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EP4556589A1 - Alliage à faible dilatation thermique - Google Patents

Alliage à faible dilatation thermique Download PDF

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Publication number
EP4556589A1
EP4556589A1 EP23839656.8A EP23839656A EP4556589A1 EP 4556589 A1 EP4556589 A1 EP 4556589A1 EP 23839656 A EP23839656 A EP 23839656A EP 4556589 A1 EP4556589 A1 EP 4556589A1
Authority
EP
European Patent Office
Prior art keywords
thermal expansion
forged product
less
coefficient
product
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP23839656.8A
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German (de)
English (en)
Inventor
Shingo Matsumura
Haruyasu Ohno
Kotaro ONA
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.)
Shinhokoku Material Corp
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Shinhokoku Material Corp
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
Application filed by Shinhokoku Material Corp filed Critical Shinhokoku Material Corp
Publication of EP4556589A1 publication Critical patent/EP4556589A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/001—Heat treatment of ferrous alloys containing Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/007—Heat treatment of ferrous alloys containing Co
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C21D1/30—Stress-relieving
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys

Definitions

  • the present invention relates to a low thermal expansion alloy, and more particularly, to a low thermal expansion alloy having excellent machinability.
  • Invar alloys having high thermal stability are widely used as component materials for electronics, semiconductor-related equipment, laser working machines, and ultra-precision working equipment.
  • conventional Invar alloy has low machinability, and therefore it is limited to a very narrow field of practical use.
  • Patent Literature 1 discloses a low thermal expansion alloy having excellent machinability in which S is used as a machinable element.
  • the alloy comprises, by weight%, C:0.05% or less, Si:0.3%, Mn:0.45 to 1.2%, P:0.5% or less, S:0.015 to 0.035%, Ni:33.0 to 34.5%, Co:3.0 to 4.0%, and the balance of substantially Fe, [Mn]/[S] is 15 or more when [Mn] represents the weight% of Mn and [S] represents the weight% of S, and the alloy has an average coefficient of thermal expansion of 1.0 ⁇ 10 -6 /°C or less.
  • Patent Literature 2 discloses a low thermal expansion cast iron in which C is used as a machinable element, and a graphite structure is comprised in the austenite base iron.
  • the alloy comprises, by weight%, the solid solution C: 0.09% or more and 0.43% or less, Si: less than 1.0%, Ni: 29% or more and 34% or less, Co: 4% or more and 8% or less, and the balance of Fe, and the coefficient of thermal expansion in the temperature range of 0 to 200°C is 4 ⁇ 10 -6 /°C or less.
  • Patent Literature 3 discloses a cast iron comprising C: 0.8 to 3.0%, Si: 1.0 to 3.0%, Mn: 0.4 to 2.0%, Ni: 30.0 to 33.0%, and Co: 4.0 to 6.0%, in which C is used as a machinable element.
  • the object of the present invention is to provide a low thermal expansion alloy excellent in machinability.
  • the inventors have intensively studied a method of obtaining a low thermal expansion alloy with further improved machinability. As a result, it was found that a low thermal expansion alloy having a small coefficient of thermal expansion and excellent machinability can be obtained by appropriately controlling the contents of Si, Mn, S, Ni, and Co.
  • the present invention has been made based on the above knowledge, and the gist thereof is as follows.
  • a low thermal expansion alloy comprising, by mass%, C: 0.050% or less, Si: 0.30 to 1.00%, Mn: 0.50 to 2.00%, S : 0.030 to 0.150%, Ni: 27.00 to 38.00%, Co: 0 to 12.00%, Sol.Al: 0.003 to 0.100%, O: 0.010% or less, and balance of Fe and impurities, wherein [Mn], [S], [Ni], [Co], and [Si], which represent the content of Mn, S, Ni, Co, and Si, by mass%, respectively, satisfy [Mn]/[S] ⁇ 10.0, 32.0% ⁇ [Ni]+0.4[Co] ⁇ 38.0%, and [Si]+[Mn] ⁇ 2.50%; and the average coefficient of thermal expansion at 25 to 100° of the low thermal expansion alloy is 3.0 ⁇ 10 -6 /°C or less.
  • C is an element which crystallizes as graphite in castings and improves machinability. However, C is also an element which increases the coefficient of thermal expansion.
  • the C content is 0.050% or less. It is preferably 0.040% or less, more preferably 0.030% or less, and still more preferably 0.020% or less.
  • Si is an element which improves machinability by combining with S. Since the coefficient of thermal expansion increases as the content of Si increases, Si content is set to 0.30 to 1.00%, considering the balance between machinability and coefficient of thermal expansion.
  • the lower limit of Si content may be 0.40% or 0.50%.
  • the upper limit of Si content may be 0.90% or 0.80%.
  • Mn is an element which forms a compound with S and improves machinability. Mn is also an element for suppressing cracking during casting and forging. Since the coefficient of thermal expansion increases as the content of Mn increases, Mn content is set to 0.50 to 2.00%, considering the balance between machinability and coefficient of thermal expansion.
  • the lower limit of Mn content may be 0.60%, 0.70%, or 0.80%.
  • the upper limit of Mn content may be 1.90%, 1.80%, or 1.70%.
  • S is an element which forms a compound with Mn and improves machinability.
  • the S content is 0.030 set to 0.150%, considering the balance between machinability and embrittlement of the alloy.
  • the lower limit of the S content may be 0.040%, 0.050%, or 0.060%.
  • the upper limit of the S content may be 0.140%, 0.130%, or 0.120%.
  • Ni is an element which decreases the coefficient of thermal expansion.
  • the low thermal expansion alloys of the present invention have an average coefficient of thermal expansion of 3.0 ⁇ 10 -6 /°C or less at the range of 25 to 100°C.
