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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
ceramic
ptc thermistor
lead
far infrared
sintering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011142932.1A
Other languages
Chinese (zh)
Other versions
CN112279638A (en
Inventor
张路路
李明阳
王玉宝
宋涛
魏华阳
王浩然
张永翠
徐先豹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Industrial Ceramics Research and Design Institute Co Ltd
Original Assignee
Shandong Industrial Ceramics Research and Design Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Industrial Ceramics Research and Design Institute Co Ltd filed Critical Shandong Industrial Ceramics Research and Design Institute Co Ltd
Priority to CN202011142932.1A priority Critical patent/CN112279638B/en
Publication of CN112279638A publication Critical patent/CN112279638A/en
Application granted granted Critical
Publication of CN112279638B publication Critical patent/CN112279638B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/022Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
    • H01C7/023Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
    • H01C7/025Perovskites, e.g. titanates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N5/0613Apparatus adapted for a specific treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N5/0613Apparatus adapted for a specific treatment
    • A61N5/0625Warming the body, e.g. hyperthermia treatment
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116Ag or Au
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • C04B41/88Metals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N2005/0658Radiation therapy using light characterised by the wavelength of light used
    • A61N2005/0659Radiation therapy using light characterised by the wavelength of light used infrared
    • A61N2005/066Radiation therapy using light characterised by the wavelength of light used infrared far infrared
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225Yttrium oxide or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227Lanthanum oxide or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229Cerium oxides or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3294Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38Non-oxide ceramic constituents or additives
    • C04B2235/3817Carbides
    • C04B2235/3826Silicon carbides

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

Lead-free PTC thermistor ceramic with far infrared performance and preparation method thereof
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.
CN202011142932.1A 2020-10-23 2020-10-23 Lead-free PTC thermistor ceramic with far infrared performance and preparation method thereof Active CN112279638B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011142932.1A CN112279638B (en) 2020-10-23 2020-10-23 Lead-free PTC thermistor ceramic with far infrared performance and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011142932.1A CN112279638B (en) 2020-10-23 2020-10-23 Lead-free PTC thermistor ceramic with far infrared performance and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112279638A CN112279638A (en) 2021-01-29
CN112279638B true CN112279638B (en) 2022-09-20

Family

ID=74424214

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011142932.1A Active CN112279638B (en) 2020-10-23 2020-10-23 Lead-free PTC thermistor ceramic with far infrared performance and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112279638B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113402986B (en) * 2021-08-20 2022-06-24 光之科技(北京)有限公司 Preparation method of PTC material and PTC material
CN114133237A (en) * 2021-10-28 2022-03-04 江苏钧瓷科技有限公司 Manufacturing method of zero-power ceramic wafer of PTC heater

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3106136A1 (en) * 1981-02-19 1982-08-19 Draloric Electronic GmbH, 8672 Selb Process for producing polycrystalline ceramic PTC thermistor bodies
GB2097778B (en) * 1981-05-06 1984-11-21 Toyoda Chuo Kenkyusho Kk Barium titanate composition
RU2326856C2 (en) * 2006-06-08 2008-06-20 ОАО "Центральный научно-исследовательский институт "Электрон" Ceramic pyroelectrical material for ir radiation receivers without cooling
CN102503408A (en) * 2011-10-12 2012-06-20 华中科技大学 Preparation method of laminated barium titanate PTC (positive temperature coefficient) ceramic
CN107500751A (en) * 2017-08-03 2017-12-22 无锡南理工科技发展有限公司 The preparation method of nanometer piezoceramic material

Also Published As

Publication number Publication date
CN112279638A (en) 2021-01-29

Similar Documents

Publication Publication Date Title
CN112279638B (en) Lead-free PTC thermistor ceramic with far infrared performance and preparation method thereof
JP5218042B2 (en) Semiconductor porcelain composition
JP5757239B2 (en) Semiconductor porcelain composition and method for producing the same, PTC element and heating module
CN109942292B (en) Sodium bismuth titanate-based transparent ceramic material and preparation method and application thereof
JPWO2008053813A1 (en) Semiconductor porcelain composition and method for producing the same
JP2019182689A (en) Manufacturing method for sintered body and sintered body
CN108546125A (en) A kind of piezoceramic material and preparation method thereof towards hot environment application
CN110294629A (en) A kind of chromic lanthanum ceramics and preparation method thereof
WO2009119335A1 (en) Process for producing semiconductor porcelain composition/electrode assembly
CN102515754B (en) Barium zirconate titanate-barium calciate titanate (BZT-BCT) ceramic modified by doping of lanthanum oxide and preparation method for same
CN104311004B (en) PTC ceramic material and method for improving resistance temperature stability below curie point of PTC ceramic material
CN106365636A (en) High-Curie-temperature strontium-barium niobate pyroelectric ceramic material and preparation method thereof
JP5844507B2 (en) Method for producing semiconductor porcelain composition and heater using semiconductor porcelain composition
CN101792312A (en) SrTiO3 ceramic dielectric material and preparation method of capacitor thereof
CN114031395B (en) BNT-BKT-BT-AlN composite piezoelectric material and preparation and application thereof
CN105198409A (en) Preparation method of barium-strontium-titanate-based glass composite ceramic with high energy storage density
Wang et al. Fabrication of High‐Curie‐Point Barium‐Lead Titanate PTCR Ceramics
JP3077054B2 (en) Heat-resistant conductive ceramics
Shut et al. PTCR ceramics produced from oxalate-derived barium titanate
CN114276128B (en) Method for reducing leakage current of bismuth ferrite-barium titanate piezoelectric ceramic and improving high-temperature resistivity of bismuth ferrite-barium titanate piezoelectric ceramic
JP2010168265A (en) Method for manufacturing semiconductor ceramic composition
CN105461298A (en) High-energy storage density barium strontium titanate-based ceramic with titanium ions partially replaced by manganese ions and preparation method of ceramic
CN115101659A (en) Bismuth ferrite-barium titanate lead-free piezoelectric ceramic material and preparation method thereof
CN116313515A (en) Sodium niobate-based leadless relaxation antiferroelectric energy storage ceramic capacitor and preparation method thereof
CN117602934A (en) LiNbO 3 Modified PNN-PZT ceramic material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant