WO2013069588A1 - 白金系熱電対 - Google Patents
白金系熱電対 Download PDFInfo
- Publication number
- WO2013069588A1 WO2013069588A1 PCT/JP2012/078576 JP2012078576W WO2013069588A1 WO 2013069588 A1 WO2013069588 A1 WO 2013069588A1 JP 2012078576 W JP2012078576 W JP 2012078576W WO 2013069588 A1 WO2013069588 A1 WO 2013069588A1
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- WO
- WIPO (PCT)
- Prior art keywords
- thermocouple
- wire
- temperature
- present
- alloy
- Prior art date
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
- G01K7/04—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples the object to be measured not forming one of the thermoelectric materials
Definitions
- the present invention relates to a Pt-PtRh-based thermocouple composed of a Pt-to-Pt-Rh alloy.
- thermocouple is one of the most widely used temperature sensors in the industry.
- the thermocouple as this temperature sensor is typically a Pt-PtRh-based thermocouple such as an S thermocouple (Pt to Pt-Rh 10% alloy) or an R thermocouple (Pt to Pt-Rh 13% alloy). It has been known.
- thermocouple high purity platinum (5 N or more) from which impurities are removed as much as possible is usually used as a Pt wire.
- a Pt-Rh alloy is used on the positive electrode (+) side to be a pair. Therefore, when disconnection of the thermocouple occurs during use or handling, most of them occur on the side of the Pt wire which is weak in strength.
- the present invention has been made under the circumstances as described above, and has a Pt-PtRh-based thermocouple which has temperature characteristics equivalent to conventional ones and does not cause breakage of wires during handling or use.
- the purpose is to propose.
- the inventors of the present invention conducted intensive studies on a method of improving the strength of a strand of a Pt-PtRh-based thermocouple, but contrary to expectation, when Pt having an oxide finely dispersed is used as the Pt strand. It has been found that the strength of a Pt wire can be improved while maintaining the temperature characteristics of Pt, and the present invention has been conceived.
- the present invention is characterized in that in a Pt-PtRh-based thermocouple of a Pt-to-Pt-Rh alloy, a Pt wire has a Pt purity of 5 N or more, and an oxide is dispersed.
- thermoelectromotive force is It is known to reduce (see Non-Patent Document 1). Therefore, from the point of view of strengthening the thermocouple wire, mixing of other metals has not been completely omitted.
- the metal is finely dispersed in high purity Pt not as it is in the form of an oxide but as an oxide, the value of the thermoelectromotive force hardly decreases. Was found to improve.
- thermoelectromotive force can realize class 1 (Class 1) level.
- the Pt wire in the Pt-PtRh-based thermocouple according to the present invention is high in creep strength at the same level as the temperature coefficient (TCR) of Pt alone, so that breakage of the Pt wire is difficult to occur.
- TCR temperature coefficient
- a Pt oxide wire is dispersed in an amount of 0.02 to 0.5 mass% of Zr oxide in terms of Zr.
- the temperature coefficient (TCR) at 0 ° C. to 100 ° C. is 3919 ppm / ° C. to 3925 ppm / ° C.
- the creep strength is in the range of 1400 ° C., 10 MPa to 20 MPa and 100 hours or more It will have a breaking strength.
- the Zr oxide content is less than 0.02 mass% in terms of Zr, the high temperature creep strength improvement is insufficient, and if it exceeds 0.5 mass%, the plastic formability is reduced and the shape to be used as a thermocouple is Wire drawing becomes difficult.
- the Pt wire in the Pt—PtRh-based thermocouple according to the present invention can be realized as follows. It is important to prepare Pt with a purity of 5N or more as a starting material so that mixing of impurities other than finely dispersed oxides does not occur. Specifically, high frequency melting of 5N Pt material is performed, and casting Afterward, it is forged and drawn into linear Pt. Using this, it is atomized in water with a flame gun, arc gun or the like to produce Pt powder. The Pt powder is charged into a zirconia pot, and zirconia balls as media and purified water are also charged, and a stirring process is carried out by an attritor having a strengthened platinum agitator.
- the Pt powder and the zirconia balls are separated.
- the separated Pt powder is subjected to high temperature sintering treatment in an inert atmosphere, and then the sintered body is subjected to hot forging and wire drawing treatment to manufacture a Pt wire having a predetermined shape.
- a Pt strand of a Pt-PtRh-based thermocouple can be realized.
- thermocouple which has temperature characteristics equivalent to those of the prior art and does not cause breakage of a Pt wire during handling or use.
