JP5162492B2 - Ni-based intermetallic alloy with high hardness - Google Patents
Ni-based intermetallic alloy with high hardness Download PDFInfo
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- JP5162492B2 JP5162492B2 JP2009031412A JP2009031412A JP5162492B2 JP 5162492 B2 JP5162492 B2 JP 5162492B2 JP 2009031412 A JP2009031412 A JP 2009031412A JP 2009031412 A JP2009031412 A JP 2009031412A JP 5162492 B2 JP5162492 B2 JP 5162492B2
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- 239000001995 intermetallic alloy Substances 0.000 title claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000000956 alloy Substances 0.000 claims description 23
- 229910000765 intermetallic Inorganic materials 0.000 claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 229910052715 tantalum Inorganic materials 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005259 measurement Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 8
- 238000007542 hardness measurement Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000012795 verification Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910018507 Al—Ni Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Description
本発明は、高い硬度を有するＮｉ基金属間化合物合金に関する。 The present invention relates to a Ni-based intermetallic compound alloy having high hardness.
従来、Ｎｉ3Ａｌ−Ｎｉ3Ｎｂ−Ｎｉ3Ｖ系金属間化合物合金が知られている（例えば，特許文献１を参照）。
この金属間化合物合金は、高温での機械的特性が極めて優れているので、ジェットエンジンやガスタービンのタービン部材といった高温構造材料としての応用が期待されている。
Conventionally, Ni 3 Al—Ni 3 Nb—Ni 3 V-based intermetallic compound alloys are known (see, for example, Patent Document 1).
Since this intermetallic compound alloy has extremely high mechanical properties at high temperatures, it is expected to be applied as a high-temperature structural material such as a jet engine or a turbine member of a gas turbine.
上記のようなＮｉ3Ａｌ−Ｎｉ3Ｎｂ−Ｎｉ3Ｖ系金属間化合物合金は、そのままでも優れた特性を有しているが、耐摩耗性を必要とする用途（例：機械要素部品）に用いる場合には、より優れた硬さを有していることが望まれる。 The Ni 3 Al—Ni 3 Nb—Ni 3 V-based intermetallic compound alloy as described above has excellent characteristics as it is, but it is suitable for applications that require wear resistance (eg, machine element parts). When used, it is desired to have better hardness.
本発明はこのような事情に鑑みてなされたものであり、硬さが向上したＮｉ基金属間化合物合金を提供するものである。 The present invention has been made in view of such circumstances, and provides a Ni-based intermetallic compound alloy with improved hardness.
本発明のＮｉ基金属間化合物合金は、Ｎｉを主成分とし且つＡｌ：２〜９原子％，Ｖ：１０〜１７原子％，（Ｔａ及び／又はＷ）：０．５〜８原子％，Ｎｂ：０〜６原子％，Ｃｏ：０〜６原子％，Ｃｒ：０〜６原子％を含む合計１００原子％の組成の合計重量に対してＢ：１０〜１０００重量ｐｐｍを含む。 The Ni-based intermetallic alloy of the present invention contains Ni as a main component and Al: 2-9 atomic%, V: 10-17 atomic%, (Ta and / or W): 0.5-8 atomic%, Nb : 0 to 6 atomic%, Co: 0 to 6 atomic%, Cr: 10 to 1000 ppm by weight with respect to the total weight of the total composition of 100 atomic% including 0 to 6 atomic%.
本発明者らは鋭意検討を行った結果、Ｎｉ，Ａｌ，Ｖを含む金属間化合物合金において、Ｔａ及び／又はＷの含有量が０．５〜８原子％になるようにＴａとＷのうちの少なくとも一方を含有させることによって、硬さを飛躍的に向上させることができることを見出し、本発明の完成に到った。なお、Ｔａ及び／又はＷの含有量とは、ＴａとＷの何れか一方のみが含まれる場合はＴａ又はＷの含有量を意味し、ＴａとＷの両方が含まれる場合はＴａとＷの含有量の合計を意味する。
以下、本発明の種々の実施形態を例示する。
As a result of intensive studies, the inventors of the present invention have determined that Ta and / or W content is 0.5 to 8 atomic% in the intermetallic compound alloy containing Ni, Al and V. It has been found that by containing at least one of these, the hardness can be dramatically improved, and the present invention has been completed. The content of Ta and / or W means the content of Ta or W when only one of Ta and W is included, and when both Ta and W are included, the content of Ta and W It means the total content.
Hereinafter, various embodiments of the present invention will be exemplified.
