WO2014112151A1 - Alliage et procédé permettant de produire ce dernier - Google Patents

Alliage et procédé permettant de produire ce dernier Download PDF

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Publication number
WO2014112151A1
WO2014112151A1 PCT/JP2013/073399 JP2013073399W WO2014112151A1 WO 2014112151 A1 WO2014112151 A1 WO 2014112151A1 JP 2013073399 W JP2013073399 W JP 2013073399W WO 2014112151 A1 WO2014112151 A1 WO 2014112151A1
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atomic
alloy
composition ratio
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samples
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PCT/JP2013/073399
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English (en)
Japanese (ja)
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吉見享祐
丸山公一
後藤孝
宮本慎平
金子昂弘
森山貴裕
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国立大学法人東北大学
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Priority to JP2014557315A priority Critical patent/JP5876943B2/ja
Publication of WO2014112151A1 publication Critical patent/WO2014112151A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/06—Casting non-ferrous metals with a high melting point, e.g. metallic carbides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon

Definitions

  • the present invention relates to an alloy and a manufacturing method thereof, for example, an alloy containing Mo, Si and B and a manufacturing method thereof.
  • Alloys used for high-pressure turbines and the like are required to be lightweight, high in strength and excellent in heat resistance.
  • an alloy there is a molybdenum alloy containing molybdenum (Mo).
  • Mo molybdenum
  • an alloy containing Mo, Si (silicon) and B (boron) for example, Patent Documents 1 and 2) and an MHC alloy containing hafnium (Hf) are known.
  • Non-patent Documents 1 and 2 the eutectic reaction temperature between Mo and Mo 5 SiB 2 is about 2060 ° C. to 2100 ° C.
  • Mo and TiC titanium carbide
  • Mo and ZrC zirconium carbide
  • Mo and ZrC zirconium carbide
  • Molybdenum alloy has a high melting point, and is formed by extruding powder sintered body. For this reason, in order to mold a complicated shape, cutting or the like is performed, and the manufacturing cost is increased. On the other hand, when a molded body is formed with powder sintering, problems such as a decrease in strength occur. On the other hand, expensive equipment is used to melt and cast the molybdenum alloy. Therefore, there is a demand for an alloy that is lightweight, has high strength, has excellent heat resistance, and can be melted at a relatively low temperature so that it can be easily manufactured by a casting method.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide an alloy that is lightweight, has high strength, has excellent heat resistance, and is soluble at a relatively low temperature.
  • the present invention is an alloy having Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N as main components.
  • ADVANTAGE OF THE INVENTION According to this invention, the alloy which is lightweight and high intensity
  • At least one element of Ti, Zr, and Hf may be Ti, and at least one element of C and N may be C.
  • the structure is a co-phase Mo 5 SiB 2 and TiC to.
  • the Mo composition ratio is 52 atomic% or more and 80 atomic% or less
  • the Si composition ratio is 1.5 atomic% or more and 25 atomic% or less
  • the B composition ratio is 3 atomic% or more and It is 25 atomic% or less
  • the composition ratio of Ti is 0.1 atomic% or more and 15 atomic% or less
  • the composition ratio of C is 0.1 atomic% or more and 15 atomic% or less. it can.
  • the Mo composition ratio is 60 atomic% or more and 75 atomic% or less
  • the Si composition ratio is 1.7 atomic% or more and 6.7 atomic% or less
  • the B composition ratio is 3.3 atomic%.
  • the composition ratio of Ti is 5.0 atomic% or more and 15.0 atomic% or less
  • the composition ratio of C is 5.0 atomic% or more and 15.0 atomic%. It can be set as the structure which is atomic% or less.
  • the composition ratio of Ti is 10 atomic% or more, and the composition ratio of C is 10 atomic% or less.
  • At least one element of Ti, Zr, and Hf may be Zr, and at least one element of C and N may be C.
  • the structure is a co-phase Mo 5 SiB 2 and ZrC to.
