WO2018117135A1 - Alliage d'iridium résistant à la chaleur - Google Patents

Alliage d'iridium résistant à la chaleur Download PDF

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Publication number
WO2018117135A1
WO2018117135A1 PCT/JP2017/045632 JP2017045632W WO2018117135A1 WO 2018117135 A1 WO2018117135 A1 WO 2018117135A1 JP 2017045632 W JP2017045632 W JP 2017045632W WO 2018117135 A1 WO2018117135 A1 WO 2018117135A1
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WIPO (PCT)
Prior art keywords
element group
mass
alloy
heat
oxidation
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PCT/JP2017/045632
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English (en)
Japanese (ja)
Inventor
俊介 横田
土井　義規
亮平 秋吉
端無　憲
Original Assignee
石福金属興業株式会社
株式会社デンソー
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.)
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Priority claimed from JP2017242366A external-priority patent/JP7057935B2/ja
Application filed by 石福金属興業株式会社, 株式会社デンソー filed Critical 石福金属興業株式会社
Priority to CN201780079568.9A priority Critical patent/CN110139939A/zh
Priority to US16/471,054 priority patent/US11131008B2/en
Priority to DE112017006519.4T priority patent/DE112017006519T5/de
Publication of WO2018117135A1 publication Critical patent/WO2018117135A1/fr
Priority to US17/412,661 priority patent/US11773473B2/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal

