JPWO2006093334A1 - Method for melting high vapor pressure metal-containing alloys - Google Patents
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- 239000000956 alloy Substances 0.000 title claims abstract description 78
- 230000008018 melting Effects 0.000 title claims abstract description 58
- 238000002844 melting Methods 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 74
- 239000001307 helium Substances 0.000 claims abstract description 44
- 229910052734 helium Inorganic materials 0.000 claims abstract description 44
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
- B22D23/06—Melting-down metal, e.g. metal particles, in the mould
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C22/00—Alloys based on manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- Chemical & Material Sciences (AREA)
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- Metallurgy (AREA)
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract
Ｍｇ，Ｃａ，Ｌｉ，Ｚｎ，ＭｎおよびＳｒ等の低融点、低沸点でかつ高い蒸気圧を有する金属を含有する合金を溶解して製造する方法において、その溶解の雰囲気ガスとして、ヘリウム含有ガスを用いる。その結果、上記の金属を含む合金を、蒸発した活性金属の微粉による発火等の危険や汚染を招くことなく、目標とする化学成分の合金を精度よく安全にかつ低コストで製造することができる。さらに、雰囲気ガスとしてヘリウム含有ガスを用いることによって、ヘリウムガスが有する高い熱伝導率により、溶解した金属の急冷凝固が可能となるので、特殊な合金を、通常の溶解装置でも製造することが可能となる。In a method for melting and producing an alloy containing a metal having a low melting point, a low boiling point, and a high vapor pressure, such as Mg, Ca, Li, Zn, Mn, and Sr, a helium-containing gas is used as an atmosphere gas for the melting. Use. As a result, it is possible to manufacture an alloy containing the above-mentioned metal accurately, safely and at low cost without causing danger or contamination such as ignition due to evaporated active metal fine powder. . Furthermore, by using a helium-containing gas as the atmospheric gas, the high thermal conductivity of helium gas enables rapid solidification of the molten metal, so special alloys can be produced even with ordinary melting equipment. It becomes.
Description
関連出願の記載
本出願は、２００５年３月２日に出願された日本特許出願２００５−５６９８５号を基礎出願として、優先権主張する出願である。
［技術分野］
本発明は、Ｍｇ，Ｃａ，Ｌｉ，Ｚｎ，ＭｎおよびＳｒ等の融点や沸点が低く、高い蒸気圧を有する金属を含有する合金を、溶解法により製造する際の溶解方法について提案するものである。Description of Related Application This application claims priority from Japanese Patent Application No. 2005-56985 filed on March 2, 2005.
[Technical field]
The present invention proposes a melting method for producing an alloy containing a metal having a low melting point and boiling point such as Mg, Ca, Li, Zn, Mn, and Sr and having a high vapor pressure by a melting method. .
Ｍｇ，Ｃａ，ＺｎおよびＬｉ等に代表される金属やこれらの金属を含む合金は、鉄等の遷移金属やそれらの合金などと比較すると軽量で比強度が高いことから、構造材料や機能性材料としての応用が広く期待されている。中でも、ＭｇおよびＣａは、地殻や海水中に豊富に存在し、低コストであること、また、人体に悪影響を及ぼすことがないことから、その利用拡大への期待が大きい。
しかしながら、Ｍｇ，Ｃａ，ＺｎおよびＬｉ等の金属およびこれらの合金は、融点や沸点が低く、蒸気圧が高いことから、これらを含有する合金を溶解法により製造しようとすると、蒸発により発生した金属微粉が溶解炉内を汚染するという問題がある。とくにＭｇは、非常に活性であり、これが溶解炉の内壁等に付着すると、大気に触れた際に、発火や爆発を起こす等の危険性が高い。
また、蒸発した金属微粉の煙により、溶解炉の目視観察用窓が汚染されたり、視界が遮断されたりして、合金が完全に溶解したか否かの判断や、攪拌が充分であるか否かなどの目視による確認や判断ができない等の問題もある。さらに、正確な蒸発量の推測が困難になるため、目標とする化学成分の合金を製造することができないという問題もある。
なお、上記Ｍｇ，Ｃａ，ＺｎおよびＬｉ等を含有する合金は、溶解法の他に、ボールミリング等のメカニカルアロイング法によっても製造することができる。この合金製造方法は、原料の金属を溶解せずに製造する方法であるため、金属微粉発生による上記のような問題は生じないものの、ミルポットからの鉄等の混入による汚染や合金の均質性の低下が起こる等の問題がある。また、製造に長時間を要するため、製造コストが高いという問題もあり、大量生産には適していない。Metals typified by Mg, Ca, Zn and Li, and alloys containing these metals are lighter and have higher specific strength than transition metals such as iron and their alloys, so structural materials and functional materials The application is widely expected. Among them, Mg and Ca are abundant in the earth's crust and seawater, are low in cost, and do not adversely affect the human body.