  • the present invention is to manufacture an alloy containing Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N by using a casting method.
  • An alloy production method characterized by the following. ADVANTAGE OF THE INVENTION According to this invention, the alloy which is lightweight and high intensity
  • At least one element of Ti, Zr, and Hf may be Ti, and at least one element of C and N may be C.
  • At least one element of Ti, Zr, and Hf may be Zr, and at least one element of C and N may be C.
  • FIG. 1 is a diagram showing a method for manufacturing an alloy in Examples and Comparative Examples.
  • FIG. 2A and FIG. 2B are observation photographs of the microstructures of samples A1 and A2, respectively.
  • FIGS. 3A and 3B are observation photographs of the microstructures of samples A3 and A4, respectively.
  • 4 (a) and 4 (b) are observation photographs of the microstructures of samples B1 and B2, respectively.
  • FIG. 5A and FIG. 5B are observation photographs of the microstructures of samples B3 and B4, respectively.
  • FIG. 6 is a diagram showing the measurement results of the stress-strain curve at 1400 ° C. for samples A1 to A4.
  • FIG. 7 is a diagram showing measurement results of stress-strain curves at 1400 ° C. for samples B1 to B4.
  • FIG. 1 is a diagram showing a method for manufacturing an alloy in Examples and Comparative Examples.
  • FIG. 2A and FIG. 2B are observation photographs of the microstructures of samples A1 and A2, respectively.
  • FIG. 8 is a diagram showing the measurement results of peak stress with respect to the temperature of samples A3 and B3.
  • FIG. 9 is a diagram showing the measurement results of Young's modulus with respect to the temperatures of samples A3 and B3.
  • FIG. 10 is a diagram showing the densities of samples A1 to A4 and B1 to B4.
  • FIG. 1 is a diagram showing a method for manufacturing an alloy in Examples and Comparative Examples. Referring to FIG. 1, each material is weighed (step S10). As materials, Mo, Si, B, TiC and Ti were used. The weighed material is melted using the arc melting method (step S12). An alloy is cast from the melted material (step S14).
  • Table 1 is a table showing the weight% (wt%) and atomic% (at%) of each element of the prepared sample.
  • No. Samples 2, 5, 9 and 14 correspond to samples A1 to A4, respectively.
  • Samples 4, 8, 13 and 16 correspond to samples B1 to B4, respectively.
  • No. 1 to No. 28, Si: B 1: 2 (atomic ratio).
  • No. 1 to No. 16, Ti: C 1: 1 (atomic ratio).
  • No. 17 to No. 28, Ti: C x (1 ⁇ x ⁇ 2): 1 (atomic ratio).
  • Table 2 is a table showing the density of each sample and the results of investigation on dissolution at 1800 ° C., 1900 ° C. and 2000 ° C.
  • Table 3 is a table showing the results of investigating the weight% (wt%), atomic% (at%), and dissolution at 1800 ° C., 1900 ° C., 2000 ° C. and 2100 ° C. of each element of a sample prepared as a comparative example. .
  • the density of all the measured samples of Examples is 9.01 g / cm 3 or less.
  • Sample No. All samples after 5 were dissolved at 2000 ° C. It can be seen that the melting point decreases when the Mo composition ratio is 60 atomic% or more and 75 atomic% or less. Moreover, it turns out that a density is small.
  • a sample to be dissolved tends to have a high composition ratio of Si and B and a small composition ratio of Ti and C.
  • the Si composition ratio is preferably 1.7 atomic percent or more, more preferably 3.3 atomic percent or more, and even more preferably 5.0 atomic percent or more.
  • the composition ratio of Si is preferably 6.7 atomic% or less.
  • the composition ratio of B is preferably 3.3 atomic% or more, more preferably 6.7 atomic% or more, and further preferably 10 atomic% or more.
  • the composition ratio of B is preferably 13.3 atomic% or less.
  • the composition ratio of Ti is preferably 15.0 atomic% or less, more preferably 13.3 atomic% or less, and further preferably 12.5 atomic% or less.
  • the composition ratio of Ti is preferably 5.0 atomic% or more.
  • the composition ratio of C is preferably 15.0 atomic% or less, more preferably 13.3 atomic% or less, and further preferably 12.5 atomic% or less.
  • the composition ratio of C is preferably 5.0 atomic% or more.
  • the composition ratio of Ti is made larger than the composition ratio of C.