Ａｌ：２．５〜８原子％，Ｖ：１０〜１４．５原子％，（Ｔａ及び／又はＷ）：１〜５原子％，Ｎｂ：０〜４原子％であってもよい。
Ｔａ：０．５原子％以上であってもよい。Ｗ：０．５原子％以上であってもよい。何れの場合であっても、ビッカース硬さの向上効果が得られる。
初析Ｌ１2相と（Ｌ１2＋Ｄ０22）共析組織とからなる２重複相組織を有してもよい。この場合、引張強度の機械的特性が優れた金属間化合物合金が得られる。
室温でのビッカース硬さが５５０〜１０００であってもよい。室温と９００℃のビッカース硬さの差が１０〜３００であってもよい。本発明によれば、このようなビッカース硬さを有する金属間化合物合金が容易に得られる。
ここで示した実施形態は、互いに組み合わせることができる。
本明細書において、「〜」は、両端の点を含む。
Al: 2.5-8 atomic%, V: 10-14.5 atomic%, (Ta and / or W): 1-5 atomic%, Nb: 0-4 atomic% may be sufficient.
Ta: 0.5 atomic% or more may be sufficient. W: 0.5 atomic% or more may be sufficient. In any case, the effect of improving the Vickers hardness can be obtained.
Proeutectoid L1 2 phase and (L1 2 + D0 22) may have two multi-phase structure consisting of eutectoid tissue. In this case, an intermetallic compound alloy excellent in mechanical properties of tensile strength can be obtained.
The Vickers hardness at room temperature may be 550 to 1000. The difference between Vickers hardness at room temperature and 900 ° C. may be 10 to 300. According to the present invention, an intermetallic compound alloy having such Vickers hardness can be easily obtained.
The embodiments shown here can be combined with each other.
In the present specification, “to” includes both end points.
以下、本発明の一実施形態を図面を用いて説明する。図面や以下の記述中で示す内容は、例示であって、本発明の範囲は、図面や以下の記述中で示すものに限定されない。 Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The contents shown in the drawings and the following description are examples, and the scope of the present invention is not limited to those shown in the drawings and the following description.
１．Ｎｉ基金属間化合物合金
本発明の一実施形態のＮｉ基金属間化合物合金は、Ｎｉを主成分とし且つＡｌ：２〜９原子％，Ｖ：１０〜１７原子％，（Ｔａ及び／又はＷ）：０．５〜８原子％，Ｎｂ：０〜６原子％，Ｃｏ：０〜６原子％，Ｃｒ：０〜６原子％を含む合計１００原子％の組成の合計重量に対してＢ：１０〜１０００重量ｐｐｍを含む。
以下、各構成要素について詳述する。
1. Ni-based intermetallic compound alloy An Ni-based intermetallic compound alloy according to an embodiment of the present invention is mainly composed of Ni, and Al: 2-9 atomic%, V: 10-17 atomic%, (Ta and / or W) : 0.5 to 8 atomic%, Nb: 0 to 6 atomic%, Co: 0 to 6 atomic%, Cr: 0 to 6 atomic%, and B: 10 Contains 1000 ppm by weight.
Hereinafter, each component will be described in detail.
１−１．組成
本実施形態のＮｉ基金属間化合物合金は、実質的にＮｉ，Ａｌ，Ｖ，Ｔａ，Ｗ，Ｎｂ，Ｃｏ，Ｃｒ，Ｂのみからなってもよく、これ以外の不純物元素を含んでいてもよい。
1-1. Composition The Ni-based intermetallic alloy of this embodiment may consist essentially of Ni, Al, V, Ta, W, Nb, Co, Cr, B, or may contain other impurity elements. Good.
Ｎｉの含有量（含有率）は、例えば、６９〜７８原子％であり、具体的には例えば、６９，６９．５，７０，７０．５，７１，７１．５，７２，７２．５，７３，７３．５，７４，７４．５，７５，７５．５，７６，７６．５，７７，７７．５，７８原子％である。Ｎｉの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The content (content ratio) of Ni is, for example, 69 to 78 atomic%, and specifically, for example, 69, 69.5, 70, 70.5, 71, 71.5, 72, 72.5, 73, 73.5, 74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78 atomic%. The Ni content may be within a range between any two of the numerical values exemplified here.
Ａｌの含有量は、２〜９原子％であり、具体的には例えば２，２．５，３，３．５，４，４．５，５，５．５，６，６．５，７，７．５，８，８．５又は９原子％である。Ａｌの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The Al content is 2 to 9 atomic%, specifically, for example, 2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7. 7.5, 8, 8.5 or 9 atomic%. The Al content may be within a range between any two of the numerical values exemplified here.
Ｖの含有量は、１０〜１７原子％であり、具体的には例えば１０，１０．５，１１，１１．５，１２，１２．５，１３，１３．５，１４，１４．５，１５，１５．５，１６，１６．５又は１７原子％である。Ｖの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The V content is 10 to 17 atomic%, specifically, for example, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15 , 15.5, 16, 16.5 or 17 atomic%. The V content may be within a range between any two of the numerical values exemplified here.
