WO2016136321A1 - Matériau composite et son procédé de fabrication - Google Patents

Matériau composite et son procédé de fabrication Download PDF

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Publication number
WO2016136321A1
WO2016136321A1 PCT/JP2016/051152 JP2016051152W WO2016136321A1 WO 2016136321 A1 WO2016136321 A1 WO 2016136321A1 JP 2016051152 W JP2016051152 W JP 2016051152W WO 2016136321 A1 WO2016136321 A1 WO 2016136321A1
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composite material
conductive particles
insulating substrate
volume
powder
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PCT/JP2016/051152
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English (en)
Japanese (ja)
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勝　勇人
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株式会社村田製作所
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Publication of WO2016136321A1 publication Critical patent/WO2016136321A1/fr

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    • 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

Definitions

  • the present invention relates to a composite material having a positive temperature coefficient and a manufacturing method thereof.
  • PTC thermistor Various materials having a positive temperature coefficient are used as materials constituting a positive temperature coefficient thermistor (PTC thermistor).
  • PTC thermistor a material having a positive temperature coefficient
  • a barium titanate ceramic semiconductor is widely known.
  • various attempts have been made to further improve the electrical characteristics of PTC thermistors.
  • Patent Document 1 is characterized in that 10 to 90% by weight of Bi metal having an average particle diameter of 0.5 to 500 ⁇ m that decreases in volume by melting is dispersed in SiO 2 —PbO—B 2 O 3 glass.
  • a PTC composite material for a thermistor the resistance change of the PTC element obtained by using the composite material for the PTC thermistor is 10 8 or more PTC composite material for a thermistor is described.
  • the composite material described in Patent Document 1 exhibits a low resistance because a conduction path is formed between metal particles at low temperatures, and at high temperatures, the dispersed metal or alloy particles cause a rapid volume reduction at the melting point. This breaks the metal or alloy network, resulting in a sharp increase in the resistance of the composite material.
  • An object of the present invention is to provide a composite material having a low specific resistance at room temperature and a small rate of change in specific resistance at room temperature when left at high temperature, and a method for producing the same.
  • the present inventors have included the composite material by controlling the amount of carbon contained in the degreased body and performing firing in a reducing atmosphere or an inert atmosphere in the composite material manufacturing process. It has been found that the oxidation of Bi can be suppressed. Furthermore, by suppressing the oxidation of Bi contained in the composite material, the specific resistance at room temperature of the composite material can be lowered, and the rate of change in the specific resistance at room temperature when left at high temperature can be reduced. As a result, the present invention has been completed.
  • a matrix comprising an insulating material; A composite material comprising conductive particles dispersed in a matrix, The conductive particles include at least one of Bi metal particles and Bi alloy particles whose volume is reduced by melting, A composite material is provided in which the abundance ratio O / Bi of Bi and O on the surface of the conductive particles is 1.0 or less.
  • the relative density defined by the ratio of the actual measurement value to the theoretical density value of the composite material is preferably 96% or more.
  • the relative density is more preferably 98% or more.
  • the insulating material preferably has a specific resistance of 10 +8 ⁇ ⁇ cm or more.
  • the composite material may have a specific resistance of 1.0 ⁇ ⁇ cm or less at 25 ° C. Further, when the composite material is allowed to stand at 150 ° C. for 100 hours, the rate of change in specific resistance at 25 ° C. can be 20% or less.
  • an element body including any one of the above composite materials;
  • a positive temperature coefficient thermistor including a terminal electrode disposed on a surface of an element body.
  • an insulating substrate A first lead electrode disposed inside the insulating substrate, wherein one end of the first lead electrode is exposed at the first end surface of the insulating substrate; A second lead electrode disposed inside the insulating substrate, one end of which is exposed at the second end face of the insulating substrate; A first external electrode disposed on the first end face of the insulating substrate and electrically connected to the first lead electrode; A second external electrode disposed on the second end face of the insulating substrate and electrically connected to the second lead electrode; Including any of the composite materials described above sealed within an insulating substrate; The composite material is provided with a positive temperature coefficient thermistor arranged to connect the first extraction electrode and the second extraction electrode.