  • the density becomes 8.6 g / cm 3 or less and can be dissolved at 2000 ° C.
  • the C composition ratio is 10 atomic% or less and the Ti composition ratio is 10 atomic% or more.
  • FIGS. 2A to 3B are observation photographs of the microstructures of samples A1 to A4, respectively. The fine structure was observed using SEM (scanning electron microscope). Mo ss is a solid solution phase of Mo, T 2 is a phase of Mo 5 SiB 2 , Mo 2 C is a phase of Mo 2 C, and TiC is a phase of TiC. As shown in FIGS. 2A to 3B, samples A1 to A4 are found to be a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC.
  • FIGS. 4A to 5B are observation photographs of the microstructures of samples B1 to B4, respectively. Similar to FIGS. 2A to 3B, the microstructure was observed using a SEM (scanning electron microscope). As shown in FIGS. 4 (a) to 5 (b), the samples B1 to B4, like the samples A1 to B4, are a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC. Recognize.
  • FIG. 6 is a diagram showing the measurement results of the stress-strain curve at 1400 ° C. for samples A1 to A4. For comparison, a stress-strain curve of an MHC alloy is shown. Referring to FIG. 6, the yield strength of each sample was more than twice that of the MHC alloy. In particular, a sample having a small composition ratio of TiC and a high composition ratio of SiB 2 has a high yield strength. Thus, it can be seen that Samples A1 to A4 have high strength at high temperatures.
  • FIG. 7 is a diagram showing measurement results of stress-strain curves at 1400 ° C. for samples B1 to B4. For comparison, a stress-strain curve of an MHC alloy is shown. Referring to FIG. 7, the yield strength of each sample was higher than that of the MHC alloy. In particular, a sample having a small composition ratio of TiC and a high composition ratio of SiB 2 has a high yield strength. Thus, it can be seen that the samples B1 to B4 are high in strength at high temperatures, similar to the samples A1 to A4.
  • FIG. 8 is a diagram showing the measurement results of peak stress with respect to the temperature of samples A3 and B3.
  • the peak stress ⁇ indicates the peak value of the stress ⁇ in the stress-strain curve.
  • the peak stresses of MHC (molybdenum / hafnium carbide) alloy, TZM (titanium / zirconium / molybdenum) alloy, and Mo0.6-Si7.9-B are shown.
  • the white circle is B3, the white square is A3, the black circle is the MHC alloy, and the black square is the measurement point of the TZM alloy.
  • the slanted white square is the value described in the literature of Mo-6.1Si-7.9B.
  • the curve is an approximate curve.
  • Sample B3 has a higher peak stress at any temperature than Mo-6.1Si-7.9B, MHC alloy and TZM alloy known as heat-resistant alloys. At 1000 ° C., the peak stress is 1800 MPa, which is very large compared to MHC alloy, TZM alloy, and Mo-6.1Si-7.9B alloy. Moreover, at 1600 degreeC, it has a peak stress of about 400 MPa. Sample A3 has a peak stress comparable to that of sample B3 at 1400 ° C. The sample A3 is considered to have a peak stress comparable to that of the sample B3 at other temperatures. In addition, it is considered that the peak stress at a high temperature is large in the other samples as well as the sample B3. As described above, an alloy containing Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N as a main component is at a high temperature of 1000 ° C. or more. Excellent high strength.
  • FIG. 9 is a diagram showing the measurement results of Young's modulus with respect to the temperatures of samples A3 and B3. For comparison, the Young's modulus of W (tungsten), Mo, Mo-2Si alloy and Mo-3Si alloy is shown. Referring to FIG. 9, each sample has a higher Young's modulus from room temperature to 1000 ° C. than Mo and Mo—Si alloy. Thus, it can be seen that Samples A3 and B3 have high rigidity at high temperatures.
  • FIG. 10 is a diagram showing the densities of samples A1 to A4 and B1 to B4. For comparison, the densities of pure Ni (nickel), Rene′N5 alloy, TMS-138 alloy, Mo 5 SiB 2 and pure Mo are shown. Referring to FIG. 6, the density of samples A1 to A4 and B1 to B4 is 8.7 g / cm 3 to 9.01 g / cm 3 . Samples A1 to A4 and B1 to B4 have a density lower than that of pure Mo, and the same density as that of Ni 'alloys Rene′N5 alloy, TMS-138 alloy, and Mo 5 SiB 2 .
