing the alumina crucible in an electric furnace, and performing heat preservation for 2-6 h at 980-1080 ℃ to perform pre-synthesis to prepare a pre-synthesized material;
2) then adding (0.0003 to 0.0005) MnO2、(0.0001～0.0010)Al2O3And (0.0001 to 0.0010) SiO2The pre-obtained in the step 1) is mixed according to the molar ratioIn the synthetic material, deionized water and alumina balls, zirconia balls or agate balls are used as ball milling media, and the synthetic material comprises the following components in percentage by weight: deionized water: ball milling media are (1-1.5) to (2-3) to (3.5-4.5) in mass ratio, then ball milling is carried out for 4-24 hours, the mixture is uniformly mixed, ball grinding materials are dried in drying equipment at the temperature of 110-120 ℃, and the mixture is sieved by a 40-mesh sieve for later use;
3) adding 5-8 wt% of PVA aqueous solution into the mixture which is dried and sieved by a 40-mesh sieve for granulation, forming under the pressure of 50-150 MPa, putting the formed blank into an electric furnace, removing PVA adhesive under the temperature of 550-600 ℃, then, carrying out heat preservation for 20-60 min at the temperature of 1230-1350 ℃, firing, cooling along with the furnace after power failure, and preparing BaTiO3A base positive temperature coefficient thermistor porous ceramic sheet;
4) the porous ceramic plate is sintered with ohmic contact silver electrodes on the upper and lower symmetrical planes, the room temperature resistance of the porous ceramic plate is tested by a precise universal bridge, and the resistance temperature characteristic of the porous ceramic plate is tested by a resistance-temperature characteristic testing device;
5) dripping aniline with the volume of 0.8-1.2 into hydrochloric acid solution with the volume of 1N with the volume of 23-28, stirring and mixing uniformly, dripping ammonium persulfate with the same mole as the aniline into the mixed solution of the aniline and the hydrochloric acid, and stirring and mixing uniformly to obtain mixed solution;
6) then BaTiO obtained in the step 3)3Immersing the porous ceramic chip of the base positive temperature coefficient thermistor into the mixed solution obtained in the step 5), and continuously stirring for 2-12 h; after stirring, taking out the porous ceramic wafer immersed in the mixed solution, standing for 2-20 h, washing with deionized water, drying at 110-120 ℃, and grinding off a polyaniline film on the surface to prepare polyaniline and BaTiO3A composite material sheet compounded by the base positive temperature coefficient thermistor porous ceramic material;
7) ohmic contact electrodes are prepared on the up-down symmetrical parallel planes of the composite material sheet, the room temperature resistance of the composite sheet is tested by a precise universal bridge, and the resistance temperature characteristic of the composite material sheet is tested by a resistance-temperature characteristic testing device.
The preparation process of the ohmic contact electrode comprises the following steps: and preparing ohmic contact electrodes on the upper symmetrical plane and the lower symmetrical plane of the composite material sheet by adopting processes of coating In-Ga, chemically plating Ni, spraying Al, sputtering Ni or sputtering Al, and testing the performance of the composite material.
The concrete description is as follows:
the composite positive temperature coefficient thermistor material and the preparation method mainly comprise the following parts:
1、BaTiO3the molar ratio formula of the base positive temperature coefficient thermistor porous ceramic material is as follows:
BaCO3:0.6100～1.0000；
SrCO3:0～0.3100；
Pb3O4:0～0.0250；
TiO2：1.0060～1.0120；
Sb2O3：0.0003～0.0007；
Nb2O5：0.0001～0.0011；
MnO2：0.0003～0.0005；
Al2O3：0.0001～0.0010；
SiO2：0.0001～0.0010。
2. preparing ingredients:
1) mixing (0.6100-1.0000) BaCO3、(0～0.3100)SrCO3、(0～0.0250)Pb3O4、(1.0060～1.0120)TiO2、(0.0003～0.0007)Sb2O3、(0.0001～0.0011)Nb2O5The method comprises the following steps of preparing materials according to a molar ratio, wherein deionized water and alumina balls, zirconia balls or agate balls (with the diameter of 5-20 mm) are used as ball milling media, and the materials are as follows: deionized water: wet grinding alumina balls (zirconia balls or agate balls) in a mass ratio of (1-1.5) to (2-3) to (3.5-4.5) in an alumina-lined or polyurethane-lined ball mill for 4-24 hours, drying ball grinding materials in drying equipment at 110-120 ℃, placing the dried materials in an alumina crucible, placing in an electric furnace, and preserving heat at 980-1080 ℃ for 2-6 hours to perform pre-synthesis to prepare pre-synthesized materials;