- thermocouple Graph showing creep test results Graph showing measurement results of thermoelectromotive force Graph showing the results of measuring the long-term stability of the thermocouple
- the Pt wire of the thermocouple in this embodiment was manufactured as follows. First, a sponge-like high-purity Pt (purity 5N: 99.999% Pt) raw material was charged into an alumina crucible, and high-frequency melting was performed in an air atmosphere. Then, it was cast with a water-cooled copper mold and formed into a rod shape by hot forging the ingot. The rod-like forged product was drawn using a grooved roll to produce a Pt wire of ⁇ 1.37 mm. In addition, one part was drawn to (phi) 0.5 mm, and was used as a material of a comparison control. The characteristics of this Pt wire are shown as Original Pure Pt in FIG. 2 described later and Pure Pt in Table 1 and FIG. + For Pt-RH13% of the side, which has been produced in normal commercial (wire that meets the specifications of JIS C 1602 -1995), Taiashi for electromotive force measurement example shown this, measure all the same thing It is used for
- the temperature coefficient of resistance which is an index of the purity of a Pt wire (hereinafter referred to as an ODS material) in which the manufactured zirconium oxide is dispersed, is 3922 ppm /% in the case of a sponge-like high purity Pt raw material before the stirring process.
- the temperature was 0 ° C. to 100 ° C. in the temperature range of 0 to 100 ° C., and it was found that the produced ODS material had substantially the same temperature characteristics.
- W (Ga) which determines the condition as a standard platinum resistance thermometer for the international temperature scale in 1990, was 1.1800 to 1.11809 compared to the original high purity Pt wire.
- the present ODS material was confirmed to be electrically sufficiently pure although it slightly decreased to 1.11780 to 1.11802.
- the creep test result of the produced ODS material is shown in FIG.
- the relationship between the initial stress at 1400 ° C. of this ODS material and the rupture time is shown.
- the straight line is obtained by measuring conventional oxide dispersion strengthened Pt (trade name: GTH: manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) as a comparison control (K. Maruyama, H. Yamasaki, T. Hamada, Materials Science and Engineering A 510-511 (2009) pp. 312-316 (from High-temperature creep of GTH), the result of this measurement is shown by ⁇ . It was confirmed that the produced ODS material had a strength equal to or more than that of the conventional oxide dispersion strengthened Pt (GTH).
- thermocouple was produced by inserting the ODS material produced and a Pt—Rh 13% alloy wire (positive electrode (+)), which is usually used as a standard, into an insulating tube and joining them.
- thermoelectromotive force of the produced ODS material is shown.
- the measurement of this thermoelectromotive force is carried out by combining the ODS material ( ⁇ 0.5 mm ⁇ 3 m) with Pt-Rh 13% after conducting heat annealing for 3 hours at a current of 14 A (132 V) (corresponding to a temperature of about 1710 ° C.)
- Thermocouples were prepared, and the thermoelectromotive force was measured at each temperature fixed point of Sn, Zn, Al, Ag, Au, and Pd.
- FIG. 2 shows the results of Table 1 in a graph, in which the abscissa represents the measured temperature and the ordinate represents the deviation from the JIS (IEC) standard.
- Original Pure Pt in FIG. 2 is a comparative control material collected from the middle of the manufacturing process of the present ODS material, and manufactured in the same process as that used for a normal commercial thermocouple.
- Pt-Rh 13% of the opposite leg is measured using the same wire.
- thermoelectromotive force is slightly lowered compared to the original high purity Pt, all are values within the Class 1 standard according to the JIS (IEC) standard. There is no problem at all in practical terms.
- FIG. 3 shows the results of measurement of long-term stability of a thermocouple using the present ODS material as a Pt wire of a Pt-to-Pt-Rh alloy thermocouple. It exposed to the temperature of 1400 degreeC and measured the value of Au fixed point regularly. The horizontal axis is the exposure time, and the vertical axis is the deviation of the Au fixed point from the JIS (IEC) standard value. The measurement conditions were measured by changing the applied current to 14 A (corresponding to about 1710 ° C.), 13 A (corresponding to about 1560 ° C.), and 12 A (corresponding to 1420 ° C.). Also, the result of a normal thermocouple using high purity Pt as a control is also shown in FIG.
- thermocouple in the present invention the thermocouple of a conventional article for temperature measurement in high temperature is explained.
- thermocouple of the present invention an ODS material ( ⁇ 0.5 mm ⁇ 3 m) is heated and annealed at a current of 14 A (132 V) (corresponding to a temperature of about 1710 ° C.) for 3 hours, and then combined with Pt-Rh 13%.
- the prepared thermocouple was used, and as a conventional product, a Pt wire containing no oxide was used as a Pt wire.
- Pt-Rh 13% the same lot of normal products was used for both thermocouples.
