WO2022151673A1 - 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法 - Google Patents

一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法 Download PDF

Info

Publication number
WO2022151673A1
WO2022151673A1 PCT/CN2021/104885 CN2021104885W WO2022151673A1 WO 2022151673 A1 WO2022151673 A1 WO 2022151673A1 CN 2021104885 W CN2021104885 W CN 2021104885W WO 2022151673 A1 WO2022151673 A1 WO 2022151673A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat
thermistor element
temperature coefficient
ceramic tile
positive temperature
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.)
Ceased
Application number
PCT/CN2021/104885
Other languages
English (en)
French (fr)
Inventor
傅邱云
何正安
周东祥
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.)
Jiangsu New Linzhi Electronic Technology Co Ltd
Original Assignee
Jiangsu New Linzhi Electronic Technology 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 Jiangsu New Linzhi Electronic Technology Co Ltd filed Critical Jiangsu New Linzhi Electronic Technology Co Ltd
Priority to EP21918869.5A priority Critical patent/EP4297052A4/en
Priority to US18/281,762 priority patent/US12354774B2/en
Publication of WO2022151673A1 publication Critical patent/WO2022151673A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-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
    • H01C7/02—Non-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
    • H01C7/022—Non-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
    • H01C7/023—Non-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
    • H01C7/025—Perovskites, e.g. titanates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/028—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles by means of an interlayer consisting of an organic adhesive, e.g. phenol resin or pitch
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/0072—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating 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
    • C04B41/5022—Coating 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 with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/02—Housing; Enclosing; Embedding; Filling the housing or enclosure
    • H01C1/024—Housing; Enclosing; Embedding; Filling the housing or enclosure the housing or enclosure being hermetically sealed
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points specially adapted for resistors; Arrangements of terminals or tapping points on resistors
    • H01C1/1406—Terminals or electrodes formed on resistive elements having positive temperature coefficient
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits or green body
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits or green body characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits or green body characterised by the resistive component composed of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/07—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by resistor foil bonding, e.g. cladding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-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
    • H01C7/02—Non-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
    • H01C7/021—Non-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 formed with two or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-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
    • H01C7/02—Non-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
    • H01C7/022—Non-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
    • H01C7/023—Non-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
    • H01C7/026—Vanadium oxides or oxidic compounds, e.g. VOx
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/10—Glass interlayers, e.g. frit or flux
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/345—Refractory metal oxides
    • C04B2237/346—Titania or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/74—Forming laminates or joined articles comprising at least two different interlayers separated by a substrate

