WO2018117135A1 - Heat-resistant ir alloy - Google Patents

Heat-resistant ir alloy Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
element group
mass
alloy
heat
oxidation
Prior art date
Application number
PCT/JP2017/045632
Other languages
French (fr)
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.)
Filing date
Publication date
Priority claimed from JP2017242366A external-priority patent/JP7057935B2/en
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 US16/471,054 priority Critical patent/US11131008B2/en
Priority to CN201780079568.9A priority patent/CN110139939A/en
Priority to DE112017006519.4T priority patent/DE112017006519T5/en
Publication of WO2018117135A1 publication Critical patent/WO2018117135A1/en
Priority to US17/412,661 priority patent/US11773473B2/en

Links

Images

Classifications

    • 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.

Abstract

The purpose of the present invention is to provide an Ir alloy which exhibits excellent high-temperature strength, while ensuring oxidation wear resistance at high temperatures. A heat-resistant Ir alloy according to the present invention is characterized by containing 5-30 mass% of Rh, 0.3-5 mass% of an element group A that is composed of at least one of Ta and Re, and 0-5 mass% of an element group B that is composed of at least one of Co, Cr and Ni, with the total of the element group A and the element group B being 5 mass% or less. This heat-resistant Ir alloy is also characterized in that in cases where the element group A is composed of Re, the element group B is composed only of Co or Cr, or is alternatively composed of two or more elements selected from among Co, Cr and Ni.

