WO1994024680A1 - Thermistance a caracteristique positive - Google Patents

Thermistance a caracteristique positive Download PDF

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Publication number
WO1994024680A1
WO1994024680A1 PCT/JP1994/000622 JP9400622W WO9424680A1 WO 1994024680 A1 WO1994024680 A1 WO 1994024680A1 JP 9400622 W JP9400622 W JP 9400622W WO 9424680 A1 WO9424680 A1 WO 9424680A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermistor
composition
positive
temperature coefficient
mol
Prior art date
Application number
PCT/JP1994/000622
Other languages
English (en)
Japanese (ja)
Inventor
Hiroshi Sasaki
Hiroshi Inagaki
Takuji Okumura
Masatoshi Tamura
Katsuhiko Sugisawa
Original Assignee
Kabushiki Kaisha Komatsu Seisakusho
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
Priority claimed from JP8754993A external-priority patent/JPH06302402A/ja
Priority claimed from JP5281352A external-priority patent/JPH06349604A/ja
Application filed by Kabushiki Kaisha Komatsu Seisakusho filed Critical Kabushiki Kaisha Komatsu Seisakusho
Priority to KR1019950704028A priority Critical patent/KR960701453A/ko
Priority to EP94912679A priority patent/EP0694930A4/fr
Publication of WO1994024680A1 publication Critical patent/WO1994024680A1/fr