Definitions

  • the invention belongs to the technical field of electronic components and their preparation, and in particular relates to a positive temperature coefficient ceramic thermistor element with strong reducing atmosphere and a preparation method thereof.
  • PTC ceramic thermal elements are generally made of barium titanate-based semiconductor ceramic materials. order of magnitude, resulting in the so-called PTC effect.
  • the origin of this PTC effect is caused by the grain boundary barrier, and the height of the grain boundary barrier is closely related to the concentration of oxygen atoms adsorbed on the grain boundary. Oxygen loss in the boundary, resulting in component performance failure or even loss of PTC effect.
  • PTC thermal components generally used in new energy vehicles, air conditioning electric auxiliary heating and other fields often work in this environment.
  • PTC components are in When assembled into a heating component, it is usually fixed on the metal radiator with organic glue. This organic glue will emit a reducing atmosphere at high temperature ( ⁇ 200 ° C) to damage the PTC components, thereby reducing the service life of the components. .
  • PTC thermal components are easily affected by harsh environments is that it is a polycrystalline ceramic material, which not only has grain boundaries, but also has a large number of micro pores. Various bad atmospheres can enter the grain boundaries through these micro pores, thereby damaging The macroscopic electrical properties of the component, such as the loss of self-temperature control function due to redox.
  • the primary task of the present invention is to provide a channel that helps to block external harmful gases from invading the ceramic grain boundaries from the micropores on the ceramic surface, so as to improve the resistance to harsh environments, prolong the service life, and meet the service requirements in an environment containing a reducing atmosphere A positive temperature coefficient ceramic thermistor element with strong reducing atmosphere.
  • Another task of the present invention is to provide a preparation method of a positive temperature coefficient ceramic thermistor element with strong reducing atmosphere, the preparation process of the method is simple, and there are no extremely harsh process elements, which can meet the requirements of industrial preparation and can guarantee The technical effect of the obtained positive temperature coefficient ceramic thermistor element is fully manifested.
  • a positive temperature coefficient ceramic thermistor element with strong resistance to reducing atmosphere comprising a lead-barium titanate-based and sintered heat-sensitive ceramic tile and a heat-sensitive ceramic tile located in the heat-sensitive ceramic
  • the metal ohmic electrodes on both sides of the ceramic sheet are characterized by further comprising a microporous channel blocking layer, the microporous channel blocking layer comprising a glass sealing layer or an organic sealant, and when the microporous channel blocking layer is a glass sealing layer, the glass sealing layer
  • the layer is integrally covered on the outer surface of the heat-sensitive ceramic tile, and the metal ohmic electrodes are combined on both sides of the glass sealing layer; and when the microporous channel barrier layer is an organic sealant, the organic sealant is filled in It is combined in the micropores on the surface of the metal ohmic electrode on both sides of the thermosensitive ceramic tile and at the same time seals the surface voids of the metal ohmic electrode-free region at the
  • 0.0001-0.0005 moles of MnN 2 O 6 , NiN 2 O 6 or FeN 3 O 9 are further included in the raw material composition of the heat-sensitive ceramic tile.
  • the trivalent rare earth oxide is a mixture of one or more of La 2 O 3 , Y 2 O 3 and Sm 2 O 3 ;
  • the metal oxide is Nb 2 O 5 .
  • the glass sealing layer is obtained from a glass paste for encapsulation, and the glass paste for encapsulation is prepared by adopting a molten water quenching method to prepare a particle size smaller than 500nm glass micropowder and organic matter are added and mixed at the same time to obtain a glass paste for encapsulation of the glass sealing layer used as the microporous channel barrier layer.
  • the mass ratio of the glass micropowder with a particle size of less than 500 nm to the organic matter is 1:1.2, and the organic matter is composed of the following raw materials in parts by weight: 0.1-0.3 part of mixture, 0.001-0.01 part of dispersant and 1 part of solvent; the binder is PVB, the dispersant is low molecular wax, and the solvent is acetone.
  • the glass paste for encapsulation is coated on the surface of the heat-sensitive ceramic tile by any one of the dipping method or the spraying method, it is placed on the High temperature heat treatment device and heat treatment at 500-600°C for 8-12min.
  • the organic sealant is filled in the micropores of the surface of the metal ohmic electrode combined on both sides of the heat-sensitive ceramic tile and simultaneously removes the heat
  • the method for filling and plugging the surface of the surface of the area without metal ohmic electrodes at the peripheral edge of the sensitive ceramic tile includes any one of the following two methods: Method 1, combining the metal ohmic electrodes on both sides The heat-sensitive ceramic tile is put into a hot isostatic press containing the organic sealant as a void blocking medium, pressurizing the hot isostatic press and controlling the void blocking medium when the pressure is applied The temperature, the pressure of the pressure and the time of the pressure are controlled, and the surface is cleaned and dried in sequence after the pressure is applied; Method 2, the heat-sensitive ceramic tiles with the metal ohmic electrodes combined on both sides are put into a container The organic sealant is immersed in a container, the container is evacuated and the degree of vacuum of the vacuum and the time of immersion are controlled, the vacuum is combined and taken
  • the raw material composition of the organic sealant is: polydimethylsiloxane, transition metal oxide nano-powder, cross-linking agent, catalyst and organic solvent;
  • the amount of the transition metal oxide nano-powder added to the polydimethylsiloxane is 0.001-0.01% of the weight of the polydimethylsiloxane;
  • the added amount of the crosslinking agent is polydimethylsiloxane 1-3% of the weight of the alkane;
  • the added amount of the catalyst is 0.05-0.1% of the weight of the polydimethylsiloxane.
  • the transition metal oxide nano-powder is MnO 2 , Fe 3 O 4 or Co 3 O 4 nano-powder;
  • the cross-linking agent is hydrogen-containing silicone oil ;
  • Described catalyst is platinum ethylene complex;
  • Described organic solvent is xylene.
  • Another task of the present invention is accomplished in this way, a preparation method of a positive temperature coefficient ceramic thermistor element with strong reducing atmosphere, which is based on lead barium titanate and sintered thermal ceramics
  • the outer surface of the ceramic sheet is integrally covered with a glass sealing layer as a barrier layer for the microporous channel, and then metal ohmic electrodes are combined on both sides of the glass sealing layer, or a heat-sensitive ceramic ceramic sheet based on lead barium titanate is first used.
  • Metal ohmic electrodes are combined on both sides, and then the organic sealant as a microporous channel barrier layer is filled in the micropores on the surface of the metal ohmic electrode, and at the same time, the metal-free ohmic electrodes on the surrounding edges of the heat-sensitive ceramic tile are sealed. The voids on the surface of the region are blocked to obtain a positive temperature coefficient ceramic thermistor element with strong reducing atmosphere.
  • the technical effect of the technical solution provided by the present invention is: because the glass sealing layer or the organic sealing agent is used as the micro-porous channel for blocking the micro-porous channel generated on the heat-sensitive ceramic tile based on lead barium titanate and sintered
  • the barrier layer and when the glass sealing layer is used, the outer surface of the heat-sensitive ceramic tile is integrally wrapped by the glass sealing layer, and the metal ohmic electrodes are combined on both sides of the glass sealing layer, and when the organic sealing agent is used, the organic matter is sealed
  • the agent is filled in the micropores on the surface of the metal ohmic electrodes combined on both sides of the heat-sensitive ceramic tile, and at the same time, the gaps on the surface of the metal ohmic electrode-free area around the edge of the heat-sensitive ceramic tile are blocked, Therefore, it can isolate the harmful gases and/or attached foreign objects from the outside and the grain boundaries of the heat-sensitive ceramic tiles, so as to avoid the loss of the automatic temperature control function and even the electrical short circuit caused by the reduction.
  • the method can meet the requirements of improving the reliability of the relevant heating group and the expected service requirements in the devices containing the thermal management system of new energy vehicles, air conditioners and other household appliances such as electric auxiliary constant temperature heaters in the environment of reducing atmosphere;
  • the method has simple process steps and no harsh process elements, and can ensure that the technical effect of the positive temperature coefficient ceramic thermistor element can be fully reflected.
  • FIG. 1 is a cross-sectional view of a positive temperature coefficient ceramic thermistor element having strong reducing atmosphere resistance according to Examples 1 to 3 of the present invention.
  • FIG. 2 is a cross-sectional view of the positive temperature coefficient ceramic thermistor elements having strong reducing atmosphere resistance according to Examples 4 to 7 of the present invention.
  • FIG. 4 is a schematic diagram of a reducing atmosphere test device for the PTC ceramic thermistor element with strong reducing resistance atmosphere of the present invention.
  • a positive temperature coefficient ceramic thermistor element with strong resistance to reducing atmosphere includes a lead barium titanate-based and sintered specification of 24 ⁇ 15 ⁇ 2.4 mm (not The heat-sensitive ceramic tile 1 and the metal ohmic electrodes 2 located on both sides of the heat-sensitive ceramic tile 1, as the technical points of the technical solution provided by the present invention: also include a microporous channel barrier layer 3.
  • the microporous channel barrier layer 3 is a glass sealing layer, and the glass sealing layer is integrally covered on the outer surface of the aforementioned heat-sensitive ceramic tile 1 with a thickness of 5 ⁇ m.
  • the aforementioned metal ohmic electrode 2 is preferably It is not absolutely limited to use aluminum, copper, silver-zinc alloy or base metal as the metal ohmic electrode, and the metal ohmic electrode 2 may adopt a sintering method, a melt spraying method, a sputtering method, a coating method or other similar equivalent methods. Combined on both sides of the aforementioned glass sealing layer as the micro-pore channel blocking layer 3 .
  • the raw material composition of the aforementioned thermosensitive ceramic tile 1 is: 0.64BaTiO 3 +0.3PbTiO 3 +0.06(CaO+SrO)+0.005(BN+V 2 O 3 +Li 2 CO 3 +Al 2 O 3 ) + 0.003 La 2 O 3 + 0.0003 moles of MnN 2 O 6 .
  • the glass sealing layer described in this embodiment is obtained (that is, produced) from a glass paste for encapsulation, and the glass paste for encapsulation is prepared by adopting a molten water quenching method to produce particles with a particle size of less than 500 nm.
  • the glass micropowder is mixed with organic matter (also referred to as "adhesive" or "organic adhesive") at the same time to obtain the encapsulation glass paste used as the glass sealing layer of the aforementioned microporous channel barrier layer 3.
  • the mass ratio of the glass micropowder with the aforementioned particle size less than 500nm to the organic matter is 1: 1.2, and the organic matter is made up of the following raw materials proportioned in parts by weight: 0.2 part of PVB as a binder, 0.001 of a low-molecular-weight wax as a dispersant and acetone as a solvent, since the solvent can be added as required, there is no need to limit the amount of the solvent.
  • the aforementioned glass paste for encapsulation is coated on the surface of the aforementioned heat-sensitive ceramic tile 1 by dipping method, and then placed in a high-temperature heat treatment device and heat-treated at 500° C. for 12 minutes.
  • the aforementioned glass sealing layer is a glass sealing layer of a glass system, and the glass system is composed of the following raw materials in terms of gram molecular weight: K 2 SiF 6 +ZnO+Al 2 O 3 +SiO 2 +0.2(Na 2 O+K 2 O)+0.5(B 2 O 3 +Li 2 O)+0.005Fe 3 O 4 , the sum is one mole.
  • a positive temperature coefficient ceramic thermistor element with strong resistance to reducing atmosphere includes a lead barium titanate-based and sintered specification of 24 ⁇ 15 ⁇ 2.4 mm (not The heat-sensitive ceramic tile 1 and the metal ohmic electrodes 2 located on both sides of the heat-sensitive ceramic tile 1, as the technical points of the technical solution provided by the present invention: also include a microporous channel barrier layer 3.