  • Ni, ReneN5 alloy and TMS-138 alloy are small in density and lightweight, but have a melting point of about 1400 ° C. and cannot be used as a high heat-resistant alloy used at about 1500 ° C.
  • Mo 5 SiB 2 is lightweight and highly heat resistant, but has a melting point of about 2200 ° C. and is difficult to manufacture by a casting method.
  • the alloys according to the examples are mainly composed of Mo, Si, B, Ti and C. Thereby, as shown in Table 3, it can melt
  • the composition ratio of Mo is 52 atomic% or more and 80 atomic% or less
  • the composition ratio of Si is 1.5 atomic% or more and 25 atomic% or less
  • the composition ratio of B is 3 atomic% or more and 25 atomic% or less.
  • the composition ratio of Ti is preferably 0.1 atomic% or more and 15 atomic% or less
  • the composition ratio of C is preferably 0.1 atomic% or more and 15 atomic% or less.
  • the Mo composition ratio is preferably 80 atomic% or less in order to lower the melting point. In order to increase the strength, the Mo composition ratio is preferably 52 atomic% or more. Since it is based on the Mo—Si—B ternary system, the composition ratio of Si is 1.5 atomic% or more and 25 atomic% or less, and the composition ratio of B is 3 atomic% or more and 25 atomic% or less. Is preferred. Ti and C are preferably 0.1 atomic percent or more for lowering the melting point.
  • these alloys have a low melting point, high strength and high strength due to the co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC. Light weight can be realized.
  • the melting temperature is set to 2100 ° C. or lower, so that the Mo composition ratio is 65 atomic% or more and the B composition ratio is 20 It is preferably at most atomic%. Further, the Mo composition ratio is preferably 75 atomic% or less.
  • the composition ratio of B is preferably 10 atomic% or more. In order to set the melting temperature to 2000 ° C. or less, it is preferable that the Mo composition ratio is 67 atomic% or more and the B composition ratio is 15 atomic% or less.
  • the composition ratio of Mo is preferably 73 atomic percent or less.
  • the composition ratio of B is preferably 10 atomic% or more.
  • the density is 9.1 g / cm 3 or more. Therefore, it is difficult to reduce the weight of the alloy.
  • the density of the alloy can be about 8.8 g / cm 3 .
  • the melting temperature increases. In the examples, the density can be reduced to about 9.0 g / cm 3 or less, and the melting temperature can be lowered. Therefore, it can be melted at a relatively low temperature and the alloy can be easily reduced in weight.
  • Zr and Hf have the same period as Ti in the periodic table, and the properties are similar to Ti.
  • the affinity with C or N is large. Therefore, Zr and Hf can be used instead of Ti.
  • Ti is preferable for weight reduction.
  • N shows the same behavior as C when alloyed, N can be used instead of C. Therefore, the alloy may be composed mainly of Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N.
  • the alloy can be mainly composed of Mo, Si, B, Zr and C. Further, the alloy can contain Mo, Si, B, Ti, Zr and C as main components. In this case, since the alloy is a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and ZrC, the melting point is low, and high strength and light weight can be realized.
  • Mo, Si, B, TiC, TiN, Ti, Zr, or the like can be used as appropriate.
  • a material melting method in step S12 a plasma melting method or the like can be used in addition to the arc melting method.
  • An alloy mainly composed of Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N is dissolved at a temperature of about 2000 ° C. It can be manufactured using inexpensive equipment. Further, a product having a complicated shape and / or a large product can be easily manufactured. Further, the strength can be increased at a temperature of 1000 ° C. or higher, and the weight can be reduced. For this reason, this alloy can be applied to a high-pressure turbine blade of a jet engine or a gas turbine as a heat-resistant alloy. Moreover, it can be applied to various processing tools and special molds in place of WC (tungsten carbide). Furthermore, it can be used for a high-temperature and high-pressure vessel.
  • WC tungsten carbide