2) then adding (0.0003 to 0.0005) MnO2、(0.0001～0.0010)Al2O3、(0.0001～0.0010)SiO2The material is prepared into a pre-synthetic material according to a molar ratio, deionized water and alumina balls, zirconia balls or agate balls (the diameter is 5-20 mm) are taken as ball milling media, and the material is as follows: deionized water: the mass ratio of alumina balls (zirconia balls or agate balls) to (1-1.5) to (2-3) to (3.5-4.5) is then subjected to ball milling for 4-24 hours, the mixture is uniformly mixed, the ball grinding materials are dried in drying equipment at the temperature of 110-120 ℃, and the mixture is screened by a 40-mesh sieve to obtain a mixture;
3、BaTiO3preparing a base positive temperature coefficient thermistor porous ceramic sheet:
1) adding 5-8 wt% of PVA aqueous solution into the mixture which is dried and sieved by a 40-mesh sieve for granulation, and forming under the condition that the pressure is 50-150 MPa;
2) placing the formed blank into an electric furnace, removing PVA binder at 550-600 ℃, then carrying out heat preservation at 1230-1350 ℃ for 20-60 min, firing, cooling along with the furnace after power failure, and preparing BaTiO3A base positive temperature coefficient thermistor porous ceramic sheet;
3) mixing the BaTiO with a solvent3The porous ceramic chip of the thermistor with positive temperature coefficient is sintered and infiltrated with ohmic contact silver electrodes on the upper and lower symmetrical planes, and the BaTiO is tested by a precise universal bridge3Room temperature resistor of porous ceramic chip based on positive temperature coefficient thermistor, and BaTiO tested by resistor-temperature characteristic testing device3The resistance temperature characteristic of the porous ceramic chip of the thermistor with the positive temperature coefficient is based. Testing and preparing BaTiO3The room temperature resistivity of the base positive temperature coefficient thermistor porous ceramic sheet is 38.3-735.4 omega cm, and the lift-to-drag ratio is (4.84-8.85) × 103。
4. Polyaniline and BaTiO3Preparing a composite material sheet compounded by the base positive temperature coefficient thermistor porous ceramic material (hereinafter referred to as the composite material sheet):
1) dripping aniline with the volume of 0.8-1.2 into hydrochloric acid solution with the volume of 1N with the volume of 23-28, stirring and mixing uniformly, dripping ammonium persulfate with the same mole as the aniline into the mixed solution of the aniline and the hydrochloric acid, and stirring and mixing uniformly; then BaTiO is added3Thermistor with basic positive temperature coefficientImmersing the porous ceramic plate into the mixed solution, and continuously stirring for 2-12 h;
2) after stirring, immersing the BaTiO in the mixed solution3Taking out the porous ceramic chip of the base positive temperature coefficient thermistor, standing for 2-20 h, washing with deionized water, drying at 110-120 ℃, and grinding off a polyaniline film on the surface to prepare polyaniline and BaTiO3A composite material sheet compounded by the base positive temperature coefficient thermistor porous ceramic material;
3) preparing ohmic contact electrodes on the upper symmetrical parallel plane and the lower symmetrical parallel plane of the composite material sheet by adopting the processes of coating In-Ga, chemically plating Ni, spraying Al, sputtering Ni or sputtering Al, testing the room temperature resistance of the composite material sheet by using a precise universal bridge, and testing the resistance temperature characteristic of the composite material sheet by using a resistance-temperature characteristic testing device. The test shows that the room temperature resistivity of the composite material sheet is (2.42-4.89) omega cm, and the lift-drag ratio is (3.34-6.86) multiplied by 103。
ADVANTAGEOUS EFFECTS OF INVENTION
The composite positive temperature coefficient thermistor material and the original BaTiO3Compared with the base positive temperature coefficient thermistor ceramic material, the room temperature resistivity of the composite material is obviously reduced, and a higher lift-to-drag ratio is maintained. And a good foundation is laid for the wider application of the positive temperature coefficient thermistor.
