CN112279638B - Lead-free PTC thermistor ceramic with far infrared performance and preparation method thereof - Google Patents
Lead-free PTC thermistor ceramic with far infrared performance and preparation method thereof Download PDFInfo
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- CN112279638B CN112279638B CN202011142932.1A CN202011142932A CN112279638B CN 112279638 B CN112279638 B CN 112279638B CN 202011142932 A CN202011142932 A CN 202011142932A CN 112279638 B CN112279638 B CN 112279638B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 15
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 11
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 230000006378 damage Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 13
- 229910010271 silicon carbide Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 238000003825 pressing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000554 physical therapy Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention discloses a lead-free PTC thermistor ceramic with far infrared performance and a preparation method thereof, wherein the lead-free PTC thermistor ceramic comprises the following steps: (1) preparing ceramic slurry, wherein the ceramic slurry comprises BaTiO 3 、SiO 2 、Al 2 O 3 A first doping component and a second doping component; (2) molding and sintering the ceramic slurry to obtain PTC thermistor ceramic; wherein the first doping component is formed from Nb 2 O 5 、Y 2 O 3 、Sb 2 O 3 、Ce 2 O 3 、La 2 O 3 The second doping component consists of SiC and ZrO 2 And (4) forming. The PTC ceramic prepared by the invention has far infrared performance, infrared radiance of 0.6-0.95, wavelength of 4-14 μm, no damage to human body, Curie temperature of more than 120 ℃ and maximum 262 ℃, and in addition, the preparation of raw materials can be accurately controlled.
Description
Technical Field
The invention belongs to the field of ceramic materials, and particularly relates to a lead-free PTC thermistor ceramic with far infrared performance and a preparation method thereof.
Background
In production and life, the PTC thermistor ceramic can realize automatic temperature control due to PTC effect, PTC ceramics with different Curie temperatures, namely different heat preservation temperatures, can be obtained by selecting different materials and preparation methods, and the PTC ceramic material with high Curie temperature is used as a heating device, so that the PTC thermistor ceramic can be automatically controlled in temperature and heated at high temperature. Therefore, PTC ceramics have become a preferred material for high-temperature heating, but the following problems still remain:
on one hand, infrared pollution can be caused by high-temperature heating, and certain influence is caused on a human body, and researches show that infrared rays with the wavelength range of 4-14 mu m are beneficial to the human body, and the infrared rays outside the range can cause damage to the human body;
on the other hand, BaTiO 3 The base PTC thermistor ceramic is generally added with Pb 3 O 4 The Curie temperature is increased, but lead volatilization in the manufacturing and using process of the resistance ceramic material causes pollution to the environment and harm to human bodies. The existing lead-free solution for improving the Curie temperature of PTC thermistor ceramics generally adopts Bi 3+ Obtaining Ba 2+ However, Bi 3+ Substituted Ba 2+ Has strict requirements on the substitution amount of Bi 2 O 3 Has a low melting point and is easily volatilized in the preparation process, so that the substitution amount in the prepared sample is not accurate, in addition, the single Bi doping has influence on the room temperature resistivity, the improvement on the Curie temperature is limited, and the BaTiO with accurate proportion needs to be prepared firstly in the preparation process 3 The Bi substituent is doped with other elements, the preparation process is complex, and the cost of the required raw materials is high.
Therefore, it is a problem to be solved to prepare a PTC thermosensitive ceramic having a high curie temperature which is not harmful to the human body.
Disclosure of Invention
Aiming at the problems, the invention provides the lead-free PTC thermistor ceramic with far infrared performance and the preparation method thereof, and the PTC thermistor ceramic has the Curie temperature of more than 120 ℃, the maximum temperature of 262 ℃ and the far infrared performance.
The application provides a preparation method of a lead-free PTC thermistor ceramic with far infrared performance, which comprises the following steps:
(1) preparing ceramic slurry, wherein the ceramic slurry comprises BaTiO 3 、SiO 2 、Al 2 O 3 A first doping component and a second doping component;
(2) molding and sintering the ceramic slurry to obtain PTC thermistor ceramic;
wherein the first doping component consists of Nb 2 O 5 、Y 2 O 3 、Sb 2 O 3 、Ce 2 O 3 、La 2 O 3 The second doping component is composed of SiC and ZrO 2 And (4) forming.
