JPH07161502A - Ptcr element - Google Patents
Ptcr elementInfo
- Publication number
- JPH07161502A JPH07161502A JP31599193A JP31599193A JPH07161502A JP H07161502 A JPH07161502 A JP H07161502A JP 31599193 A JP31599193 A JP 31599193A JP 31599193 A JP31599193 A JP 31599193A JP H07161502 A JPH07161502 A JP H07161502A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- metal
- ptcr
- phase
- specific resistance
- 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.)
- Granted
Links
- 239000012071 phase Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 43
- 239000011133 lead Substances 0.000 claims abstract description 29
- 239000011135 tin Substances 0.000 claims abstract description 15
- 229910052738 indium Inorganic materials 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 229910052745 lead Inorganic materials 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 8
- 150000004767 nitrides Chemical class 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 7
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 6
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 6
- 229910002975 Cd Pb Inorganic materials 0.000 claims abstract description 5
- 229910020220 Pb—Sn Inorganic materials 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZIXVIWRPMFITIT-UHFFFAOYSA-N cadmium lead Chemical compound [Cd].[Pb] ZIXVIWRPMFITIT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- -1 Wi2 Inorganic materials 0.000 abstract description 5
- 230000007246 mechanism Effects 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 abstract description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052580 B4C Inorganic materials 0.000 abstract 1
- 229910019918 CrB2 Inorganic materials 0.000 abstract 1
- 229910020968 MoSi2 Inorganic materials 0.000 abstract 1
- 229910033181 TiB2 Inorganic materials 0.000 abstract 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 abstract 1
- 229910003465 moissanite Inorganic materials 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 238000010304 firing Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 229910020174 Pb-In Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000013038 hand mixing Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＰＴＣＲ素子に関す
る。FIELD OF THE INVENTION The present invention relates to a PTCR element.
【０００２】[0002]
【従来の技術】ＰＴＣＲ特性、すなわち正の比抵抗温度
係数 ( Positive Temperature Coefficient of Resisti
vity )を示す材料として、現在のところＢａＴｉＯ3 系
セラミックス、ＰｂＴｉＯ3 −ＴｉＯ2 系セラミック
ス、（Ｖ、Ｃｒ）2 Ｏ3 セラミックス、カーボンとポリ
マーの複合材などが知られている。2. Description of the Related Art PTCR characteristics, that is, the Positive Temperature Coefficient of Resistance
At present, BaTiO 3 -based ceramics, PbTiO 3 —TiO 2 -based ceramics, (V, Cr) 2 O 3 ceramics, carbon-polymer composite materials, and the like are known as materials exhibiting vity).
【０００３】これらのＰＴＣＲ特性の発現は、ＢａＴｉ
Ｏ3 系セラミックスおよびＰｂＴｉＯ3 −ＴｉＯ2 系セ
ラミックスについては、強誘電−常誘電相変態、（Ｖ、
Ｃｒ）2 Ｏ3 セラミックスについては、金属−絶縁体転
移、カーボンとポリマーの複合材については、ポリマー
の熱膨張に起因すると考えられている。The expression of these PTCR characteristics is expressed by BaTi.
For O 3 -based ceramics and PbTiO 3 —TiO 2 -based ceramics, ferroelectric-paraelectric phase transformation (V,
It is believed that for Cr) 2 O 3 ceramics it is due to the metal-insulator transition and for carbon-polymer composites it is due to the thermal expansion of the polymer.
【０００４】[0004]
【発明の目的】本発明は、従来のものとは異なる発現機
構に基づく全く新しいＰＴＣＲ素子を提供することを目
的とするものである。OBJECT OF THE INVENTION It is an object of the present invention to provide a completely new PTCR element based on an expression mechanism different from the conventional one.
【０００５】[0005]
【発明の構成】ところで、実用金属便覧（日刊工業新聞
社昭和３７年１０月３０日発行）の主な金属の比抵抗温
度特性（図１参照）にも示されているように、金属のな
かには、例えば、Ｐｂ、Ｓｎ、Ｉｎ等のように、融点に
おいて固体から液体に転移する際、その比抵抗が急激に
上昇するものがある。Structure of the Invention By the way, as shown in the resistivity temperature characteristics of main metals (see FIG. 1) of the Practical Metal Handbook (published by Nikkan Kogyo Shimbun, October 30, 1937), some of the metals are For example, there are some materials such as Pb, Sn, In, etc., in which the specific resistance thereof rapidly increases when transitioning from solid to liquid at the melting point.
【０００６】しかしながら、この現象をＰＴＣＲ素子に
応用するには、金属単体では、液相状態を利用するため
実用化が難しい。However, in order to apply this phenomenon to a PTCR element, it is difficult to put the metal into practical use because it uses the liquid phase state.
【０００７】本発明は、以上の事柄に着目してなされた
もので、下記（１）〜（８）の発明からなる。The present invention was made by paying attention to the above matters, and comprises the following inventions (1) to (8).
【０００８】（１）金属化合物の主相間に、固相−液相
間での相転移に伴いＰＴＣＲ特性を示す金属または合金
を分散させたことを特徴とするＰＴＣＲ素子。 （２）前記化合物が、酸化物、窒化物、ケイ化物、炭化
物、ホウ化物および硫化物の一種以上である上記（１）
のＰＴＣＲ素子。 （３）前記酸化物が、チタン、亜鉛、スズ、インジウ
ム、鉄、バリウム、ストロンチウム、ニッケル、マンガ
ンおよび鉛の１種以上を含む酸化物である上記（２）の
ＰＴＣＲ素子。 （４）前記主相の電気抵抗が１０3 Ωｍオーダー以下で
ある上記（１）ないし（３）のいずれかのＰＴＣＲ素
子。 （５）前記主相の電気抵抗が１０-1Ωｍオーダー以上で
ある上記（４）のＰＴＣＲ素子。 （６）前記金属または合金が１１００℃以下の融点を有
する上記（１）ないし（５）のいずれかのＰＴＣＲ素
子。 （７）前記金属がＰｂ、Ｓｎ、Ｉｎ、Ｃｓ、Ａｌ、Ａｇ
またはＣｄであり、合金がＰｂ−Ｓｎ合金、Ａｇ−Ｐｂ
合金またはＣｄ−Ｐｂ合金である上記（１）ないし
（６）のいずれかのＰＴＣＲ素子。 （８）前記金属または合金の含有量が５〜５０vol ％で
ある上記（１）ないし（７）のいずれかのＰＴＣＲ素
子。(1) A PTCR element characterized in that a metal or an alloy exhibiting PTCR characteristics along with a phase transition between a solid phase and a liquid phase is dispersed between main phases of a metal compound. (2) The above compound (1), wherein the compound is one or more of oxides, nitrides, silicides, carbides, borides and sulfides.