Detailed Description
Example 1:
0.894BaC03、0.10SrCO3、0.002Pb3O4、1.0070TiO2、0.0004Sb2O3、0.0011Nb2O5Batching is carried out according to a molar ratio, and the batching uses deionized water and alumina balls (with the diameter of 5-20 mm) as ball milling media according to the following steps: deionized water: wet grinding alumina balls in a polyurethane-lined ball mill for 6 hours at a mass ratio of 1:2:4, drying the ball grinding materials in a drying device at 115 ℃, putting the ball grinding materials into an alumina crucible, putting the alumina crucible into an electric furnace, and preserving heat for 3 hours at 1030 ℃ to perform pre-synthesis to prepare pre-synthesized materials; then 0.0003MnO is added2、0.0004Al2O3、0.0010SiO2Pre-mixing by mol ratioIn the finished materials, deionized water and alumina balls (with the diameter of 5-20 mm) are used as ball milling media, and the materials are as follows: deionized water: and (3) performing ball milling on the alumina balls according to the mass ratio of 1:2:4 for 8h, uniformly mixing, drying the ball grinding materials in drying equipment at 115 ℃, and sieving the dried materials with a 40-mesh sieve for later use. And adding 7 wt% of PVA aqueous solution into the mixture which is dried and sieved by a 40-mesh sieve for granulation, and forming into blank sheets with the diameter of 20 multiplied by 2.5mm under the pressure of 70 MPa. Placing the formed blank into an electric furnace, removing PVA binder at 580 deg.C, then calcining at 1250 deg.C for 30min, cooling with the furnace after power failure to obtain BaTiO3The porous ceramic chip of the thermistor with the basic positive temperature coefficient. The porous ceramic plate is sintered and infiltrated with an ohmic contact silver electrode on the upper and lower symmetrical planes, and a precise universal bridge is used for testing BaTiO3Room temperature resistor of porous ceramic chip based on positive temperature coefficient thermistor, and BaTiO tested by resistor-temperature characteristic testing device3The resistance temperature characteristic of the porous ceramic chip of the thermistor with the positive temperature coefficient is based. Testing and preparing BaTiO3The room temperature resistivity of the porous ceramic plate of the base positive temperature coefficient thermistor is 547.4 omega cm, and the lift-drag ratio is 5.58 multiplied by 103。
Preparation and performance test of the composite material sheet:
dripping 10ml of aniline into 250ml of 1N hydrochloric acid solution, stirring and mixing uniformly, dripping ammonium persulfate with the same mole as the aniline into the aniline and hydrochloric acid solution, and stirring and mixing uniformly; then BaTiO is added3Immersing the porous ceramic chip of the base positive temperature coefficient thermistor into the mixed solution, and continuously stirring for 5 hours; after stirring, taking out the porous ceramic plate immersed in the mixed solution, standing for 6h, washing with deionized water, drying at 120 ℃, and grinding to remove the polyaniline film on the surface to obtain polyaniline and BaTiO3A composite material sheet compounded by the base positive temperature coefficient thermistor porous ceramics; spraying Al on the symmetrical plane of the composite material sheet to prepare an ohmic contact electrode, testing the room temperature resistance of the composite material sheet by using a precise universal bridge, and testing the resistance temperature characteristic of the composite material sheet by using a resistance-temperature characteristic testing device. The test shows that the room temperature resistivity of the composite material sheet is 2.96 omega cm, and the lift-drag ratio is 5.31 multiplied by 103。
Example 2:
0.9400BaC03、0.0200Pb3O4、1.0100TiO2、0.0003Sb2O3、0.0011Nb2O5Batching according to a molar ratio, wherein deionized water and zirconia balls (with the diameter of 5-20 mm) are used as ball milling media in the batching, and the batching comprises the following steps: deionized water: wet grinding zirconia balls in a ball mill with an alumina ceramic lining for 8 hours at a mass ratio of 1.5:3:4.5, drying the ball grinding materials in an oven at 120 ℃, then placing the ball grinding materials in an alumina crucible, placing the alumina crucible into an electric furnace, and preserving heat for 4 hours at 1050 ℃ to perform pre-synthesis to prepare a pre-synthesized material; then 0.0004MnO is added2、0.0003Al2O3、0.0011SiO2Mixing the raw materials into a pre-synthesized material according to a molar ratio, taking deionized water and zirconia balls (with the diameter of 5-20 mm) as ball milling media, and mixing the raw materials: deionized water: and (3) ball-milling the zirconium oxide balls for 8 hours according to the mass ratio of 1.5:3:4.5, uniformly mixing, drying the ball-milled materials in an oven at 120 ℃, and sieving the