Preferably, BaTiO in the ceramic slurry 3 、SiO 2 、Al 2 O 3 The mol ratio of the first doping component to the second doping component is as follows: 80-90: 1-5: 0.1-0.4: 0.1-0.2: 8-18.
Preferably, the SiC and ZrO 2 The molar ratio of (A) to (B) is 0.8-1.8.
Preferably, the sintering is reduction sintering followed by oxidation sintering.
Preferably, the reduction sintering condition is that the sintering is carried out for 150min to 180min at the temperature of 1230 ℃ to 1260 ℃; the condition of the oxidation sintering is that the sintering is carried out for 40min to 180min at the temperature of 700 ℃ to 800 ℃.
Preferably, the ceramic slurry forming step is drying, granulating and pressing forming.
Preferably, the drying condition is that the temperature is kept at 80-95 ℃ for 24-36 h; the particle size of the particles prepared by granulation is 425-600 mu m; the pressure of the compression molding is 100 MPa-180 MPa.
The application also provides the lead-free PTC thermistor ceramic with far infrared performance prepared by any one of the preparation methods.
Preferably, the PTC thermistor ceramic has an infrared radiance of 0.6-0.95, a wavelength of 4-14 μm, and a Curie temperature of 120-262 ℃.
The application also provides a lead-free PTC thermistor with far infrared performance, which comprises the PTC thermistor ceramic.
The technical scheme of the invention has the beneficial effects that:
the PTC thermistor ceramic prepared by the invention has far infrared performance, the infrared radiance is between 0.6 and 0.95, the wavelength is between 4 and 14 mu m, and the PTC thermistor ceramic cannot cause damage to human bodies;
ZrO 2 as a far infrared radiation material, the far infrared radiation frequency of the material is close to the natural vibration frequency of a human organic functional group peptide chain, the invention leads the prepared PTC ceramic to have the far infrared performance by introducing ZrO2, but only introduces ZrO2 doped BaTiO 3 The ceramic may be BaTiO 3 The Curie temperature of the base ceramic is reduced, and the effect of high-temperature heating cannot be achieved, but the invention adds SiC and SiO 2 、Al 2 O 3 、Nb 2 O 5 、Y 2 O 3 、Sb 2 O 3 、Ce 2 O 3 、La 2 O 3 So that the prepared PTC ceramic not only has far infrared performance, but also can ensure that the PTC ceramic heats and has Curie temperature under the electrified condition>120 ℃ and even up to 262 ℃.
The invention does not pass Bi 3+ Substituted Ba 2+ To improve BaTiO 3 Based on the Curie temperature of the PTC ceramic, but the high Curie temperature BaTiO is prepared by adjusting the basic components 3 The base PTC ceramic can more accurately control the preparation of the raw materials, and Bi-doped BaTiO does not need to be prepared first 3 The preparation process is more optimized due to the base material;
in addition, the PTC ceramic prepared by the invention can be used as a physiotherapy instrument, integrates temperature-controllable heating and far infrared radiation, and has simpler manufacturing process compared with the existing infrared physiotherapy instrument combining a heating element and a far infrared radiation element.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
The embodiment provides a preparation method of a lead-free PTC thermistor ceramic with far infrared performance, which comprises the following steps:
(1) preparing ceramic slurry, wherein the ceramic slurry comprises BaTiO with a molar ratio of 80-90: 1-5: 0.1-0.4: 0.1-0.2: 8-18 3 、SiO 2 、Al 2 O 3 First, aA doping component and a second doping component;
(2) keeping the temperature of the ceramic slurry at 80-95 ℃ for 24-36 h, drying, then granulating to make the particle size of the particles be 425-600 mu m, pressing and molding at 100-180 MPa, reducing and sintering the molded green body at 1230-1260 ℃ for 150-180 min, oxidizing and sintering at 700-800 ℃ for 40-180 min to obtain the PTC thermistor ceramic;
wherein the first doping component is formed from Nb 2 O 5 、Y 2 O 3 、Sb 2 O 3 、Ce 2 O 3 、La 2 O 3 The second doping component is composed of SiC and ZrO with a molar ratio of 0.8-1.8 2 And (4) forming.