Definitions

  • the present invention relates to a heat resistant Ir alloy.
  • Main heat-resistant materials include heat-resistant steel, nickel-base superalloy, platinum alloy, tungsten and the like. Heat resistant steels, nickel-base superalloys, platinum alloys, etc. cannot be used at temperatures above 2000 ° C. because the solidus point is less than 2000 ° C. On the other hand, refractory metals such as tungsten and molybdenum are heavily oxidized and consumed in a high temperature atmosphere. Therefore, an Ir alloy has been developed as a heat-resistant material having a high melting point and high oxidation resistance.
  • Patent Document 1 discloses an IrRh alloy to which 3 wt% to 30 wt% of Rh is added in order to prevent high temperature volatility of Ir used for a noble metal tip of a spark plug for an internal combustion engine. It is described that by using such an alloy, a chip having excellent high-temperature heat resistance and improving wear resistance can be obtained.
  • Ir alloys used as heat-resistant materials are required to further increase the high-temperature strength while ensuring oxidation resistance at high temperatures.
  • an object of the present invention is to provide an Ir alloy that is excellent in high-temperature strength while ensuring oxidation resistance at high temperatures.
  • the present invention Rh 5-30 mass%, As element group A, at least one element of Ta and Re is 0.3 to 5 mass%, 0-5 mass% of at least one element of Cr, Ni, Co as the element group B, Element group A and element group B are contained in a total of 5 mass% or less, When the element belonging to the element group A is Re, the element belonging to the element group B is Co alone or Cr alone, or two or more kinds from Co, Cr and Ni. This is a heat-resistant Ir alloy.
  • Example 2 is a tissue observation image of Example 1.
  • Rh is 5 to 30 mass%
  • at least one element of Ta and Re as element group A is 0.3 to 5 mass%
  • at least one element of Cr, Ni, and Co is 0 to 5 mass% as element group B.
  • the element group A and the element group B are contained in a total of 5 mass% or less and the element belonging to the element group A is Re
  • the element belonging to the element group B is Co alone or Cr alone, or Co, Cr
  • Rh is 5 to 30 mass%
  • Ta is 0.3 to 5 mass%
  • element group B is at least one element of Co, Cr, and Ni, 0 to 5 mass%
  • Ta and element group B are combined.
  • the heat-resistant Ir alloy is characterized by containing 5 mass% or less.
  • the element group B containing 0 to 5 mass% of at least one element of Co, Cr, and Ni means that the element group B does not contain elements of Co, Cr and Ni, or contains 5 mass% or less.
  • the content of Ta is preferably 0.5 mass% or more.
  • the Ta content is more preferably 0.7 mass% or more.
  • Rh is 5 to 30 mass%
  • Ta is the element group A
  • Re is 0.3 to 5 mass% in total
  • the element group B is at least one element of Co, Cr, and Ni is 0 to 5 mass%
  • It is a heat resistant Ir alloy characterized by containing a total of 5 mass% of element group A and element group B.
  • the element group B containing 0 to 5 mass% of at least one element of Co, Cr, and Ni means that the element group B does not contain elements of Co, Cr and Ni, or contains 5 mass% or less.
  • the content of the element group A is preferably 0.5 mass% or more. As for content of the element group A, 0.7 mass% or more is more preferable.
  • Rh is 5 to 30 mass%
  • Re is 0.3 to 5 mass%
  • element group B is Co alone or Cr alone, or two or more kinds of Co, Cr, and Ni in total 0.1.
  • a heat-resistant Ir alloy characterized by containing up to 4.7 mass%, Re and element group B in total of 5 mass% or less.
  • Ir alloys containing 5-30 mass% of Rh suppress the oxidation and volatilization of Ir from the crystal grain boundaries in a high-temperature atmosphere or oxidizing atmosphere, and the oxidation consumption resistance is remarkably improved. If the Rh content is less than 5 mass%, the oxidation resistance of the Ir alloy is insufficient. On the other hand, if the Rh content exceeds 30 mass%, the oxidation resistance and wear resistance of the Ir alloy is good, but the melting point and recrystallization temperature are lowered.
  • An IrRh alloy containing 0.3 to 5 mass% of element group A has improved strength due to solid solution hardening by element group A. Moreover, since the recrystallization temperature also rises, softening at a high temperature is suppressed.
  • the element group A is Ta alone or both Ta and Re, the effect of increasing the high temperature strength and the recrystallization temperature is higher than that of Re alone, and a composite oxide film of Ta and Rh is formed in the atmosphere near 1000 ° C. Oxidation resistance is improved.
  • the content of the element group A is less than 0.3 mass%, the IrRh alloy has little solid solution hardening and the strength is insufficient.
  • the content of the element group A is preferably 0.5 mass% or more. As for content of the element group A, 0.7 mass% or more is more preferable.
  • the strength of the IrRhA alloy containing 5 mass% or less of element group B is further improved by solid solution hardening with element group B.
  • the element group B is oxidized in a high temperature atmosphere (for example, 1200 ° C. or more) or an oxidizing atmosphere and the oxide is distributed at the grain boundaries, the outdiffusion of Ir and the subsequent oxidation and volatilization are suppressed. It is possible to increase the wear resistance. If the content of the element group B exceeds 5 mass%, the oxide of the element group B becomes excessive, and on the contrary, the oxidation consumption resistance is lowered and the melting point is also lowered.
  • the content of the element group B is preferably 0.3 mass% or more.
  • Each of the above alloys is a single-phase solid solution that does not have a second phase, so it has good ductility and can be plastically processed into various shapes and dimensions by known warm processing or hot processing. Machining and welding are also easy.