Links

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
    • 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 positive-characteristic temperature sensor, and more particularly to a composition of a thermistor body.
  • porcelain consisting B a T i 0 3 system base perovskite-type compound is a dielectric, piezoelectric, pyroelectric, have electrical have utility value properties such as abnormal resistance, widely various electronic devices Used.
  • the added oxide semiconductors 3at% is because it has a large positive temperature coefficient, it referred to as PTC thermistor evening.
  • PTC thermistor evening the temperature range having a large positive temperature coefficient can be adjusted by adding Sr, Pb, etc., so that the temperature can be measured and overcurrent can be prevented. It must be in a wide variety of fields, such as circuit elements for demagnetization and low-temperature heaters.
  • a first object of the present invention one force, low room temperature resistivity p 25, can resistance temperature coefficient ⁇ is large, there is provided a mono mistakes evening with stable characteristics.
  • a second object of the present invention is to provide a highly reliable positive-characteristic thermistor with low power consumption, no generation of Pb vapor, and high reliability.
  • the present invention in the semi-conductor composition of B a T i 0 3 perovskite type compounds constituting the mono- thermistor body, the better to you in excess T i amount It is characterized in that the composition that has been set is a composition in which the Ti amount is less than the stoichiometric ratio.
  • thermistor main body made of a rhodium titanate-based semiconductor formed so as to satisfy the following formula, and a power supply electrode attached to the thermistor main body.
  • S at least one element selected from Sr, Sn, Zr, Ca, Pb
  • M Nb, Ta, Bi, Sb, Y, La, Nd, W, Th, Ce, Sm, Gd,
  • A At least one element selected from Mn, Fe, Cu, Cr, F, CI, Br, K, and V
  • the present inventors have repeated various experiments by changing the composition ratio, and as a result, have found that a composition in which the Ti amount is less than the stoichiometric ratio is better, and the present invention has been made by paying attention to this. as hereinbefore, by using the above composition, and smaller room temperature resistivity p 25, alpha is possible force to provide a mono thermistor with a large listening stable characteristics.
  • the element of S mainly has an action of controlling the Curie temperature
  • the element of ⁇ ⁇ ⁇ ⁇ has an action of mainly converting the composition into a semiconductor
  • the element of ⁇ controls the surface state of the crystal grain boundary. It is believed to be something.
  • the present invention is characterized in that the composition of the semiconductor constituting the thermistor body is constituted by the following titanate / ⁇ calcium-lium-thiocyanate-based semiconductor.
  • the present inventors have conducted various experiments by changing the composition, and as a result, have found that the use of the above composition makes it possible to obtain a positive characteristic thermistor with low power consumption. Is made by paying attention to this.
  • Ca has the effect of refining the crystal grains and improving the withstand voltage characteristics.
  • the reason why the composition range is set to 0.01 ⁇ x ⁇ 0.2 is that when X is smaller than 0.01, there is no effect of improving the characteristics, and when X exceeds 0.2, the specific resistance of the element becomes large and the practicality is lost.
  • Y has an effect of imparting semiconductivity to titanium titanate.
  • its composition range In order to reduce the specific resistance to a practically low value (10 to 1 kQ * cm), its composition range must be within the range of 0.002 ⁇ y ⁇ 0.006.
  • Excess Ti content than the stoichiometric composition has a large effect on the crystal grain size and the temperature coefficient of resistance of the device, and therefore has the greatest effect on power consumption during energization.
  • the composition range of T i is set to 0.001 ⁇ z ⁇ 0.010 because the temperature coefficient of resistance is smaller for a table with a value of less than 0.001. Therefore, the element resistance at the time of applying a voltage is reduced, and the power consumption during energization is increased. For such a reason, the above range is determined.
  • S i 0 2 lowers the sintering temperature, the effect of suppressing abnormal grain growth of crystal grains.
  • the reason for setting 0.005 ⁇ p ⁇ 0.03 is that bananas smaller than 0.005 have insufficient effect of suppressing abnormal grain growth, and larger than 0.03, and conversely, cause abnormal grain growth of crystal grains.
  • Mn has the effect of increasing the temperature coefficient of resistance above the Curie temperature. However, since the addition of Mn also increases the specific resistance, the composition range must be 0.0005 ⁇ q ⁇ 0.0015 in order to obtain the above effect within the practical range of the specific resistance of the element (l kQ * cm or less).
  • FIG. 1 is a diagram showing a positive characteristic thermistor according to the first embodiment of the present invention.
  • FIG. 2 is a diagram showing the relationship between the composition ratio of the positive temperature coefficient thermistor of the embodiment of the present invention and the conventional example, and the specific resistance at room temperature and the temperature coefficient of resistance.
  • Fig. 3 shows anomalous resistance at positive temperature thermistors.
  • FIG. 4 is a diagram showing a positive characteristic thermistor according to the second embodiment of the present invention.
  • FIG. 5 is a diagram showing a circuit for measuring power consumption in a positive temperature coefficient thermistor according to the present invention.
  • FIG. 1 is a diagram showing a positive characteristic thermistor according to an embodiment of the present invention.