  • the microporous channel barrier layer 3 is a glass sealing layer, and the glass sealing layer is integrally covered on the outer surface of the aforementioned thermosensitive ceramic tile 1 with a thickness of 2 ⁇ m.
  • the aforementioned metal ohmic electrode 2 is preferably It is not absolutely limited to use aluminum, copper, silver-zinc alloy or base metal as the metal ohmic electrode, and the metal ohmic electrode 2 may adopt a sintering method, a melt spraying method, a sputtering method, a coating method or other similar equivalent methods. Combined on both sides of the aforementioned glass sealing layer as the micro-pore channel blocking layer 3 .
  • the raw material composition of the aforementioned heat-sensitive ceramic tile 1 is: 0.897BaTiO 3 +0.003PbTiO 3 +0.1CaO+0.05(BN+V 2 O 3 +Li 2 CO 3 +Al 2 O 3 )+0.001 Y 2 O 3 and 0.001 Nb 2 O 5 + 0.0001 mol of NiN 2 O 6 .
  • the aforementioned glass paste for encapsulation is coated on the surface of the aforementioned heat-sensitive ceramic tile 1 by dipping method, and then placed in a high-temperature heat treatment device and heat-treated at 600° C. for 8 minutes.
  • the aforementioned glass sealing layer is a glass sealing layer of a glass system, and the glass system is composed of the following raw materials in terms of gram molecular weight: K 2 SiF 6 +ZnO+Al 2 O 3 +SiO 2 +0.1(Na 2 O+K 2 O)+0.5Li 2 O+0.01MnO 2 , the sum is one mole.
  • a positive temperature coefficient ceramic thermistor element with strong resistance to reducing atmosphere includes a lead barium titanate-based and sintered specification of 24 ⁇ 15 ⁇ 2.4 mm (not The heat-sensitive ceramic tile 1 and the metal ohmic electrodes 2 located on both sides of the heat-sensitive ceramic tile 1, as the technical points of the technical solution provided by the present invention: also include a microporous channel barrier layer 3.
  • the microporous channel barrier layer 3 is a glass sealing layer, and the glass sealing layer is integrally covered on the outer surface of the aforementioned heat-sensitive ceramic tile 1 with a thickness of 3.5 ⁇ m, and the aforementioned metal ohmic electrode 2
  • the metal ohmic electrode 2 may adopt a sintering method, a melt spraying method, a sputtering method, a coating method or other similar equivalents The method is combined on both sides of the aforementioned glass sealing layer as the microporous channel barrier layer 3 .
  • the raw material composition of the aforementioned heat-sensitive ceramic tile 1 is: 0.498BaTiO 3 +0.5PbTiO 3 +0.002SrO+0.01(BN+V 2 O 3 +Li 2 CO 3 +Al 2 O 3 )+0.0025 Y 2 O 3 and 0.0025Sm 2 O 3 + 0.0003 mol of FeN 3 O 9 .
  • the mass ratio of the glass micropowder with the aforementioned particle size less than 500nm and the organic matter is 1: 1.2, and the organic matter is made up of the following raw materials proportioned by parts by weight: 0.3 part of PVB as adhesive, 0.01 part of low-molecular-weight wax as dispersant and acetone as a solvent, since the solvent can be added as required, there is no need to limit the amount of the solvent.
  • the aforementioned glass paste for encapsulation is coated on the surface of the aforementioned heat-sensitive ceramic tile 1 by spraying, and then placed in a high-temperature heat treatment device and heat-treated at 550° C. for 10 minutes.
  • the aforementioned glass sealing layer is a glass sealing layer of a glass system, and the glass system is composed of the following raw materials in terms of gram molecular weight: K 2 SiF 6 +ZnO+Al 2 O 3 +SiO 2 +0.3(Na 2 O+K 2 O)+0.5V 2 O 5 +0.055CO 3 O 4 , the sum is one mole.
  • Preparation example is preparation method 1:
  • the outer surface of the sintered heat-sensitive ceramic tile 1 based on lead barium titanate described in any one of Embodiments 1 to 3 is integrally coated with a glass sealing layer serving as a microporous channel barrier layer 3, Then, metal ohmic electrodes 2 are bonded to both sides of the glass sealing layer to obtain a positive temperature coefficient ceramic thermistor element shown in FIG. 1 with a strong reduction-resistant atmosphere.
  • the micro-porous channel blocking layer 3 is an organic sealant, and the organic sealant is used to seal the sealant in the heat-sensitive ceramic.
  • the pores 11 shown in FIG. 3 ) on the surface of the metal ohmic electrode 2 on both sides of the ceramic tile 1 and the surface of the area without the metal ohmic electrode 2 at the peripheral edge of the thermosensitive ceramic tile 1 are sealed at the same time. (i.e. "filling in").
  • the aforementioned organic sealant is filled in the micropores on the surface of the aforementioned metal ohmic electrodes 2 bonded to both sides of the heat-sensitive ceramic tile 1 , and at the same time, the surrounding edges of the heat-sensitive ceramic tile 1 are sealed.
  • the filling method for filling the voids 11 on the surface of the area of the metal ohmic electrode 2 is as follows: the aforementioned heat-sensitive ceramic tile 1 with the aforementioned metal ohmic electrodes 2 combined on both sides is put into a cavity filled with the aforementioned organic sealant as a void blocking medium. In the hot isostatic press of After finishing, clean and dry the surface in sequence.
  • the raw materials of the organic sealant described in this embodiment are: polydimethylsiloxane, transition metal oxide nano-powder, namely MnO 2 nano-powder, cross-linking agent, namely hydrogen-containing silicone oil, catalyst, namely platinum ethylene complex and
  • the organic solvent is xylene, wherein the amount of MnO2 nano-powder added to the polydimethylsiloxane is 0.001% of the weight of the polydimethylsiloxane, and the amount of hydrogen-containing silicone oil added is polydimethylsiloxane. 2% by weight of oxane, and the addition amount of platinum vinyl complex is 0.08% by weight of polydimethylsiloxane.
  • the rest are the same as those described in Embodiments 1 to 3, respectively.
  • the microporous channel blocking layer 3 is an organic sealant, and the organic sealant is used to seal the sealant which is bonded to the thermosensitive ceramics.
  • the pores 11 shown in FIG. 3 ) on the surface of the metal ohmic electrode 2 on both sides of the ceramic tile 1 and the surface of the area without the metal ohmic electrode 2 at the peripheral edge of the thermosensitive ceramic tile 1 are sealed at the same time. (i.e. "filling in").
  • the aforementioned organic sealant is filled in the micropores on the surface of the aforementioned metal ohmic electrodes 2 bonded to both sides of the heat-sensitive ceramic tile 1 , and at the same time, the surrounding edges of the heat-sensitive ceramic tile 1 are sealed.
  • the filling method for filling the voids 11 on the surface of the area of the metal ohmic electrode 2 is as follows: the aforementioned heat-sensitive ceramic tile 1 with the aforementioned metal ohmic electrodes 2 combined on both sides is put into a cavity filled with the aforementioned organic sealant as a void blocking medium. In the hot isostatic press of After finishing, clean and dry the surface in sequence.
  • the raw materials of the organic sealant described in this embodiment are: polydimethylsiloxane, transition metal oxide nano-powder, namely Fe 3 O 4 nano-powder, cross-linking agent, hydrogen-containing silicone oil, catalyst, platinum-ethylene complex
  • the amount of Fe 3 O 4 nano-powder added to the polydimethylsiloxane is 0.01% of the weight of the polydimethylsiloxane
  • the amount of hydrogen-containing silicone oil is polydimethylsiloxane.
  • 1% by weight of dimethylsiloxane, and the addition amount of platinum vinyl complex is 0.05% by weight of polydimethylsiloxane.
  • the rest are the same as those described in Embodiments 1 to 3, respectively.
  • the micro-porous channel blocking layer 3 is an organic sealant, and the organic sealant is used to seal the sealant in the heat-sensitive ceramic.
  • the pores 11 shown in FIG. 3 ) on the surface of the metal ohmic electrode 2 on both sides of the ceramic tile 1 and the surface of the area without the metal ohmic electrode 2 at the peripheral edge of the thermosensitive ceramic tile 1 are sealed at the same time. (i.e. "filling in").
  • the aforementioned organic sealant is filled in the micropores on the surface of the aforementioned metal ohmic electrodes 2 bonded to both sides of the heat-sensitive ceramic tile 1 , and at the same time, the surrounding edges of the heat-sensitive ceramic tile 1 are sealed.
  • the filling method for filling the voids 11 on the surface of the area of the metal ohmic electrode 2 is as follows: the aforementioned heat-sensitive ceramic tile 1 with the aforementioned metal ohmic electrodes 2 combined on both sides is put into a cavity filled with the aforementioned organic sealant as a void blocking medium. In the hot isostatic press of After finishing, clean and dry the surface in sequence.
  • the raw materials of the organic sealant described in this embodiment are: polydimethylsiloxane, transition metal oxide nano-powder, namely Co 3 O 4 nano-powder, cross-linking agent, hydrogen-containing silicone oil, catalyst, platinum-ethylene complex
  • the amount of Co 3 O 4 nano-powder added to the polydimethylsiloxane is 0.006% of the weight of the polydimethylsiloxane
  • the amount of hydrogen-containing silicone oil added is polydimethylsiloxane.
  • 3% by weight of dimethylsiloxane, and the addition amount of platinum vinyl complex is 0.1% by weight of polydimethylsiloxane.
  • the rest are the same as those described in Embodiments 1 to 3, respectively.
  • Impregnation in the container the process parameters of the impregnation are: the vacuum degree of vacuuming is less than 10KPa, and the impregnation time is preferably controlled to be 280-320min, preferably 290-310min, preferably 300min (this embodiment selects 300min), after the impregnation is completed Ultrasonic cleaning was carried out on the surface by using an ultrasonic cleaning machine, and the rest were the same as those described in Example 4, 5 or 6.
  • Preparation example 2 is preparation method 2:
  • metal ohmic electrodes 2 are combined on both sides of the lead-barium titanate-based and sintered heat-sensitive ceramic tile 1 in any one of Examples 4 to 7, and then the metal ohmic electrodes 2 are used as microporous channel barriers.
  • the organic sealant of the layer 3 is filled in the micropores on the surface of the metal ohmic electrode 2 and at the same time, the gaps in the area without the metal ohmic electrode 2 around the heat-sensitive ceramic tile 1 are blocked, and the result shown in FIG. 2 is obtained.
  • PTC ceramic thermistor element with strong reducing atmosphere is obtained.
  • the following properties are only for the positive temperature coefficient ceramic thermistor elements with strong reduction-resistant atmosphere obtained in Examples 1 and 4 to 5 respectively, and the reason is not for the reduction-resistant ceramic thermistor elements obtained in other examples.
  • the performance test of the positive temperature coefficient ceramic thermistor element with strong atmosphere is because on the one hand, the products obtained in Examples 1 and 4 to 5 have been tested enough to reflect and prove the desired technical effect, and because other examples obtained
  • the product also has a technical effect that is not inferior to the product obtained by implementing 1 and 4 to 5, but also because of the consideration of avoiding excessive text.
  • the product structure currently in the test state shown in FIG. 4 (that is, the tested state) is essentially the product structure obtained in Examples 4 to 5, and the test method for the product obtained in Example 1 is the same, only It is only necessary to replace the product obtained from the different embodiment.
  • the performance testing system of PTC ceramic thermistor element in reducing atmosphere includes vacuum container 4 , vacuum pump 5 , volatile reducing solvent 6 and regulated power supply 7 , etc.
  • the volume of the vacuum container 4 is about 10,000 cubic centimeters, and 50 grams of acetone reagent with a concentration of 100% is placed in the vacuum container 4.
  • the positive temperature coefficient ceramic thermistor element with strong reducing resistance atmosphere obtained in the embodiment to be tested into the system and use the vacuum pump 5 to pump the pressure of the vacuum container 4 to 20kPa (negative pressure). More specifically, a power frequency voltage of 270 volts was continuously applied to the metal ohmic electrodes 2 on both sides of the element until the element was destroyed and the failure time was recorded.
  • the specific implementation method is as follows: select the PTC ceramic thermistor elements prepared in the same batch, select elements with similar zero-power resistance values at room temperature, seal half of them, and do not seal the other half, and perform anti-reduction in the test system at the same time.
  • the comparison results are shown in the table below.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Thermistors And Varistors (AREA)