  • Table 1 shows the compositions of the alloys of Examples and Comparative Examples
  • Table 2 shows the test results.
  • each raw material powder Ir powder, Rh powder, Ta powder, Re powder, Cr powder, Ni powder, Co powder
  • the obtained mixed powder was molded using a uniaxial pressure molding machine to obtain a green compact.
  • the obtained green compact was melted by an arc melting method to produce an ingot.
  • the produced ingot was hot forged at 1500 ° C. or more to obtain a 15 mm wide square bar.
  • This square bar was subjected to groove rolling, swaging and die drawing at 1000 ° C. to 1400 ° C. to obtain a wire having a diameter of 0.5 mm.
  • Oxidation resistance was defined as mass change in the high temperature oxidation test.
  • the surface area S (mm ⁇ 2 >) of the test piece was computed from the dimension of the test piece.
  • oxidation consumption resistance was performed at 1000 ° C. in view of the characteristic that Ir is easily oxidized and consumed at around 1000 ° C., and also at 1200 ° C. to evaluate oxidation resistance consumption at higher temperatures.
  • oxidation resistance at 1000 ° C. indicated that the alloy having ⁇ M of ⁇ 0.10 or more was particularly good in oxidation resistance consumption (small amount of oxidation consumption), and is indicated by a symbol “ ⁇ ” in Table 2.
  • An alloy having ⁇ M of less than ⁇ 0.10 and ⁇ 0.25 or more has good oxidation resistance, and is indicated by a symbol ⁇ in Table 2. Alloys with ⁇ M less than ⁇ 0.25 are considered to have poor oxidation consumption resistance (high oxidation consumption) and are indicated by a symbol x in Table 2.
  • oxidation wear resistance at 1200 ° C. indicated that the alloy having ⁇ M of ⁇ 0.20 or more has particularly good oxidation wear resistance (low oxidation consumption), and is indicated by symbol ⁇ in Table 2.
  • An alloy having ⁇ M of less than ⁇ 0.20 and ⁇ 0.35 or more has good oxidation resistance and is indicated by a symbol “ ⁇ ” in Table 2.
  • An alloy having ⁇ M of less than ⁇ 0.35 has poor oxidation consumption resistance (high oxidation consumption) and is indicated by a symbol x in Table 2.
  • the solid phase point was evaluated by heating each test piece to 2100 ° C. with an electric furnace in an Ar atmosphere and observing the appearance and cross section.
  • the cross section was polished, and the polished surface was observed with a metal microscope (magnification 100 times) after Ar ion etching. If there was no change in the external appearance and the cross section, the solid phase point was 2100 ° C. or higher ( ⁇ ), and if the trace of melting was observed in the external appearance or the cross section, the solid phase point was set below 2100 ° C. ( ⁇ ).
  • the recrystallization temperature is obtained by treating the test piece for 30 minutes at 1000 ° C., 1050 ° C., 1100 ° C., 1150 ° C., 1200 ° C., 1250 ° C., and 1300 ° C. in an electric furnace in an Ar atmosphere, and polishing the cross section of the test piece, The polished surface was determined by Ar ion etching and observing the structure with a metal microscope (magnification 100 times). One test piece was heat-treated at one temperature.
  • the heat treatment temperature of the test piece in which recrystallized grains were observed was defined as the recrystallization temperature of the alloy.
  • the recrystallization temperature was set to 1100 ° C.
  • the recrystallization temperature was evaluated as ⁇ when the temperature was 1000 ° C. or lower, ⁇ when the temperature was higher than 1000 ° C. and lower than 1100 ° C., and ⁇ when the temperature was higher than 1100 ° C.
  • the high temperature strength was determined by a tensile test at a high temperature.
  • the test piece used was a wire of ⁇ 0.5 ⁇ 150 mm annealed at 1500 ° C.
  • the tensile test conditions were a temperature of 1200 ° C., an air atmosphere, and a crosshead speed of 10 mm / min.
  • the high temperature strength was evaluated as ⁇ for 200 MPa or less, ⁇ for more than 200 MPa and 400 MPa or less, and ⁇ for more than 400 MPa.
  • the oxidation consumption resistance at 1000 ° C. is ⁇
  • the oxidation resistance consumption at 1000 ° C. in Examples 22 and 23 is ⁇ . Is better than Re addition. Further, it can be seen from the comparison between Examples 11 and 22 and the comparison between Examples 21 and 23 that the Ta recrystallization temperature and the high temperature strength are better than the Re addition.
  • the high-temperature strength is improved by the addition of Cr.
  • the high temperature strength is improved by adding Ni.
  • the high temperature strength is improved by the addition of Co.
  • the alloy of the example can be plastically processed to a fine wire of ⁇ 0.5 mm, and products of various shapes can be easily obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention concerne un alliage d'Ir qui présente une excellente résistance à haute température, tout en assurant une résistance à l'usure par oxydation à haute température. Un alliage d'Ir résistant à la chaleur selon l'invention est caractérisé en ce qu'il contient de 5 à 30 % en masse de Rh, de 0,3 à 5 % en masse d'un groupe d'éléments A qui est composé d'au moins un élément parmi le Ta et le Re, et de 0 à 5 % en masse d'un groupe d'éléments B qui est composé d'au moins un élément parmi le Co, le Cr et le Ni, le total du groupe d'éléments A et du groupe d'éléments B étant de 5 % en masse ou moins. Leidt alliage d'Ir résistant à la chaleur est également caractérisé en ce que dans les cas où le groupe d'éléments A est composé de Re, le groupe d'éléments B est composé uniquement de Co ou de Cr, ou il est en variante composé d'au moins deux éléments choisis parmi le Co, le Cr et le Ni.
PCT/JP2017/045632 2016-12-22 2017-12-20 Alliage d'iridium résistant à la chaleur WO2018117135A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780079568.9A CN110139939A (zh) 2016-12-22 2017-12-20 耐热性铱合金
US16/471,054 US11131008B2 (en) 2016-12-22 2017-12-20 Heat-resistant Ir alloy
DE112017006519.4T DE112017006519T5 (de) 2016-12-22 2017-12-20 Hitzebeständige Ir-Legierung
US17/412,661 US11773473B2 (en) 2016-12-22 2021-08-26 Heat-resistant IR alloy