ball-milled materials by a 40-mesh sieve to prepare a mixture for later use. And adding 6 wt% of PVA aqueous solution into the mixture which is dried and sieved by a 40-mesh sieve for granulation, and forming into blank sheets with the diameter of 20 multiplied by 2.5mm under the pressure of 75 MPa. Placing the formed blank into an electric furnace, removing PVA binder at 600 deg.C, then calcining at 1270 deg.C for 20min, cooling with the furnace after power failure to obtain BaTiO3A base positive temperature coefficient thermistor porous ceramic sheet. The porous ceramic plate is sintered and infiltrated with an ohmic contact silver electrode on the upper and lower symmetrical planes, and a precise universal bridge is used for testing BaTiO3Room temperature resistor of porous ceramic chip based on positive temperature coefficient thermistor, and BaTiO tested by resistor-temperature characteristic testing device3The resistance temperature characteristic of the porous ceramic chip of the thermistor with the positive temperature coefficient is based. Testing and preparing BaTiO3The room temperature resistivity of the porous ceramic chip of the base positive temperature coefficient thermistor is 342.6 omega cm, and the lift-to-drag ratio is 6.24 multiplied by 103。
Preparation and performance test of the composite material sheet:
dropping 9.5ml aniline into 260ml 1N hydrochloric acid solution, stirring and mixing uniformly, and dropping ammonium persulfate whose mole is equal to that of aniline into the above-mentioned benzeneAmine and hydrochloric acid solution, and stirring and mixing uniformly; then BaTiO is added3Immersing the porous ceramic chip of the base positive temperature coefficient thermistor into the mixed solution, and continuously stirring for 3 hours; after stirring, taking out the porous ceramic plate immersed in the mixed solution, standing for 8 hours, washing with deionized water, drying at 120 ℃, and grinding off a polyaniline film on the surface to prepare the composite material sheet; coating In-Ga ohmic contact electrodes on the symmetrical plane of the prepared composite material sheet, testing the room temperature resistance of the composite material sheet by using a precise universal bridge, and testing the resistance temperature characteristic of the composite material sheet by using a resistance-temperature curve testing device. The test shows that the room temperature resistivity of the composite material sheet is 3.65 omega cm, and the lift-drag ratio is 5.46 multiplied by 103。
Example 3:
0.9200BaC03、0.0800SrCO3、1.0105TiO2、0.0004Sb2O3、0.0010Nb2O5The method comprises the following steps of (1) preparing materials according to a molar ratio, wherein the materials are prepared by taking deionized water and agate balls (with the diameter of 5-20 mm) as ball milling media: deionized water: wet grinding agate balls in a polyurethane-lined ball mill for 6 hours at a mass ratio of 1:2.5:4, drying the ball-milled materials in an oven at 120 ℃, placing the ball-milled materials in an alumina crucible, placing the alumina crucible into an electric furnace, and preserving heat for 3 hours at 1060 ℃ to prepare pre-synthesized materials; then 0.0004MnO is added2、0.0003Al2O3、0.0010SiO2Adding the mixture into a pre-synthesized material according to a molar ratio, taking deionized water and agate balls (with the diameter of 5-20 mm) as ball milling media, and mixing the materials: deionized water: and (3) performing ball milling on agate balls according to the mass ratio of 1:2:4.5 for 6h, uniformly mixing, drying the ball grinding materials in a drying device at 120 ℃, and sieving the dried materials with a 40-mesh sieve to prepare a mixture for later use. And adding 6 wt% of PVA aqueous solution into the mixture which is dried and sieved by a 40-mesh sieve for granulation, and forming into blank sheets with the diameter of 20 multiplied by 2.5mm under the pressure of 75 MPa. Placing the formed blank into an electric furnace, removing PVA binder at 600 deg.C, then calcining at 1280 deg.C for 20min, cooling with the furnace after power failure to obtain BaTiO3The porous ceramic chip of the thermistor with the basic positive temperature coefficient. Burning and infiltrating the porous ceramic sheet on the upper and lower symmetrical planesMu-contact silver electrode, BaTiO test with precision universal bridge3Room temperature resistor of porous ceramic chip based on positive temperature coefficient thermistor, and BaTiO tested by resistor-temperature characteristic testing device3The resistance temperature characteristic of the porous ceramic chip of the base positive temperature coefficient thermistor. Testing and preparing BaTiO3The room temperature resistivity of the porous ceramic chip of the base positive temperature coefficient thermistor is 257.6 omega cm, and the lift-to-drag ratio is 5.38 multiplied by 103。