PTCR element. (3) The PTCR element according to the above (2), wherein the oxide is an oxide containing one or more of titanium, zinc, tin, indium, iron, barium, strontium, nickel, manganese, and lead. (4) The PTCR element according to any one of (1) to (3), wherein the main phase has an electric resistance of 10 3 Ωm or less. (5) The PTCR element according to (4), wherein the electrical resistance of the main phase is 10 -1 Ωm order or more. (6) The PTCR element according to any one of (1) to (5), wherein the metal or alloy has a melting point of 1100 ° C. or lower. (7) The metal is Pb, Sn, In, Cs, Al, Ag
Or Cd, the alloy is Pb-Sn alloy, Ag-Pb
The PTCR element according to any of (1) to (6) above, which is an alloy or a Cd-Pb alloy. (8) The PTCR element according to any one of (1) to (7) above, wherein the content of the metal or alloy is 5 to 50 vol%.
【０００９】[0009]
【作用・効果】本発明においては、金属あるいは合金の
比抵抗がその固相−液相間の転移により急激に変化する
現象を利用し、該金属または合金を化合物である主相内
に封じ込めて、金属または合金が溶融し液相状態となっ
たときにもこれを担持することができるようにし、これ
によって、ＰＴＣＲ特性の全く新たな発現機構に基づく
ＰＴＣＲ素子を得ることができた。In the present invention, the phenomenon in which the resistivity of a metal or alloy rapidly changes due to the transition between the solid phase and the liquid phase is used to contain the metal or alloy in the main phase which is a compound. The metal or alloy is made to be able to be supported even when it melts into a liquid phase state, whereby a PTCR element based on a completely new expression mechanism of PTCR characteristics can be obtained.
【００１０】また、本発明のＰＴＣＲ素子は、従来のＰ
ＴＣＲ素子と同様、サーミスタ等の自己発熱型ヒータと
して用いることができるほか、ＰＴＣＲ特性が得られる
温度を、金属自体を選択したり、融点を調節した合金を
設計するなどして、希望の温度のセンシングを行なうセ
ンサ等も自由に得ることができる。The PTCR element of the present invention is a conventional P
Like the TCR element, it can be used as a self-heating heater such as a thermistor, and the temperature at which the PTCR characteristic is obtained can be selected by selecting the metal itself or designing an alloy with a controlled melting point. Sensors and the like for sensing can be freely obtained.
【００１１】[0011]
【具体的構成】以下、本発明の具体的構成を詳細に説明
する。Specific Structure The specific structure of the present invention will be described in detail below.
【００１２】本発明のＰＴＣＲ素子は、金属化合物であ
る主相間に、固相−液相間での相転移に伴いＰＴＣＲ特
性を示す金属または合金を分散させたものである。The PTCR element of the present invention is one in which a metal or an alloy exhibiting PTCR characteristics is dispersed between the main phases which are metal compounds, with the phase transition between the solid phase and the liquid phase.
【００１３】主相としての上記化合物は、酸化物、窒化
物、ケイ化物、炭化物、ホウ化物および硫化物の１種以
上のいずれを用いてもよく、酸化物としては、チタン、
亜鉛、スズ、インジウム、鉄、バリウム、ストロンチウ
ム、ニッケル、マンガンおよび鉛の１種以上を含む酸化
物、例えば、酸化チタン（ＴｉＯ2 ）、酸化亜鉛（Ｚｎ
Ｏ）、酸化スズ（ＳｎＯ2 ）、酸化インジウム（Ｉｎ2
Ｏ3 ）、酸化鉄およびその化合物（例えばフェライ
ト）、チタン酸バリウム（ＢａＴｉＯ3 ）およびチタン
酸ストロンチウム（ＳｒＴｉＯ3 ）、チタン酸鉛（Ｐｂ
ＴｉＯ3 ）等の１種以上を含むものであることが望まし
く、窒化物としては、ＴｉＮ、ＴａＮなどを用いること
ができる。The above-mentioned compound as the main phase may be any one or more of oxides, nitrides, silicides, carbides, borides and sulfides. As the oxide, titanium,
Oxides containing one or more of zinc, tin, indium, iron, barium, strontium, nickel, manganese and lead, such as titanium oxide (TiO 2 ), zinc oxide (Zn oxide).
O), tin oxide (SnO 2 ), indium oxide (In 2
O 3 ), iron oxide and its compounds (for example, ferrite), barium titanate (BaTiO 3 ) and strontium titanate (SrTiO 3 ), lead titanate (Pb).
TiO 3 ), etc. are preferably contained, and the nitride may be TiN, TaN, or the like.
【００１４】また、ケイ化物、炭化物、ホウ化物または
硫化物としては、ＭｏＳｉ2 、ＷＳｉ2 、ＳｉＣ、Ｂ4
Ｃ、ＴｉＢ2 、ＣｒＢ2 、ＣｄＳ、Ｃｕ2 Ｓを用いるこ
とができる。As the silicide, carbide, boride or sulfide, MoSi 2 , WSi 2 , SiC or B 4 can be used.
C, TiB 2 , CrB 2 , CdS, Cu 2 S can be used.