Ａｌ，Ｖを上記範囲にしたのは、この範囲であれば、Ｔａ及び／又はＷの添加によってビッカース硬さの向上効果が得られるからである。
ところで、後述するように本実施形態のＮｉ基金属間化合物合金は、２重複相組織を有することが好ましく、Ｎｉ，Ａｌ，Ｖは、２重複相組織の形成のために添加される。Ｎｉ，Ａｌ，Ｖが上記範囲の場合、２重複相組織が形成されやすい。
また、Ａｌの含有量は、５．５原子％以上が好ましい。この場合、２重複相組織がさらに形成されやすいからである。
The reason why Al and V are set in the above range is that, within this range, the effect of improving Vickers hardness can be obtained by the addition of Ta and / or W.
By the way, as described later, the Ni-based intermetallic compound alloy of the present embodiment preferably has a double-phase structure, and Ni, Al, and V are added to form a double-phase structure. When Ni, Al, and V are in the above range, a double-duplex structure is likely to be formed.
The Al content is preferably 5.5 atomic% or more. This is because in this case, a two-phase structure is more easily formed.
本実施形態のＮｉ基金属間化合物合金は、ＴａとＷの少なくとも一方（つまり，一方又は両方）を含む。
Ｔａ及び／又はＷの含有量は、０．５〜８原子％であり、具体的には例えば０．５，１，１．５，２，２．５，３，３．５，４，４．５，５，５．５，６，６．５，７，７．５又は８原子％である。Ｔａ及び／又はＷの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。
Ｔａ及び／又はＷの含有量を上記範囲にしたのは、この範囲であれば、Ｔａ及び／又はＷの添加によってビッカース硬さの向上効果が得られるからであり、また、上限値である８原子％を超える量を添加しても硬さ向上には大きくは寄与しないからである。
Ｔａの含有量は、０〜８原子％であり、具体的には例えば０，０．５，１，１．５，２，２．５，３，３．５，４，４．５，５，５．５，６，６．５，７，７．５又は８原子％である。Ｔａの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。
Ｗの含有量は、０〜８原子％であり、具体的には例えば０，０．５，１，１．５，２，２．５，３，３．５，４，４．５，５，５．５，６，６．５，７，７．５又は８原子％である。Ｗの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The Ni-based intermetallic compound alloy of this embodiment includes at least one of Ta and W (that is, one or both).
The content of Ta and / or W is 0.5 to 8 atomic%, and specifically, for example, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4 .5, 5, 5.5, 6, 6.5, 7, 7.5, or 8 atomic%. The content of Ta and / or W may be within a range between any two of the numerical values exemplified here.
The reason why the content of Ta and / or W is in the above range is that if it is within this range, the effect of improving Vickers hardness can be obtained by the addition of Ta and / or W, and the upper limit is 8 This is because even if an amount exceeding atomic% is added, it does not greatly contribute to the improvement of hardness.
The content of Ta is 0 to 8 atomic%. Specifically, for example, 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 , 5.5, 6, 6.5, 7, 7.5, or 8 atomic%. The content of Ta may be within a range between any two of the numerical values exemplified here.
The W content is 0 to 8 atomic%, specifically, for example, 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 , 5.5, 6, 6.5, 7, 7.5, or 8 atomic%. The content of W may be within a range between any two of the numerical values exemplified here.
Ｎｂ，Ｃｏ，Ｃｒは、それぞれ、任意成分であり、含まれていてもいなくてもよい。Ｎｂ，Ｃｏ，Ｃｒが含まれているかどうかに関わらず、Ｔａ又はＷの添加によって硬さが向上するからである。Ｎｂは、２重複相組織の強度向上のために添加される。また、Ｃｏ，Ｃｒは、耐酸化性向上のために添加される。 Nb, Co, and Cr are optional components and may or may not be included. This is because the hardness is improved by the addition of Ta or W regardless of whether Nb, Co, or Cr is contained. Nb is added to improve the strength of the two-phase structure. Co and Cr are added to improve oxidation resistance.
Ｎｂの含有量は、０〜６原子％であり、具体的には例えば０，０．５，１，１．５，２，２．５，３，３．５，４，４．５，５，５．５，又は６原子％である。Ｎｂの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。
Ｃｏの含有量は、０〜６原子％であり、具体的には例えば、０，０．５，１，１．５，２，２．５，３，３．５，４，４．５，５，５．５，６原子％である。Ｃｏの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。
Ｃｒの含有量は、０〜６原子％であり、具体的には例えば、０，０．５，１，１．５，２，２．５，３，３．５，４，４．５，５，５．５，６原子％である。Ｃｒの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。
Ｎｂ，Ｃｏ，Ｃｒの含有量を上記範囲にしたのは、この範囲であれば、Ｔａ及び／又はＷの添加によってビッカース硬さの向上効果が得られるからである。
The Nb content is 0 to 6 atomic%, specifically, for example, 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 , 5.5, or 6 atomic%. The Nb content may be within a range between any two of the numerical values exemplified here.