  • a process comprising at least one of Bi metal particles and Bi alloy particles to be reduced, wherein the ratio of the volume of the conductive particles to the total volume of the powder of the insulating material and the conductive particles is 10% by volume to 30% by volume , (2) drying the paste to obtain a powder aggregate, (3) a step of sizing the powder aggregate to obtain a sized powder; (4) a step of pressure-molding the sized powder to obtain a molded body, (5) Degreasing the molded body at a temperature of 250 ° C.
  • a method for producing a composite material includes the step of obtaining the composite material by firing under pressure.
  • the degreased body is preferably fired at a temperature of 450 ° C. or higher and 550 ° C. or lower.
  • the composite material according to the present invention has the above characteristics, and therefore has a low specific resistance at room temperature and a low rate of change in specific resistance at room temperature when left at high temperature.
  • the method of the present invention can produce a composite material having a low specific resistance at room temperature and a small change rate of specific resistance when left at a high temperature due to the above characteristics.
  • room temperature means 25 ° C.
  • FIG. 1 is a SEM photograph of the surface of the composite material of Example 1.
  • FIG. FIG. 2 is a schematic diagram illustrating a configuration of a positive temperature coefficient thermistor according to an embodiment of the present application.
  • FIG. 3 is a graph showing the measurement results of the specific resistance at room temperature of the composite materials of the example and the comparative example and the rate of change in specific resistance after being left at high temperature.
  • the composite material according to the present embodiment includes a matrix including an insulating material and conductive particles present dispersed in the matrix.
  • the “insulating material” means a material having a specific resistance of 10 +8 ⁇ ⁇ cm or more at room temperature (25 ° C.).
  • the insulating material that can be used in this embodiment include glass materials such as borosilicate glass, and resin materials such as silicone resin.
  • a glass material having a softening point of 500 ° C. or less is preferably used.
  • the manufacturing process of the composite material includes a step of obtaining the composite material by firing the degreased body as described later. In this firing step, Bi contained in the degreased body is in a dissolved state, and the dissolved Bi tends to aggregate.
  • the composite material according to the present embodiment preferably includes 70% by volume or more and 90% by volume or less of an insulating material based on the total volume of the composite material.
  • the content of the insulating material is 70% by volume or more, the insulating property can be ensured when the conductive particles are dissolved.
  • the content of the insulating material is 90% by volume or less, the conductive particles form a three-dimensional network, and as a result, an energizable composite material can be obtained.
  • the content of the insulating material in the composite material can be measured by binarizing the conductive particles and the insulating material and numerically processing them on the polished surface.
  • the composition of the composite material can also be analyzed using a technique such as inductively coupled plasma emission spectroscopy (ICP-AES).
  • the conductive particles are present dispersed in a matrix containing an insulating material.
  • the conductive particles include at least one of Bi metal particles and Bi alloy particles whose volume is reduced by melting.
  • Bi alloy particles for example, Bi—Sn alloy particles can be used.
  • the conductive particles one kind of Bi metal particles or Bi alloy particles may be used alone, or two or more kinds of Bi metal particles or Bi alloy particles may be used in combination. Alternatively, it is possible to use a combination of one or more types of Bi metal particles and one or more types of Bi alloy particles.
  • the composite material according to the present embodiment preferably includes 10% by volume or more and 30% by volume or less of conductive particles based on the total volume of the composite material.
  • the conductive particles When the content of the conductive particles is 10% by volume or more, the conductive particles form a three-dimensional network, and as a result, a composite material that can be energized can be obtained. When the content of the conductive particles is 30% by volume or less, the insulating property can be ensured when the conductive particles are dissolved.
  • the volume content of the conductive particles in the composite material can be measured by binarizing the conductive particles and the insulating material and numerically processing them on the polished surface.
  • Metals and alloys generally increase in volume due to melting.
  • Bi metal and Bi alloy have the property that the volume is reduced by melting at the melting point.
  • the composite material according to the present embodiment utilizes such properties of Bi metal and Bi alloy.
  • the conductive particles present in the composite material are in contact with each other to form a continuous electrical conduction path (percolation path). At this time, the composite material has conductivity and is in a low resistance state.
  • the conductive particles are reduced in volume by melting, and the electric conduction path in the composite material is broken. As a result, the resistance value of the composite material increases abruptly and enters a high resistance state.