  • the coefficient of thermal expansion can be obtained mainly by setting the content of Ni and Co to an appropriate range. Even if the Ni content is too large or too small, the coefficient of thermal expansion is not sufficiently low.
  • Ni content is set to 27.00 to 38.00%.
  • the lower limit of the Ni content may be 28.00%, 29.00%, or 30.00%.
  • the upper limit of the Ni content may be 37.00%, 36.00%, or 35.00%.
  • Co contributes to a decrease in the coefficient of thermal expansion by being combined with Ni.
  • the Co content may be 0.
  • Co is set to 0 to 12.00%.
  • the upper limit of Co content may be 11.00%, 10.00%, or 8.00%.
  • Sol.Al is an element which improves machinability. Since sol.Al is also an element which increases the coefficient of thermal expansion, considering the balance between machinability and the coefficient of thermal expansion, sol.Al is set to 0.003 to 0.100%. Sol.Al means an acid-soluble Al which is not a part of an oxide such as Al 2 O 3 and can be soluble in acid. The content of sol.Al is determined as an Al measured by subtracting the undissolved residue on the filter paper generated in the analytical process of Al. The lower limit of sol.Al content may be 0.010%, 0.020%, or 0.030%. The upper limit of sol.Al content may be 0.090%, 0.080%, or 0.070%.
  • O is an element contained as an impurity, and is not an essential element.
  • the lower limit of the O content is 0.
  • O combines with Al to form alumina.
  • Alumina is hard and thus promotes tool wear.
  • the formation of alumina reduces sol.Al content and lowers the machinability. Therefore, the O content is set to 0.010% or less.
  • the O content is preferably 0.008% or less, more preferably 0.007% or less, and still more preferably 0.006% or less.
  • the balance of chemical composition consists of Fe and impurities.
  • the impurities mean elements other than the elements described above which, if contained, do not deteriorate machinability and coefficient of thermal expansion of the low thermal expansion alloys of the present invention, and which are mainly unavoidably contained from raw materials, manufacturing environment, etc., during the industrial manufacture of cast steel with the chemical compositions specified in the present invention.
  • P of 0.050% or less is included.
  • [Mn], [S], [Ni], [Co], and [Si], which represent the content of Mn, S, Ni, Co, and Si, by mass%, respectively, satisfy the following formula. Mn / S ⁇ 10.0
  • [Mn]/[S] is set to 10.0 or more in order for S to sufficiently form a compound with Mn to improve the machinability.
  • [Mn]/[S] is preferably 15.0 or more, more preferably 20.0 or more, and still more preferably 30.0 or more.
  • the small [Mn]/[S] means that the S content is relatively large with respect to Mn content, and since the amount of S segregating at the grain boundaries increases, cracking may occur easily during casting or forging. 32.0 % ⁇ Ni + 0.4 Co ⁇ 38.0 %
  • Both Ni and Co are elements which decrease the coefficient of thermal expansion.
  • the coefficient of thermal expansion can be further decreased, in particular, [Ni]+0.4[Co] is set to 32.0 to 38.0%.
  • the lower limit of [Ni]+0.4[Co] is preferably 32.5%, more preferably 33.0%.
  • the upper limit of [Ni]+0.4[Co] is preferably 37.0%, more preferably 36.0%, and even more preferably 35.0%.
  • Si and Mn are elements which improve machinability but increase the coefficient of thermal expansion. Therefore, the sum of the contents is set to 2.50% or less.
  • [Si]+[Mn] is preferably 2.30% or less, more preferably 2.00% or less.
  • the low thermal expansion alloy of the present invention has an average coefficient of thermal expansion at 25 to 100°C of 3.0 ⁇ 10 -6 /°C or less. As described above, this coefficient of thermal expansion is obtained mainly by setting the content of Ni and Co to the appropriate range.
  • the average coefficient of thermal expansion at 25 to 100°C may be 2.80 ⁇ 10 -6 /°C or less, 2.60 ⁇ 10 -6 /°C or less, 2.40 ⁇ 10 -6 /°C or less, 2.20 ⁇ 10 -6 /°C or less, 2.00 ⁇ 10 -6 /°C or less, or 1.80 ⁇ 10 -6 /°C or less.
  • the coefficient of thermal expansion is measured at the range of -1 to 130°C using a thermal expansion measuring device at a heating rate of 3°C/min.
  • a thermal expansion measuring device As the thermal expansion measuring device, TD5030S manufactured by BRUKER can be used.
  • the low thermal expansion alloy of the present invention is manufactured by a manufacturing method comprising the steps of:
  • the cast product obtained by the above manufacturing method may be forged to form a forged product.
  • the forging is performed after manufacturing the cast alloy and before performing solution treatment.
  • the low thermal expansion alloy of the present invention comprises the steps of:
  • a mold used for manufacturing the cast product, an injection device used for injecting a molten alloy into the mold, and an injection method are not particularly limited, and known devices and methods can be used.
  • the cast product is heated to 750 to 850°C, held for 0.5 to 3hr, and then quenched.
  • the cooling rate is preferably 10°C/min or more, and more preferably 100°C/min or more.
  • the cast product In the stress-relief annealing, the cast product is maintained at 300 to 350°C for 1 to 5hr, and then, the cast product is air cooled.
  • the solution treatment and the stress relief annealing may be performed after the forging instead of after the casting.
  • the cast product When forging the cast product, the cast product is heated to 1050 to 1250°C in a heating furnace, and then hot forged. In this case, the forging ratio is preferably 3 or more. Even if hot forged, the low thermal expansion characteristic of the low thermal expansion alloy of the present invention is substantially maintained. Further, it is also possible to be worked to a thickness of 0.1 to 10mm by hot rolling or cold rolling. Even in this case, the low thermal expansion characteristic is substantially maintained.
  • the alloy has the chemical composition of the present invention has a low thermal expansion alloy excellent in machinability without using a special manufacturing method, as described above.
