EP0129997B1 - Process for the production of ptc thermistors - Google Patents

Process for the production of ptc thermistors Download PDF

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Publication number
EP0129997B1
EP0129997B1 EP84303796A EP84303796A EP0129997B1 EP 0129997 B1 EP0129997 B1 EP 0129997B1 EP 84303796 A EP84303796 A EP 84303796A EP 84303796 A EP84303796 A EP 84303796A EP 0129997 B1 EP0129997 B1 EP 0129997B1
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EP
European Patent Office
Prior art keywords
pbo
glass
process according
sealing
sio
Prior art date
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Expired
Application number
EP84303796A
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German (de)
French (fr)
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EP0129997A1 (en
Inventor
Keiichi Minegishi
Tokuji Akiba
Tadao Katoh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiheiyo Cement Corp
Original Assignee
Chichibu Cement Co Ltd
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Publication of EP0129997A1 publication Critical patent/EP0129997A1/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C17/00Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/02Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistors with envelope or housing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C1/00Details
    • H01C1/02Housing; Enclosing; Embedding; Filling the housing or enclosure
    • H01C1/024Housing; Enclosing; Embedding; Filling the housing or enclosure the housing or enclosure being hermetically sealed
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/022Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
    • H01C7/023Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
    • H01C7/025Perovskites, e.g. titanates

Definitions

  • the present invention relates to a process for the production of PTC thermistors.
  • a thermistor aimed at sensing temperature alone includes a thermistor element sealed in glass or resin so as to keep it from being affected by other factors such as humidity or gas.
  • NTC thermistors there are available glass-sealed type thermistors which are inexpensive, easy to mass-produce and have stabilized properties, in addition to resin-sealed type disc-form thermistors.
  • PTC thermistors use is made of resin-sealed disc-form PTC thermistors or PTC thermistors in which metals are mechanically pressed onto electrodes.
  • U.S. Patent 3,377,561 discloses a process for the production of PTC thermistors comprising the step of sealing a positive temperature coefficient semiconductor ceramic material in glass in the presence of air.
  • a main object of the present invention is to provide inexpensive glass-sealed type PTC thermistors which show a great change in resistance, especially a markedly increased change in resistance at switching temperatures, and which have stabilized properties.
  • a process for the production of PTC thermistors by sealing a positive temperature coefficient semiconductor ceramic material in low-melting glass having a softening point of no higher than 560°C in the presence of air, oxygen or an air/oxygen mixture containing higher than 0% to lower than 100% volume of air.
  • the semiconductor ceramic material having a positive temperature coefficient used in the present invention there are mentioned those obtained by adding to barium titanate base compositions any one of trivalent antimony, trivalent bismuth, pentavalent tantalum, pentavalent niobium or a rare earth metal.
  • the glass used has a softening point of 450°C-560°C inclusive, and includes those glasses based on B 2 0 3 -PbO-ZnO, B 2 0 3 -PbO-SiO 2 , B 2 0 3 -PbO-TiO 2 , B 2 0 3 -Pb0-Si0 2 -AI 2 0 3 -ZnO, B 2 0 3 -Pb0-V 2 0 5 , S!0 2 -PbO-K 2 0, Si0 2 -PbO-Na 2 O and SiO 2 -PbO-K 2 0-Na 2 O, Preference is given to a Si0 2 -PbO-K 2 0 base glass, since this glass shows desirous thermal expansion and wettability with respect to lead wires (Dumet wires, viz., Fe-Ni alloy wires plated with Cu).
  • a semiconductor barium titanate ceramic material 1 is first sliced to any suitable thickness having regard to the length of a glass tube 4 in which the finished thermistor element is to be sealed.
  • Silver electrodes 2 and 2 are applied to both sides of the thus obtained element, and deposited thereto for 20 minutes at 600°C.
  • Figure 1(a) shows a section of the electrode-provided element.
  • the element is then cut to any length corresponding to the diameter of the glass tube 4.
  • the element is placed in the tube 4 of a glass having a softening point of no higher than 560°C, into both ends of which Dumet wires 3 and 3 are inserted. Finally, the glass tube 4 is sealed by means of a carbon heater jig.
  • the sealing temperature is determined depending upon the softening point of the glass used, and is generally higher than the softening point of the glass used by 50°C or more.
  • NTC glass sealed thermistors a glass having a softening point exceeding 560°C is used and sealing is carried out at a temperature exceeding 610°C. If sealing of a PTC thermistor is carried out under such conditions, there is a marked drop in the properties of the resulting PTC thermistor. According to the present invention, however, it is possible to obtain stable PTC thermistors whose properties drop only slightly by sealing the thermistor elements in a low-melting glass having a softening point of no higher than 560°C.
  • Figure 2 shows the results of an experiment run wherein PTC thermistor elements having a Curie point of 120°C were sealed in glasses in the art.
  • Figure 3 is a characteristic diagram of a PTC thermistor sealed in glass in various atmospheres.
  • the PTC thermistor used had a Curie point of 120°C, and sealing was carried out at 610°C.
  • Figure 4 is a graphical view showing the relation between the specific resistance and the temperature of PTC thermistors obtained by sealing a PTC thermistor element having a Curie point of 120°C in glass in air and/or oxygen gas. The results of Figure 4 are numerically given in Table 3.
  • the present invention makes it possible to inexpensively prepare PTC thermistors having excellent properties, and is therefore of industrially high value.