Abstract

一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法，包括以钛酸铅钡为基并且经烧结的热敏陶瓷瓷片和位于热敏陶瓷瓷片两侧面的金属欧姆电极，特点：还包括微气孔通道阻隔层，该微气孔通道阻隔层包括玻璃密封层或有机物密封剂，当微气孔通道阻隔层为玻璃密封层时，玻璃密封层整体包覆在热敏陶瓷瓷片的外表面，金属欧姆电极结合在玻璃密封层的两侧面；当微气孔通道阻隔层为有机物密封剂时，有机物密封剂填堵于结合在热敏陶瓷瓷片的两侧面的金属欧姆电极的表面的微孔内且同时将热敏陶瓷瓷片的四周边缘部位的无金属欧姆电极的区域的表面的空隙封堵。提高抗恶劣环境能力及延长使用寿命，提高相关发热组的可靠性和期望的服役要求。

Description

一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法 技术领域
本发明属于电子元器件及其制备技术领域，具体涉及一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，并且还涉及其制备方法。
技术背景
正温度系数(以下简称PTC)陶瓷热敏元件一般是以钛酸钡为基的半导体陶瓷材料制备的，这种热敏元件的特点是当温度超过居里温度时其常温电阻值将猛增几个数量级，即产生所谓PTC效应。这种PTC效应的起源是由晶界势垒引起的，晶界势垒的高度与晶界上吸附的氧原子浓度息息相关，当热敏元件长期在还原性气氛等恶劣环境下工作时将导致晶界失氧，造成元件性能衰竭甚至失去PTC效应。一般应用在新能源汽车、空调电辅加热等领域的PTC热敏元件往往都是工作在这种环境下，这一方面由于工作场所(如汽车)本身环境的恶劣性，另一方面PTC元件在被组装成发热组件时，通常都是用有机胶粘固在金属散热器上，这种有机胶在高温下(≥200℃)会散发出还原性气氛损伤PTC元件，进而降低元器件的使用寿命。
PTC热敏元件之所以容易受到恶劣环境的影响，主要原因它是一种多晶陶瓷材料，不仅存在晶界，同时存在大量微气孔，各种不良气氛可以通过这些微气孔进入晶界，从而损害元件的宏观电学性能，例如因被氧化还原而丧失自控温功能。
发明内容
本发明的首要任务在于提供一种有助于阻隔外部有害气体从陶瓷表面的微气孔侵入陶瓷晶界的通道而得以提高抗恶劣环境能力及延长使用寿命并且满足在含还原气氛环境下的服役要求的耐还原性气氛强的正温度系数陶瓷热敏电阻元件。
本发明的另一任务在于提供一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件的制备方法，该方法制备过程简单、无极端苛刻的工艺要素而得以满足产业化制备要求并且能保障得到的正温度系数陶瓷热敏电阻元件的所述技术效果得以全面体现。
本发明的首要任务是这样来完成的，一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，包括以钛酸铅钡为基并且经烧结的热敏陶瓷瓷片和位于热敏陶瓷瓷片两侧面的金属欧姆电极，特征在于还包括微气孔通道阻隔层，该微气孔通道阻隔层包括玻璃密封层或有机物密封剂，并且当微气孔通道阻隔层为玻璃密封层时，该玻璃密封层整体包覆在所述热敏陶瓷瓷片的外表面，所述金属欧姆电极结合在玻璃密封层的两侧面；而当微气孔通道阻隔层为有机物密封剂时，该有机物密封剂填堵于结合在热敏陶瓷瓷片的两侧面的所述金属欧姆电极的表面的微孔内并且同时将热敏陶瓷瓷片的四周边缘部位的无金属欧姆电极的 区域的表面的空隙封堵。
在本发明的一个具体的实施例中，所述热敏陶瓷瓷片的原料组成为：(1-x-y)BaTiO 3+xPbTiO 3+yR+zS+wT，式中R为CaO、SrO或(CaO+SrO)，S为(BN+V 2O 3+Li 2CO 3+Al 2O 3)，T为3价稀土氧化物和5价金属氧化物中的一种或者两者的组合；x＜0.5，y＜0.1，z＜0.05，w＝0.001～0.005。
在本发明的另一个具体的实施例中，在所述热敏陶瓷瓷片的原料组成中还包括有0.0001～0.0005克分子的MnN 2O 6、NiN 2O 6或FeN 3O 9。
在本发明的又一个具体的实施例中，所述的3价稀土氧化物为La 2O 3、Y 2O 3和Sm 2O 3中的一种或多种的混合物；所述的5价金属氧化物为Nb 2O 5。
在本发明的再一个具体的实施例中，所述玻璃密封层是由包封用玻璃浆料得到的，该包封用玻璃浆料是这样来制备的：采用熔融水淬法制备粒径小于500nm的玻璃微粉并同时加入有机物混合，得到用作所述微气孔通道阻隔层的所述玻璃密封层的包封用玻璃浆料。
在本发明的还有一个具体的实施例中，所述粒径小于500nm的玻璃微粉与所述有机物的质量比为1∶1.2，所述有机物由以下按重量份数配比的原料组成：粘合剂0.1-0.3份、分散剂0.001-0.01份和溶剂1份；所述粘合剂为PVB，所述分散剂为低分子蜡，所述溶剂为丙酮。
在本发明的更而一个具体的实施例中，在将所述包封用玻璃浆料以浸渍法或喷涂法中的任意一种方法包覆在所述热敏陶瓷瓷片的表面后置于高温热处理装置并且在500-600℃下热处理8-12min。
在本发明的进而一个具体的实施例中，所述玻璃密封层为玻璃体系的玻璃密封层，所述玻璃体系由以下按克分子量比的原料组成：K 2SiF 6+ZnO+Al 2O 3+SiO 2+αM+N+βP，其中：M为Na 2O+K 2O，且α＝0.1～0.3；N为B 2O 3、Li 2O和V 2O 5中之一种或几种的组合，且总和为一克分子；P为MnO 2、Fe 3O 4或Co 3O 4，且β＝0.001～0.01。
在本发明的又更而一个具体的实施例中，所述有机密封剂填堵于结合在所述热敏陶瓷瓷片的两侧面的所述金属欧姆电极的表面的微孔内并且同时将热敏陶瓷瓷片的四周边缘部位的无金属欧姆电极的区域的表面的空隙填堵的填堵方法包括以下两种方法中的任意一种方法：方法一，将两侧面结合有所述金属欧姆电极的所述热敏陶瓷瓷片投入盛有以所述有机物密封剂作为空隙封堵介质的热等静压机内，对热等静压机施压并且控制施压时的所述空隙封堵介质的温度、控制施压的压力以及控制施压时间，施压结束后依次进行表面清洗和烘干；方法二，将两侧面结合有所述金属欧姆电极的所述热敏陶瓷瓷片投入盛有所述有机物密封剂的容器中浸渍，对容器抽真空并且控制抽真空的真空度和控制浸渍的时 间，抽真空结合后从容器中取出，并依次进行表面清洗的烘干。
在本发明的又进而一个具体的实施例中，所述控制施压时的所述空隙填堵介质的温度是将空隙填堵介质的温度控制为100-200℃，所述控制施压的压力是将压力控制为1-10MPa，所述控制施压时间是将施压时间控制为60-120min；所述控制抽真空的真空度是将真空度控制为小于10KPa，所述控制浸渍的时间是将浸渍的时间控制为280-320min；所述表面清洗为采用超声波洗机清洗。
在本发明的还更而一个具体的实施例中，所述有机物密封剂的原料组成为：聚二甲基硅氧烷、过渡金属氧化物纳米粉体、交联剂、催化剂和有机溶剂；所述过渡金属氧化物纳米粉体加入到聚二甲基硅氧烷中的量为聚二甲基硅氧烷重量的0.001-0.01％；所述交联剂的加入量为聚二甲基硅氧烷重量的1-3％；所述催化剂的加入量为聚二甲基硅氧烷重量的0.05-0.1％。
在本发明的还进而一个具体的实施例中，所述的过渡金属氧化物纳米粉体为MnO 2、Fe 3O 4或Co 3O 4纳米粉体；所述的交联剂为含氢硅油；所述催化剂为铂乙烯配合物；所述有机溶剂为二甲苯。
在本发明的更进而一个具体的实施例中，所述的玻璃密封层的厚度为2-5μm。