However, metals such as Mg, Ca, Zn and Li and alloys thereof have a low melting point and boiling point, and a high vapor pressure. Therefore, when an alloy containing these metals is manufactured by a melting method, the metal generated by evaporation There is a problem that fine powder contaminates the melting furnace. In particular, Mg is very active, and if it adheres to the inner wall of the melting furnace, there is a high risk of ignition or explosion when it comes into contact with the atmosphere.
In addition, the smoke of the evaporated metal fine powder contaminates the visual observation window of the melting furnace or blocks the field of view, and it is judged whether the alloy is completely dissolved and whether the stirring is sufficient. There are also problems such as being unable to confirm and judge visually. Furthermore, since it is difficult to accurately estimate the amount of evaporation, there is a problem that an alloy having a target chemical component cannot be manufactured.
The alloy containing Mg, Ca, Zn, Li and the like can be manufactured by a mechanical alloying method such as ball milling in addition to the melting method. This alloy manufacturing method is a method of manufacturing without melting the raw material metal, so the above problems due to the generation of fine metal powder do not occur, but contamination of the iron from the mill pot and the homogeneity of the alloy. There are problems such as reduction. Further, since it takes a long time to manufacture, there is a problem that the manufacturing cost is high, and it is not suitable for mass production.
以上説明したように、Ｍｇ，Ｃａ，ＺｎおよびＬｉ等を含有する合金を製造する従来の方法は、いずれも様々な問題を抱えているため、こうした問題点のない、新しい製造技術の開発が強く望まれていた。そこで、本発明の主たる目的は、低融点、低沸点で蒸気圧の高い金属を含有する合金を、溶解法で製造するのに有利な溶解方法について提案するものである。
また、本発明の他の目的は、目標とする化学成分の合金を、蒸発した活性な金属微粉による発火等の危険や汚染を低減しつつ、目標とする化学成分の合金を精度よく、多量に、しかも安全に製造する方法を提案することにある。
発明者らは、上記目的を実現するために鋭意研究を重ねた。その結果、溶解雰囲気を構成するガス成分を適正化すること、とくにヘリウムガスを用いることが有効であるとの知見を得て、本発明を開発するに至った。
即ち、本発明は、Ｍｇ，Ｃａ，Ｌｉ，Ｚｎ，ＭｎおよびＳｒのうちのいずれか１種以上を含有する合金を、溶解して製造する方法において、その溶解の雰囲気ガスとして、ヘリウム含有ガスを用いることを特徴とする高蒸気圧金属含有合金の溶解方法である。
なお、本発明においては、前記雰囲気ガス中のヘリウム濃度は、１０ｖｏｌ％以上であること、また、前記雰囲気ガスは、ヘリウムと、窒素やアルゴンなどの原料金属と反応しないガスとの混合ガスであることが好ましい。また、前記雰囲気ガスの圧力は、０．０１ＭＰａ〜１ＭＰａであることが好ましい。
以上の構成とした本発明方法によれば、Ｍｇ，Ｃａ，ＬｉおよびＺｎ等の低融点、低沸点で高蒸気圧の金属を含む合金、例えば、前記金属とＡｌやＮｉ等との合金を、蒸発した活性金属の微粉による発火等の危険や汚染を招くことなく、目標とする化学成分の合金を精度よく安全にかつ低コストで多量に製造することができる。
さらに、雰囲気ガスとしてヘリウム含有ガスを用いる本発明の溶解方法は、上述した活性金属微粉による問題点を解決できること以外に、ヘリウムガスが有する高い熱伝導率によって、溶解した金属の凝固速度を高める、すなわち、急冷凝固の効果が得られるという特徴を併せ持っている。従って、本発明の方法によれば、従来、急冷凝固専用の溶解装置を用いて製造していた特殊な合金を、通常の溶解装置でも製造することが可能となる。
以上のことから、次世代で用いられる軽量金属や合金からなる構造材料や機能性材料の開発および実用化が、本発明の溶解方法を用いることで、大きく進展することが期待される。As described above, the conventional methods for producing alloys containing Mg, Ca, Zn, Li, etc. all have various problems. Therefore, the development of new production techniques that do not have such problems is strong. It was desired. Accordingly, the main object of the present invention is to propose a melting method that is advantageous for producing an alloy containing a metal having a low melting point, a low boiling point, and a high vapor pressure by the melting method.