The Co content is 0 to 6 atomic%. Specifically, for example, 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 and 6 atomic%. The Co content may be within a range between any two of the numerical values exemplified here.
The Cr content is 0 to 6 atomic%, specifically, for example, 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 and 6 atomic%. The Cr content may be within a range between any two of the numerical values exemplified here.
The reason why the content of Nb, Co, and Cr is in the above range is that if the content is within this range, the effect of improving Vickers hardness can be obtained by the addition of Ta and / or W.
Ｂは、得られる合金の延性向上のために添加される。Ｂの含有量は、上記の組成の合計重量に対して１０〜１０００重量ｐｐｍであり、具体的には例えば、１０，５０，１００，１５０，２００，２５０，３００，３５０，４００，４５０，５００，５５０，６００，６５０，７００，７５０，８００，８５０，９００，９５０又は１０００重量ｐｐｍである。Ｂの含有量は、ここで例示した数値の何れか２つの間の範囲内であってもよい。
Ｂの含有量を上記範囲にしたのは、この範囲であれば、Ｔａ及び／又はＷの添加によってビッカース硬さの向上効果が得られるからである。
B is added to improve the ductility of the obtained alloy. The content of B is 10 to 1000 ppm by weight with respect to the total weight of the above composition. Specifically, for example, 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500 , 550, 600, 650, 700, 750, 800, 850, 900, 950 or 1000 ppm by weight. The content of B may be within a range between any two of the numerical values exemplified here.
The reason why the content of B is in the above range is that if it is within this range, the effect of improving the Vickers hardness can be obtained by adding Ta and / or W.
１−２．微細組織
本実施形態の金属間化合物合金の微細組織は、特に限定されないが、本実施形態の金属間化合物合金は、初析Ｌ１2相と（Ｌ１2＋Ｄ０22）共析組織とからなる２重複相組織を有していることが好ましい。この場合、引張強度等の機械的特性が高いという利点がある。
1-2. Microstructure The microstructure of the intermetallic compound alloy of the present embodiment is not particularly limited, but the intermetallic compound alloy of the present embodiment has two overlapping layers consisting of a proeutectoid L1 2 phase and a (L1 2 + D0 22 ) eutectoid structure. It preferably has a phase structure. In this case, there is an advantage that mechanical properties such as tensile strength are high.
２重複相組織は、最初に、比較的高い温度において初析Ｌ１2相とＡ１相とからなる上部複相組織を形成し、その後、温度を下げることによってＡ１相をＬ１2相とＤ０22相とに分解させることによって形成することができる。これによって、図１（ａ）のＴＥＭ写真や図１（ｂ）の模式図に示すような初析Ｌ１2相と（Ｌ１2＋Ｄ０22）共析組織とからなる２重複相組織が形成される。なお、Ｌ１2相は、Ｎｉ3Ａｌ金属間化合物相であり、Ａ１相は、ｆｃｃ固溶体相であり、Ｄ０22相は、Ｎｉ3Ｖ金属間化合物相である。 The two-phase structure first forms an upper double-phase structure composed of a pro-eutectoid L1 2 phase and an A1 phase at a relatively high temperature, and then lowers the temperature to change the A1 phase into the L1 2 phase and the D0 22 phase. It can be formed by decomposing it. As a result, a double- phase structure composed of a proeutectoid L1 2 phase and a (L1 2 + D0 22 ) eutectoid structure as shown in the TEM photograph of FIG. 1A and the schematic diagram of FIG. 1B is formed. . Incidentally, L1 2 phase is Ni 3 Al intermetallic phase, A1 phase is an fcc solid solution phase, D0 22 phase is Ni 3 V intermetallic compound phase.
２重複相組織を有する金属間化合物合金は、特許文献１に記載された方法によって作製することができる。但し、特許文献１では、独立したプロセスとして初析Ｌ１2相とＡ１相とが共存する温度での熱処理を行うことによって上部複相組織を形成しているが、この熱処理を行う代わりに金属間化合物合金の鋳塊を作製する際に溶湯を徐冷することによっても上部複相組織を形成することができる。徐冷を行った場合、溶湯が凝固した後に初析Ｌ１2相とＡ１相とが共存する温度に比較的長い時間滞在することになるので、上記熱処理を行った場合と同様に初析Ｌ１2相とＡ１相とからなる上部複相組織が形成されるからである。 An intermetallic compound alloy having a two-duplex structure can be produced by the method described in Patent Document 1. However, Patent Document 1, although the pro-eutectoid L1 2 phase and A1 phase as a separate process forms the upper duplex structure by performing a heat treatment at a temperature coexisting, intermetallic instead of performing the heat treatment The upper multiphase structure can also be formed by slowly cooling the molten metal when producing the ingot of the compound alloy. When performing the slow cooling, the melt is to stay relatively long time to a temperature that coexist with proeutectoid L1 2 phase and A1 phase after coagulation, similar to the case of performing the heat treatment proeutectoid L1 2 This is because an upper multiphase structure composed of a phase and an A1 phase is formed.