Description

耐熱性Ｉｒ合金Heat resistant Ir alloy
　本発明は、耐熱性Ｉｒ合金に関する。 The present invention relates to a heat resistant Ir alloy.
　高温用るつぼ、耐熱器具、ガスタービン、スパークプラグ、高温用センサ、ジェットエンジンなどに用いる耐熱材料として種々の合金が開発されている。主な耐熱材料として耐熱鋼、ニッケル基超合金、白金合金、タングステンなどが挙げられる。耐熱鋼、ニッケル基超合金、白金合金などは固相点が２０００℃未満でそれ以上の温度では使用できない。一方、タングステンやモリブデンなどの高融点金属は高温の大気中では酸化消耗が激しい。そこで高融点であって、かつ、耐酸化消耗性の高い耐熱材料としてＩｒ合金が開発されている。 Various alloys have been developed as heat-resistant materials for use in high-temperature crucibles, heat-resistant appliances, gas turbines, spark plugs, high-temperature sensors, jet engines, and the like. 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.
　特許文献１には、内燃機関用スパークプラグの貴金属チップに用いる、Ｉｒの高温揮発性を防止するためにＲｈを３ｗｔ％～３０ｗｔ％添加したＩｒＲｈ合金が開示されている。そのような合金を採用することにより高温耐熱性に優れ、耐消耗性を向上させるチップが得られることが記載されている。 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.
特開平０９－００７７３３JP 09-007733 A
　耐熱材料として用いられるＩｒ合金は、高温における耐酸化消耗性を確保しつつ、高温強度をさらに高めることが求められている。 Ir alloys used as heat-resistant materials are required to further increase the high-temperature strength while ensuring oxidation resistance at high temperatures.
　そこで、本発明の目的は、高温における耐酸化消耗性を確保しつつ、高温強度に優れるＩｒ合金を提供することである。 Therefore, 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.
　本発明は、
　Ｒｈを５～３０ｍａｓｓ％、
　元素群ＡとしてＴａ、Ｒｅの少なくとも一種の元素を０．３～５ｍａｓｓ％、
　元素群ＢとしてＣｒ、Ｎｉ、Ｃｏの少なくとも一種の元素を０～５ｍａｓｓ％、
　元素群Ａと元素群Ｂとを合計で５ｍａｓｓ％以下含有し、
　元素群Ａに属する元素がＲｅである場合は、元素群Ｂに属する元素はＣｏ単独又はＣｒ単独、若しくは、Ｃｏ、Ｃｒ、Ｎｉから二種以上である、
　ことを特徴とする耐熱性Ｉｒ合金である。 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.
　本発明によれば、高温における耐酸化消耗性を確保しつつ、高温強度に優れたＩｒ合金を提供することができる。 According to the present invention, it is possible to provide an Ir alloy excellent in high temperature strength while ensuring oxidation resistance at high temperatures.
実施例１の組織観察像である。2 is a tissue observation image of Example 1.
　本発明は、Ｒｈを５～３０ｍａｓｓ％、元素群ＡとしてＴａ、Ｒｅの少なくとも一種の元素を０．３～５ｍａｓｓ％、元素群ＢとしてＣｒ、Ｎｉ、Ｃｏの少なくとも一種の元素を０～５ｍａｓｓ％、元素群Ａと元素群Ｂとを合計で５ｍａｓｓ％以下含有し、元素群Ａに属する元素がＲｅである場合は、元素群Ｂに属する元素はＣｏ単独又はＣｒ単独、若しくは、Ｃｏ、Ｃｒ、Ｎｉから二種以上であることを特徴とする耐熱性Ｉｒ合金である。 In the present invention, Rh is 5 to 30 mass%, at least one element of Ta and Re as element group A is 0.3 to 5 mass%, and at least one element of Cr, Ni, and Co is 0 to 5 mass% as element group B. In addition, when 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, It is a heat-resistant Ir alloy characterized by being two or more types from Ni.
　より具体的には、Ｒｈを５～３０ｍａｓｓ％、Ｔａを０．３～５ｍａｓｓ％、元素群ＢとしてＣｏ、Ｃｒ、Ｎｉの少なくとも一種の元素を０～５ｍａｓｓ％、Ｔａと元素群Ｂとを合計で５ｍａｓｓ％以下含有することを特徴とする耐熱性Ｉｒ合金である。ここで、元素群ＢとしてＣｏ、Ｃｒ、Ｎｉの少なくとも一種の元素を０～５ｍａｓｓ％含むとは、元素群ＢとしてＣｏ、Ｃｒ、Ｎｉの元素を含まないか、または５ｍａｓｓ％以下含むことを意味する。Ｔａの含有量は０．５ｍａｓｓ％以上が好ましい。Ｔａの含有量は０．７ｍａｓｓ％以上がより好ましい。 More specifically, 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%, and Ta and element group B are combined. The heat-resistant Ir alloy is characterized by containing 5 mass% or less. Here, 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. To do. The content of Ta is preferably 0.5 mass% or more. The Ta content is more preferably 0.7 mass% or more.
　また具体的には、Ｒｈを５～３０ｍａｓｓ％、元素群ＡとしてＴａ、Ｒｅを合計で０．３～５ｍａｓｓ％、元素群ＢとしてＣｏ、Ｃｒ、Ｎｉの少なくとも一種の元素を０～５ｍａｓｓ％、元素群Ａと元素群Ｂとを合計で５ｍａｓｓ％以下含有することを特徴とする耐熱性Ｉｒ合金である。ここで、元素群ＢとしてＣｏ、Ｃｒ、Ｎｉの少なくとも一種の元素を０～５ｍａｓｓ％含むとは、元素群ＢとしてＣｏ、Ｃｒ、Ｎｉの元素を含まないか、または５ｍａｓｓ％以下含むことを意味する。元素群Ａの含有量は０．５ｍａｓｓ％以上が好ましい。元素群Ａの含有量は０．７ｍａｓｓ％以上がより好ましい。 More specifically, Rh is 5 to 30 mass%, Ta is the element group A, and Re is 0.3 to 5 mass% in total, and 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. Here, 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. To do. 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.
　また具体的には、Ｒｈを５～３０ｍａｓｓ％、Ｒｅを０．３～５ｍａｓｓ％、元素群Ｂとして、Ｃｏ単独又はＣｒ単独、若しくは、Ｃｏ、Ｃｒ、Ｎｉから二種以上を合計で０．１～４．７ｍａｓｓ％、Ｒｅと元素群Ｂとを合計で５ｍａｓｓ％以下含有することを特徴とする耐熱性Ｉｒ合金である。 Specifically, 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.
　Ｒｈを５～３０ｍａｓｓ％含有するＩｒ合金は、高温の大気又は酸化雰囲気において結晶粒界からのＩｒの酸化揮発が抑制され、耐酸化消耗性が著しく改善される。Ｒｈの含有量が５ｍａｓｓ％を下回る場合には、Ｉｒ合金の耐酸化消耗性が不十分である。一方、Ｒｈの含有量が３０ｍａｓｓ％を超えると、Ｉｒ合金の耐酸化消耗性は良いが、融点及び再結晶温度が低下する。 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.