Another object of the present invention is to reduce the risk and contamination of the target chemical component alloy, such as ignition by the evaporated active metal fine powder, while accurately adding a large amount of the target chemical component alloy. In addition, the object is to propose a method of manufacturing safely.
Inventors repeated earnest research in order to implement | achieve the said objective. As a result, the inventors have obtained the knowledge that it is effective to optimize the gas components constituting the dissolution atmosphere, particularly using helium gas, and have developed the present invention.
That is, the present invention relates to a method for melting and producing an alloy containing any one or more of Mg, Ca, Li, Zn, Mn, and Sr. A method for melting a high vapor pressure metal-containing alloy, characterized by being used.
In the present invention, the helium concentration in the atmospheric gas is 10 vol% or more, and the atmospheric gas is a mixed gas of helium and a gas that does not react with a source metal such as nitrogen or argon. It is preferable. In addition, the pressure of the atmospheric gas is preferably 0.01 MPa to 1 MPa.
According to the method of the present invention configured as described above, an alloy containing a metal having a low melting point, a low boiling point, and a high vapor pressure, such as Mg, Ca, Li and Zn, for example, an alloy of the metal and Al, Ni, or the like, A target chemical component alloy can be produced in a large amount accurately, safely and at low cost without incurring dangers such as ignition by the fine powder of active metal evaporated or contamination.
Furthermore, the melting method of the present invention using a helium-containing gas as the atmospheric gas can solve the problems caused by the active metal fine powder described above, and increases the solidification rate of the dissolved metal due to the high thermal conductivity of the helium gas. That is, it has the feature that the effect of rapid solidification can be obtained. Therefore, according to the method of the present invention, it is possible to manufacture a special alloy which has been conventionally manufactured using a melting apparatus dedicated to rapid solidification even with an ordinary melting apparatus.
From the above, it is expected that the development and practical application of structural materials and functional materials made of lightweight metals and alloys used in the next generation will be greatly advanced by using the melting method of the present invention.
図１は、ＣａＭｇ２合金を溶解する際の雰囲気ガス中のヘリウムガス濃度が、Ｍｇの溶解歩留まりに及ぼす影響を示すグラフである。
図２は、ＣａＭｇ２合金を溶解する際の雰囲気ガスとして、ヘリウムガスを用いた場合とアルゴンガスを用いた場合に、得られた合金のＸ線回折曲線を比較して示した図である。
図３は、Ｌａ−Ｎｉ系水素吸蔵合金を、ヘリウムガス雰囲気中で溶解したＬａ−Ｎｉ系水素吸蔵合金と、アルゴンガス雰囲気中で溶解した同じ合金の圧力組成等温線図を比較して示した図である。FIG. 1 is a graph showing the effect of the helium gas concentration in the atmospheric gas when melting the CaMg 2 alloy on the dissolution yield of Mg.
FIG. 2 is a diagram comparing the X-ray diffraction curves of the obtained alloys when helium gas and argon gas are used as the atmospheric gas for dissolving the CaMg 2 alloy.