【００１５】そして、上記主相の比抵抗は、ある程度低
いもの、具体的には１０3 Ωｍオーダー以下であって、
主相中に分散される金属または合金より高く設定され
る。具体的には、１×１０3 Ωｍ以下が好ましい。また
下限値は１×１０-1Ωｍ、より好ましくは１×１０0 Ω
ｍ、特に１×１０1 Ωｍが好ましい。主相の比抵抗が１
０3 Ωｍオーダー以下が好ましいのは、発熱体やセンサ
ーとして使用する上では、ある程度の比抵抗が必要であ
るからである。このため、上記酸化物等には、比抵抗を
低下させるため、添加剤を添加することが望ましい。こ
の添加剤としては、例えば、主相がＴｉＯ2 であるとき
にはＮｂ、Ｔａ、Ｓｂを、ＺｎＯのときにはＡｌ、Ｇ
ａ、Ｉｎを選択するのがよい。このとき 、添加量は、
０．００１〜１０．０モル％とする。０．００１未満で
は半導体化が不十分で比抵抗が十分低下せず１０．０を
こえると比抵抗が再び増大するからである。The specific resistance of the main phase is low to some extent, specifically 10 3 Ωm or less,
It is set higher than the metal or alloy dispersed in the main phase. Specifically, it is preferably 1 × 10 3 Ωm or less. The lower limit is 1 × 10 −1 Ωm, more preferably 1 × 10 0 Ω.
m, particularly 1 × 10 1 Ωm is preferable. Main phase resistivity is 1
The reason why it is preferably on the order of 0 3 Ωm or less is that a certain degree of specific resistance is required for use as a heating element or a sensor. Therefore, it is desirable to add an additive to the above oxides or the like in order to reduce the specific resistance. Examples of the additive include Nb, Ta and Sb when the main phase is TiO 2 , and Al and G when ZnO is the main phase.
It is preferable to select a and In. At this time, the addition amount is
The amount is 0.001 to 10.0 mol%. This is because if it is less than 0.001, the formation of a semiconductor is insufficient and the specific resistance does not sufficiently decrease, and if it exceeds 10.0, the specific resistance increases again.
【００１６】上記のような添加剤としては、Ｎｂ、Ｔ
ａ、Ｓｂ、Ａｌ、Ｇａ、Ｉｎの他に、主相の酸化物の種
類によりＶ、Ｗ、Ｙ、希土類、Ｓｂ、Ｂを用いることが
できる。なお、主相の比抵抗は、実際の素子と同一の条
件で主相材料単独で単層膜を作製して測定すればよい。As the above-mentioned additives, Nb, T
In addition to a, Sb, Al, Ga and In, V, W, Y, rare earths, Sb and B can be used depending on the type of oxide of the main phase. The resistivity of the main phase may be measured by forming a single layer film using the main phase material alone under the same conditions as in the actual device.
【００１７】上記のように、主相の比抵抗を、主相中に
分散される金属または合金より高く設定するのは、電流
の多くが上記金属や合金中に流れずに主相中に流れてし
まい、ＰＴＣＲ特性を示さなくなってしまうからであ
る。As described above, the specific resistance of the main phase is set higher than that of the metal or alloy dispersed in the main phase, so that most of the electric current does not flow in the metal or alloy but flows in the main phase. This is because the PTCR characteristic is not exhibited.
【００１８】主相の融点は、少なくとも上記金属または
合金の融点以上で、具体的には、１１００℃程度以上が
選択される。主相が金属とともに融けてしまったので
は、素子としての態をなさなくなってしまうからであ
る。The melting point of the main phase is selected to be at least the melting point of the above-mentioned metal or alloy, specifically about 1100 ° C. or higher. This is because if the main phase melts together with the metal, it will no longer function as an element.
【００１９】また、上記主相は、通常０．１μｍ〜１ｍ
ｍのグレインサイズであって、走査型電子顕微鏡等で観
察することができる。The main phase is usually 0.1 μm to 1 m.
It has a grain size of m and can be observed with a scanning electron microscope or the like.
【００２０】本発明で用いることのできる金属または合
金は、固相−液相間での相転移に伴いＰＴＣＲ特性を示
す金属または合金である。このような金属等の融点は、
上記主相の融点より低いものが選択される。具体的に
は、１１００℃以下、特に８００℃以下が好ましい。こ
の金属等の融点の下限値は、−５０℃程度が望ましい。The metal or alloy that can be used in the present invention is a metal or alloy that exhibits PTCR characteristics with the phase transition between the solid phase and the liquid phase. The melting point of such metals is
A material having a melting point lower than that of the main phase is selected. Specifically, it is preferably 1100 ° C. or lower, particularly 800 ° C. or lower. The lower limit of the melting point of this metal or the like is preferably about -50 ° C.
【００２１】これにより低温でのセンシングも可能とな
るからである。This is because sensing at low temperature is also possible.
【００２２】以上のような金属としては、Ｐｂ、Ｓｎ、
Ｉｎ、Ｃｓ、Ａｌ、Ａｇ、Ｃｄ等を用いることが望まし
い。また、合金としては、Ｓｎ量３０〜９０wt％のＰｂ
−Ｓｎ合金、Ｐｂ量１０〜９０wt％のＡｇ−Ｐｂ合金ま
たはＰｂ量５〜９５wt％のＣｄ−Ｐｂ合金を用いること
が望ましい。用いることのできる合金としては、この
他、Ｐｂ−Ｉｎ、Ｐｂ−Ｍｎ、Ｐｂ−Ａｌ、Ｃｄ−Ｓ
ｎ、等がある。The metals mentioned above include Pb, Sn,
It is desirable to use In, Cs, Al, Ag, Cd or the like. Further, as an alloy, Pb with an Sn content of 30 to 90 wt% is used.
It is desirable to use -Sn alloy, Ag-Pb alloy having a Pb content of 10 to 90 wt% or Cd-Pb alloy having a Pb content of 5 to 95 wt%. Other alloys that can be used include Pb-In, Pb-Mn, Pb-Al, and Cd-S.
n, etc.