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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)
  • Manufacturing & Machinery (AREA)
  • Thermistors And Varistors (AREA)
  • Ceramic Products (AREA)
  • Glass Compositions (AREA)

Description

  • The present invention relates to a process for the production of PTC thermistors.
  • As is well-known in the art, a thermistor aimed at sensing temperature alone includes a thermistor element sealed in glass or resin so as to keep it from being affected by other factors such as humidity or gas. Referring especially to NTC thermistors, there are available glass-sealed type thermistors which are inexpensive, easy to mass-produce and have stabilized properties, in addition to resin-sealed type disc-form thermistors.
  • Turning to PTC thermistors, however, use is made of resin-sealed disc-form PTC thermistors or PTC thermistors in which metals are mechanically pressed onto electrodes.
  • This may be attributable to the properties of PTC thermistors which are significantly affected by the temperature and atmosphere at and in which the thermistor elements are sealed in glass.
  • Conventional-NTC thermistors are prepared by glass sealing in vacuum or an atmosphere such as N2 or Ar gas so as to prevent Dumet wires or heaters from being oxidized. In consequence of the studies made by the present inventors, it has been revealed that the application of such glass sealing in a reducing atmosphere to PCT thermistors causes the properties thereof to deteriorate to a considerable extent. It has also been found that, under such conditions, the glass sealing temperature reaches as high at 650°C, at which temperature the properties of PTC thermistors deteriorate significantly.
  • U.S. Patent 3,377,561 discloses a process for the production of PTC thermistors comprising the step of sealing a positive temperature coefficient semiconductor ceramic material in glass in the presence of air.
  • In view of the foregoing, a main object of the present invention is to provide inexpensive glass-sealed type PTC thermistors which show a great change in resistance, especially a markedly increased change in resistance at switching temperatures, and which have stabilized properties.
  • According to the present invention, there is provided a process for the production of PTC thermistors by sealing a positive temperature coefficient semiconductor ceramic material in low-melting glass having a softening point of no higher than 560°C in the presence of air, oxygen or an air/oxygen mixture containing higher than 0% to lower than 100% volume of air.
  • The invention will be more particularly described with reference to the accompanying drawings, in which:-
    • Figure 1 is a schematic view showing one embodiment of the steps of a process according to the present invention; and '
    • . Figures 2 to 4 inclusive are views showing the temperature-specific resistance characteristics of the products prepared under different conditions.
  • As the semiconductor ceramic material having a positive temperature coefficient used in the present invention, there are mentioned those obtained by adding to barium titanate base compositions any one of trivalent antimony, trivalent bismuth, pentavalent tantalum, pentavalent niobium or a rare earth metal. The glass used has a softening point of 450°C-560°C inclusive, and includes those glasses based on B203-PbO-ZnO, B203-PbO-SiO2, B203-PbO-TiO2, B203-Pb0-Si02-AI203-ZnO, B203-Pb0-V205, S!02-PbO-K20, Si02-PbO-Na2O and SiO2-PbO-K20-Na2O, Preference is given to a Si02-PbO-K20 base glass, since this glass shows desirous thermal expansion and wettability with respect to lead wires (Dumet wires, viz., Fe-Ni alloy wires plated with Cu).
  • When a glass having a softening point of below 450°C is used, certain limitations are imposed upon the temperature at which the resulting glass-sealed type PTC thermistors are employed.
  • Referring now to Figure 1, a semiconductor barium titanate ceramic material 1 is first sliced to any suitable thickness having regard to the length of a glass tube 4 in which the finished thermistor element is to be sealed. Silver electrodes 2 and 2 are applied to both sides of the thus obtained element, and deposited thereto for 20 minutes at 600°C. Figure 1(a) shows a section of the electrode-provided element.
  • As shown in Figure 1 (b), the element is then cut to any length corresponding to the diameter of the glass tube 4.
  • The element is placed in the tube 4 of a glass having a softening point of no higher than 560°C, into both ends of which Dumet wires 3 and 3 are inserted. Finally, the glass tube 4 is sealed by means of a carbon heater jig. The sealing temperature is determined depending upon the softening point of the glass used, and is generally higher than the softening point of the glass used by 50°C or more.
  • In the prior art NTC glass sealed thermistors, a glass having a softening point exceeding 560°C is used and sealing is carried out at a temperature exceeding 610°C. If sealing of a PTC thermistor is carried out under such conditions, there is a marked drop in the properties of the resulting PTC thermistor. According to the present invention, however, it is possible to obtain stable PTC thermistors whose properties drop only slightly by sealing the thermistor elements in a low-melting glass having a softening point of no higher than 560°C.
  • Figure 2 shows the results of an experiment run wherein PTC thermistor elements having a Curie point of 120°C were sealed in glasses in the art.
  • Although the resulting properties having slightly dropped from the initial ones (prior to sealing), yet the PTC thermistor element sealed in a glass having a softening point of 536°C or 560°C has been found to show excellent properties. It has also been found that similar results are obtained with PTC thermistor elements having different Curie points. The results of Figure 2 are also numerically given in Table 1.
  • Figure 3 is a characteristic diagram of a PTC thermistor sealed in glass in various atmospheres. The PTC thermistor used had a Curie point of 120°C, and sealing was carried out at 610°C.
  • It is clear from the diagram that sealing in air or oxygen gas yields a better PTC thermistor as compared with one treated in vacuo or in an inert or reducing gas atmosphere. The results of Figure 3 are numerically given in Table 2.
  • It is to be understood that similar results are obtained in air/oxygen mixture and/or with a PTC thermistor element having a different Curie point.
  • Figure 4 is a graphical view showing the relation between the specific resistance and the temperature of PTC thermistors obtained by sealing a PTC thermistor element having a Curie point of 120°C in glass in air and/or oxygen gas. The results of Figure 4 are numerically given in Table 3.
  • From these results, it is found that by a process according to the present invention PTC thermistors are obtained which show a large change in resistance, which is comparable to the properties prior to sealing.
  • It is to be understood that similar results are obtained in an air/oxygen mixture and/or with PTC thermistor elements having a different Curie point.
  • It is to be understood that, in place of a carbon heater jig, other heater jigs, for instance, a metal heating jig, may be used for sealing the glass tube 4.
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
  • As explained above, the present invention makes it possible to inexpensively prepare PTC thermistors having excellent properties, and is therefore of industrially high value.