FIG. 3 shows a comparison of pressure composition isotherms of a La—Ni-based hydrogen storage alloy dissolved in a helium gas atmosphere and a La—Ni-based hydrogen storage alloy dissolved in an argon gas atmosphere. FIG.
以下、本発明の溶解方法について詳細に説明する。
本発明の溶解方法は、Ｍｇ，Ｃａ，ＬｉおよびＺｎ等の低融点、低沸点でしかも蒸気圧が高い金属のうちの１種以上を含有する合金を溶解する際に、その溶解雰囲気としてヘリウム含有ガスを用いる点に特徴がある。このヘリウム含有ガスを溶解雰囲気として用いた場合には、溶解時に蒸発して発生した金属微粉の凝集を防ぐことが可能となり、金属微粉の凝集体による発火等の危険性や汚染を大幅に低減することができるとともに、目標とする化学成分の合金を高精度で多量に、しかも安全に製造することができる。
このヘリウム含有ガスによる上記効果は、ヘリウムが他の不活性ガスと比較して、熱伝導率が高く（アルゴンの約３倍）、密度が低く（アルゴンの０．１倍）さらに平均自由行程が長い（アルゴンの約３倍）ことにより得られるものと推察している。なお、ヘリウム以外では、水素が同様の特徴を有しているが、水素は原料金属と反応して金属水素化物を構成することがあるので、溶解雰囲気ガスとしては適当ではない。ただし、水素と反応しないような低融点、低沸点かつ高蒸気圧の金属を溶解する場合であれば、水素含有ガスを雰囲気ガスとして用いた場合には、ヘリウムと同様の効果を期待することができる。
ただし、ヘリウムガスは、非常に高価である。従って、コスト低減の観点からは、このヘリウムガスを、前記原料金属と反応しない、安価なガスで一部置換して用いることが好ましい。そこで、発明者らは、ヘリウムを他の様々なガスで置換する実験を行った結果、ヘリウムガスの一部を窒素やアルゴンなどの原料金属と反応しないガスで置換したガスであれば、蒸発により発生した金属微粉が凝集することによる発火等の危険性や汚染を、かなり低減することができることがわかった。
なお、ヘリウムガスを置換するガスとしては、アルゴンガスが最も好ましい。その理由は、アルゴンガスは安価であり、高温においてもＭｇ，Ｃａ，ＬｉおよびＺｎなどと反応することがないためである。
ただし、ヘリウムと他の不活性ガスとの置換には限界があることがわかった。発明者らの知見したところによれば、かかる混合ガス中のヘリウム含有量は、少なくとも１０ｖｏｌ％とすることが必要であり、好ましくは２５ｖｏｌ％以上、より好ましくは５０ｖｏｌ％以上である。さらに好ましくは、９５ｖｏｌ％以上であるが、もちろん、９０〜１００ｖｏｌ％であってもよい。このように、雰囲気ガスとしてヘリウムが占める割合の下限を、１０ｖｏｌ％としたのは、１０ｖｏｌ％未満であるとヘリウムの上述した作用効果が得られないためである。
また、本発明に係る溶解方法においては、ヘリウム含有ガスからなる溶解雰囲気の圧力は、０．０１ＭＰａ〜１ＭＰａであることが好ましい。その理由は、この圧力が０．０１ＭＰａ未満では蒸発温度が著しく低下するため、蒸発が促進されて、金属微粉の発生量を低減することができないからである。一方、１ＭＰａを超えると、蒸発量は減少するものの、融点が上昇して溶解が困難となるためである。
なお、前記ヘリウム含有ガスの圧力範囲は、溶解前の室温の状態における圧力のことであり、溶解工程中に炉内が高温になった場合には、前記範囲を超える場合がある。
また、上記の雰囲気ガスとして用いるヘリウムの濃度および圧力の最適範囲は、主にコストの観点から考察、開発を重ねた結果、得られたものである。
また、本発明の溶解方法においては、雰囲気ガスとして供給する前記ヘリウム含有ガス中には、酸素、二酸化炭素、水蒸気等の不純物ガスを、本発明の作用を害さない範囲で含有していてもよいが、その含有量は、１ｍａｓｓ％以下とすることが好ましい。その理由は、１ｍａｓｓ％を超えると、溶解中にこれらのガスとＭｇ，Ｃａ，ＬｉおよびＺｎ等とが反応し、酸化物、水酸化物および炭化物等が生成して、目標とする化学組成合金および化合物を製造することができなくなるためである。Hereinafter, the dissolution method of the present invention will be described in detail.