【００２３】因みに、上記実用金属便覧によると、Ｐｂ
では、その融点の３２７℃の近傍において、比抵抗が立
ち上がり、３．７×１０-5Ωｃｍ（３．７×１０-3Ω
ｍ）であったものが約３倍の９．５×１０-5Ωｃｍ
（９．５×１０-3Ωｍ）と増大しており、また、Ｓｎで
は、その融点の２３２℃近傍で比抵抗が立ち上がり、
２．６×１０-5Ωｃｍ（２．６×１０-3Ωｍ）であった
ものが４．７×１０-5Ωｃｍ（４．７×１０-3Ωｍ）と
増大している。Incidentally, according to the above-mentioned practical metal handbook, Pb
Then, in the vicinity of the melting point of 327 ° C., the specific resistance rises to 3.7 × 10 −5 Ωcm (3.7 × 10 −3 Ω).
m) was about three times 9.5 × 10 -5 Ωcm
(9.5 × 10 −3 Ωm), and in Sn, the specific resistance rises near 232 ° C., which is the melting point of Sn.
What was 2.6 × 10 −5 Ωcm (2.6 × 10 −3 Ωm) increased to 4.7 × 10 −5 Ωcm (4.7 × 10 −3 Ωm).
【００２４】金属の種類によっては、Ｃｓのように１０
０℃近傍の比較的低い温度で比抵抗の立ち上がりを示す
ものから、Ｃｕのようにその融点の１０８３℃近傍の比
較的高い温度で比抵抗の立ち上がりを示すものまで幅広
く存在し、しかもＰｂ−Ｓｎ合金等のように成分の含有
比率を変えることによりその融点を変動させることがで
き、使用目的に応じて、金属または合金を自由に選択す
ることができる。Depending on the type of metal, it is 10 like Cs.
There are a wide variety of materials, such as those exhibiting a specific resistance rising at a relatively low temperature near 0 ° C. to those having a specific resistance rising at a relatively high temperature near a melting point of 1083 ° C. such as Cu, and moreover, Pb-Sn The melting point can be changed by changing the content ratio of components such as alloys, and the metal or alloy can be freely selected according to the purpose of use.
【００２５】上記金属または合金は、主相中に金属粒子
または合金粒子の形態で分散していることが望ましく、
その平均粒径は０．０１〜１００μｍ程度であることが
望ましい。ただし、金属粒子または合金粒子は、粒子状
態で離間して存在する状態の他、互いに接した状態や融
合した状態で存在してもよい。The above metal or alloy is preferably dispersed in the main phase in the form of metal particles or alloy particles,
The average particle size is preferably about 0.01 to 100 μm. However, the metal particles or the alloy particles may exist in a state of being separated from each other in a particle state, or in a state of being in contact with each other or a state of being fused.
【００２６】上記金属または合金の含有量は、５〜５０
vol ％の範囲内であることが望ましい。含有量が少なす
ぎるとＰＴＣＲ特性を示さなくなり、多すぎると試料の
形状を堅持できなくなるからである。The content of the above metal or alloy is 5 to 50.
It is desirable to be within the range of vol%. This is because if the content is too small, the PTCR characteristics will not be exhibited, and if it is too large, the shape of the sample cannot be retained.
【００２７】本発明のＰＴＣＲ素子の製造には、一般に
固相反応法が用いられる。A solid-phase reaction method is generally used for manufacturing the PTCR element of the present invention.
【００２８】製造にあたっては、まず主相用の原料粉末
と、金属または合金の原料粉末を準備する。主相用の原
料粉末は、主相の組成の化合物の粉末を準備することが
望ましい。本発明のＰＴＣＲ素子の焼成においては、所
望の比抵抗およびＰＴＣＲ特性を維持するため、金属ま
たは合金の酸化を防止する必要があり、通常Ａｒガス等
の非酸化性雰囲気中で行なう。それにより、焼成工程に
おいては、酸化物等の形成を最小限に抑制できる。In the production, first, the raw material powder for the main phase and the raw material powder for the metal or alloy are prepared. As the raw material powder for the main phase, it is desirable to prepare a powder of the compound having the composition of the main phase. In the firing of the PTCR element of the present invention, it is necessary to prevent the metal or alloy from being oxidized in order to maintain desired specific resistance and PTCR characteristics, and it is usually performed in a non-oxidizing atmosphere such as Ar gas. Thereby, in the firing step, formation of oxides and the like can be suppressed to a minimum.
【００２９】主相用の原料粉末の平均粒径は、０．１〜
１０μｍ、金属または合金の原料粉末の平均粒径は、
０．１〜１００μｍ程度のものが選択される。The average particle size of the raw material powder for the main phase is from 0.1 to 0.1
10 μm, the average particle size of the metal or alloy raw material powder is
A material having a thickness of about 0.1 to 100 μm is selected.
【００３０】このような原料を用い混合を行なう。混合
方法に特に制限はないが、例えばエタノール、水、ヘキ
サン等と共に手混合やボールミル等による湿式混合が好
ましい。次いで、混合物を乾燥し、所定の形状に圧縮成
形する。この時の成形圧は、１００kg/cm2 〜２t/cm2
程度とする。Mixing is performed using such raw materials. The mixing method is not particularly limited, but for example, hand mixing with ethanol, water, hexane or the like, or wet mixing with a ball mill or the like is preferable. The mixture is then dried and compression molded into the desired shape. The molding pressure at this time is 100 kg / cm 2 to 2 t / cm 2
The degree.
【００３１】次いで、例えば、Ａｒガス中で、昇温速度
を５０〜５００℃/h程度、降温速度を５０〜５００℃/h
程度として、８００〜１４００℃程度で３０分〜４時間
程度、で焼成し、焼結体を得る。Then, for example, in Ar gas, the temperature raising rate is about 50 to 500 ° C./h and the temperature lowering rate is 50 to 500 ° C./h.
The sintering is performed at about 800 to 1400 ° C. for about 30 minutes to 4 hours to obtain a sintered body.