  • the composite material according to the present embodiment has a sudden increase in resistance at the melting point of Bi metal or Bi alloy, so that it can be used as a material constituting the PTC thermistor.
  • Bi contained in the conductive particles tends to be oxidized particularly at the time of melting.
  • the specific resistance value of the composite material at room temperature increases.
  • an increase in specific resistance at room temperature is not preferable. Therefore, it is desired to improve the stability of the composite material by suppressing the oxidation of Bi contained in the conductive particles.
  • the composite material according to the present embodiment has a low specific resistance at room temperature by suppressing the oxidation of Bi contained in the conductive particles.
  • the oxidation of Bi contained in the conductive particles mainly occurs on the surface of the conductive particles. Therefore, the degree of oxidation of Bi can be evaluated by measuring the abundance ratio O / Bi of Bi and O on the surface of the conductive particles. You may consider that the oxidation of electroconductive particle is suppressed, so that the value of O / Bi is small.
  • O / Bi is 1.0 or less. When O / Bi is 1.0 or less, the value of the specific resistance at room temperature of the composite material can be lowered.
  • O / Bi can be measured by energy dispersive X-ray analysis (EDX).
  • O / Bi can be measured by the following procedure.
  • the composite material is broken to form a fracture surface.
  • the breaking method is not particularly limited, and any method can be appropriately selected.
  • the surface of the conductive particles exposed on the fracture surface of the composite material is measured by energy dispersive X-ray analysis (EDX).
  • EDX energy dispersive X-ray analysis
  • the acceleration voltage is set so that an element present on the surface of the conductive particles can be detected.
  • the acceleration voltage is about 7 kV, for example, it is possible to detect elements existing in the surface region from the outermost surface of the conductive particles exposed on the fracture surface of the composite material to about 200 nm.
  • the abundance ratio O / Bi of Bi and O on the surface of the conductive particles is calculated.
  • the relative density defined by the ratio of the measured value to the theoretical density value of the composite material is preferably 96% or more.
  • the smaller the relative density of the composite material the more pores (pores) tend to exist in the composite material.
  • the more vacancies present in the composite material the easier it is for oxygen present in the surrounding environment to enter the composite material and Bi in the composite material is more likely to be oxidized. Therefore, if a composite material having a small relative density is left in a high temperature environment, the specific resistance of the composite material may increase due to oxidation of Bi. As a result, the rate of change in resistivity at room temperature when the composite material is left in a high temperature environment becomes large.
  • the oxidation of Bi can be suppressed as the relative density of the composite material is 96% or more.
  • the specific resistance at room temperature of the composite material can be reduced, and the rate of change in specific resistance at room temperature when left at high temperatures can be reduced.
  • the relative density is more preferably 98% or more.
  • the relative density is 98% or more, the specific resistance at room temperature of the composite material can be further reduced, and the change rate of the specific resistance at room temperature when left at high temperature can be further reduced.
  • the measured value of the density of the composite material can be measured by the Archimedes method.
  • the composite material according to the present embodiment may contain carbon in addition to the above-described insulating material and conductive particles. This carbon is derived from the organic binder used during production.
  • the composite material may include up to 100 ppm by weight carbon based on the total weight of the composite material. When the carbon content is 100 ppm by weight or less, the sintered density necessary to ensure the reliability of the composite material can be achieved.
  • the carbon content in the composite material can be measured using, for example, a carbon / sulfur analyzer (EMIA-920V2 manufactured by Horiba, Ltd.).
  • the composite material according to the present embodiment may have a specific resistance of 1.0 ⁇ ⁇ cm or less at room temperature (25 ° C.). This can be achieved by the O / Bi in the conductive particles present in the composite material being 1.0 or less and the relative density of the composite material being 96% or more. Moreover, when the composite material according to the present embodiment is allowed to stand at 150 ° C. for 100 hours, the change rate of the specific resistance at 25 ° C. can be 20% or less. This can be achieved by the relative density of the composite material being 96% or higher.
  • the composite material according to this embodiment can be used as a material constituting a positive temperature coefficient thermistor (PTC thermistor).