In the melting method of the present invention, when melting an alloy containing one or more metals of low melting point, low boiling point and high vapor pressure, such as Mg, Ca, Li and Zn, helium is contained as the melting atmosphere. It is characterized in that gas is used. When this helium-containing gas is used as a melting atmosphere, it becomes possible to prevent the aggregation of metal fines generated by evaporation at the time of melting, greatly reducing the risk of ignition and contamination due to the aggregates of metal fines. In addition, it is possible to manufacture a large amount of an alloy having a target chemical component with high accuracy and safely.
The effect of this helium-containing gas is that helium has a higher thermal conductivity (about 3 times that of argon), a lower density (0.1 times that of argon), and a mean free path than other inert gases. It is presumed to be obtained by being long (about 3 times that of argon). Other than helium, hydrogen has the same characteristics, but hydrogen may react with the raw material metal to form a metal hydride, so that it is not suitable as a dissolved atmosphere gas. However, if a low melting point, low boiling point and high vapor pressure metal that does not react with hydrogen is dissolved, the same effect as helium can be expected when a hydrogen-containing gas is used as the atmospheric gas. it can.
However, helium gas is very expensive. Therefore, from the viewpoint of cost reduction, it is preferable to use this helium gas by partially replacing it with an inexpensive gas that does not react with the raw metal. Therefore, the inventors conducted experiments to replace helium with various other gases. As a result, if a gas in which part of the helium gas is replaced with a gas that does not react with a source metal such as nitrogen or argon, evaporation is performed. It has been found that the risk and contamination such as ignition due to the aggregation of the generated fine metal powder can be considerably reduced.
Argon gas is most preferable as a gas for replacing helium gas. The reason is that argon gas is inexpensive and does not react with Mg, Ca, Li, Zn and the like even at high temperatures.
However, it has been found that there is a limit to the replacement of helium with other inert gases. According to the knowledge of the inventors, the helium content in the mixed gas needs to be at least 10 vol%, preferably 25 vol% or more, more preferably 50 vol% or more. More preferably, it is 95 vol% or more, but of course 90-100 vol% may be sufficient. Thus, the lower limit of the proportion of helium as the atmospheric gas is set to 10 vol% because the above-described effects of helium cannot be obtained when it is less than 10 vol%.
In the melting method according to the present invention, the pressure of the melting atmosphere made of helium-containing gas is preferably 0.01 MPa to 1 MPa. The reason is that if the pressure is less than 0.01 MPa, the evaporation temperature is remarkably lowered, and thus evaporation is promoted and the amount of metal fine powder generated cannot be reduced. On the other hand, if it exceeds 1 MPa, the amount of evaporation decreases, but the melting point rises and dissolution becomes difficult.
The pressure range of the helium-containing gas is a pressure at a room temperature before melting, and may exceed the above range when the temperature of the furnace becomes high during the melting step.
Further, the optimum range of the concentration and pressure of helium used as the atmospheric gas is obtained as a result of repeated consideration and development mainly from the viewpoint of cost.
In the melting method of the present invention, the helium-containing gas supplied as the atmospheric gas may contain an impurity gas such as oxygen, carbon dioxide, and water vapor as long as the effects of the present invention are not impaired. However, the content is preferably 1% by mass or less. The reason is that if it exceeds 1 mass%, these gases react with Mg, Ca, Li, Zn, etc. during melting, and oxides, hydroxides, carbides, etc. are produced, and the target chemical composition alloy This is because the compound cannot be produced.