【００３２】上記の望ましい焼成条件は、使用する材料
の組成等によってことなるが、一般に温度が低すぎた
り、時間が短すぎたりすると焼結体の密度が不十分で多
孔質なために、焼結体中の金属等が後に酸化してしま
う。他方、焼成温度が高すぎたり、焼成時間が長すぎた
りすると、室温での比抵抗が上昇してしまう。これは、
主に、金属等の一部が蒸発してしまうからであると考え
られる。The above desirable firing conditions vary depending on the composition of the material used and the like. Generally, if the temperature is too low or the time is too short, the density of the sintered body is insufficient and the firing is porous, The metal etc. in the bound body will be oxidized later. On the other hand, if the firing temperature is too high or the firing time is too long, the specific resistance at room temperature increases. this is,
It is considered that this is mainly because a part of metal or the like is evaporated.
【００３３】本発明のＰＴＣＲ素子の焼成にあたって
は、金属等の酸化を防止することができるなら、焼成雰
囲気として空気を用いてもよい。When firing the PTCR element of the present invention, air may be used as the firing atmosphere as long as it is possible to prevent the oxidation of metals and the like.
【００３４】なお、上記主相中には、主相の比抵抗を低
減するための上記のような成分を添加することが望まし
く、このような成分の添加は、材料粉末中に予め行なっ
ても、素子の焼成工程前の材料の混合工程において行な
っても、いずれでもよい。It should be noted that it is desirable to add the above-mentioned components to the main phase for reducing the specific resistance of the main phase. Even if such components are added in advance to the material powder. Alternatively, it may be performed in the material mixing step before the element firing step.
【００３５】また、主相の原料粉末と金属等の粉末を単
に混合するのではなく、主相の原料粉末である例えばセ
ラミック粉末上に、蒸着、スパッタリング等により金属
等をコーティングし、これを焼成して焼結体を得てもよ
い。Further, instead of simply mixing the raw material powder of the main phase and the powder of metal or the like, the raw material powder of the main phase, for example, ceramic powder is coated with metal or the like by vapor deposition, sputtering or the like and fired. You may obtain a sintered compact.
【００３６】本発明のＰＴＣＲ素子は、例えば自己制御
型発熱体、カラーテレビの消磁素子、モータの起動素
子、過電流制限素子、特定温度のセンサ、特定温度で使
用されるスイッチング素子等に利用される。The PTCR element of the present invention is used as, for example, a self-controlled heating element, a color television degaussing element, a motor starting element, an overcurrent limiting element, a sensor at a specific temperature, a switching element used at a specific temperature, and the like. It
【００３７】[0037]
【実施例】以下、本発明の具体的実施例を示し、本発明
をさらに詳細に説明する。EXAMPLES The present invention will be described in more detail below by showing specific examples of the present invention.
【００３８】実施例１ 原料粉末は、主相用として平均粒径１〜２μm ＴｉＯ2
の粉末、金属相用として平均粒径５〜１０μｍのＰｂ
（融点：３２７℃）の粉末を使用した。なお、ＴｉＯ2
の比抵抗の低下を促進するため、Ｎｂを添加した。この
Ｎｂの添加は、モル比で（Ｔｉ0.99Ｎｂ0.01）となるよ
うに行なった。また、Ｎｂとしては、Ｎｂ2 Ｏ5 粉末の
形で添加し、その平均粒径は１〜２μｍであった。これ
らを上記の方法で混合し、得られた混合物粉末を約１０
mmφ×５mmの円柱状に成形した。この成形体を１２００
℃、２時間、Ａｒ雰囲気中で焼成して組成ｘ（Ｐｂ）−
（１００−ｘ）（Ｔｉ0.99Ｎｂ0.01）Ｏ2 の焼結体を得
た。Example 1 Raw material powder was used for the main phase and had an average particle size of 1 to 2 μm TiO 2.
Powder, Pb with an average particle size of 5 to 10 μm for the metal phase
Powder having a melting point of 327 ° C. was used. In addition, TiO 2
Nb was added in order to accelerate the decrease in the specific resistance. This addition of Nb was performed so that the molar ratio would be (Ti 0.99 Nb 0.01 ). Further, Nb was added in the form of Nb 2 O 5 powder, and the average particle size was 1 to 2 μm. These were mixed by the above method, and the resulting mixture powder was mixed with about 10
It was formed into a cylindrical shape of mmφ × 5 mm. This molded body is 1200
The composition x (Pb)-
A sintered body of (100-x) (Ti 0.99 Nb 0.01 ) O 2 was obtained.
【００３９】上記の焼結体のｘ（Ｐｂ）−（１００−
ｘ）（Ｔｉ0.99Ｎｂ0.01）Ｏ2 の組成で、ｘを２０およ
び３０モル％（Ｐｂが約２０および約３０vol ％）にな
るように変化させ、試料１および２を得た。図５の試料
１の切断面ＳＥＭ写真から、Ｐｂ（黒い部分）の主相
（白い部分）への分散状態が確認された。X (Pb)-(100- of the above sintered body
x) (Ti 0.99 Nb 0.01 ) O 2 was used, and x was changed to 20 and 30 mol% (Pb is about 20 and about 30 vol%) to obtain Samples 1 and 2. From the SEM photograph of the cut surface of Sample 1 in FIG. 5, the dispersed state of Pb (black portion) in the main phase (white portion) was confirmed.
【００４０】ついで得られた焼結体のＰＴＣＲ特性を、
下記の比抵抗温度特性測定法により測定した。Then, the PTCR characteristics of the obtained sintered body were
It was measured by the following specific resistance temperature characteristic measuring method.
【００４１】＜比抵抗温度特性測定法＞焼結体の比抵抗
温度特性は、直流二端子法を用いて測定した。まず、Ｉ
ｎ−Ｇａ電極を焼結体表面に塗布してオーミック接合を
得た。さらに昇温による電極の酸化および蒸発を防ぐた
めにステンレス板で試料をはさんだ。測定は、大気中で
焼結体試料を昇温および降温し、試料を流れる電流値の
変化を記録することで行った。昇温速度は５℃／min と
して３５０℃まで昇温し、降温は炉冷速度とした。測定
装置として定電圧電源／モニタ（アドバンテスト；ＴＲ
−６１４３）を用いて５mV/cm の電界を試料に印加して
電流値を測定し、下記式により比抵抗（ρ）を算出し
た。<Specific Resistance Temperature Characteristic Measurement Method> The specific resistance temperature characteristic of the sintered body was measured by using the DC two-terminal method. First, I
An n-Ga electrode was applied on the surface of the sintered body to obtain ohmic contact. Furthermore, the sample was sandwiched with a stainless steel plate to prevent oxidation and evaporation of the electrode due to temperature rise. The measurement was performed by raising and lowering the temperature of the sintered body sample in the air and recording the change in the current value flowing through the sample. The temperature raising rate was 5 ° C./min and the temperature was raised to 350 ° C., and the temperature lowering was the furnace cooling rate. Constant voltage power supply / monitor (Advantest; TR
-6143), an electric field of 5 mV / cm 2 was applied to the sample, the current value was measured, and the specific resistance (ρ) was calculated by the following formula.