  • PTC thermistor a positive temperature coefficient thermistor
  • the structural example of the PTC thermistor using the composite material which concerns on this embodiment is demonstrated, the PTC thermistor which concerns on this invention is not limited to the structural example shown below.
  • the PTC thermistor includes an element body including the composite material according to the present embodiment and a terminal electrode disposed on the surface of the element body.
  • the dimensions of the element body and the terminal electrode and the arrangement of the terminal electrodes on the element body surface are not particularly limited, and may be appropriately set according to the application.
  • the terminal electrode may be, for example, an Ag electrode or a Cu electrode.
  • the method for forming the terminal electrode is not particularly limited, but can be formed by, for example, baking or sputtering.
  • FIG. 2A is a vertical sectional view of the PTC thermistor 1 according to this embodiment
  • FIG. 2B is a horizontal sectional view of the PTC thermistor 1 taken along the line AA ′ in FIG.
  • the PTC thermistor 1 shown in FIG. 2 includes an insulating substrate 2, a first extraction electrode 31 disposed inside the insulating substrate 2, and a second extraction electrode 32 disposed inside the insulating substrate 2.
  • the first external electrode 51 disposed on the first end surface of the insulating substrate, the second external electrode 52 disposed on the second end surface of the insulating substrate, and the inside of the insulating substrate 2 are sealed.
  • Composite material 4 4.
  • the composite material according to this embodiment can be used as the composite material 4.
  • the composite material 4 is disposed so as to connect the first extraction electrode 31 and the second extraction electrode 32, and the first extraction electrode 31 and the second extraction electrode 32 face each other with the composite material 4 interposed therebetween.
  • the insulating substrate 2 may be a glass sheet, for example.
  • the first extraction electrode 31 and the second extraction electrode 32 may be, for example, an Ag electrode, a Cu electrode, or the like.
  • the first external electrode 51 and the second external electrode 52 are electrodes provided for connecting the PTC thermistor chip 1 to the substrate, and may be made of a metal material such as Ag or Cu. Further, if necessary, Ni / Sn plating may be applied to the surfaces of the first external electrode 51 and the second external electrode 52 in order to improve mountability and environmental resistance.
  • the method according to this embodiment includes the following steps (1) to (6).
  • a step of preparing a paste by mixing an insulating material powder, conductive particles, and an organic binder (2) A step of drying the paste to obtain a powder aggregate.
  • a step of sizing the powder aggregate to obtain a sized powder (2) A step of pressing the sized powder to obtain a molded body.
  • Step (1) is a step of preparing a paste by mixing an insulating material powder, conductive particles, and an organic binder.
  • a powder of a glass material such as borosilicate glass or a powder of a resin material such as ethyl cellulose resin may be used.
  • the average particle size of the insulating material powder is preferably 1 ⁇ m or more and 10 ⁇ m or less. When the average particle size of the insulating material powder is 1 ⁇ m or more and 10 ⁇ m or less, the dispersibility of the conductive particles is improved.
  • the conductive particles include at least one of Bi metal particles and Bi alloy particles whose volume is reduced by melting.
  • the average particle diameter of the conductive particles is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the ratio of the volume of the conductive particles to the total volume of the powder of the insulating material and the conductive particles used for the preparation of the paste may be appropriately set according to the average particle diameter of the powder of the insulating material and the conductive particles. it can.
  • the ratio of the volume of the conductive particles to the total volume of the insulating material powder and the conductive particles is preferably 10% by volume to 30% by volume.
  • the conductive particles are electrically conductive in the three-dimensional direction in the obtained composite material.
  • a path can be formed.
  • the organic binder an ethyl cellulose organic vehicle, an acrylic organic vehicle, or the like may be used.
  • the content of the organic binder in the paste is preferably 0.5% by weight or more and 5% by weight or less in the solid content ratio. If the solid content of the organic binder is 0.5% by weight or more, press molding with good moldability is possible in the pressure molding described later, and if it is 5% by weight or less, the degreasing property of the composite material is improves.
  • Step (2) is a step of obtaining a powder aggregate by drying the paste obtained in step (1).
  • Step (2) may be performed at a temperature of 120 ° C. or higher and 180 ° C. or lower, for example.
  • Step (3) is a step of obtaining a sized powder by sizing the powder aggregate.