以下に、実施例を掲げて本発明を詳しく説明するが、本発明はこれらの実施例に限定されるものではないことは勿論である。
（発明例１）
水素吸蔵合金ＣａＭｇ２の原料として、ＭｇとＣａの金属を、それらのモル比が２：１となるように、合計１ｋｇ用意し、これらの全量を誘導溶融型溶解炉内に装入し、この炉内を８×１０−３Ｔｏｒｒにまで排気し、次いで、雰囲気ガスとしてヘリウムガス（濃度１００ｖｏｌ％）を６００Ｔｏｒｒになるまで導入した。その後、この雰囲気ガスで炉内を満たしながら、溶解炉の温度を１１００℃まで加熱して上記原料を溶解し、さらに、上記合金の溶湯温度を１０５０℃に維持しつつ３０分間保持した。その後、上記合金の溶湯を、水冷した定盤上に注いで、冷却速度１０００℃／秒で冷却して凝固させ、ＣａＭｇ２合金を作製した。このようにして得たＣａＭｇ２合金について、下記（１）および（２）の方法で、溶解歩留まりおよび化学成分を測定した。
（１）溶解歩留まりの測定
溶解前の原料の質量および溶解鋳造後の合金の質量を、それぞれ測定することにより、蒸発による減少した質量を求め、溶解歩留まりを算出した。
（２）化学成分の測定
ＩＣＰ発光分光分析法により、溶解鋳造後の合金の化学成分を定量分析した。
上記測定の結果を表１に示した。この結果から、溶解雰囲気ガスとしてヘリウムガスを用いた本発明例１では、溶解歩留まりは９８．２％以上と高く、さらに目標合金組成に対して±１％以内の高い精度で合金が製造できていることがわかる。
雰囲気ガスとしてアルゴンガス（濃度１００ｖｏｌ％）を用いた以外は、発明例１と同様にしてＣａＭｇ２合金を作製した。このＣａＭｇ２合金について、上記（１）および（２）の方法で溶解歩留まりおよび化学成分を測定し、結果を表１に併記して示した。
（発明例２〜４）
雰囲気ガスとして導入するヘリウムガスの濃度を、７５，５０，２５ｖｏｌ％（残部アルゴンガス）と変化させたこと以外は、上記発明例１と同様にしてＣａＭｇ２合金を作製した。これらのＣａＭｇ２合金について、上記（１）および（２）の方法で溶解歩留まりおよび化学成分を測定し、そ結果を表１に併記して示した。これらの結果から、ヘリウムガス濃度が５０ｖｏｌ％を超える場合（発明例２および３）には、溶解歩留まりが９８％程度と高く、さらに目標とする合金組成が高い精度で得られることがわかる。一方、ヘリウムガス濃度が２５ｖｏｌ％の場合（発明例４）には、溶解歩留まりおよび合金組成が、発明例１〜３に劣るものの、ヘリウムガスを含有していない場合（比較例１）より溶解歩留まりおよび合金組成の精度が向上しており、ヘリウムガス導入の効果が確認できる。
上記発明例１〜４および比較例１の結果から得られるヘリウムガス濃度と溶解歩留まりとの関係を図１に示す。図１より、ヘリウムガス濃度が高くなるとともに溶解歩留まりが向上していることがわかる。
さらに、上記発明例１および比較例１で得られたＣａＭｇ２合金について、Ｘ線回折強度の測定を行い、合金および化合物が目標通りの単相構造を有しているか否かを確認し、その結果を図２に示した。図２より、発明例１のＣａＭｇ２合金は、ＣａＭｇ２相の単相構造合金となっているが、比較例１の合金は、ＣａＭｇ２相とＣａ相の２相が混在した構造の合金となっていることがわかる。
以上、表１、図１および図２からわかるように、本発明の方法に従えば、目的とする組成の単相合金をばらつきなく製造することが可能である。これに対し、比較例の方法では、原料の蒸発損失が制御できず、目標組成から大きくはずれ、しかも合金組成のばらつきが生じている。
（発明例５）
合金原料としてＣａとＡｌを用いたこと以外は、上記発明例１と同様にしてＣａＡｌ２合金を作製し、得られたＣａＭｇ２合金について、上記（１）および（２）の方法により、溶解歩留まりおよび化学成分を測定し、その結果を表１に併記して示した。この結果から、本発明例５では、溶解歩留まりが９８％程度と高く、さらに目標のＡｌ組成に対して±１％以内の高い精度で目標合金が得られていることがわかる。
（発明例６）
合金原料としてＭｇとＮｉを用いたこと以外は、上記発明例１と同様にしてＭｇＮｉ２合金を作製し、得られたＭｇＮｉ２合金について、上記（１）および（２）の方法により、溶解歩留まりおよび化学成分を測定し、その結果を表１に併記して示した。この結果から、本発明例６では、溶解歩留まりが９８％程度と高く、さらに目標のＮｉ組成比に対して±２％以内の高い精度で目標合金が得られていることがわかる。
（発明例７）
合金原料としてＣａとＮｉを用いたこと以外は、上記実験例１と同様にしてＣａＮｉ２合金を作製し、得られたＣａＮｉ２合金について、上記（１）および（２）の方法により、溶解歩留まりおよび化学成分を測定し、その結果を表１に併記して示した。この結果から、本発明例７では、溶解歩留まりが９８％程度と高く、さらに目標のＮｉ組成比に対して±２％以内の高い精度で目標合金が得られていることがわかる。
（発明例８および比較例２）
本発明に従って、ヘリウムガス１００ｖｏｌ％雰囲気中で溶解作製したＬａ−Ｎｉ系水素吸蔵合金（発明例８）およアルゴンガス１００ｖｏｌ％雰囲気中で溶解作製した同じ化学組成のＬａ−Ｎｉ系水素吸蔵合金（比較例２）について、圧力組成等温線図を測定し、その結果を図３に示した。この図３から、発明例８の合金は、比較例２の合金に比べてプラトー領域が平坦でかつ広くなっており、ヘリウムガスにより急冷凝固された発明例８の合金は、均質性に優れた合金となっていることがわかる。Hereinafter, the present invention will be described in detail with reference to examples, but it is needless to say that the present invention is not limited to these examples.