　元素群Ａを０．３～５ｍａｓｓ％含有するＩｒＲｈ合金は、元素群Ａによる固溶硬化により強度が向上する。また再結晶温度も上昇するため高温での軟化が抑制される。元素群ＡがＴａ単独又はＴａとＲｅ両方の場合、Ｒｅ単独の場合よりも高温強度及び再結晶温度上昇の効果が高く，１０００℃付近の大気中ではＴａとＲｈの複合酸化膜を形成し，耐酸化消耗性が改善される。元素群Ａの含有量が０．３ｍａｓｓ％を下回るとＩｒＲｈ合金の固溶硬化が少なく強度が不十分である。一方、元素群Ａの含有量が５ｍａｓｓ％を超えるとＩｒＲｈ合金の強度はさらに高まり、塑性変形能が低下して加工が困難になるとともに、同元素群の酸化が顕著になり耐酸化消耗性が低下する。元素群Ａの含有量は０．５ｍａｓｓ％以上が好ましい。元素群Ａの含有量は０．７ｍａｓｓ％以上がより好ましい。 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. When 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. When 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. On the other hand, when the content of the element group A exceeds 5 mass%, the strength of the IrRh alloy is further increased, the plastic deformability is lowered and the processing becomes difficult, and the oxidation of the element group becomes remarkable and the oxidation consumption resistance is increased. descend. 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.
　元素群Ｂを５ｍａｓｓ％以下含有するＩｒＲｈＡ合金は、元素群Ｂによる固溶硬化によりさらに強度が向上する。また、高温（例えば１２００℃以上）の大気中又は酸化雰囲気において元素群Ｂが酸化してその酸化物が粒界に分布することによりＩｒの外方拡散及びそれに続く酸化揮発を抑制するため、耐酸化消耗性を高めることができる。元素群Ｂの含有量が５ｍａｓｓ％を超えると、元素群Ｂの酸化物が過剰となり、かえって耐酸化消耗性が低下するとともに、融点も低下する。元素群Ｂの含有量は０．３ｍａｓｓ％以上が好ましい。 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. In addition, since 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.
　上記の各合金は、各々が第２相を持たない単相の固溶体であるため展延性が良好で、公知の温間加工又は熱間加工により、いろいろな形状・寸法に塑性加工することができ、機械加工及び溶接も容易である。 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.
　本発明の実施例について説明する。実施例及び比較例の合金の組成を表１に、試験結果を表２に示す。
　まず、各原料粉末（Ｉｒ粉末、Ｒｈ粉末、Ｔａ粉末、Ｒｅ粉末、Ｃｒ粉末、Ｎｉ粉末、Ｃｏ粉末）を所定の割合で混合し、混合粉末を作製した。次いで、得られた混合粉末を一軸加圧成形機を用いて成形し圧粉体を得た。得られた圧粉体をアーク溶解法により溶解し、インゴットを作製した。 Examples of the present invention will be described. Table 1 shows the compositions of the alloys of Examples and Comparative Examples, and Table 2 shows the test results.
First, each raw material powder (Ir powder, Rh powder, Ta powder, Re powder, Cr powder, Ni powder, Co powder) was mixed at a predetermined ratio to produce a mixed powder. Next, 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.
　次いで、作製したインゴットを１５００℃以上で熱間鍛造し、幅１５ｍｍの角棒とした。この角棒を１０００℃～１４００℃で溝圧延、スウェージング加工及びダイス伸線加工してφ０．５ｍｍの線材を得た。 Next, 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.
　加工性はインゴットから伸線までの上記加工工程にて、評価した。φ０．５の線材を得られたものを○、加工途中で割れが発生して線材が得られなかったものを×とした。 Processability was evaluated in the above processing steps from ingot to wire drawing. The case where a wire having a diameter of 0.5 was obtained was marked with ◯, and the case where a wire was not obtained due to cracking during the machining was marked with x.
　耐酸化消耗性の評価は、線材を長さ０．８ｍｍ切り出した各試験片を用いて高温酸化試験により行った。高温酸化試験は、電気炉内に試験片をセットし、大気中、１０００℃、１２００℃の条件で２０時間保持した。耐酸化消耗性は、前記高温酸化試験における質量変化と定義した。質量変化ΔＭ（ｍｇ／ｍｍ２）は、試験片の試験前の質量をＭ０（ｍｇ）、試験後の質量をＭ１（ｍｇ）、試験片の試験前の表面積をＳ（ｍｍ２）とし、ΔＭ＝（Ｍ１－Ｍ０）／Ｓの式から求めた。また、試験片の表面積Ｓ（ｍｍ２）は、試験片の寸法から算出した。 The evaluation of oxidation resistance was performed by a high-temperature oxidation test using each test piece obtained by cutting a wire 0.8 mm in length. In the high-temperature oxidation test, a test piece was set in an electric furnace and held in the atmosphere at 1000 ° C. and 1200 ° C. for 20 hours. Oxidation resistance was defined as mass change in the high temperature oxidation test. The mass change ΔM (mg / mm 2 ) is defined as M0 (mg) before the test of the test piece, M1 (mg) after the test, and S (mm 2 ) as the surface area of the test piece before the test. = (M1-M0) / S. Moreover, the surface area S (mm < 2 >) of the test piece was computed from the dimension of the test piece.
　耐酸化消耗性の評価は、Ｉｒが１０００℃付近で酸化消耗しやすいという特性に鑑み１０００℃で実施するとともに、より高温での耐酸化消耗を評価するため、１２００℃でも評価した。 The evaluation of 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.
　１０００℃での耐酸化消耗性の評価は、ΔＭが－０．１０以上の合金は耐酸化消耗性が特に良好（酸化消耗量が少ない）とし、表２に記号◎で示した。ΔＭが－０．１０未満、－０．２５以上の合金は耐酸化消耗性が良好とし、表２に記号○で示した。ΔＭが－０．２５未満の合金は耐酸化消耗性が悪い（酸化消耗量が多い）とし、表２に記号×で示した The evaluation of oxidation resistance at 1000 ° C. indicated that the alloy having ΔM of −0.10 or more was particularly good in oxidation resistance consumption (small amount of oxidation consumption), and is indicated by a symbol “記号” in Table 2. An alloy having ΔM 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 ΔM 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.