  • the low thermal expansion alloy (including cast product and forged product) of the present invention By working the low thermal expansion alloy (including cast product and forged product) of the present invention, it is possible to obtain, for example, alloy parts used in electronics, semiconductor-related equipment, laser working machines, and ultra-precision working equipment.
  • the low thermal expansion alloy of the present invention is suitable as a material of an alloy component since it is thermally stable and excellent in machinability.
  • a cast product (Y-type test material, and ingot of 10kg) was fused so as to have the chemical composition shown in Table 1.
  • the obtained ingot was heated to 1200°C in a heating furnace and then hot forged to obtain a forged product (40mm square bar).
  • the forging ratio was 5 or more.
  • the obtained cast product and forged product were each subjected to solution annealing treatment by heating to 800°C and holding for 1.5hr, and after the solution treatment, were each subjected to a stress-annealing treatment by holding for 3hr at 300°C and air-cooling.
  • the coefficient of thermal expansion was measured by using a thermal expansion measuring device (TD5030S manufactured by BRUKER Co., Ltd.) from -1 to 130°C at a temperature increase rate of 3°C/min to obtain the average coefficient of thermal expansion from 25°C to 100°C.
  • a thermal expansion measuring device (TD5030S manufactured by BRUKER Co., Ltd.) from -1 to 130°C at a temperature increase rate of 3°C/min to obtain the average coefficient of thermal expansion from 25°C to 100°C.
  • Machinability and crushability of chips were evaluated by 13mm depth hole drilling the test piece for evaluating machinability (non-step working) with a drill (TiN coated Co-HSS) having a diameter of 2.6 mm and a water-soluble cutting fluid at a cutting speed of 45 m/min and a feed rate of 0.052 mm/min.
  • a drill TiN coated Co-HSS having a diameter of 2.6 mm and a water-soluble cutting fluid at a cutting speed of 45 m/min and a feed rate of 0.052 mm/min.
  • the machinability was evaluated according to tool wear amount and crushability of chips.
  • the tool wear amount is explained with reference to Fig. 1 .
  • the tool wear amount was defined as a distance in the drill after drilling 100 holes from from the place where the base metal of the drill is visible (1) to the cutting edge (2), as shown in in Fig. 1 , and the tool wear amount of 0.05 mm or less was judged to be good.
  • "not borable” indicates that breakage or defect of the drill was confirmed, or abnormal noise was generated during the drilling, and it was determined that the drill cannot bore the test piece. Further, in the example described as "forging crack”, since cracks occurred during forging, coefficient of thermal expansion, tool wear amount, and crushability of chips was not evaluated.
  • Fig. 2 The crushability of the chips is explained with reference to Fig. 2 .
  • Crushability of the chips was evaluated as good as "G", if 80% or more of the chips are divided in the length of 1cm or less when the chips were observed.
  • Fig. 2A is an example in which the crushability of chips is good
  • Fig. 2B is an example in which the crushability is poor.
  • “P-elongated” in Table 2 means that the length exceeded 1cm in the chips of more than 20%.
  • Table 2 shows the results. It was judged that machinability was good when both tool wear amount and crushability of the chips were evaluated as good.
  • Table 2 No. Coefficient of thermal expansion (25 to 100°C) [ ⁇ 10 -6 /°C] Tool wear amount [mm] crushability of chips 1 forged product 1.86 0.043 G Inv. Ex. 2 forged product 2.13 0.024 G Inv. Ex. 3 forged product 2.70 0.021 G Inv. Ex. 4 cast product 1.15 0.035 G Inv. Ex. forged product 1.04 0.038 G Inv. Ex. 5 forged product 1.62 0.015 G Inv. Ex. 6 cast product 2.96 0.021 G Inv. Ex. forged product 2.73 0.016 G Inv. Ex.
  • Nos. 1 to 14 are inventive examples, in which the coefficient of thermal expansion is small, the tool wear amount and the crushability of the chips is also good. Therefore, the low thermal expansion alloy of the present invention was confirmed to have good machinability in both cast product and forged product.
  • No. 15 had a small amount of Si, and as a result, had large tool wear amount.
  • No. 16 had a large amount of Si amount and a large [Si]+[Mn], and as a result, had a large coefficient of thermal expansion.
  • No. 17 had a small amount of Mn and a small [Mn]/[S], and as a result, forging cracks occurred.
  • No. 18 had a large amount of Mn and a large [Si]+[Mn], and as a result, had a large coefficient of thermal expansion.
  • No. 19 had a small amount of S, and as a result, had a large tool wear amount and poor crushability of chips.
  • No. 21 had a small amount of Ni, and as a result, had a large coefficient of thermal expansion.
  • No. 22 had a large amount of Ni, and as a result, had a large coefficient of thermal expansion.
  • No. 23 had a large amount of Co, and as a result, had a large coefficient of thermal expansion.
  • No. 24 had a small amount of sol.Al and a large amount of O, and as a result, had a larger tool wear amount.
  • No. 26 had a small [Ni]+0.4[Co], and as a result, had a large coefficient of thermal expansion.
  • No. 27 had a large [Ni]+0.4[Co] and a large [Si]+[Mn], and as a result, had a large coefficient of thermal expansion.
  • No. 28 had a large [Si]+[Mn], and as a result, had a large coefficient of thermal expansion.
  • Nos. 29 to 33 had a small amount of Si, Mn, and S, and as a result, had a large tool wear amount and poor crushability of the chips.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Forging (AREA)
  • Compositions Of Oxide Ceramics (AREA)
EP23839656.8A 2022-07-12 2023-07-12 Alliage à faible dilatation thermique Pending EP4556589A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022111934 2022-07-12
PCT/JP2023/025751 WO2024014484A1 (fr) 2022-07-12 2023-07-12 Alliage à faible dilatation thermique