The embodiment also provides the lead-free PTC thermistor ceramic with far infrared performance, which is prepared by the preparation method, wherein the PTC thermistor ceramic has the infrared radiance of 0.6-0.95, the wavelength of 4-14 mu m and the Curie temperature of 120-262 ℃.
The embodiment also provides a lead-free PTC thermistor with far infrared performance, which comprises the PTC thermistor ceramic.
The invention adopts the dry pressing forming method to ensure that the blank has accurate size, simple operation and convenient realization of mechanized operation; the dry-pressed green body has low water content and binder content, and has small drying and firing shrinkage. The barium titanate ceramic fired in the reducing atmosphere has good conductivity, and the re-oxidation treatment can sharply increase the lift-drag ratio and enhance the PTC effect.
In the present invention, the rare earth ion radius Y 3+ 、Sb 3+ 、Ce 3+ 、La 3+ And Ba 2+ Similarly, Ba may be substituted 2+ ，Nb 5+ Radius and Ti 4+ May be substituted for Ti 4+ Such high valence doped, easily valence-changeable Ti for maintaining the material electrically neutral 4+ Convert the trapped electrons into Ti 4+ E, i.e. Ti 3+ Electrons e and T 4+ Are weakly bound and become conductive carriers.
SiO 2 And Al 2 O 3 As sintering aid, the temperature of liquid phase can be reducedThe sintering temperature is reduced, and the temperature range of the semiconducting shrinkage is expanded; the growth of crystal grains is inhibited, and the voltage resistance strength of the ceramic is improved; inhibiting harmful semiconductor impurities, improving the distribution of donor impurities and enhancing PTC effect; the batch stability and the repeatability in the production of the PTC ceramic are improved. Al (Al) 2 O 3 Doping can also introduce a large number of defects into the silicon carbide crystal lattice, so that the silicon carbide crystal structure is locally changed, and the infrared radiation performance of the material is greatly improved.
ZrO 2 As a far infrared radiation material, the far infrared radiation frequency of the material is close to the natural vibration frequency of a human organic functional group peptide chain, and Al 2 O 3 、SiO 2 Can strengthen ZrO 2 Far infrared emissivity, Al 2 O 3 Has the function of a dispersant to enable ZrO to be 2 The particle size becomes smaller and the phase transition temperature decreases. But Zr 4+ As Ti 4+ The equivalent impurities are not easy to change in price in the heating process, and the migration of electrons is hindered under the action of an electric field, so that the resistance is increased, and the Zr content is reduced 4+ Have been regarded as impurities of PTC ceramic materials and have been attempted to be removed or avoided from introduction.
The invention introduces ZrO 2 And adding SiO 2 、Al 2 O 3 、Nb 2 O 5 、Y 2 O 3 、Sb 2 O 3 、Ce 2 O 3 、La 2 O 3 SiC, so that the prepared PTC ceramic has far infrared performance, and the PTC ceramic material can still be ensured to be heated under the power-on condition and the Curie temperature>120 ℃ and even up to 262 ℃. The reason for this may be that the addition of SiC to ZrO 2 The doping of (a) has some influence, and other components play a certain synergistic role.