　１２００℃での耐酸化消耗性の評価は、ΔＭが－０．２０以上の合金は耐酸化消耗性が特に良好（酸化消耗量が少ない）とし、表２に記号◎で示した。ΔＭが－０．２０未満、－０．３５以上の合金は耐酸化消耗性が良好とし、表２に記号○で示した。ΔＭが－０．３５未満の合金は耐酸化消耗性が悪い（酸化消耗量が多い）とし、表２に記号×で示した。 The evaluation of oxidation wear resistance at 1200 ° C. indicated that the alloy having ΔM 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 ΔM 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 ΔM of less than −0.35 has poor oxidation consumption resistance (high oxidation consumption) and is indicated by a symbol x in Table 2.
　固相点は、各試験片をＡｒ雰囲気の電気炉で２１００℃まで昇温し、外観及び断面を観察することで評価した。断面は研磨し、その研磨面をＡｒイオンエッチング後、金属顕微鏡（倍率１００倍）で観察した。外観及び断面に変化が無ければ固相点２１００℃以上（○）、外観又は断面で溶融の痕跡が認められれば固相点２１００℃未満（×）とした。 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. (×).
　再結晶温度は、試験片をＡｒ雰囲気の電気炉中で１０００℃、１０５０℃、１１００℃、１１５０℃、１２００℃、１２５０℃、１３００℃にて３０ｍｉｎ処理し、その試験片の断面を研磨し、研磨面をＡｒイオンエッチングして金属顕微鏡（倍率１００倍）で組織観察して決定した。一つの試験片について一つの温度で熱処理した。 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.
　組織観察の結果、再結晶粒が認められた試験片の熱処理温度をその合金の再結晶温度と定義した。例えば図１に示すように１０００℃で再結晶粒が認められず、１１００℃で再結晶粒が認められた場合、再結晶温度を１１００℃とした。再結晶温度は１０００℃以下を△，１０００℃超１１００℃以下を○，１１００℃超を◎と評価した。 As a result of structural observation, the heat treatment temperature of the test piece in which recrystallized grains were observed was defined as the recrystallization temperature of the alloy. For example, as shown in FIG. 1, when recrystallized grains were not observed at 1000 ° C. and recrystallized grains were observed at 1100 ° C., the recrystallization temperature was set to 1100 ° C. The recrystallization temperature was evaluated as Δ 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.
　高温強度は高温での引張試験によって引張強さを求めた。試験片は、φ０．５×１５０ｍｍの線材を１５００℃で焼鈍して用いた。引張試験の条件は、温度１２００℃、大気中、クロスヘッドスピード１０ｍｍ／ｍｉｎとした。高温強度は２００ＭＰａ以下を△、２００ＭＰａ超４００ＭＰａ以下を○、４００ＭＰａ超を◎と評価した。 The high temperature strength was determined by a tensile test at a high temperature. The test piece used was a wire of φ0.5 × 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 Δ for 200 MPa or less, ◯ for more than 200 MPa and 400 MPa or less, and ◎ for more than 400 MPa.
　総合評価として１０００℃及び１２００℃での耐酸化消耗性，再結晶温度，高温強度の項目で◎：３、○：２、△：１、×：０として合計が１２の場合にＡ、８～１１の場合にＢ、７以下の場合にＣとした。加工性もしくは固相点が×の場合はＤとした。 As a comprehensive evaluation, in terms of oxidation resistance at 1000 ° C. and 1200 ° C., recrystallization temperature, and high-temperature strength, ◎: 3, ○: 2, Δ: 1, x: 0, and A, 8 to B in the case of 11, and C in the case of 7 or less. D when the workability or solid phase point was x.
　表２に示す結果から、実施例の合金は耐酸化性が良好であり、かつ、固相点、再結晶温度及び高温強度が高く、耐熱材料として特に好ましい特性を有することが確認された。 From the results shown in Table 2, it was confirmed that the alloys of the examples had good oxidation resistance, high solidus point, recrystallization temperature and high temperature strength, and particularly preferable characteristics as heat resistant materials.
　実施例１１と２１では１０００℃の耐酸化消耗性が◎であり、実施例２２と２３での１０００℃の耐酸化消耗性が○であることより、１０００℃での耐酸化消耗性はＴａ添加がＲｅ添加より良好となることが判る。また、実施例１１と２２との比較、実施例２１と２３との比較より、再結晶温度、高温強度はＴａ添加がＲｅ添加より良好となることが判る。 In Examples 11 and 21, the oxidation consumption resistance at 1000 ° C. is ◎, and 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.
　元素群Ｂの添加効果を見ると、例えば、実施例７と１１とを比較すると、Ｃｒ添加により、高温強度が向上している。また、例えば、実施例６、１６、１７を比較すると、Ｎｉ添加により高温強度が向上している。また、例えば、実施例７と２１とを比較すると、Ｃｏ添加により高温強度が向上している。 Looking at the effect of addition of element group B, for example, when Examples 7 and 11 are compared, the high-temperature strength is improved by the addition of Cr. For example, when Examples 6, 16, and 17 are compared, the high temperature strength is improved by adding Ni. For example, when Examples 7 and 21 are compared, the high temperature strength is improved by the addition of Co.
　また、実施例の合金はφ０．５ｍｍという細線にまで塑性加工ができ、さまざまな形状の製品が容易に得られることが示唆された。 Also, it was suggested that the alloy of the example can be plastically processed to a fine wire of φ0.5 mm, and products of various shapes can be easily obtained.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (1)