Preparation and performance test of the composite material sheet:
dripping 10.5ml of aniline into 252ml of 1N hydrochloric acid solution, stirring and mixing uniformly, dripping ammonium persulfate with the same mole of aniline into the aniline and hydrochloric acid solution, and stirring and mixing uniformly; then BaTiO is added3Immersing the porous ceramic chip of the base positive temperature coefficient thermistor into the mixed solution, and continuously stirring for 4 hours; after stirring, taking out the porous ceramic plate immersed in the mixed solution, standing for 10 hours, washing with deionized water, drying at 120 ℃, and grinding off a polyaniline film on the surface to prepare the composite material sheet; sputtering Ni ohmic contact electrode on the symmetrical plane of the composite material sheet, testing the room temperature resistance of the composite material sheet by a precise universal bridge, and testing the resistance temperature characteristic of the composite material sheet by a resistance-temperature characteristic testing device. The test shows that the room temperature resistivity of the composite material sheet is 2.48 omega cm, and the lift-drag ratio is 5.24 multiplied by 103。
Example 4:
mixing BaC03、1.0100TiO2、0.0003Sb2O3、0.0010Nb2O5Batching according to a molar ratio, wherein deionized water and zirconia balls (with the diameter of 5-20 mm) are used as ball milling media in the batching, and the batching comprises the following steps: deionized water: wet grinding zirconia balls in a polyurethane-lined ball mill for 8 hours at a mass ratio of 1.2:2.5:4, drying the ball grinding materials in an oven at 120 ℃, then placing the ball grinding materials in an alumina crucible, placing the alumina crucible in an electric furnace, and preserving heat for 5 hours at 1040 ℃ to perform pre-synthesis to prepare pre-synthesized materials; then 0.0004MnO is added2、0.0003Al2O3、0.0011SiO2Adding the mixture into a pre-synthetic material according to a molar ratio, and adding deionized water and agate balls(diameter 5-20 mm) is a ball milling medium, and the ball milling medium comprises the following materials: deionized water: and (3) performing ball milling on agate balls according to the mass ratio of 1.2:2.5:4 for 8 hours, uniformly mixing, drying the ball grinding materials in a drying device at 120 ℃, and sieving the ball grinding materials by a 40-mesh sieve to prepare a mixture for later use. And adding 6 wt% of PVA aqueous solution into the mixture which is dried and sieved by a 40-mesh sieve for granulation, and forming into blank sheets with the diameter of 20 multiplied by 2.5mm under the pressure of 75 MPa. Placing the formed blank into an electric furnace, removing PVA binder at 600 deg.C, then calcining at 1320 deg.C for 40min, cooling with the furnace after power failure, and making into BaTiO3The porous ceramic chip of the thermistor with the basic positive temperature coefficient. The porous ceramic plate is sintered and infiltrated with an ohmic contact silver electrode on the upper and lower symmetrical planes, and a precise universal bridge is used for testing BaTiO3Room temperature resistance based on positive temperature coefficient thermistor porous ceramic chip, and BaTiO tested by resistance-temperature characteristic testing device3The resistance temperature characteristic of the porous ceramic chip of the thermistor with the positive temperature coefficient is based. Testing and preparing BaTiO3The room temperature resistivity of the porous ceramic plate of the base positive temperature coefficient thermistor is 483.9 omega cm, and the lift-drag ratio is 7.36 multiplied by 103。
Preparing a composite material sheet and testing the performance:
dripping 10ml of aniline into 250ml of 1N hydrochloric acid solution, stirring and mixing uniformly, dripping ammonium persulfate with the same mole as the aniline into the aniline and hydrochloric acid solution, and stirring and mixing uniformly; then BaTiO is added3Immersing the porous ceramic chip of the base positive temperature coefficient thermistor into the mixed solution, and continuously stirring for 5 hours; after stirring, taking out the porous ceramic plate immersed in the mixed solution, standing for 10 hours, washing with deionized water, drying at 120 ℃, and grinding off a polyaniline film on the surface to prepare the composite material sheet; coating In-Ga ohmic contact electrodes on the symmetrical plane of the prepared composite material sheet, testing the room temperature resistance of the composite material sheet by using a precise universal bridge, and testing the resistance temperature characteristic of the composite material sheet by using a resistance-temperature curve testing device. The test shows that the room temperature resistivity of the composite material sheet is 3.78 omega cm, and the lift-drag ratio is 5.35 multiplied by 103。