１−３．ビッカース硬さ
本実施形態の金属間化合物合金の室温でのビッカース硬さは、特に限定されないが、５５０〜１０００が好ましい。室温でビッカース硬さは、具体的には例えば５５０，６００，６５０，７００，７５０，８００，９００，１０００である。このビッカース硬さは、ここで例示した数値の何れか２つの間の範囲内であってもよく、何れか１つ以上であってもよい。
1-3. Vickers hardness Although the Vickers hardness at room temperature of the intermetallic compound alloy of this embodiment is not specifically limited, 550-1000 are preferable. Specifically, the Vickers hardness at room temperature is, for example, 550, 600, 650, 700, 750, 800, 900, 1000. This Vickers hardness may be in the range between any two of the numerical values exemplified here, or may be any one or more.
本実施形態の金属間化合物合金の９００℃でのビッカース硬さは、特に限定されないが、５５０〜１０００が好ましい。９００℃でのビッカース硬さは、具体的には例えば５５０，６００，６５０，７００，７５０，８００，９００，１０００である。このビッカース硬さは、ここで例示した数値の何れか２つの間の範囲内であってもよく、何れか１つ以上であってもよい。 Although the Vickers hardness in 900 degreeC of the intermetallic compound alloy of this embodiment is not specifically limited, 550-1000 are preferable. Specifically, the Vickers hardness at 900 ° C. is, for example, 550, 600, 650, 700, 750, 800, 900, 1000. This Vickers hardness may be in the range between any two of the numerical values exemplified here, or may be any one or more.
また、本実施形態の金属間化合物合金では、室温と９００℃のビッカース硬さの差（室温での値−９００℃での値）は、特に限定されないが、例えば、１０〜３００であり、具体的には例えば１０，２０，３０，４０，５０，１００，１５０，２００，２５０，３００である。この差は、ここで例示した数値の何れか２つの間の範囲内であってもよい。
本発明において、「ビッカース硬さ」とは、別段の指示がない限り、荷重３００ｇ、保持時間２０秒の条件で測定したものを意味する。
Further, in the intermetallic compound alloy of the present embodiment, the difference between the Vickers hardness at room temperature and 900 ° C. (value at room temperature−value at 900 ° C.) is not particularly limited, but is, for example, 10 to 300. Specifically, for example, 10, 20, 30, 40, 50, 100, 150, 200, 250, 300. This difference may be within a range between any two of the numerical values exemplified herein.
In the present invention, “Vickers hardness” means a value measured under conditions of a load of 300 g and a holding time of 20 seconds unless otherwise specified.
以上の実施形態で示した種々の特徴は、互いに組み合わせることができる。１つの実施形態中に複数の特徴が含まれている場合、そのうちの１又は複数個の特徴を適宜抜き出して、単独で又は組み合わせて、本発明に採用することができる。 Various features shown in the above embodiments can be combined with each other. In the case where a plurality of features are included in one embodiment, one or a plurality of features can be appropriately extracted and used alone or in combination in the present invention.
２．効果実証実験
以下、本発明の効果を実証するための実験について説明する。以下の実験では、ＴａとＷの少なくとも一方を含む金属間化合物合金と、どちらも含まない金属間化合物合金のそれぞれについて室温硬さと高温硬さの少なくとも一方を測定し、測定結果を比較することによって、ＴａとＷの少なくとも一方を添加することの効果を調べた。
2. Effect verification experiment Hereinafter, an experiment for verifying the effect of the present invention will be described. In the following experiments, by measuring at least one of room temperature hardness and high temperature hardness for each of an intermetallic alloy containing at least one of Ta and W and an intermetallic alloy containing neither, and comparing the measurement results The effect of adding at least one of Ta and W was investigated.