- thermocouple of the present invention The measurement of durability was performed by installing 13 pairs of the thermocouple of the present invention and the conventional thermocouple in the fining tank of the glass production line. As a result of measurement at 1550 ° C., when used for three months, in the conventional thermocouple, three pairs out of 13 pairs of Pt wires were broken and became unusable. On the other hand, it was found that the thermocouple of the present invention does not have a break and can be used without any problem.
- thermocouple having pure Pt as a leg and a Pt wire of S thermocouple
- it is very hard to break off in high temperature use, substantially almost breaking. It is possible to achieve long-term high-temperature measurement stably, because it is possible to realize a low level of thermocouple.
Abstract
Description
Claims (2)
- Pt対Pt-Rh合金のPt-PtRh系熱電対において、
Pt素線は、Pt純度5N以上であり、酸化物が分散されたことを特徴とするPt-PtRh系熱電対。 - Pt素線は、Zr換算で0.02~0.5質量%のZr酸化物が分散されている請求項1にPt-PtRh系熱電対。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/352,574 US20140328374A1 (en) | 2011-11-11 | 2012-11-05 | Platinum-based thermocouple |
CN201280055500.4A CN103930756B (zh) | 2011-11-11 | 2012-11-05 | 铂系热电偶 |
KR1020147012668A KR101627056B1 (ko) | 2011-11-11 | 2012-11-05 | 백금계 열전대 및 Pt-PtRh계 열전대의 Pt 소선을 제조하는 방법 |
EP12847513.4A EP2778639B1 (en) | 2011-11-11 | 2012-11-05 | Platinum-based thermocouple |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-247104 | 2011-11-11 | ||
JP2011247104A JP5308499B2 (ja) | 2011-11-11 | 2011-11-11 | 白金系熱電対 |
Publications (1)
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WO2013069588A1 true WO2013069588A1 (ja) | 2013-05-16 |
Family
ID=48289962
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2012/078576 WO2013069588A1 (ja) | 2011-11-11 | 2012-11-05 | 白金系熱電対 |
Country Status (7)
Country | Link |
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US (1) | US20140328374A1 (ja) |
EP (1) | EP2778639B1 (ja) |
JP (1) | JP5308499B2 (ja) |
KR (1) | KR101627056B1 (ja) |
CN (1) | CN103930756B (ja) |
TW (1) | TWI548867B (ja) |
WO (1) | WO2013069588A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2512402A (en) * | 2013-02-22 | 2014-10-01 | Weston Aerospace Ltd | Method of producing a thermocouple having a tailored thermoelectric response |
US9786828B2 (en) | 2013-02-22 | 2017-10-10 | Weston Aerospace Limited | Method of producing a thermocouple having a tailored thermoelectric response |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5722515B1 (ja) * | 2014-04-04 | 2015-05-20 | 株式会社フルヤ金属 | 白金熱電対素線 |
JP5769854B1 (ja) * | 2014-09-08 | 2015-08-26 | 石福金属興業株式会社 | 白金族金属又は白金族基合金の製造方法 |
JP6752556B2 (ja) * | 2015-07-31 | 2020-09-09 | 株式会社フルヤ金属 | 熱電対の取り付け構造及び熱電対の取り付け方法 |
CN105483583B (zh) * | 2015-12-25 | 2017-07-28 | 无锡英特派金属制品有限公司 | 弥散强化铂偶丝的制备方法 |
JP6152463B1 (ja) | 2016-07-29 | 2017-06-21 | 株式会社フルヤ金属 | 熱電対 |
GB201615272D0 (en) * | 2016-09-08 | 2016-10-26 | Johnson Matthey Plc | Method |
Citations (5)
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JPH07270251A (ja) | 1994-03-30 | 1995-10-20 | Tanaka Kikinzoku Kogyo Kk | 熱電対の取付け構造 |
JPH08136357A (ja) | 1994-11-11 | 1996-05-31 | Tanaka Kikinzoku Kogyo Kk | 熱電対 |
JP2002012926A (ja) * | 2000-06-28 | 2002-01-15 | Tanaka Kikinzoku Kogyo Kk | 酸化物分散強化型の白金材料及びその製造方法 |
JP2004053502A (ja) * | 2002-07-23 | 2004-02-19 | Sukegawa Electric Co Ltd | 分散強化型貴金属熱電対 |
JP2011158424A (ja) * | 2010-02-03 | 2011-08-18 | Tanaka Kikinzoku Kogyo Kk | 熱電対の取付構造 |
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US3176386A (en) * | 1961-10-26 | 1965-04-06 | Grant | Dispersion strengthening of metals |