  1. 　Ｒｈを５～３０ｍａｓｓ％、
    　元素群ＡとしてＴａ、Ｒｅの少なくとも一種の元素を０．３～５ｍａｓｓ％、
    　元素群ＢとしてＣｏ、Ｃｒ、Ｎｉの少なくとも一種の元素を０～５ｍａｓｓ％、
    　元素群Ａと元素群Ｂとを合計で５ｍａｓｓ％以下含有し、
    　元素群Ａに属する元素がＲｅである場合は、元素群Ｂに属する元素はＣｏ単独又はＣｒ単独、若しくは、Ｃｏ、Ｃｒ、Ｎｉから二種以上である、
    　ことを特徴とする耐熱性Ｉｒ合金。     Rh 5-30 mass%,
    As element group A, at least one element of Ta and Re is 0.3 to 5 mass%,
    As element group B, at least one element of Co, Cr, and Ni is 0 to 5 mass%,
    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.
    A heat-resistant Ir alloy characterized by the above.
PCT/JP2017/045632 2016-12-22 2017-12-20 Heat-resistant ir alloy WO2018117135A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/471,054 US11131008B2 (en) 2016-12-22 2017-12-20 Heat-resistant Ir alloy
CN201780079568.9A CN110139939A (en) 2016-12-22 2017-12-20 Heat resistance iridium alloy
DE112017006519.4T DE112017006519T5 (en) 2016-12-22 2017-12-20 Heat resistant Ir alloy
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
JP2016-249860 2016-12-22
JP2016249860 2016-12-22
JP2017242366A JP7057935B2 (en) 2016-12-22 2017-12-19 Heat resistant Ir alloy
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