本发明的另一任务是这样来完成的，一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件的制备方法，其是先在以钛酸铅钡为基并且经烧结的热敏陶瓷瓷片的外表面整体包覆作为微气孔通道阻隔层的玻璃密封层，而后在该玻璃密封层的两侧面各结合金属欧姆电极，或者先在以钛酸铅钡为基的热敏陶瓷瓷片的两侧面各结合金属欧姆电极，而后将作为微气孔通道阻隔层的有机物密封剂填堵于金属欧姆电极的表面的微孔内并且同时将热敏陶瓷瓷片的四周边缘部位的无金属欧姆电极的区域的表面的空隙封堵，得到耐还原性气氛强的正温度系数陶瓷热敏电阻元件。
本发明提供的技术方案的技术效果在于：由于以玻璃密封层或有机物密封剂作为对以钛酸铅钡为基并且经烧结的产生于热敏陶瓷瓷片上的微气孔通道实施阻隔的微气孔通道阻隔层，并且当使用玻璃密封层时，由玻璃密封层对热敏陶瓷瓷片的外表面整体包裹，金属欧姆电极结合在玻璃密封层的两侧面，而当使用有机物密封剂时，将有机物密封剂填堵于结合在热敏陶瓷瓷片的两侧面的金属欧姆电极的表面的微孔内并且同时将热敏陶瓷瓷片的四周边缘部位的无金属欧姆电极的区域的表面的空隙封堵，因而能使外界的有害气体和/或附着异物与热敏陶瓷瓷片晶界隔绝，避免被还原导致自控温功能丧失乃至引起电气短路，既可显著提高抗恶劣环境能力及延长使用寿命，又能满足在含有还原气氛环境下的诸如新能源汽车热管理系统、空调之类的家用电器电辅恒温加热器等的装置上，可提高相关发热组的可靠性和期望的服役要求；提供的制备方法工艺步骤简洁以及无苛刻的工艺要 素，并且能保障所述正温度系数陶瓷热敏电阻元件的所述技术效果得以全面体现。
附图说明
图1为本发明实施例1至3的耐还原性气氛强的正温度系数陶瓷热敏电阻元件的剖面图。
图2为本发明实施例4至7的耐还原性气氛强的正温度系数陶瓷热敏电阻元件的剖面图。
图3为图2的A部放大图。
图4为对本发明耐还原性气氛强的正温度系数陶瓷热敏电阻元件的还原气氛试验装置示意图。
具体实施方式
实施例1：
请参见图1，图1所示的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，包括以钛酸铅钡为基并且经烧结的规格为24×15×2.4mm(并不受到该例举尺寸的限定)的热敏陶瓷瓷片1和位于热敏陶瓷瓷片1两侧的金属欧姆电极2，作为本发明提供的技术方案的技术要点：还包括有微气孔通道阻隔层3，在本实施例中，该微气孔通道阻隔层3为玻璃密封层，该玻璃密封层以5μm的厚度整体包覆在前述热敏陶瓷瓷片1的外表面，前述的金属欧姆电极2优选而非绝对限于地使用铝、铜、银锌合金或贱金属作为金属欧姆电极，并且该金属欧姆电极2可以采用烧渗法、熔融喷涂法、溅射法、镀膜法或其它类似的等效方法结合在前述作为微气孔通道阻隔层3的玻璃密封层的两侧面。
在本实施例中，前述热敏陶瓷瓷片1的原料组成为：0.64BaTiO 3+0.3PbTiO 3+0.06(CaO+SrO)+0.005(BN+V 2O 3+Li 2CO 3+Al 2O 3)+0.003La 2O 3+0.0003克分子的MnN 2O 6。
本实施例中所述的玻璃密封层是由包封用玻璃浆料得到的(即制得的)，该包封用玻璃浆料是这样来制备的：采用熔融水淬法制粒径小于500nm的玻璃微粉并同时加入有机物(也可称“粘合物”或“有机粘合物”)混合，得到用作前述微气孔通道阻隔层3的所述玻璃密封层的包封用玻璃浆料。前述粒径小于500nm的玻璃微粉与有机物的质量比为1∶1.2，该有机物由以下按重量份数配比的原料组成：作为粘合剂的PVB0.2份、作为分散剂的低分子蜡0.001份和作为溶剂的丙酮，由于溶剂可根据需要加入，因而无需对其取量限定。
在本实施例中，前述包封用玻璃浆料以浸渍法包覆于前述热敏陶瓷瓷片1的表面后置于高温热处理装置并且在500℃下热处理12min。
在本实施例中，前述玻璃密封层为玻璃体系的玻璃密封层，该玻璃体系由以下按克分子量比的原料组成：K 2SiF 6+ZnO+Al 2O 3+SiO 2+0.2(Na 2O+K 2O)+0.5(B 2O 3+Li 2O) +0.005Fe 3O 4，总和为一克分子。
实施例2：
请参见图1，图1所示的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，包括以钛酸铅钡为基并且经烧结的规格为24×15×2.4mm(并不受到该例举尺寸的限定)的热敏陶瓷瓷片1和位于热敏陶瓷瓷片1两侧的金属欧姆电极2，作为本发明提供的技术方案的技术要点：还包括有微气孔通道阻隔层3，在本实施例中，该微气孔通道阻隔层3为玻璃密封层，该玻璃密封层以2μm的厚度整体包覆在前述热敏陶瓷瓷片1的外表面，前述的金属欧姆电极2优选而非绝对限于地使用铝、铜、银锌合金或贱金属作为金属欧姆电极，并且该金属欧姆电极2可以采用烧渗法、熔融喷涂法、溅射法、镀膜法或其它类似的等效方法结合在前述作为微气孔通道阻隔层3的玻璃密封层的两侧面。
在本实施例中，前述热敏陶瓷瓷片1的原料组成为：0.897BaTiO 3+0.003PbTiO 3+0.1CaO+0.05(BN+V 2O 3+Li 2CO 3+Al 2O 3)+0.001Y 2O 3和0.001Nb 2O 5+0.0001克分子的NiN 2O 6。
本实施例中所述的玻璃密封层是由包封用玻璃浆料得到的(即制得的)，该包封用玻璃浆料是这样来制备的：采用熔融水淬法制粒径小于500nm的玻璃微粉并同时加入有机物(也可称“粘合物”或“有机粘合物”)混合，得到用作前述微气孔通道阻隔层3的所述玻璃密封层的包封用玻璃浆料。前述粒径小于500nm的玻璃微粉与有机物的质量比为1∶1.2，该有机物由以下按重量份数配比的原料组成：作为粘合剂的PVB0.1份、作为分散剂的低分子蜡0.006份和作为溶剂的丙酮，由于溶剂可根据需要加入，因而无需对其取量限定。
在本实施例中，前述包封用玻璃浆料以浸渍法包覆于前述热敏陶瓷瓷片1的表面后置于高温热处理装置并且在600℃下热处理8min。
在本实施例中，前述玻璃密封层为玻璃体系的玻璃密封层，该玻璃体系由以下按克分子量比的原料组成：K 2SiF 6+ZnO+Al 2O 3+SiO 2+0.1(Na 2O+K 2O)+0.5Li 2O+0.01MnO 2，总和为一克分子。
实施例3：
请参见图1，图1所示的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，包括以钛酸铅钡为基并且经烧结的规格为24×15×2.4mm(并不受到该例举尺寸的限定)的热敏陶瓷瓷片1和位于热敏陶瓷瓷片1两侧的金属欧姆电极2，作为本发明提供的技术方案的技术要点：还包括有微气孔通道阻隔层3，在本实施例中，该微气孔通道阻隔层3为玻璃密封层，该玻璃密封层以3.5μm的厚度整体包覆在前述热敏陶瓷瓷片1的外表面，前述的金属欧姆电极2优选而非绝对限于地使用铝、铜、银锌合金或贱金属作为金属欧姆电极，并且该金属欧姆电极2可以采用烧渗法、熔融喷涂法、溅射法、镀膜法或其它类似的 等效方法结合在前述作为微气孔通道阻隔层3的玻璃密封层的两侧面。
在本实施例中，前述热敏陶瓷瓷片1的原料组成为：0.498BaTiO 3+0.5PbTiO 3+0.002SrO+0.01(BN+V 2O 3+Li 2CO 3+Al 2O 3)+0.0025Y 2O 3和0.0025Sm 2O 3+0.0003克分子的FeN 3O 9。
本实施例中所述的玻璃密封层是由包封用玻璃浆料得到的(即制得的)，该包封用玻璃浆料是这样来制备的：采用熔融水淬法制粒径小于500nm的玻璃微粉并同时加入有机物(也可称“粘合物”或“有机粘合物”)混合，得到用作前述微气孔通道阻隔层3的所述玻璃密封层的包封用玻璃浆料。前述粒径小于500nm的玻璃微粉与有机物的质量比为1∶1.2，该有机物由以下按重量份数配比的原料组成：作为粘合剂的PVB0.3份、作为分散剂的低分子蜡0.01份和作为溶剂的丙酮，由于溶剂可根据需要加入，因而无需对其取量限定。
在本实施例中，前述包封用玻璃浆料以喷涂法包覆于前述热敏陶瓷瓷片1的表面后置于高温热处理装置并且在550℃下热处理10min。