  • the positive characteristics of the thermistor are characterized in that the composition of the thermistor body 1 is configured as shown in the following equation.
  • this positive temperature coefficient thermistor is composed of A first electrode layer 2a, 2 made of a Ni vapor-deposited layer formed so that the edge comes to a position slightly entering from the outer peripheral edge, and first electrode layers 2a, 2b on this upper layer. Second electrode layers 3a and 3b containing silver as a main component and formed so that their edges coincide with each other.
  • T i C 1 was diluted with distilled water so that the volume of the stock solution is doubled, a portion of the T i C 1 4 is hydrated, concentration of T i 1 mole per 239. 6 g T i C 17] Japanese. Here, the concentration was quantified by Coulomb analysis.
  • the granulated powder was reduced to 60 m or less by a spray drier, formed into pellets by a hydraulic press, and fired at 141 CTC for 1 hour to obtain semiconductor porcelain. An electrode was attached to this porcelain and the temperature resistance characteristics were measured. The results are shown in Table 1.
  • composition of the thermistor body 1 was configured as shown in the following equation.
  • B a 0.7744 S r 0.2217 Y 0.0039 ⁇ T i 0.9961 ° 3 + 0 " 00 1Mn (Formula)
  • the manufacturing process of the positive temperature coefficient thermistor will be described.
  • the T i C 1 stock solution was diluted with distilled water and the concentration was
  • T i C 1 4 hydrate 245 g T g of T i C 1 4 hydrate was prepared, and this T i C 1 4 hydrate 122. 1 g (T i: 0. 499 mol) were collected and the T i C 1 4 ⁇ solution was added further distilled water 200 g.
  • composition power of the thermistor body 1 was configured as shown in the following equation.
  • composition of the thermistor body 1 was configured as shown in the following equation.
  • the composition of the thermistor body 1 was configured as shown in the following equation. (Ba 0 7778 S r 0 2180 Y 0 0042 ) T i 1 0033 O 3 + ⁇ . ⁇ ⁇ (Formula) This composition exceeds the upper limit of the composition range of T i.
  • the composition of the thermistor body 1 was configured as shown in the following equation.
  • Example 1 shows the measurement results of the characteristics of the rice thermistor element as Comparative Example B.
  • FIG. 4 is a diagram showing a PTC thermistor according to the embodiment of the present invention.
  • This positive temperature coefficient thermistor is characterized in that the composition of the thermistor body 1S has a composition ratio as shown in the following table, and is constituted by potassium titanate-calcium titanate semiconductor shown below.
  • this positive characteristic ceramic is formed such that the main body 1S of the above composition, which is composed of titanium titanate, and the upper surface and the T® have an edge at a position slightly entering from the outer peripheral edge.
  • a first electrode layer 2a, 2b formed of a Ni vapor-deposited layer, and a second layer mainly composed of silver formed on the first electrode layer 2a, 2b so as to match the edge force of the first electrode layer 2a, 2b.
  • two electrode layers 3a and 3b are two electrode layers.
  • the obtained granulated powder is formed by a hydraulic press to a density of 2.5-3.Og / cm 3 , and then fired at 135 CTC for 1 hour in the air to have a diameter of 20 mm and a thickness of 2. 5 Obtained barium titanate-based semiconductor porcelain.
  • Commercially available Ag electrodes were printed and printed on both end surfaces of the semiconductor porcelain, and the specific resistance and power consumption were measured.
  • the power consumption was measured using a measurement circuit as shown in FIG. In this measurement circuit, the positive characteristic error signal 10 is connected to the power supply 12 via the load resistor 11, and this connection can be turned on and off by the switch 13.
  • the voltage at both ends of the positive temperature coefficient thermistor 1 ⁇ is measured by the connected voltmeter 14, and the voltage is measured by the The current flowing is measured. In this way, the voltage at both ends of the positive characteristic thermistor 10 and the current flowing through the positive characteristic thermistor 10 are measured to calculate the power consumption.
  • the power consumption P (W) was obtained by the following equation.
  • compositions Nos. 1 to 5, 8, and 9 indicate the present invention
  • compositions Nos. 6, 7, 10, and 11 indicate comparative examples.
  • composition Nos. 1 to 5 By comparing composition Nos. 1 to 5 with compositions Nos. 6 and 7, the amount of excess Ti 0 2 was 0.001 to O. Olmol (total Ti 0 3 ⁇ 4 100.1 -101.0 mol), It can be seen that a small power consumption equal to or less than the power consumption (3.0 W) of composition No. 11 can be obtained. If the amount of excess Ti is 0.001 mol or less or O.Olmol or more, the power consumption is 3. Ow or more.
  • the composition of the semiconductor constituting the semiconductor body is composed of barium titanate-calcium titanate-based semiconductor containing no Pb, Pb vapor is emitted during firing. And a positive temperature coefficient thermistor with low power consumption during energization can be provided.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Thermistance présentant une faible résistance spécifique ς25 à température ambiante, une valeur α élevée et des caractéristiques stables. Le semiconducteur constituant le corps principal de la thermistance est un composé de type perovskite BaTiO3. La quantité de Ti est inférieure à celle déterminée par le rapport st÷chiométrique, lequel a été de préférence excédentaire conventionnellement.
PCT/JP1994/000622 1993-04-14 1994-04-14 Thermistance a caracteristique positive WO1994024680A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019950704028A KR960701453A (ko) 1993-04-14 1994-04-14 정특성 서미스터
EP94912679A EP0694930A4 (fr) 1993-04-14 1994-04-14 Thermistance a caracteristique positive