２−１．鋳塊作製工程
実施例１〜６、１０〜１２及び比較例１〜２については、表１に示す組成になるように表１の元素の地金（それぞれ純度９９．９重量％）とＢを秤量したものをアーク溶解炉で溶解、鋳造することによって鋳塊からなる試料を作製した。ここで作製した鋳塊のサイズは、３０〜５０ｍｍφサイズの小型ボタン状であり、以下の２−２に示した室温でのビッカース硬さ測定用試料は、この鋳塊から１０ｍｍ×５ｍｍ×１ｍｍの試験片を切り出して行い、２−３に示した高温でのビッカース硬さ測定用試料は、１０ｍｍφ×５ｍｍの試験片を切り出して行った。アーク溶解炉の雰囲気は、まず、溶解室内を真空排気し、その後不活性ガス（アルゴンガス）に置換した。電極は、非消耗タングステン電極を用い、鋳型には水冷式銅ハースを使用した。
実施例７，８，９及び比較例３については、表１に示す組成になるように表１の元素の地金（それぞれ純度９９．９重量％）とＢを秤量したものを真空誘導溶解炉で溶解した後、セラミック鋳型で溶湯を凝固させることによって鋳塊からなる試料を作製した。実施例７，８及び比較例３で作製した鋳塊のサイズは、８３ｍｍφ×７００ｍｍであり、実施例９で作製した鋳塊のサイズは、７７ｍｍφ×２８０ｍｍであった。以下の２−２に示した室温でのビッカース硬さ測定用試料は、この鋳塊から１０ｍｍ×１０ｍｍ×１ｍｍの試験片を切り出して行い、２−３に示した高温でのビッカース硬さ測定用試料は、１０ｍｍφ×５ｍｍの試験片を切り出して行った。
比較例４については、表１に示す組成になるように表１の元素の地金（それぞれ純度９９．９重量％）とＢを秤量したものを真空誘導溶解炉で溶解した後、金型で溶湯を凝固させることによって鋳塊からなる試料を作製した。ここで作製した鋳塊のサイズは、直径８０ｍｍφ×長さ１９０ｍｍであり、以下の実験は、この鋳塊から１０ｍｍφ×５ｍｍの試験片を切り出して行った。
2-1. Ingot production process About Examples 1-6, 10-12 and Comparative Examples 1-2, the ingots of the elements in Table 1 (purity 99.9% by weight, respectively) and B so as to have the composition shown in Table 1 A sample made of an ingot was prepared by melting and casting the weighed one in an arc melting furnace. The size of the ingot produced here is a small button shape of 30 to 50 mmφ size, and the sample for measuring the Vickers hardness at room temperature shown in the following 2-2 is 10 mm × 5 mm × 1 mm from the ingot. The test piece was cut out and the sample for measuring the Vickers hardness at high temperature shown in 2-3 was cut out from a 10 mmφ × 5 mm test piece. As for the atmosphere of the arc melting furnace, first, the melting chamber was evacuated and then replaced with an inert gas (argon gas). The electrode used was a non-consumable tungsten electrode, and a water-cooled copper hearth was used as the mold.
For Examples 7, 8, 9 and Comparative Example 3, a vacuum induction melting furnace was prepared by weighing ingots of elements of Table 1 (purity 99.9% by weight respectively) and B so as to have the composition shown in Table 1 Then, the molten metal was solidified with a ceramic mold to prepare a sample made of an ingot. The size of the ingot produced in Examples 7 and 8 and Comparative Example 3 was 83 mmφ × 700 mm, and the size of the ingot produced in Example 9 was 77 mmφ × 280 mm. The sample for measuring the Vickers hardness at room temperature shown in the following 2-2 is obtained by cutting out a 10 mm × 10 mm × 1 mm test piece from the ingot and measuring the Vickers hardness at a high temperature shown in 2-3. The sample was cut out from a 10 mmφ × 5 mm test piece.
For Comparative Example 4, a base metal (purity: 99.9% by weight) and B as measured in Table 1 were dissolved in a vacuum induction melting furnace so as to have the composition shown in Table 1, and then the mold was used. A sample made of an ingot was produced by solidifying the molten metal. The size of the ingot produced here is diameter 80 mmφ × length 190 mm, and the following experiment was performed by cutting out a test piece of 10 mmφ × 5 mm from the ingot.
２−２．室温でのビッカース硬さ測定
実施例１〜６，１０〜１２及び比較例１〜３について，室温でのビッカース硬さを測定した。実施例１〜６及び比較例１〜２については、ビッカース硬さの測定は、１２８０℃−３時間の熱処理（炉冷）を行う前と行った後に行った。実施例１０〜１２については、ビッカース硬さの測定は、１２８０℃−５時間の熱処理（炉冷）を行う前と行った後に行った。比較例３については、ビッカース硬さの測定は、１０００℃−１０時間の熱処理（炉冷）を行った後に行った。荷重は３００ｇで、保持時間は２０秒であった。測定結果を図２に示す。
2-2. Vickers hardness measurement at room temperature Vickers hardness at room temperature was measured for Examples 1 to 6, 10 to 12, and Comparative Examples 1 to 3. About Examples 1-6 and Comparative Examples 1-2, the measurement of Vickers hardness was performed before and after performing heat treatment (furnace cooling) for 1280 degreeC-3 hours. About Examples 10-12, the measurement of Vickers hardness was performed before performing after heat processing (furnace cooling) for 1280 degreeC-5 hours. About the comparative example 3, the measurement of Vickers hardness was performed after performing the heat processing (furnace cooling) for 1000 degreeC-10 hours. The load was 300 g and the holding time was 20 seconds. The measurement results are shown in FIG.