在本实施例中，前述玻璃密封层为玻璃体系的玻璃密封层，该玻璃体系由以下按克分子量比的原料组成：K 2SiF 6+ZnO+Al 2O 3+SiO 2+0.3(Na 2O+K 2O)+0.5V 2O 5+0.055CO 3O 4，总和为一克分子。
制备例即制备方法1：
先在实施例1至3的任一实施例所述的以钛酸铅钡为基并经烧结的热敏陶瓷瓷片1的外表面整体包覆作为微气孔通道阻隔层3的玻璃密封层，而后在该玻璃密封层的两侧面各结合金属欧姆电极2，得到由图1所示的耐还原性气氛强的正温度系数陶瓷热敏电阻元件。
实施例4：
请参见图2和图3，本实施例4相对于实施例1或2或3而言，所述的微气孔通道阻隔层3为有机物密封剂，该有机物密封剂填堵于结合在热敏陶瓷瓷片1的两侧面的金属欧姆电极2的表面的微孔内并且同时将热敏陶瓷瓷片1的四周边缘部位的无金属欧姆电极2的区域的表面的空隙11(图3示)封堵(即“填堵”)。在本实施例中，前述有机密封剂填堵于结合在热敏陶瓷瓷片1两侧面的前述金属欧姆电极2的表面的微孔内并且同时将热敏陶瓷瓷片1的四周边缘部位的无金属欧姆电极2的区域的表面的空隙11填堵的填堵方法为：将两侧面结合有前述金属欧姆电极2的前述热敏陶瓷瓷片1投入盛有以前述有机物密封剂作为空隙封堵介质的热等静压机内，对热等静压机施压，施压工艺参数为：将所述空隙填堵介质温度控制为200℃，压力控制为10MPa，施压时间控制为60min，施压结束后依次进行表面清洁和烘干。本实施例所述的有机物密封剂的原料为：聚二甲基硅氧烷、过渡金属氧化物纳米粉体即MnO 2纳米粉体、交联剂即含氢硅油、催化剂即铂乙烯配合物 和有机溶剂即二甲苯，其中，MnO 2纳米粉体加入到聚二甲基硅氧烷中的量为聚二甲基硅氧烷重量的0.001％，含氢硅油的加入量为聚二甲基硅氧烷重量的2％，铂乙烯配合物的加入量为聚二甲基硅氧烷重量的0.08％。其余分别同对实施例1至3的描述。
实施例5：
请参见图2和图3，本实施例5相对于实施例1或2或3而言，所述的微气孔通道阻隔层3为有机物密封剂，该有机物密封剂填堵于结合在热敏陶瓷瓷片1的两侧面的金属欧姆电极2的表面的微孔内并且同时将热敏陶瓷瓷片1的四周边缘部位的无金属欧姆电极2的区域的表面的空隙11(图3示)封堵(即“填堵”)。在本实施例中，前述有机密封剂填堵于结合在热敏陶瓷瓷片1两侧面的前述金属欧姆电极2的表面的微孔内并且同时将热敏陶瓷瓷片1的四周边缘部位的无金属欧姆电极2的区域的表面的空隙11填堵的填堵方法为：将两侧面结合有前述金属欧姆电极2的前述热敏陶瓷瓷片1投入盛有以前述有机物密封剂作为空隙封堵介质的热等静压机内，对热等静压机施压，施压工艺参数为：将所述空隙填堵介质温度控制为150℃，压力控制为6MPa，施压时间控制为90min，施压结束后依次进行表面清洁和烘干。本实施例所述的有机物密封剂的原料为：聚二甲基硅氧烷、过渡金属氧化物纳米粉体即Fe 3O 4纳米粉体、交联剂即含氢硅油、催化剂即铂乙烯配合物和有机溶剂即二甲苯，其中，Fe 3O 4纳米粉体加入到聚二甲基硅氧烷中的量为聚二甲基硅氧烷重量的0.01％，含氢硅油的加入量为聚二甲基硅氧烷重量的1％，铂乙烯配合物的加入量为聚二甲基硅氧烷重量的0.05％。其余分别同对实施例1至3的描述。
实施例6：
请参见图2和图3，本实施例6相对于实施例1或2或3而言，所述的微气孔通道阻隔层3为有机物密封剂，该有机物密封剂填堵于结合在热敏陶瓷瓷片1的两侧面的金属欧姆电极2的表面的微孔内并且同时将热敏陶瓷瓷片1的四周边缘部位的无金属欧姆电极2的区域的表面的空隙11(图3示)封堵(即“填堵”)。在本实施例中，前述有机密封剂填堵于结合在热敏陶瓷瓷片1两侧面的前述金属欧姆电极2的表面的微孔内并且同时将热敏陶瓷瓷片1的四周边缘部位的无金属欧姆电极2的区域的表面的空隙11填堵的填堵方法为：将两侧面结合有前述金属欧姆电极2的前述热敏陶瓷瓷片1投入盛有以前述有机物密封剂作为空隙封堵介质的热等静压机内，对热等静压机施压，施压工艺参数为：将所述空隙填堵介质温度控制为100℃，压力控制为1MPa，施压时间控制为120min，施压结束后依次进行表面清洁和烘干。本实施例所述的有机物密封剂的原料为：聚二甲基硅氧烷、过渡金属氧化物纳米粉体即Co 3O 4纳米粉体、交联剂即含氢硅油、催化剂即铂乙烯配合物和有机溶剂即二甲苯，其中，Co 3O 4纳米粉体加入到聚二甲基硅氧烷中的量为聚二甲基硅 氧烷重量的0.006％，含氢硅油的加入量为聚二甲基硅氧烷重量的3％，铂乙烯配合物的加入量为聚二甲基硅氧烷重量的0.1％。其余分别同对实施例1至3的描述。
实施例7：
仅将有机密封剂填堵于结合在热敏陶瓷瓷片1的两侧面的所述金属欧姆电极2的表面的微孔内并且同时将热敏陶瓷瓷片1的四周边缘部位的无金属欧姆电极2的区域的表面的空隙11的填堵方法改用如下方法：将两侧结合有所述金属欧姆电极2的热敏陶瓷瓷片1投入盛有如同实施例4至6所述有机物密封剂的容器中浸渍，浸渍的工艺参数为：抽真空的真空度小于10KPa，浸渍时间优选控制为280-320min，较好地为290-310min，最好为300min(本实施例选择300min)，浸渍完成后采用超声波清洗机对表面进行超声波清洗，其余均同对实施例4、5或6的描述。
制备例2即制备方法2：
先在实施例4至7的任一实施例的所述的钛酸铅钡为基的并且经烧结的热敏陶瓷瓷片1的两侧面各结合金属欧姆电极2，而后将作为微气孔通道阻隔层3的有机物密封剂填堵于金属欧姆电极2的表面的微孔内并且同时将热敏陶瓷瓷片1的四周部位的无金属欧姆电极2的区域的空隙封堵，得到图2所示的耐还原性气氛强的正温度系数陶瓷热敏电阻元件。
以上内容是结合具体的优选实施方式对本发明所做的进一步详细说明，不能认定本发明的具体实施仅限于这些说明。对于本发明所属技术领域的普通技术人员而言，在不脱离本发明构思的前提下，还可以作出若干简单推演或替换，都应视为本发明公开的技术内涵范畴。
性能测试
下面的性能仅分别针对实施例1和4至5该三个实施例得到的耐还原性气氛强的正温度系数陶瓷热敏电阻元件而言的，而之所以未对其它实施例得到的耐还原性气氛强的正温度系数陶瓷热敏电阻元件进行性能测试，是因为一方面对实施例1和4至5得到的产品进行检测已经足以能够体现并证明期望的技术效果，又因为其它实施例得到的产品也同样具有并不逊色于实施1和4至5得到的产品技术效果，还因为出于避免文本过于冗长考虑。此外，处于目前由图4所示的测试状态(即被测状态)的产品结构实质上是实施例4至5得到的产品结构，对实施例1得到的产品的测试方式是相同的，仅仅是只需更换由不同实施例得到的产品而已。
请参见图4，PTC陶瓷热敏电阻元件在还原气氛下性能测试系统，系统包括真空容器4、真空泵5、易挥发的还原性溶剂6及稳压电源7等。
优选的，真空容器4的容积约为10000立方厘米，真空容器4内放有浓度为100％的 丙酮试剂50克。
将待测本发明的由实施例得到的耐还原性气氛强的正温度系数陶瓷热敏电阻元件放入系统中，用真空泵5将真空容器4的压强抽至20kPa(负压)。对元件更具体地讲对前述两侧面的金属欧姆电极2持续施加270伏工频电压，直至元件破坏实效，记录失效时间。
具体实施方法为：将同一批制备出的PTC陶瓷热敏电阻元件，选择常温零功率电阻值相近的元件，一半进行密封处理，另一半不做密封处理，同时在所述测试系统中进行抗还原性试验，对比结果见下面的表所示。
结果显示，本发明的PTC陶瓷热敏元件具有很强的抗还原特性。
对实施例1得到的产品的性能测试表
Figure PCTCN2021104885-appb-000001
对实施例4得到的产品的性能测试表
Figure PCTCN2021104885-appb-000002
Figure PCTCN2021104885-appb-000003
对实施例5得到的产品的性能测试表
Figure PCTCN2021104885-appb-000004