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP5/87549 1993-04-14
JP8754993A JPH06302402A (ja) 1993-04-14 1993-04-14 正特性サーミスタ
JP5/87550 1993-04-14
JP8755093 1993-04-14
JP5281352A JPH06349604A (ja) 1993-04-14 1993-11-10 正特性サーミスタ
JP5/281352 1993-11-10

Publications (1)

Publication Number Publication Date
WO1994024680A1 true WO1994024680A1 (fr) 1994-10-27

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1994/000622 WO1994024680A1 (fr) 1993-04-14 1994-04-14 Thermistance a caracteristique positive

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EP (1) EP0694930A4 (fr)
KR (1) KR960701453A (fr)
WO (1) WO1994024680A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4058140B2 (ja) * 1997-09-05 2008-03-05 Ｔｄｋ株式会社 チタン酸バリウム系半導体磁器
JP4080576B2 (ja) * 1997-09-05 2008-04-23 Ｔｄｋ株式会社 正特性半導体磁器の製造方法
JP3506044B2 (ja) * 1999-04-28 2004-03-15 株式会社村田製作所 半導体セラミック、半導体セラミック素子、および回路保護素子
KR100674692B1 (ko) * 1999-06-03 2007-01-26 마쯔시다덴기산교 가부시키가이샤 박막서미스터소자 및 박막서미스터소자의 제조방법
DE10026261A1 (de) * 2000-05-26 2001-12-06 Epcos Ag Keramisches Material, Verfahren zu dessen Herstellung, Bauelement mit dem keramischen Material und Verwendung des Bauelements
DE10061458B4 (de) * 2000-12-09 2005-12-15 Eichenauer Heizelemente Gmbh & Co. Kg Verfahren und Vorrichtung zum Regeln einer Kfz-Zusatzheizung

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4898396A (fr) * 1972-03-28 1973-12-13
JPS5410110B2 (fr) * 1974-03-20 1979-05-01
JPH02192456A (ja) * 1989-01-21 1990-07-30 Chichibu Cement Co Ltd 半導体磁器
JPH05251203A (ja) * 1992-03-04 1993-09-28 Chichibu Cement Co Ltd 半導体磁器組成物
JPH0613203A (ja) * 1992-06-25 1994-01-21 Murata Mfg Co Ltd 半導体セラミック素子の製造方法
JPH0684605A (ja) * 1992-08-31 1994-03-25 Shinagawa Refract Co Ltd 正特性サーミスタ及びその製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4175060A (en) * 1977-11-25 1979-11-20 Bell Telephone Laboratories, Incorporated Composition and processing procedure for making thermistors
JPH03155352A (ja) * 1989-11-13 1991-07-03 Nkk Corp 小型直流モーター

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4898396A (fr) * 1972-03-28 1973-12-13
JPS5410110B2 (fr) * 1974-03-20 1979-05-01
JPH02192456A (ja) * 1989-01-21 1990-07-30 Chichibu Cement Co Ltd 半導体磁器
JPH05251203A (ja) * 1992-03-04 1993-09-28 Chichibu Cement Co Ltd 半導体磁器組成物
JPH0613203A (ja) * 1992-06-25 1994-01-21 Murata Mfg Co Ltd 半導体セラミック素子の製造方法
JPH0684605A (ja) * 1992-08-31 1994-03-25 Shinagawa Refract Co Ltd 正特性サーミスタ及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0694930A4 *

Also Published As

Publication number Publication date
EP0694930A1 (fr) 1996-01-31
EP0694930A4 (fr) 1997-04-09
KR960701453A (ko) 1996-02-24

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