図２において、比較例１と、実施例１〜３，１０〜１１とを比較すると、Ｔａ又はＷを添加することによって、熱処理前後の何れにおいてもビッカース硬さの値が比較例１より大きくなったことが分かる。また、実施例１２においても熱処理後のビッカース硬さの値は、比較例１より大きくなったことが分かる。
また、図２において、比較例２と、実施例４〜６とを比較すると、Ｃｏ及びＣｒを３原子％ずつ含む試料についても、Ｔａ又はＷを添加することによって熱処理前後の何れにおいてもビッカース硬さの値が大きくなったことが分かる。
In FIG. 2, when Comparative Example 1 is compared with Examples 1 to 3 and 10 to 11, by adding Ta or W, the value of Vickers hardness is greater than that of Comparative Example 1 before and after the heat treatment. I understand that. Also in Example 12, it can be seen that the value of Vickers hardness after the heat treatment was larger than that of Comparative Example 1.
Further, in FIG. 2, when Comparative Example 2 and Examples 4 to 6 are compared, a sample containing 3 atomic% of Co and Cr is also subjected to Vickers hardness both before and after heat treatment by adding Ta or W. It can be seen that the value of the height has increased.
なお、実施例３以外の試料では、１２８０℃−３時間又は１２８０℃―５時間の熱処理を行うことによってビッカース硬さの値が大きくなった。その理由は、必ずしも明らかではないが、この熱処理を行うことによって初析Ｌ１2相と（Ｌ１2＋Ｄ０22）共析組織とからなる２重複相組織が形成されたためであると推測される。 In samples other than Example 3, the value of Vickers hardness was increased by performing heat treatment at 1280 ° C. for 3 hours or 1280 ° C. for 5 hours. The reason for this is not necessarily clear, but it is presumed that this heat treatment resulted in the formation of a double-duplex structure composed of a proeutectoid L1 2 phase and a (L1 2 + D0 22 ) eutectoid structure.
２−３．高温でのビッカース硬さ測定
実施例１，４，５，７〜９及び比較例３，４について、高温（３００℃，５００℃，８００℃，９００℃）でのビッカース硬さ測定を行った。また、実施例９、比較例４については上記温度に加えて６００℃でも測定を行った。実施例１、４、５、７、８及び比較例３の測定には、１２８０℃−３時間の熱処理（炉冷）を行った後の試料を用いた。実施例９の測定には、鋳造後の試料で熱処理を行っていない試料を用いた。比較例４の測定には、１２８０℃−３時間の熱処理を行った後に、１０００℃−１０時間の熱処理（炉冷）を行ったものを用いた。荷重は１ｋｇで，保持時間は２０秒であった。測定は還元雰囲気中（Ａｒ＋約１０％Ｈ2）で行い、昇温速度は毎分１０℃で行った。なお、上記の高温でのビッカース硬さ測定に用いたものと同一の試験片における常温でのビッカース硬さを、上記の高温での測定に先立って、同一の測定条件（荷重１ｋｇ，保持時間２０秒）で測定した。
2-3. Vickers hardness measurement at high temperature Vickers hardness measurement at high temperatures (300 ° C., 500 ° C., 800 ° C., 900 ° C.) was performed on Examples 1, 4, 5, 7 to 9 and Comparative Examples 3 and 4. Moreover, about Example 9 and Comparative Example 4, in addition to the said temperature, it measured also at 600 degreeC. For the measurements of Examples 1, 4, 5, 7, 8 and Comparative Example 3, samples after heat treatment (furnace cooling) at 1280 ° C. for 3 hours were used. In the measurement of Example 9, a sample that had not been heat-treated was used after the casting. For the measurement of Comparative Example 4, a heat treatment (furnace cooling) performed at 1000 ° C. for 10 hours after heat treatment at 1280 ° C. for 3 hours was used. The load was 1 kg and the holding time was 20 seconds. The measurement was performed in a reducing atmosphere (Ar + about 10% H 2 ), and the heating rate was 10 ° C. per minute. In addition, prior to the measurement at the high temperature, the same measurement conditions (load 1 kg, holding time 20) are used to measure the Vickers hardness at normal temperature in the same test piece used for the measurement of the Vickers hardness at the high temperature. Seconds).
測定結果を図３〜５に示す。また、図３及び図４には、ステンレス鋼中で最高硬さを示し、耐摩耗性が要求される用途で一般的に使用される材料であるＳＵＳ４４０Ｃについてのビッカース硬さのデータも合わせて示す。このデータは、上記２−３の高温でのビッカース硬さ測定と同じサイズのサンプルを用いて同じ測定条件にて実測したものである。 The measurement results are shown in FIGS. FIGS. 3 and 4 also show the Vickers hardness data for SUS440C, which is the material generally used in applications where wear resistance is required, showing the highest hardness in stainless steel. . This data was actually measured under the same measurement conditions using a sample having the same size as the above-described 2-3 Vickers hardness measurement at high temperature.