【００４２】〔比抵抗（ρ）算出式〕 ρ＝（Ｅ／Ｉ）×（Ｓ／ｈ） ただし、 Ｅ：印加電圧 Ｉ：試料を流れる電流 Ｓ：試料の断面積 ｈ：試料の厚さ 以上により算出した各温度での比抵抗（ρ）をプロット
して、図２に示すような各組成比の焼結体の比抵抗温度
特性曲線を得た。[Specific Resistance (ρ) Calculation Formula] ρ = (E / I) × (S / h) where, E: Applied voltage I: Current flowing through sample S: Cross-sectional area of sample h: Thickness of sample or more The specific resistance (ρ) at each temperature calculated by was plotted, and the specific resistance temperature characteristic curve of the sintered body having each composition ratio as shown in FIG. 2 was obtained.
【００４３】この図２から分かるように、試料１および
２で、Ｐｂの融点である３２７℃近傍で比抵抗の立ち上
がりが観察される。特に、３０Ｐｂ系の試料２では、比
抵抗が４．５×１０-4Ωｍ程度から７×１０-4Ωｍ程度
へと急激に立ち上がっている。この比抵抗の立ち上がり
を利用すれば、特定温度のセンサ等に利用するＰＴＣＲ
素子を構成することができる。As can be seen from FIG. 2, in Samples 1 and 2, the rise of the specific resistance is observed near 327 ° C., which is the melting point of Pb. Particularly, in the 30Pb-based sample 2, the specific resistance sharply rises from about 4.5 × 10 −4 Ωm to about 7 × 10 −4 Ωm. If this rise of the specific resistance is used, the PTCR used for a sensor at a specific temperature, etc.
The element can be constructed.
【００４４】実施例２ 次に、試料２の組成の材料を用いて、焼成温度を１１７
５℃および１２２５℃と変化させた以外は上記実施例と
同様にして、試料３および４を得た。Example 2 Next, using the material having the composition of Sample 2, the firing temperature was set to 117.
Samples 3 and 4 were obtained in the same manner as in the above example except that the temperature was changed to 5 ° C and 1225 ° C.
【００４５】これらの試料についても、上記実施例と同
様にして比抵抗温度特性を測定して、図３に示す比抵抗
温度特性曲線を得た。With respect to these samples as well, the specific resistance temperature characteristics were measured in the same manner as in the above example, and the specific resistance temperature characteristic curves shown in FIG. 3 were obtained.
【００４６】この図３から分かるように、焼成温度が１
１７５℃以上の試料３および４において、上記試料２と
同様にＰｂの融点である３２７℃近傍で比抵抗の良好な
立ち上がりが観察される。As can be seen from FIG. 3, the firing temperature is 1
In Samples 3 and 4 having a temperature of 175 ° C. or higher, a good rising of the specific resistance is observed near 327 ° C., which is the melting point of Pb, as in Sample 2.
【００４７】なお、１１７５℃から焼成温度が上昇する
につれて、試料の室温比抵抗が減少する傾向が見られた
が、これは主相であるＴｉＯ2 のＮｂの作用による比抵
抗の減少に伴うものであると考えられる。また、焼成温
度が所定温度以上となると、再び室温比抵抗が減少する
傾向が見られたが、これは、ＴｉＯ2 の比抵抗の減少よ
りも、Ｐｂの蒸発による全体の比抵抗の増大によるもの
であると考えられる。したがって、以上の材料を用い
て、ＰＴＣＲ素子を設計するには、焼成条件も十分に考
慮する必要がある。Although the room temperature resistivity of the sample tended to decrease as the firing temperature increased from 1175 ° C., this was due to the reduction of the resistivity due to the action of Nb of TiO 2 as the main phase. Is considered to be. When the firing temperature was higher than the predetermined temperature, the room temperature resistivity tended to decrease again. This was due to the increase in the overall resistivity due to the evaporation of Pb rather than the decrease in the resistivity of TiO 2. Is considered to be. Therefore, in designing a PTCR element using the above materials, it is necessary to sufficiently consider the firing conditions.
【００４８】実施例３ 次に、Ｔｉの代わりに、Ｚｎを用い、比抵抗制御のため
の添加物としてＡｌを用い、最終組成が２０Ｐｂ−８０
（Ｚｎ0.99Ａｌ0.01）Ｏ、すなわちＰｂが約２０vol ％
となるようにした他は、実施例１と同様にして、成形体
を得た。これを、１０５０℃、２時間、Ａｒ雰囲気中で
焼成して試料５の焼結体を得た。Example 3 Next, Zn was used instead of Ti, Al was used as an additive for controlling the specific resistance, and the final composition was 20 Pb-80.
(Zn 0.99 Al 0.01 ) O, that is, Pb is about 20 vol%
A molded product was obtained in the same manner as in Example 1 except that the above was adopted. This was fired in an Ar atmosphere at 1050 ° C. for 2 hours to obtain a sintered body of Sample 5.
【００４９】この試料５の焼結体についても、比抵抗を
測定し、図４に示すような比抵抗温度特性曲線を得た。
このように、主相の材料を代えても、金属としてＰｂを
用いるかぎりは、Ｐｂの融点である３２７℃近傍で比抵
抗の立ち上がりが見られ、ＰＴＣＲ素子として用いるこ
とができることが判明した。なお、実施例１、３の主相
（Ｔｉ0.99Ｎｂ0.01）Ｏ2 （Ｚｎ0.99Ａｌ0.01）Ｏの単
層膜についても上記と同様に、室温での比抵抗を測定し
たところ、１×１０-1Ωｍ〜１×１０3 Ωｍの範囲内で
あった。The specific resistance of the sintered body of Sample 5 was measured to obtain a specific resistance temperature characteristic curve as shown in FIG.