Example 2
The embodiment provides a preparation method of a lead-free PTC thermistor ceramic with far infrared performance, which comprises the following steps:
(1) 88.12mol of BaTiO 3 、2.08mol SiO 2 、0.23mol Al 2 O 3 、0.113mol Nb 2 O 5 +Y 2 O 3 +Sb 2 O 3 +Ce 2 O 3 +La 2 O 3 、4.20mol SiC、5.25mol ZrO 2 Adding water to prepare ceramic slurry;
(2) and (2) insulating the ceramic slurry at 95 ℃ for 24-36 h through an insulation box, drying, then manually granulating to obtain particles with the particle size of 600 microns, pressing and molding at 150MPa through a molding hydraulic press, and sequentially reducing and sintering the molded green bodies at 1260 ℃ for 180min and oxidizing and sintering at 800 ℃ for 180min to obtain the PTC thermistor ceramic.
The lead-free PTC thermistor ceramic prepared by the embodiment has the Curie temperature of 262 ℃, the infrared radiance of 0.79 and the infrared wavelength of 4-14 mu m.
Example 3
The embodiment provides a preparation method of a lead-free PTC thermistor ceramic with far infrared performance, which comprises the following steps:
(1) 83.97mol of BaTiO 3 、1.60mol SiO 2 、0.27mol Al 2 O 3 、0.13mol Nb 2 O 5 +Y 2 O 3 +Sb 2 O 3 +Ce 2 O 3 +La 2 O 3 、8.01mol SiC、6.02mol ZrO 2 Adding water to prepare ceramic slurry;
(2) and (2) preserving the heat of the ceramic slurry for 30h at 90 ℃ through a heat preservation box, drying, then manually granulating to enable the particle size of the particles to be 500 mu m, pressing and forming the particles under 150MPa through a forming hydraulic press, and sequentially reducing and sintering the formed green body at 1250 ℃ for 160min and oxidizing and sintering the formed green body at 750 ℃ for 120min to obtain the PTC thermistor ceramic.
The lead-free PTC thermistor ceramic prepared by the embodiment has the Curie temperature of 146 ℃, the infrared radiance of 0.86 and the infrared wavelength of 4-14 mu m.
Example 4
The embodiment provides a preparation method of a lead-free PTC thermistor ceramic with far infrared performance, which comprises the following steps:
(1) 82.82mol of BaTiO 3 、1.90mol SiO 2 、0.21mol Al 2 O 3 、0.17mol Nb 2 O 5 +Y 2 O 3 +Sb 2 O 3 +Ce 2 O 3 +La 2 O 3 、9.50mol SiC、5.41mol ZrO 2 Adding water to prepare ceramic slurry;
(2) and (3) preserving the heat of the ceramic slurry in a heat preservation box at 80 ℃ for 24h, drying, then manually granulating to enable the particle size of the particles to be 450 mu m, pressing and forming in a forming hydraulic press at 100MPa, and sequentially reducing and sintering the formed green body at 1230 ℃ for 150min and oxidizing and sintering the green body at 700 ℃ for 40min to obtain the PTC thermistor ceramic.
The lead-free PTC thermistor ceramic prepared by the embodiment has the Curie temperature of 138 ℃, the infrared radiance of 0.91 and the infrared wavelength of 4-14 mu m.
Example 5
The embodiment provides a preparation method of a lead-free PTC thermistor ceramic with far infrared performance, which comprises the following steps:
(1) 84.5mol of BaTiO 3 、1.76mol SiO 2 、0.37mol Al 2 O 3 、0.16mol Nb 2 O 5 +Y 2 O 3 +Sb 2 O 3 +Ce 2 O 3 +La 2 O 3 、7.21mol SiC、4.20mol ZrO 2 Adding water to prepare ceramic slurry;
(2) and (3) preserving the temperature of the ceramic slurry in a heat preservation box at 90 ℃ for 30h, drying, then manually granulating to enable the particle size of the particles to be 500 mu m, pressing and forming in a forming hydraulic press under 180MPa, and sequentially reducing and sintering the formed green body at 1240 ℃ for 170min and oxidizing and sintering the green body at 780 ℃ for 120min to obtain the PTC thermistor ceramic.
The lead-free PTC thermistor ceramic prepared by the embodiment has the Curie temperature of 143 ℃, the infrared radiance of 0.85 and the infrared wavelength of 4-14 mu m.