GB1280815A (en) * | 1968-07-12 | 1972-07-05 | Johnson Matthey Co Ltd | Improvements in and relating to the dispersion strengthening of metals |
DE19531242C1 (de) * | 1995-08-25 | 1996-10-31 | Degussa | Warmfester Platinwerkstoff |
US6070437A (en) * | 1998-11-12 | 2000-06-06 | Owens Corning Fiberglas Technology, Inc. | Tip-plate thermocouple |
DE10046456C2 (de) * | 2000-09-18 | 2003-04-10 | Heraeus Gmbh W C | Durch feinverteilte, kleine Teilchen aus Unedelmetalloxid dispersionsverfestigter, goldfreier Platin-Werkstoff |
CA2410805C (en) * | 2001-04-13 | 2008-01-22 | Tanaka Kikinzoku Kogyo K.K. | Method for preparing reinforced platinum material |
US7611280B2 (en) * | 2003-12-16 | 2009-11-03 | Harco Laboratories, Inc. | EMF sensor with protective sheath |
US7044638B2 (en) * | 2004-05-24 | 2006-05-16 | Rosemount Aerospace, Inc. | Multi-element thermocouple |
US20090047170A1 (en) * | 2004-10-08 | 2009-02-19 | Toru Shoji | Oxide-Dispersion Strengthened Platinum Material |
CN101561321B (zh) * | 2009-05-18 | 2010-11-17 | 无锡英特派金属制品有限公司 | 弥散强化铂铑10-铂热电偶丝及其生产方法 |
CN101561322B (zh) * | 2009-05-18 | 2010-11-17 | 无锡英特派金属制品有限公司 | 弥散强化铂铑13-铂热电偶丝及其生产方法 |
-
2011
- 2011-11-11 JP JP2011247104A patent/JP5308499B2/ja active Active
-
2012
- 2012-11-05 KR KR1020147012668A patent/KR101627056B1/ko active IP Right Grant
- 2012-11-05 WO PCT/JP2012/078576 patent/WO2013069588A1/ja active Application Filing
- 2012-11-05 CN CN201280055500.4A patent/CN103930756B/zh active Active
- 2012-11-05 EP EP12847513.4A patent/EP2778639B1/en active Active
- 2012-11-05 US US14/352,574 patent/US20140328374A1/en not_active Abandoned
- 2012-11-09 TW TW101141733A patent/TWI548867B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH07270251A (ja) | 1994-03-30 | 1995-10-20 | Tanaka Kikinzoku Kogyo Kk | 熱電対の取付け構造 |
JPH08136357A (ja) | 1994-11-11 | 1996-05-31 | Tanaka Kikinzoku Kogyo Kk | 熱電対 |
JP2002012926A (ja) * | 2000-06-28 | 2002-01-15 | Tanaka Kikinzoku Kogyo Kk | 酸化物分散強化型の白金材料及びその製造方法 |
JP2004053502A (ja) * | 2002-07-23 | 2004-02-19 | Sukegawa Electric Co Ltd | 分散強化型貴金属熱電対 |
JP2011158424A (ja) * | 2010-02-03 | 2011-08-18 | Tanaka Kikinzoku Kogyo Kk | 熱電対の取付構造 |
Non-Patent Citations (3)
Title |
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JOHN COCHRANE: "Relationship of chemical composition to the electrical properties of platinum", TEMPERATURE ITS MEASUREMENT AND CONTROL IN SCIENCE AND INDUSTRY, vol. 4, 1972, pages 1619 - 1632 |
K. MARUYAMA; H. YAMASAKI; T. HAMADA, MATERIALS SCIENCE AND ENGINEERING, vol. A 510-51, 2009, pages 312 - 316 |
See also references of EP2778639A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2512402A (en) * | 2013-02-22 | 2014-10-01 | Weston Aerospace Ltd | Method of producing a thermocouple having a tailored thermoelectric response |
US9786828B2 (en) | 2013-02-22 | 2017-10-10 | Weston Aerospace Limited | Method of producing a thermocouple having a tailored thermoelectric response |
GB2512402B (en) * | 2013-02-22 | 2018-04-04 | Weston Aerospace Ltd | Method of producing a thermocouple having a tailored thermoelectric response |
Also Published As
Publication number | Publication date |
---|---|
CN103930756A (zh) | 2014-07-16 |
EP2778639B1 (en) | 2017-06-28 |
TWI548867B (zh) | 2016-09-11 |
CN103930756B (zh) | 2016-02-03 |
JP5308499B2 (ja) | 2013-10-09 |
KR20140081866A (ko) | 2014-07-01 |
JP2013104705A (ja) | 2013-05-30 |
EP2778639A4 (en) | 2015-07-01 |
TW201337225A (zh) | 2013-09-16 |
EP2778639A1 (en) | 2014-09-17 |
KR101627056B1 (ko) | 2016-06-03 |
US20140328374A1 (en) | 2014-11-06 |
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