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Abstract

La présente invention se rapporte à un alliage qui est surtout composé de molybdène (Mo), de silicium (Si), de bore (B), de titane (Ti), d'un élément parmi le zirconium (Zr) et/ou le hafnium (Hf), et d'un élément parmi le carbone (C) et/ou l'azote (N). La présente invention se rapporte également à un procédé permettant de produire un alliage qui est surtout composé de molybdène (Mo), de silicium (Si), de bore (B), de titane (Ti), d'un élément parmi le zirconium (Zr) et/ou le hafnium (Hf), et d'un élément parmi le carbone (C) et/ou l'azote (N) au moyen d'un procédé de coulage.
PCT/JP2013/073399 2013-01-16 2013-08-30 Alliage et procédé permettant de produire ce dernier WO2014112151A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107034404A (zh) * 2017-04-18 2017-08-11 中南大学 一种MoHfTiBC系钼合金
WO2018042733A1 (fr) * 2016-09-05 2018-03-08 国立大学法人東北大学 ALLIAGE DE Mo-Si-B, PROCÉDÉ DE FABRICATION D'ALLIAGE DE Mo-Si-B ET OUTIL DE SOUDAGE PAR FRICTION-MALAXAGE
JP2018523010A (ja) * 2015-05-26 2018-08-16 シーメンス アクティエンゲゼルシャフト モリブデン−ケイ素−ホウ素合金及びその製造方法、並びに構成要素
JP2020535310A (ja) * 2017-09-26 2020-12-03 シーメンス アクチエンゲゼルシヤフトＳｉｅｍｅｎｓ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ モリブデン、ケイ素及びホウ素を含有する合金からなる粉末、この粉末の使用並びにこの粉末製のワークピースの付加製造方法

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JPS61501714A (ja) * 1984-02-29 1986-08-14 メタルウエルク　プランゼ−　ゲゼルシヤフト　ミツト　ベシユレンクテル　ハフツング 耐熱性モリブデン合金
JPH07331377A (ja) * 1994-06-03 1995-12-19 Sumitomo Metal Ind Ltd 耐熱性と靱性に優れる加熱炉管およびその製造方法
JPH08277435A (ja) * 1995-04-04 1996-10-22 Sumitomo Metal Ind Ltd 耐熱性に優れたＭｏ−Ｓｉ系合金
JPH10512329A (ja) * 1995-01-17 1998-11-24 ユナイテッド テクノロジーズ コーポレイション 耐酸化性モリブデン合金

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JPS61501714A (ja) * 1984-02-29 1986-08-14 メタルウエルク　プランゼ−　ゲゼルシヤフト　ミツト　ベシユレンクテル　ハフツング 耐熱性モリブデン合金
JPH07331377A (ja) * 1994-06-03 1995-12-19 Sumitomo Metal Ind Ltd 耐熱性と靱性に優れる加熱炉管およびその製造方法
JPH10512329A (ja) * 1995-01-17 1998-11-24 ユナイテッド テクノロジーズ コーポレイション 耐酸化性モリブデン合金
JPH08277435A (ja) * 1995-04-04 1996-10-22 Sumitomo Metal Ind Ltd 耐熱性に優れたＭｏ−Ｓｉ系合金

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018523010A (ja) * 2015-05-26 2018-08-16 シーメンス アクティエンゲゼルシャフト モリブデン−ケイ素−ホウ素合金及びその製造方法、並びに構成要素
JP2020059922A (ja) * 2015-05-26 2020-04-16 シーメンス アクティエンゲゼルシャフト モリブデン−ケイ素−ホウ素合金及びその製造方法、並びに構成要素
US10865467B2 (en) 2015-05-26 2020-12-15 Siemens Aktiengesellschaft Molybdenum-silicon-boron alloy and method for producing same, and component
WO2018042733A1 (fr) * 2016-09-05 2018-03-08 国立大学法人東北大学 ALLIAGE DE Mo-Si-B, PROCÉDÉ DE FABRICATION D'ALLIAGE DE Mo-Si-B ET OUTIL DE SOUDAGE PAR FRICTION-MALAXAGE
JPWO2018042733A1 (ja) * 2016-09-05 2019-06-24 国立大学法人東北大学 Ｍｏ−Ｓｉ−Ｂ系合金、Ｍｏ−Ｓｉ−Ｂ系合金の製造方法および摩擦撹拌接合用ツール
CN107034404A (zh) * 2017-04-18 2017-08-11 中南大学 一种MoHfTiBC系钼合金
JP2020535310A (ja) * 2017-09-26 2020-12-03 シーメンス アクチエンゲゼルシヤフトＳｉｅｍｅｎｓ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ モリブデン、ケイ素及びホウ素を含有する合金からなる粉末、この粉末の使用並びにこの粉末製のワークピースの付加製造方法
JP7110334B2 (ja) 2017-09-26 2022-08-01 シーメンス アクチエンゲゼルシヤフト モリブデン、ケイ素及びホウ素を含有する合金からなる粉末、この粉末の使用並びにこの粉末製のワークピースの付加製造方法

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