As described above, even if the material of the main phase was changed, as long as Pb was used as the metal, the rise of the specific resistance was observed near 327 ° C., which is the melting point of Pb, and it was found that it can be used as a PTCR element. The main phase (Ti 0.99 Nb 0.01) of Example 1,3 O 2 (Zn 0.99 Al 0.01 ) Like the above for single layer film of O, was measured the specific resistance at room temperature, 1 × 10 - It was within the range of 1 Ωm to 1 × 10 3 Ωm.
【００５０】以上の他、金属等として、融点で比抵抗の
立ち上がりがみられる、すなわち固相−液相間での相転
移でＰＴＣＲ特性を示すＰｂ以外の金属、例えばＳｎ、
Ｉｎ、Ｃｓ、Ａｌ、ＡｇまたはＣｄや、Ｐｂ−Ｓｎ合
金、Ａｇ−Ｐｂ合金またはＣｄ−Ｐｂ合金を用いても上
記実施例と同様の傾向がみられ、ＰＴＣＲ素子として使
用可能なことが分かった。In addition to the above, as a metal or the like, a rise in specific resistance is observed at the melting point, that is, a metal other than Pb which exhibits a PTCR characteristic at the phase transition between the solid phase and the liquid phase, for example, Sn,
Even if In, Cs, Al, Ag or Cd or Pb-Sn alloy, Ag-Pb alloy or Cd-Pb alloy was used, the same tendency as in the above-mentioned examples was observed, and it was found that it can be used as a PTCR element. .
【００５１】また、金属等を担持する主相としては、以
上の実施例では、酸化物のみを用いたが、上記実施例の
酸化物と同様の電気的特性を示すものであるならば、他
の化合物、すなわち窒化物、ケイ化物、炭化物、ホウ化
物または硫化物等を用いても同様の傾向が見られ、ＰＴ
ＣＲ素子として用いることが判明した。Further, as the main phase for supporting a metal or the like, only the oxide is used in the above-mentioned examples, but if the oxide has the same electrical characteristics as those of the oxides in the above-mentioned examples, other oxides are used. The same tendency is observed when the compounds of, i.e., nitrides, silicides, carbides, borides or sulfides are used, and PT
It was found to be used as a CR element.
【００５２】以上説明したように、本発明は、従来なか
った、全く新しい発現機構に基づくＰＴＣＲ素子を提供
することができる。As described above, the present invention can provide a PTCR element based on a completely new expression mechanism which has never been obtained.
【図１】代表的な金属の比抵抗温度特性を示すグラフ図
である。FIG. 1 is a graph showing a specific resistance temperature characteristic of a typical metal.
【図２】実施例１の試料における比抵抗温度特性を示す
グラフ図である。FIG. 2 is a graph showing the specific resistance temperature characteristic of the sample of Example 1.
【図３】実施例２の試料における比抵抗温度特性を示す
グラフ図である。FIG. 3 is a graph showing the specific resistance temperature characteristic of the sample of Example 2.
【図４】実施例３の試料における比抵抗温度特性を示す
グラフ図である。FIG. 4 is a graph showing the specific resistance temperature characteristic of the sample of Example 3;
【図５】図面代用写真であって、本発明の実施例の試料
１の切断面のＳＥＭ写真である。FIG. 5 is a photograph as a substitute for a drawing, which is an SEM photograph of a cross section of Sample 1 of the example of the present invention.
【手続補正書】[Procedure amendment]
【提出日】平成７年２月１６日[Submission date] February 16, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１６[Correction target item name] 0016
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１６】上記のような添加剤としては、Ｎｂ、Ｔ
ａ、Ｓｂ、Ａｌ、Ｇａ、Ｉｎの他に、主相の酸化物の種
類によりＶ、Ｗ、Ｙ、希土類、Ｓｂ、Ｂを用いることが
できる。なお、主相の比抵抗は、実際の素子と同一の条
件で主相材料単独で焼結体を作製して測定すればよい。As the above-mentioned additives, Nb, T
In addition to a, Sb, Al, Ga, and In, V, W, Y, rare earths, Sb, and B can be used depending on the type of oxide of the main phase. The resistivity of the main phase may be measured by preparing a sintered body of the main phase material alone under the same conditions as the actual element.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３０[Name of item to be corrected] 0030
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３０】このような原料を用い混合を行なう。混合
方法に特に制限はないが、例えばエタノール、水、ヘキ
サン等と共にボールミル等による湿式混合が好ましく、
手混合を行ってもよい。次いで、混台物を乾燥し、所定
の形状に圧縮成形する。この時の成形圧は、１００ｋｇ
／ｃｍ２〜２ｔ／ｃｍ２程度とする。Mixing is performed using such raw materials. Although the mixing method is not particularly limited, for example, wet mixing with a ball mill or the like together with ethanol, water, hexane or the like is preferable,
Manual mixing may be performed. Next, the mixed material is dried and compression-molded into a predetermined shape. The molding pressure at this time is 100 kg
/ Cm 2 to 2 t / cm 2 .
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３４[Correction target item name] 0034
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３４】なお、上記主相中には、主相の比抵抗を低
減するための前述のような成分を添加することが望まし
く、このような成分の添加は、材料粉末中に予め行なっ
ても、素子の焼成工程前の材料の混合工程において行な
っても、いずれでもよい。It should be noted that it is desirable to add the above-mentioned components for reducing the specific resistance of the main phase to the above-mentioned main phase. Even if such a component is added to the material powder in advance. Alternatively, it may be performed in the material mixing step before the element firing step.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４９[Correction target item name] 0049
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４９】この試料５の焼結体についても、比抵抗を
測定し、図４に示すような比抵抗温度特性曲線を得た。
このように、主相の材料を代えても、金属としてＰｂを
用いるかぎりは、Ｐｂの融点である３２７℃近傍で比抵
抗の立ち上がりが見られ、ＰＴＣＲ素子として用いるこ
とができることが判明した。なお、実施例１、３の主相
（Ｔｉ０．９９Ｎｂ０．０１）Ｏ２と（Ｚｎ０．９９Ａ
ｌ０．０１）０の焼結体についても上記と同様に、室温
での比抵抗を測定したところ、１×１０−１Ωｍ〜１×
１０３Ωｍの範囲内であった。 ─────────────────────────────────────────────────────
The specific resistance of the sintered body of Sample 5 was measured to obtain a specific resistance temperature characteristic curve as shown in FIG.