Publications (1)

Publication Number Publication Date
WO2018117135A1 true WO2018117135A1 (en) 2018-06-28

Family

ID=62626527

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/045632 WO2018117135A1 (en) 2016-12-22 2017-12-20 Heat-resistant ir alloy

Country Status (1)

Country Link
WO (1) WO2018117135A1 (en)

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 (en) 2020-11-30 2024-04-19 石福金属興業株式会社 Heat-resistant Ir alloy

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005533924A (en) * 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 alloy
WO2008013159A1 (en) * 2006-07-25 2008-01-31 Tanaka Kikinzoku Kogyo K.K. Noble metal alloy for spark plug and method for producing and processing the same
JP2014075296A (en) * 2012-10-05 2014-04-24 Ngk Spark Plug Co Ltd Spark plug
WO2016189826A1 (en) * 2015-05-28 2016-12-01 日本特殊陶業株式会社 Sparkplug

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005533924A (en) * 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 alloy
WO2008013159A1 (en) * 2006-07-25 2008-01-31 Tanaka Kikinzoku Kogyo K.K. Noble metal alloy for spark plug and method for producing and processing the same
JP2014075296A (en) * 2012-10-05 2014-04-24 Ngk Spark Plug Co Ltd Spark plug
WO2016189826A1 (en) * 2015-05-28 2016-12-01 日本特殊陶業株式会社 Sparkplug

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 (en) 2020-11-30 2024-04-19 石福金属興業株式会社 Heat-resistant Ir alloy

Similar Documents

Publication Publication Date Title
JP7057935B2 (en) Heat resistant Ir alloy
US9932656B2 (en) Nickel-based alloy with silicon, aluminum, and chromium
JP4430119B2 (en) Noble metal alloy for spark plug and manufacturing method thereof
JP5619843B2 (en) Spark plug
JP2006316343A (en) Electrode material for spark plug
JP5650969B2 (en) Electrode material, spark plug electrode, and spark plug
WO2018117135A1 (en) Heat-resistant ir alloy
US11486024B2 (en) Heat-resistant Ir alloy wire
JP4735963B2 (en) Spark plug electrode material
US11773473B2 (en) Heat-resistant IR alloy
JP5521490B2 (en) Spark plug electrode material
JP7252621B2 (en) High strength Ir alloy
JP7470937B2 (en) Heat-resistant Ir alloy
JP2019218572A (en) HEAT-RESISTANT Ir ALLOY
JP2004183079A (en) Titanium alloy and method for manufacturing titanium alloy material
JP2020193370A (en) High-strength Pt alloy
JPH02147195A (en) Production of cobalt-chromium-based alloy welding material
JP6308672B2 (en) Platinum rhodium alloy and method for producing the same
US11685970B2 (en) Iridium alloy
JP5590979B2 (en) Spark plug electrode material with excellent spark wear resistance
JP2023173090A (en) HEAT-RESISTANT Ir-Pt ALLOY
JP2020084328A (en) High strength Ir alloy
WO2011102355A1 (en) Spark plug electrode material having excellent spark consumption resistance and excellent discharge characteristics
JP5794890B2 (en) Materials for spark plug electrodes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17884008

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17884008

Country of ref document: EP

Kind code of ref document: A1