Claims (14)

  1. 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，包括以钛酸铅钡为基并且经烧结的热敏陶瓷瓷片(1)和位于热敏陶瓷瓷片(1)两侧面的金属欧姆电极(2)，特征在于还包括微气孔通道阻隔层(3)，该微气孔通道阻隔层(3)包括玻璃密封层或有机物密封剂，并且当微气孔通道阻隔层(3)为玻璃密封层时，该玻璃密封层整体包覆在所述热敏陶瓷瓷片(1)的外表面，所述金属欧姆电极(2)结合在玻璃密封层的两侧面；而当微气孔通道阻隔层(3)为有机物密封剂时，该有机物密封剂填堵于结合在热敏陶瓷瓷片(1)的两侧面的所述金属欧姆电极(2)的表面的微孔内并且同时将热敏陶瓷瓷片(1)的四周边缘部位的无金属欧姆电极(2)的区域的表面的空隙(11)封堵。
  2. 根据权利要求1所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述热敏陶瓷瓷片(1)的原料组成为：(1-x-y)BaTiO 3+xPbTiO 3+yR+zS+wT，式中R为CaO、SrO或(CaO+SrO)，S为(BN+V 2O 3+Li 2CO 3+Al 2O 3)，T为3价稀土氧化物和5价金属氧化物中的一种或者两者的组合；x＜0.5，y＜0.1，z＜0.05，w＝0.001～0.005。
  3. 根据权利要求2所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于在所述热敏陶瓷瓷片(1)的原料组成中还包括有0.0001～0.0005克分子的MnN 2O 6、NiN 2O 6或FeN 3O 9。
  4. 根据权利要求2所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述的3价稀土氧化物为La 2O 3、Y 2O 3和Sm 2O 3中的一种或多种的混合物；所述的5价金属氧化物为Nb 2O 5。
  5. 根据权利要求1所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述玻璃密封层是由包封用玻璃浆料得到的，该包封用玻璃浆料是这样来制备的：采用熔融水淬法制备粒径小于500nm的玻璃微粉并同时加入有机物混合，得到用作所述微气孔通道阻隔层(3)的所述玻璃密封层的包封用玻璃浆料。
  6. 根据权利要求5所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述粒径小于500nm的玻璃微粉与所述有机物的质量比为1∶1.2，所述有机物由以下按重量份数配比的原料组成：粘合剂0.1-0.3份、分散剂0.001-0.01份和溶剂1份；所述粘合剂为PVB，所述分散剂为低分子蜡，所述溶剂为丙酮。
  7. 根据权利要求5所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于在将所述包封用玻璃浆料以浸渍法或喷涂法中的任意一种方法包覆在所述热敏陶瓷瓷片(1)的表面后置于高温热处理装置并且在500-600℃下热处理8-12min。
  8. 根据权利要求1所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述玻璃密封层为玻璃体系的玻璃密封层，所述玻璃体系由以下按克分子量比的原料组成：K 2SiF 6+ZnO+Al 2O 3+SiO 2+αM+N+βP，其中：M为Na 2O+K 2O，且α＝0.1～0.3；N为B 2O 3、Li 2O和V 2O 5中之一种或几种的组合，且总和为一克分子；P为MnO 2、Fe 3O 4 或Co 3O 4，且β＝0.001～0.01。
  9. 根据权利要求1所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述有机密封剂填堵于结合在所述热敏陶瓷瓷片(1)的两侧面的所述金属欧姆电极(2)的表面的微孔内并且同时将热敏陶瓷瓷片(1)的四周边缘部位的无金属欧姆电极(2)的区域的表面的空隙(11)填堵的填堵方法包括以下两种方法中的任意一种方法：方法一，将两侧面结合有所述金属欧姆电极(2)的所述热敏陶瓷瓷片(1)投入盛有以所述有机物密封剂作为空隙封堵介质的热等静压机内，对热等静压机施压并且控制施压时的所述空隙封堵介质的温度、控制施压的压力以及控制施压时间，施压结束后依次进行表面清洗和烘干；方法二，将两侧面结合有所述金属欧姆电极(2)的所述热敏陶瓷瓷片(1)投入盛有所述有机物密封剂的容器中浸渍，对容器抽真空并且控制抽真空的真空度和控制浸渍的时间，抽真空结合后从容器中取出，并依次进行表面清洗的烘干。
  10. 根据权利要求9所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述控制施压时的所述空隙填堵介质的温度是将空隙填堵介质的温度控制为100-200℃，所述控制施压的压力是将压力控制为1-10MPa，所述控制施压时间是将施压时间控制为60-120min；所述控制抽真空的真空度是将真空度控制为小于10KPa，所述控制浸渍的时间是将浸渍的时间控制为280-320min；所述表面清洗为采用超声波洗机清洗。
  11. 根据权利要求1或9所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述有机物密封剂的原料组成为：聚二甲基硅氧烷、过渡金属氧化物纳米粉体、交联剂、催化剂和有机溶剂；所述过渡金属氧化物纳米粉体加入到聚二甲基硅氧烷中的量为聚二甲基硅氧烷重量的0.001-0.01％；所述交联剂的加入量为聚二甲基硅氧烷重量的1-3％；所述催化剂的加入量为聚二甲基硅氧烷重量的0.05-0.1％。
  12. 根据权利要求11所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述的过渡金属氧化物纳米粉体为MnO 2、Fe 3O 4或Co 3O 4纳米粉体；所述的交联剂为含氢硅油；所述催化剂为铂乙烯配合物；所述有机溶剂为二甲苯。
  13. 根据权利要求1或5或8所述的一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件，其特征在于所述的玻璃密封层的厚度为2-5μm。
  14. 一种如权利要求1所述的耐还原性气氛强的正温度系数陶瓷热敏电阻元件的制备方法，其特征在于其是先在以钛酸铅钡为基并且经烧结的热敏陶瓷瓷片(1)的外表面整体包覆作为微气孔通道阻隔层(3)的玻璃密封层，而后在该玻璃密封层的两侧面各结合金属欧姆电极(2)，或者先在以钛酸铅钡为基的热敏陶瓷瓷片(1)的两侧面各结合金属欧姆电极(2)，而后将作为微气孔通道阻隔层(3)的有机物密封剂填堵于金属欧姆电极(2)的表面的微孔内并且同时将热敏陶瓷瓷片(1)的四周边缘部位的无金属欧姆电极(2)的区域的表面的空隙(11)封堵，得到耐还原性气氛强的正温度系数陶瓷热敏电阻元件。
PCT/CN2021/104885 2021-01-13 2021-07-07 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法 Ceased WO2022151673A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP21918869.5A EP4297052A4 (en) 2021-01-13 2021-07-07 A ceramic thermistor element with a positive temperature coefficient, exhibiting high resistance to reducing atmospheres, and its preparation process.
US18/281,762 US12354774B2 (en) 2021-01-13 2021-07-07 Positive temperature coefficient ceramic thermistor element having strong reducing atmosphere resistance and preparation method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110039475.1A CN112802647B (zh) 2021-01-13 2021-01-13 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法
CN202110039475.1 2021-01-13