As described above, even if the material of the main phase was changed, as long as Pb was used as the metal, the rise of the specific resistance was observed near 327 ° C., which is the melting point of Pb, and it was found that it can be used as a PTCR element. The main phases (Ti 0.99 Nb 0.01 ) O 2 and (Zn 0.99 A) of Examples 1 and 3 were used.
With respect to the sintered body of l 0.01 ) 0 as well, the specific resistance at room temperature was measured in the same manner as above, and 1 × 10 −1 Ωm to 1 ×
It was within the range of 10 3 Ωm. ─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年２月１６日[Submission date] February 16, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図５[Name of item to be corrected] Figure 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図５】 [Figure 5]
フロントページの続き (72)発明者 本間 基文 宮城県仙台市太白区八木山南１丁目３−７ (72)発明者 松岡 大 東京都中央区日本橋一丁目13番１号 ティ ーディーケイ株式会社内 (72)発明者 淀川 正忠 東京都中央区日本橋一丁目13番１号 ティ ーディーケイ株式会社内Continuation of the front page (72) Inventor, Motoki Honma, 3-7 Yagiyama Minami, Taihaku-ku, Sendai-shi, Miyagi (3) (72) Inventor, Dai 13 Matsuoka, Nihonbashi, 1-13-1 Chuo-ku, Tokyo, TDC Corporation (72) Inventor Masatada Yodogawa, 13-1 Nihonbashi, Chuo-ku, Tokyo Inside TDC Corporation
Claims (8)
の相転移に伴いＰＴＣＲ特性を示す金属または合金を分
散させたことを特徴とするＰＴＣＲ素子。1. A PTCR element characterized in that a metal or an alloy exhibiting PTCR characteristics in association with a phase transition between a solid phase and a liquid phase is dispersed between main phases of a metal compound.
物、炭化物、ホウ化物および硫化物の一種以上である請
求項１のＰＴＣＲ素子。2. The PTCR element according to claim 1, wherein the compound is one or more of oxides, nitrides, silicides, carbides, borides and sulfides.
ンジウム、鉄、バリウム、ストロンチウム、ニッケル、
マンガンおよび鉛の１種以上を含む酸化物である請求項
２のＰＴＣＲ素子。3. The oxide is titanium, zinc, tin, indium, iron, barium, strontium, nickel,
The PTCR element according to claim 2, which is an oxide containing at least one of manganese and lead.
ー以下である請求項１ないし３のいずれかのＰＴＣＲ素
子。4. The PTCR element according to claim 1, wherein the electrical resistance of the main phase is on the order of 10 3 Ωm or less.
ー以上である請求項４のＰＴＣＲ素子。5. The PTCR element according to claim 4, wherein the electric resistance of the main phase is on the order of 10 −1 Ωm or more.
融点を有する請求項１ないし５のいずれかのＰＴＣＲ素
子。6. The PTCR element according to claim 1, wherein the metal or alloy has a melting point of 1100 ° C. or lower.
ｌ、ＡｇまたはＣｄであり、合金がＰｂ−Ｓｎ合金、Ａ
ｇ−Ｐｂ合金またはＣｄ−Ｐｂ合金である請求項１ない
し６のいずれかのＰＴＣＲ素子。7. The metal is Pb, Sn, In, Cs, A
l, Ag or Cd, and the alloy is a Pb-Sn alloy, A
The PTCR element according to claim 1, which is a g-Pb alloy or a Cd-Pb alloy.
vol ％である請求項１ないし７のいずれかのＰＴＣＲ素
子。8. The content of the metal or alloy is 5 to 50.
The PTCR element according to any one of claims 1 to 7, which has a vol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31599193A JP3409902B2 (en) | 1993-11-22 | 1993-11-22 | PTCR element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31599193A JP3409902B2 (en) | 1993-11-22 | 1993-11-22 | PTCR element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07161502A true JPH07161502A (en) | 1995-06-23 |
| JP3409902B2 JP3409902B2 (en) | 2003-05-26 |
Family
ID=18072029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31599193A Expired - Fee Related JP3409902B2 (en) | 1993-11-22 | 1993-11-22 | PTCR element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3409902B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218928B1 (en) | 1996-09-13 | 2001-04-17 | Tdk Corporation | PTC thermistor material |
| US6224790B1 (en) | 1998-06-22 | 2001-05-01 | Ngk Insulators, Ltd. | Conductive ceramic-metal composite body exhibiting positive temperature coefficient behavior |
| US6358436B2 (en) | 1999-07-23 | 2002-03-19 | Ngk Insulators, Ltd. | Inorganic-metal composite body exhibiting reliable PTC behavior |
-
1993
- 1993-11-22 JP JP31599193A patent/JP3409902B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218928B1 (en) | 1996-09-13 | 2001-04-17 | Tdk Corporation | PTC thermistor material |
| US6224790B1 (en) | 1998-06-22 | 2001-05-01 | Ngk Insulators, Ltd. | Conductive ceramic-metal composite body exhibiting positive temperature coefficient behavior |
| US6358436B2 (en) | 1999-07-23 | 2002-03-19 | Ngk Insulators, Ltd. | Inorganic-metal composite body exhibiting reliable PTC behavior |
| US6547989B1 (en) | 1999-07-23 | 2003-04-15 | Ngk Insulators, Ltd. | Inorganic-metal composite body exhibiting reliable PTC behavior |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3409902B2 (en) | 2003-05-26 |
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