Claims (8)

1. A process for the production of PTC thermistors comprising the step of sealing a positive temperature coefficient semiconductor ceramic material (1) in a low-melting glass (4) having a softening point of no higher than 560°C in the presence of air, oxygen or an air/oxygen mixture containing higher than 0% to lower than 100% volume of air.
2. A process according to Claim 1, characterised in that the glass (4) has a softening point of from 450°C to 560°C inclusive.
3. A process according to Claim 1 or 2, characterised in that the glass (4) is in the form of a tube sealed at both ends.
4. A process according to Claim 3, characterised in that lead wires (3) are inserted into opposite ends of the glass tube (4) prior to the sealing thereof.
5. A process according to Claim 3 or 4, characterised in that electrodes (2) are applied to opposite sides of the semiconductor material (1) prior to its insertion in the glass tube (4).
6. A process according to any one of the preceding claims, characterised in that the glass used is based on B2O3-PbO-ZnO, B203-PbO-SiO2, B203-PbO-TiO2, B2O3-PbO-SiO2-Al2O3-ZnO, B2O3-PbO-V2O5, SiO2-PbO-K20, Si02-PbO-Na20 or SiO2-PbO-K2O-Na2O.
7. A process according to any one of the preceding claims, characterised in that the semiconductor material (1) is a barium titanate ceramic material.
8. A process according to Claim 7, characterised in that the barium titanate ceramic material has added thereto any one of trivalent antimony, trivalent bismuth, pentavalent tantalum, pentavalent niobium or a rare earth metal.
EP84303796A 1983-06-11 1984-06-05 Process for the production of ptc thermistors Expired EP0129997B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP104483/83 1983-06-11
JP58104483A JPS59229803A (en) 1983-06-11 1983-06-11 Method of producing ptc thermistor

Publications (2)

Publication Number Publication Date
EP0129997A1 EP0129997A1 (en) 1985-01-02
EP0129997B1 true EP0129997B1 (en) 1988-08-31

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EP84303796A Expired EP0129997B1 (en) 1983-06-11 1984-06-05 Process for the production of ptc thermistors

Country Status (4)

Country Link
EP (1) EP0129997B1 (en)
JP (1) JPS59229803A (en)
KR (1) KR900005267B1 (en)
DE (1) DE3473801D1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62190302U (en) * 1986-05-23 1987-12-03
DE69114322T2 (en) * 1990-02-22 1996-06-05 Murata Manufacturing Co Method of making a PTC thermistor.
JPH1055903A (en) 1996-08-09 1998-02-24 Mitsubishi Materials Corp Structure of electronic component

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL287531A (en) * 1962-08-11
US3377561A (en) * 1965-07-13 1968-04-09 Bell Telephone Labor Inc Positive temperature coefficient titanate thermistor
LU69220A1 (en) * 1973-06-18 1974-04-08
US4276536A (en) * 1979-09-04 1981-06-30 Scully Electronic Systems, Inc. Self-heating thermistor probe for low temperature applications

Also Published As

Publication number Publication date
DE3473801D1 (en) 1988-10-06
JPS59229803A (en) 1984-12-24
KR900005267B1 (en) 1990-07-21
EP0129997A1 (en) 1985-01-02
JPH0145962B2 (en) 1989-10-05
KR850000811A (en) 1985-03-09

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