  • the sizing treatment may be performed, for example, by using a metal mesh having a mesh size of 150 ⁇ m according to JIS standard (JIS Z 8810-1: 2000).
  • Step (4) is a step of obtaining a compact by pressure-molding the sized powder.
  • the pressure molding may be performed, for example, by pressing the sized powder with a surface pressure of 98 MPa using a uniaxial press.
  • Step (5) is a step of degreasing the molded body at a temperature of 250 ° C. or higher and 350 ° C. or lower to obtain a degreased body containing carbon of 300 ppm to 2000 ppm by weight.
  • Carbon contained in the degreased body is derived from an organic binder.
  • the carbon content in the degreased body is 300 ppm by weight or more, carbon preferentially reacts with oxygen in the step (6) of firing the degreased body, and as a result, the oxidation of Bi contained in the conductive particles is suppressed.
  • sintering of an insulating material for example, a glass material
  • a composite material having a high relative density can be obtained.
  • the carbon content in the degreased body is 2000 ppm by weight or less, generation of CO 2 gas in the step (6) can be suppressed, and as a result, the relative density of the composite material can be increased.
  • the degreasing in the step (5) is preferably performed under a reducing atmosphere or an inert atmosphere.
  • a reducing atmosphere or an inert atmosphere By degreasing under a reducing atmosphere or an inert atmosphere, it is possible to suppress oxidation of Bi contained in the molded body.
  • Step (6) is a step of obtaining a composite material by firing the degreased body under a reducing atmosphere or an inert atmosphere.
  • the firing temperature in the step (6) can be appropriately set according to physical properties such as the softening point and viscosity of the insulating material (for example, glass material) to be used.
  • the degreased body is preferably fired at a temperature of 450 ° C. or higher and 550 ° C. or lower. When the firing temperature is 450 ° C.
  • the sintering of the insulating material can be sufficiently promoted.
  • the firing temperature is 550 ° C. or lower, the influence due to the generation of carbon dioxide gas can be reduced, and sintering can be performed at high density.
  • the above temperature range is merely an example, and the method according to the present invention is not limited to the above temperature range.
  • the composite material thus obtained has the characteristics that the specific resistance at room temperature is low and the rate of change in specific resistance at room temperature when left at high temperature is small.
  • Example 1 Bi-based borosilicate glass powder having a glass transition temperature of about 500 ° C. is used as the insulating material powder, and Bi metal particles (high-purity chemistry) having a median diameter (D50) of 28 ⁇ m are used as the conductive particles.
  • An ethyl cellulose organic vehicle was used as a binder. Glass powder, Bi metal particles, and ethyl cellulose organic vehicle were mixed in a roll to prepare a paste. The ratio of the volume of Bi metal particles to the total volume of glass powder and Bi metal particles contained in the paste was 21% by volume. The content (solid content ratio) of ethylcellulose-based organic vehicle in the paste was 1.1% by weight.
  • This paste was dried in an oven at 150 ° C. to obtain a powder aggregate.
  • This powder agglomerate was sized using a metal mesh having a mesh size of 150 ⁇ m according to JIS standard (JIS Z 8810-1-2000) to obtain a sized powder.
  • This sized powder was pressure-molded with a uniaxial press at a surface pressure of 98 MPa to produce a molded body having a diameter of 8.5 mm and a thickness of about 2 mm.
  • This molded body was degreased at 250 ° C. for 3 hours under a nitrogen atmosphere to obtain a degreased body.
  • This degreased body was fired in N 2 flow at a temperature around 500 ° C.
  • the composite material of Example 1 was obtained.
  • Example 2 A composite material of Example 2 was obtained in the same procedure as Example 1 except that degreasing was performed at 300 ° C.
  • Example 3 A composite material of Example 3 was obtained in the same procedure as Example 1 except that degreasing was performed at 350 ° C.
  • Comparative Example 1 The composite material of Comparative Example 1 was produced without performing a degreasing process. A molded body was produced in the same procedure as in Example 1. This molded body was fired in N 2 flow at a temperature around 500 ° C. In this way, a composite material of Comparative Example 1 was obtained.
  • Comparative Example 2 A composite material of Comparative Example 2 was obtained in the same procedure as Example 1 except that degreasing was performed at 400 ° C.