Publications (1)

Publication Number Publication Date
WO2022151673A1 true WO2022151673A1 (zh) 2022-07-21

Family

ID=75810255

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/104885 Ceased WO2022151673A1 (zh) 2021-01-13 2021-07-07 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法

Country Status (4)

Country Link
US (1) US12354774B2 (zh)
EP (1) EP4297052A4 (zh)
CN (1) CN112802647B (zh)
WO (1) WO2022151673A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118271914A (zh) * 2024-03-29 2024-07-02 江苏飞特尔通信有限公司 一种用于ltcc的电镀填孔剂及其制备方法与应用
CN118841228A (zh) * 2024-09-20 2024-10-25 肇庆市金龙宝电子有限公司 一种钛酸钡基热敏电阻及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112802647B (zh) * 2021-01-13 2021-11-23 江苏新林芝电子科技股份有限公司 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法
CN113265636A (zh) * 2021-05-27 2021-08-17 江苏新林芝电子科技股份有限公司 一种提高陶瓷ptc热敏元件的抗还原性的方法
CN114496432A (zh) 2022-03-10 2022-05-13 江苏新林芝电子科技股份有限公司 一种提高ptc热敏元件抗还原性能的方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2537109Y (zh) * 2002-03-08 2003-02-19 常熟市林芝电子有限责任公司 正温度系数热敏电阻器
CN1487534A (zh) * 2002-09-10 2004-04-07 ������������ʽ���� 芯片型电子部件
CN102194559A (zh) * 2010-03-17 2011-09-21 三菱综合材料株式会社 热敏电阻元件及其制造方法
CN102403077A (zh) * 2010-09-06 2012-04-04 Tdk株式会社 陶瓷层叠ptc热敏电阻
CN102522169A (zh) * 2011-12-07 2012-06-27 华中科技大学 一种多层片式热敏陶瓷电阻用端电极及其制备方法
CN104969307A (zh) * 2013-01-29 2015-10-07 株式会社村田制作所 陶瓷电子部件及其制造方法
CN106448974A (zh) * 2016-11-06 2017-02-22 合肥圣达电子科技实业有限公司 一种防止铝电极层湿热老化失效的压敏电阻及其制备方法
CN112802647A (zh) * 2021-01-13 2021-05-14 江苏新林芝电子科技股份有限公司 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996447A (en) * 1974-11-29 1976-12-07 Texas Instruments Incorporated PTC resistance heater
US5219811A (en) * 1989-08-31 1993-06-15 Central Glass Company, Limited Powder composition for sintering into modified barium titanate semiconductive ceramic
EP0620567B1 (en) * 1989-11-08 1996-07-17 Matsushita Electric Industrial Co., Ltd. A zinc oxide varistor, a method of preparing the same, and a crystallized glass composition for coating
DE69114322T2 (de) * 1990-02-22 1996-06-05 Murata Manufacturing Co Verfahren zum Herstellen eines PTC-Thermistors.
JP2008251692A (ja) * 2007-03-29 2008-10-16 Sanyo Electric Co Ltd 感熱素子、該感熱素子を備える電池パック及び電子機器、並びに該感熱素子の製造方法
JP5038950B2 (ja) * 2007-07-24 2012-10-03 Ｔｄｋ株式会社 積層電子部品およびその製造方法
WO2012111385A1 (ja) * 2011-02-17 2012-08-23 株式会社村田製作所 正特性サーミスタ
WO2014017365A1 (ja) * 2012-07-25 2014-01-30 株式会社村田製作所 積層型ｐｔｃサーミスタ素子
CN104987729A (zh) * 2015-06-04 2015-10-21 常熟市林芝电子有限责任公司 一种陶瓷热敏电阻器用高耐压有机硅包封料
CN106866134A (zh) * 2015-12-11 2017-06-20 青岛祥智电子技术有限公司 正温度系数热敏电阻材料及热敏电阻
CN207038271U (zh) * 2017-07-13 2018-02-23 广东南方宏明电子科技股份有限公司 一种片式ntc或ptc热敏电阻器
CN110467455B (zh) * 2019-08-20 2022-02-08 威海市科博乐汽车电子有限公司 电动汽车用正温度系数热敏电阻的制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2537109Y (zh) * 2002-03-08 2003-02-19 常熟市林芝电子有限责任公司 正温度系数热敏电阻器
CN1487534A (zh) * 2002-09-10 2004-04-07 ������������ʽ���� 芯片型电子部件
CN102194559A (zh) * 2010-03-17 2011-09-21 三菱综合材料株式会社 热敏电阻元件及其制造方法
CN102403077A (zh) * 2010-09-06 2012-04-04 Tdk株式会社 陶瓷层叠ptc热敏电阻
CN102522169A (zh) * 2011-12-07 2012-06-27 华中科技大学 一种多层片式热敏陶瓷电阻用端电极及其制备方法
CN104969307A (zh) * 2013-01-29 2015-10-07 株式会社村田制作所 陶瓷电子部件及其制造方法
CN106448974A (zh) * 2016-11-06 2017-02-22 合肥圣达电子科技实业有限公司 一种防止铝电极层湿热老化失效的压敏电阻及其制备方法
CN112802647A (zh) * 2021-01-13 2021-05-14 江苏新林芝电子科技股份有限公司 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4297052A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118271914A (zh) * 2024-03-29 2024-07-02 江苏飞特尔通信有限公司 一种用于ltcc的电镀填孔剂及其制备方法与应用
CN118841228A (zh) * 2024-09-20 2024-10-25 肇庆市金龙宝电子有限公司 一种钛酸钡基热敏电阻及其制备方法和应用

Also Published As

Publication number Publication date
EP4297052A1 (en) 2023-12-27
US20240312678A1 (en) 2024-09-19
EP4297052A4 (en) 2025-12-03
CN112802647B (zh) 2021-11-23
CN112802647A (zh) 2021-05-14
US12354774B2 (en) 2025-07-08

Similar Documents

Publication Publication Date Title
WO2022151673A1 (zh) 一种耐还原性气氛强的正温度系数陶瓷热敏电阻元件及其制备方法
TW201212052A (en) ZnO Varistor utilized in high temperature
CN106673660B (zh) 一种液相烧结SiC非线性电阻陶瓷及其制备方法
EP3792964B1 (en) Electrostatic chuck and manufacturing method therefor
CN108172337A (zh) 一种抗氧化性能良好的max相系列电子浆料的制备方法
CN118619683B (zh) 一种氮化铝静电卡盘及其制备方法
CN101110383A (zh) 带加热器静电卡盘
JP5445689B2 (ja) 半導体セラミックおよび抵抗素子
JP2000143349A (ja) 窒化アルミニウム質焼結体およびそれを用いた静電チャック
JPH11340090A (ja) 粒界絶縁型積層セラミックコンデンサの製造方法
CN109155172B (zh) 陶瓷材料和电阻元件
KR20240152849A (ko) 열전도성 적층 절연기판
JP3018925B2 (ja) 電気化学素子
CN116917255A (zh) 陶瓷烧结体及半导体装置用基板
KR20220069213A (ko) 낮은 수축률을 갖는 고체산화물연료전지용 유리 세라믹 복합 밀봉재
JPH1012043A (ja) 導電性組成物および粒界絶縁型半導体磁器コンデンサ
JP2537606B2 (ja) セラミツクヒ−タ
CN1461017A (zh) TiO2非线性压敏陶瓷电阻器及其制备方法
JP2002324832A (ja) 静電チャック
TW202108545A (zh) 陶瓷組成物、陶瓷燒結體、疊層型陶瓷電子元件及其製法
KR20190073900A (ko) 정전척용 세라믹 본체
JP4157237B2 (ja) 電圧非直線抵抗体及びその製造方法
JP3052860B2 (ja) 電気化学素子の製造方法
JPH11100271A (ja) セラミック抵抗体およびそれを用いた静電チャック
JP7210019B2 (ja) ヒータ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21918869

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2021918869

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 18281762

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2021918869

Country of ref document: EP

Effective date: 20230814

ENP Entry into the national phase

Ref document number: 2021918869

Country of ref document: EP

Effective date: 20230814

WWG Wipo information: grant in national office

Ref document number: 18281762

Country of ref document: US