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016249860 2016-12-22
JP2016-249860 2016-12-22
JP2017242366A JP7057935B2 (ja) 2016-12-22 2017-12-19 耐熱性Ｉｒ合金
JP2017-242366 2017-12-19

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US16/471,054 A-371-Of-International US11131008B2 (en) 2016-12-22 2017-12-20 Heat-resistant Ir alloy
US17/412,661 Continuation-In-Part US11773473B2 (en) 2016-12-22 2021-08-26 Heat-resistant IR alloy

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WO2018117135A1 true WO2018117135A1 (fr) 2018-06-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10938186B2 (en) 2017-12-19 2021-03-02 Denso Corporation Spark plug electrode and spark plug
JP7470937B2 (ja) 2020-11-30 2024-04-19 石福金属興業株式会社 耐熱性Ｉｒ合金

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005533924A (ja) * 2002-07-13 2005-11-10 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 合金
WO2008013159A1 (fr) * 2006-07-25 2008-01-31 Tanaka Kikinzoku Kogyo K.K. Alliage de métal noble pour bougie d'allumage et son procédé de fabrication et de traitement
JP2014075296A (ja) * 2012-10-05 2014-04-24 Ngk Spark Plug Co Ltd スパークプラグ
WO2016189826A1 (fr) * 2015-05-28 2016-12-01 日本特殊陶業株式会社 Bougie d'allumage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005533924A (ja) * 2002-07-13 2005-11-10 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 合金
WO2008013159A1 (fr) * 2006-07-25 2008-01-31 Tanaka Kikinzoku Kogyo K.K. Alliage de métal noble pour bougie d'allumage et son procédé de fabrication et de traitement
JP2014075296A (ja) * 2012-10-05 2014-04-24 Ngk Spark Plug Co Ltd スパークプラグ
WO2016189826A1 (fr) * 2015-05-28 2016-12-01 日本特殊陶業株式会社 Bougie d'allumage

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10938186B2 (en) 2017-12-19 2021-03-02 Denso Corporation Spark plug electrode and spark plug
JP7470937B2 (ja) 2020-11-30 2024-04-19 石福金属興業株式会社 耐熱性Ｉｒ合金

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