  • O / Bi was measured by EDX.
  • the electron beam was focused on the surface of the Bi metal particle exposed on the surface of the composite material, and the abundance ratio O / Bi of Bi and O on the Bi metal particle surface was measured.
  • the EDX measurement was performed using an OXFORD INCA ENERGY 400 attached to a scanning electron microscope (manufactured by JEOL, JSM-5900LV) under an acceleration voltage of 7 kV. The results are shown in Table 1. Further, FIG. 1 shows a scanning electron microscope (SEM) photograph of the surface of the composite material of Example 1 as a representative.
  • the relative density of the composite materials of Examples 1 to 3 is higher than the relative density of the composite materials of Comparative Examples 1 and 2, and the composite material of Example 2 in which the degreasing temperature is 300 ° C. is high relative to 98% or more. Had a density.
  • the value of O / Bi was 1.0 or less, indicating that the oxidation of Bi was suppressed.
  • the value of O / Bi was smaller as the degreasing temperature was lower.
  • the value of O / Bi was larger than 1.0.
  • the composite materials of Examples 1 to 3 had a low specific resistance value of 1.0 ⁇ ⁇ cm or less at room temperature, and in particular, the degreasing temperature was 250 ° C. to 300 ° C.
  • the composite materials of Examples 1 and 2 had a specific resistance value of 0.1 ⁇ ⁇ cm or less.
  • the composite materials of Comparative Examples 1 and 2 have a specific resistance value exceeding 1.0 ⁇ ⁇ cm, and in particular, the composite material of Comparative Example 2 having a degreasing temperature of 400 ° C. is 2.01 ⁇ 10 8. It had a very high specific resistance value of ⁇ ⁇ cm.
  • the composite materials of Examples 1 to 3 have a rate of change in specific resistance of 20% or less after being left at high temperature.
  • the composite materials of Examples 2 and 3 in which the degreasing temperature is 300 ° C. to 350 ° C. are 5 It showed a low rate of change of less than%.
  • the rate of change in specific resistance value after standing at high temperature was a very high value of 40%.
  • the composite material according to the present invention can be used as an element body of a PTC thermistor, and can provide a PTC thermistor having excellent electrical characteristics.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne un matériau composite comprenant une matrice comprenant un matériau isolant, et ayant des particules conductrices dispersées dans la matrice. Les particules conductrices comprennent des particules métalliques de Bi et/ou des particules d'alliage de Bi dont le volume est réduit par fusion, et le rapport d'abondance O/Bi de O sur Bi dans la surface de la particule conductrice est inférieur ou égal à 1,0.
PCT/JP2016/051152 2015-02-25 2016-01-15 Matériau composite et son procédé de fabrication WO2016136321A1 (fr)

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JP2015035860 2015-02-25
JP2015-035860 2015-02-25

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998011568A1 (fr) * 1996-09-13 1998-03-19 Tdk Corporation Materiau pour thermistor a ctp
JPH1197210A (ja) * 1997-09-19 1999-04-09 Murata Mfg Co Ltd 正の抵抗温度特性を有する半導体
JP2000034133A (ja) * 1998-07-15 2000-02-02 Ube Ind Ltd 複合材料
JP2001035704A (ja) * 1999-07-23 2001-02-09 Ngk Insulators Ltd 確実なｐｔｃ挙動を示す無機−金属複合体
JP2001338804A (ja) * 2000-05-26 2001-12-07 Ngk Insulators Ltd リセッタブルヒューズ素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998011568A1 (fr) * 1996-09-13 1998-03-19 Tdk Corporation Materiau pour thermistor a ctp
JPH1197210A (ja) * 1997-09-19 1999-04-09 Murata Mfg Co Ltd 正の抵抗温度特性を有する半導体
JP2000034133A (ja) * 1998-07-15 2000-02-02 Ube Ind Ltd 複合材料
JP2001035704A (ja) * 1999-07-23 2001-02-09 Ngk Insulators Ltd 確実なｐｔｃ挙動を示す無機−金属複合体
JP2001338804A (ja) * 2000-05-26 2001-12-07 Ngk Insulators Ltd リセッタブルヒューズ素子

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