Example 6
The embodiment provides a preparation method of a lead-free PTC thermistor ceramic with far infrared performance, which comprises the following steps:
(1) 86.57mol of BaTiO 3 、1.56mol SiO 2 、0.32mol Al 2 O 3 、0.16mol Nb 2 O 5 +Y 2 O 3 +Sb 2 O 3 +Ce 2 O 3 +La 2 O 3 、6.21mol SiC、5.19mol ZrO 2 Adding water to prepare ceramic slurry;
(2) and (3) preserving the heat of the ceramic slurry in a heat preservation box at 85 ℃ for 28h, drying, then manually granulating to enable the particle size of the particles to be 500 mu m, pressing and forming in a forming hydraulic machine at 160MPa, and sequentially reducing and sintering the formed green body at 1250 ℃ for 160min and oxidizing and sintering the green body at 750 ℃ for 120min to obtain the PTC thermistor ceramic.
The lead-free PTC thermistor ceramic prepared by the embodiment has the Curie temperature of 200 ℃, the infrared radiance of 0.85 and the infrared wavelength of 4-14 mu m.
Example 7
The present embodiment provides a lead-free PTC thermistor having far infrared performance:
silver paste is coated on the surface of the PTC thermistor ceramic in any one of embodiments 2 to 6 through a screen printing process, and the temperature is maintained at 600 ℃ for 10min so that the silver paste coated on the surface of the PTC thermistor ceramic is cured, thereby preparing the lead-free PTC thermistor.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; all other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of a lead-free PTC thermistor ceramic with far infrared performance is characterized by comprising the following steps:
(1) preparing ceramic slurry, wherein the ceramic slurry comprises BaTiO 3 、SiO 2 、Al 2 O 3 A first doping component and a second doping component; wherein BaTiO in the ceramic slurry 3 、SiO 2 、Al 2 O 3 The molar ratio of the first doping component to the second doping component is as follows: 80-90: 1-5: 0.1-0.4: 0.1-0.2: 8-18;
(2) molding and sintering the ceramic slurry to obtain PTC thermistor ceramic;
wherein the first doping component is formed from Nb 2 O 5 、Y 2 O 3 、Sb 2 O 3 、Ce 2 O 3 、La 2 O 3 The second doping component is composed of SiC and ZrO 2 Composition of said SiC and ZrO 2 The molar ratio of (A) to (B) is 0.8-1.8.
2. The method of preparing a lead-free PTC thermistor ceramic having far-infrared properties according to claim 1, wherein the sintering includes reduction sintering and oxidation sintering.
3. The method for preparing a lead-free PTC thermistor ceramic having far infrared properties as claimed in claim 2, wherein the reduction sintering is performed under the conditions of 1230 to 1260 ℃ for 150 to 180 min; the condition of the oxidation sintering is that the sintering is carried out for 40min to 180min at the temperature of 700 ℃ to 800 ℃.
4. The method for preparing a lead-free PTC thermistor ceramic having far-infrared properties as claimed in claim 1, wherein the ceramic slurry forming step is drying, granulation, press forming.
5. The method for preparing a lead-free PTC thermistor ceramic with far infrared performance according to claim 4, wherein the drying condition is heat preservation at 80-95 ℃ for 24-36 h; the particle size of the particles prepared by granulation is 425-600 mu m; the pressure of the compression molding is 100 MPa-180 MPa.
6. A lead-free PTC thermistor ceramic having far infrared properties, characterized in that the thermistor ceramic is prepared according to the preparation method of any one of claims 1 to 5.
7. The lead-free PTC thermistor ceramic having far infrared performance according to claim 6, wherein the PTC thermistor ceramic has an infrared emissivity of 0.6 to 0.95, a wavelength of 4 to 14 μm, and a Curie temperature of 120 to 262 ℃.
8. A lead-free PTC thermistor having far infrared properties, comprising the PTC thermistor ceramic of claim 6.
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| US4384989A (en) * | 1981-05-06 | 1983-05-24 | Kabushiki Kaisha Toyota Chuo Kenyusho | Semiconductive barium titanate |
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