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EP4556589A1 true EP4556589A1 (fr) 2025-05-21

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EP (1) EP4556589A1 (fr)
JP (1) JP7776181B2 (fr)
KR (1) KR20250012714A (fr)
TW (1) TW202405200A (fr)
WO (1) WO2024014484A1 (fr)

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WO2024214777A1 (fr) * 2023-04-13 2024-10-17 新報国マテリアル株式会社 Alliage à faible dilatation thermique

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JPS6051547B2 (ja) 1982-05-29 1985-11-14 新一 榎本 低熱膨張鋳鉄
JP2568022B2 (ja) 1988-11-02 1996-12-25 株式会社東芝 低熱膨張鋳鉄を用いた工作機械、精密測定機器、成形用金型、半導体装置および電子製造装置
JP4253100B2 (ja) * 2000-03-17 2009-04-08 日本鋳造株式会社 被削性に優れた低熱膨張合金およびその製造方法
JP4213901B2 (ja) * 2002-03-28 2009-01-28 日本鋳造株式会社 常温での硬度および強度に優れた鋳造時の割れ感受性が小さい低熱膨張鋳造合金およびその製造方法
US10435780B2 (en) * 2009-06-11 2019-10-08 Genius Solutions Engineering Company Low CTE slush molds with textured surface, and method of making and using the same
JP6793574B2 (ja) * 2017-03-07 2020-12-02 新報国製鉄株式会社 低熱膨張合金
JP6793583B2 (ja) * 2017-03-28 2020-12-02 新報国製鉄株式会社 低熱膨張合金
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KR20250012714A (ko) 2025-01-24
TW202405200A (zh) 2024-02-01
WO2024014484A1 (fr) 2024-01-18
JP7776181B2 (ja) 2025-11-26

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