図３を参照すると、実施例１、９では、測定した全温度域において、比較例４よりもビッカース硬さの値が高かったことが分かる。また、実施例１と実施例９のビッカース硬さの差は、最大でも５０程度であった。実施例１と実施例９は、それぞれ、鋳塊の作製方法が異なるだけであるので、鋳塊の作製方法の違いによってビッカース硬さは大きくは変わらないことが分かった。 Referring to FIG. 3, it can be seen that in Examples 1 and 9, the value of Vickers hardness was higher than that in Comparative Example 4 in all measured temperature ranges. The difference in Vickers hardness between Example 1 and Example 9 was about 50 at the maximum. Since Example 1 and Example 9 differ only in the production method of an ingot, respectively, it turned out that Vickers hardness does not change a lot by the difference in the production method of an ingot.
図４を参照すると、実施例４及び５では、測定した全温度域において、比較例３よりもビッカース硬さの値が高かかったことが分かる。従って、Ｔａ又はＷを添加したことによるビッカース硬さの向上効果は、測定した全温度域に及ぶことが分かる。 Referring to FIG. 4, it can be seen that in Examples 4 and 5, the value of Vickers hardness was higher than that in Comparative Example 3 in all measured temperature ranges. Therefore, it can be seen that the effect of improving the Vickers hardness by adding Ta or W extends to the entire temperature range measured.
また、図３及び図４を参照すると、ＳＵＳ４４０Ｃでは、測定温度の上昇に従ってビッカース硬さの値が急激に低下するのに対し、実施例１，４，５又は９では、温度上昇に伴うビッカース硬さの値の低下が非常に小さいことが分かる。また、測定温度が３００℃以上の場合は実施例１のビッカース硬さの値がＳＵＳ４４０Ｃよりも大きく、測定温度が５００℃以上の場合は実施例４又は５のビッカース硬さの値がＳＵＳ４４０Ｃよりも大きいこと分かる。 3 and 4, in SUS440C, the value of Vickers hardness sharply decreases as the measurement temperature increases, whereas in Examples 1, 4, 5 or 9, Vickers hardness accompanying the temperature increase. It can be seen that the decrease in value is very small. Further, when the measurement temperature is 300 ° C. or higher, the value of Vickers hardness of Example 1 is larger than SUS440C, and when the measurement temperature is 500 ° C. or higher, the value of Vickers hardness of Example 4 or 5 is higher than SUS440C. I understand that it is big.
また、図５を参照すると、実施例４と実施例７のビッカース硬さの差、実施例５と実施例８のビッカース硬さの差は、最大でも５０であった。実施例４と実施例７、実施例５と実施例８は、それぞれ、鋳塊の作製方法が異なるだけであるので、鋳塊の作製方法の違いによってビッカース硬さは大きくは変わらないことが分かった。 Further, referring to FIG. 5, the difference in Vickers hardness between Example 4 and Example 7 and the difference in Vickers hardness between Example 5 and Example 8 were 50 at the maximum. Since Example 4 and Example 7, Example 5 and Example 8 differ only in the method of producing the ingot, it is understood that the Vickers hardness does not change greatly depending on the method of producing the ingot. It was.
Claims (6)
初析Ｌ１ 2 相と（Ｌ１ 2 ＋Ｄ０ 22 ）共析組織とからなる２重複相組織を有するＮｉ基金属間化合物合金。 A l: 2 to 9 atomic%, V: 10 to 17 atomic%, Ta or W: 0.5 to 8 atomic%, Nb: 0~6 atomic%, Co: 0~6 atomic%, Cr: 0~6 B atomic% and a metal composition containing Mikatsu remainder of a total of 100 atomic% is Ni, relative to the total weight of metal in the composition: and 10 to 1000 wt ppm, consists inevitable impurities,
A Ni-based intermetallic alloy having a two-duplex structure composed of a proeutectoid L1 2 phase and a (L1 2 + D0 22 ) eutectoid structure .
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| EP2620514A4 (en) | 2010-09-24 | 2016-08-17 | Univ Osaka Prefect Public Corp | Re-ADDED Ni-BASED DUAL-PHASE INTERMETALLIC COMPOUND ALLOY AND PROCESS FOR PRODUCTION THEREOF |
| JP6573061B1 (en) | 2019-02-25 | 2019-09-11 | 中国電力株式会社 | Welding repair method for precipitation strengthened castings |
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| JP5127144B2 (en) * | 2005-03-25 | 2013-01-23 | 公立大学法人大阪府立大学 | Ni3Al-based intermetallic compound containing V and Ti having two-phase structure, method for producing the same, heat-resistant structural material |
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