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (3)
1. A composite positive temperature coefficient thermistor material is characterized in that BaTiO in the thermistor material3The base positive temperature coefficient thermistor porous ceramic material comprises the following components in molar ratio:
BaCO3:0.6100～1.0000；
SrCO3:0～0.3100；
Pb3O4:0～0.0250；
TiO2：(1.0060～1.0120)；
Sb2O3：(0.0003～0.0007)；
Nb2O5：(0.0001～0.0011)；
MnO2：(0.0003～0.0005)；
Al2O3：(0.0001～0.0010)；
SiO2：(0.0001～0.0010)。
2. the preparation method of the composite positive temperature coefficient thermistor material is characterized in that the composite positive temperature coefficient thermistor material is prepared from BaTiO3The preparation method of the porous ceramic plate and the composite material plate of the base positive temperature coefficient thermistor comprises the following steps:
1) mixing (0.6100-1.0000) BaCO3、(0～0.3100)SrCO3、(0～0.0250)Pb3O4、(1.0060～1.0120)TiO2、(0.0003～0.0007)Sb2O3、(0.0001～0.0011)Nb2O5According to the molar ratioThe material is prepared by taking deionized water and alumina balls, zirconia balls or agate balls as ball milling media, and mixing the following materials: deionized water: wet-grinding a ball-milling medium (1-1.5) to (2-3) to (3.5-4.5) in a ball mill with an alumina lining or a polyurethane lining for 4-24 h, drying a ball grinding material in drying equipment at 110-120 ℃, placing the dried material in an alumina crucible, placing the alumina crucible in an electric furnace, and performing heat preservation for 2-6 h at 980-1080 ℃ to perform pre-synthesis to prepare a pre-synthesized material;
2) then adding (0.0003 to 0.0005) MnO2、(0.0001～0.0010)Al2O3And (0.0001 to 0.0010) SiO2Mixing the materials into the pre-synthesized material obtained in the step 1) according to a molar ratio, taking deionized water and alumina balls, zirconia balls or agate balls as ball milling media, and mixing the materials according to the following ratio: deionized water: ball milling media are (1-1.5) to (2-3) to (3.5-4.5) in mass ratio, then ball milling is carried out for 4-24 hours, the mixture is uniformly mixed, ball grinding materials are dried in drying equipment at the temperature of 110-120 ℃, and the mixture is sieved by a 40-mesh sieve for later use;
3) adding 5-8 wt% of PVA aqueous solution into the mixture which is dried and sieved by a 40-mesh sieve for granulation, forming under the pressure of 50-150 MPa, putting the formed blank into an electric furnace, removing PVA adhesive under the temperature of 550-600 ℃, then, carrying out heat preservation for 20-60 min at the temperature of 1230-1350 ℃, firing, cooling along with the furnace after power failure, and preparing BaTiO3A base positive temperature coefficient thermistor porous ceramic sheet;
4) the porous ceramic plate is sintered with ohmic contact silver electrodes on the upper and lower symmetrical planes, the room temperature resistance of the porous ceramic plate is tested by a precise universal bridge, and the resistance temperature characteristic of the porous ceramic plate is tested by a resistance-temperature characteristic testing device;
5) dripping (0.8-1.2) parts by volume of aniline into (23-28) parts by volume of 1N hydrochloric acid solution, stirring and mixing uniformly, dripping ammonium persulfate with the same mole as the aniline into the aniline and hydrochloric acid mixed solution, and stirring and mixing uniformly to obtain a mixed solution;
6) then BaTiO obtained in the step 3)3Immersing the porous ceramic chip of the base positive temperature coefficient thermistor into the mixed solution obtained in the step 5), and continuously stirring for 2-12 h; the stirring is finishedThen taking out the porous ceramic plate immersed in the mixed solution, standing for 2-20 h, washing with deionized water, drying at 110-120 ℃, and grinding off a polyaniline film on the surface to prepare polyaniline and BaTiO3A composite material sheet compounded by the base positive temperature coefficient thermistor porous ceramic material;
7) ohmic contact electrodes are prepared on the up-down symmetrical parallel planes of the composite material sheet, the room temperature resistance of the composite material sheet is tested by a precise universal bridge, and the resistance temperature characteristic of the composite material sheet is tested by a resistance-temperature characteristic testing device.
3. The method according to claim 2, wherein the ohmic contact electrode of step 7) is prepared by a process comprising: ohmic contact electrodes are prepared on the upper symmetrical plane and the lower symmetrical plane of the composite material sheet by adopting the processes of coating In-Ga, chemically plating Ni, spraying Al, sputtering Ni or sputtering Al, and the performance of the composite material is tested.
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