(Invention Example 1)
As a raw material of the hydrogen storage alloy CaMg 2 , a total of 1 kg of Mg and Ca metals were prepared so that the molar ratio thereof was 2: 1, and all of these were charged into an induction melting type melting furnace. The inside of the furnace was evacuated to 8 × 10 −3 Torr, and then helium gas (concentration: 100 vol%) was introduced as an atmospheric gas until the pressure reached 600 Torr. Then, while filling the inside of the furnace with this atmospheric gas, the temperature of the melting furnace was heated to 1100 ° C. to melt the raw material, and further maintained for 30 minutes while maintaining the molten metal temperature of the alloy at 1050 ° C. Thereafter, the molten alloy was poured onto a water-cooled surface plate and cooled and solidified at a cooling rate of 1000 ° C./second to produce a CaMg 2 alloy. With respect to the CaMg 2 alloy thus obtained, the dissolution yield and chemical composition were measured by the following methods (1) and (2).
(1) Measurement of melting yield By measuring the mass of the raw material before melting and the mass of the alloy after melting casting, respectively, the mass decreased by evaporation was determined, and the melting yield was calculated.
(2) Measurement of chemical components The chemical components of the alloy after melting and casting were quantitatively analyzed by ICP emission spectroscopic analysis.
The measurement results are shown in Table 1. From this result, in Example 1 of the present invention using helium gas as the melting atmosphere gas, the melting yield is as high as 98.2% or more, and the alloy can be manufactured with high accuracy within ± 1% with respect to the target alloy composition. I understand that.
A CaMg 2 alloy was produced in the same manner as in Invention Example 1 except that argon gas (concentration: 100 vol%) was used as the atmospheric gas. With respect to this CaMg 2 alloy, the dissolution yield and chemical composition were measured by the methods (1) and (2) above, and the results are also shown in Table 1.
(Invention Examples 2 to 4)
A CaMg 2 alloy was produced in the same manner as in Invention Example 1 except that the concentration of helium gas introduced as the atmospheric gas was changed to 75, 50, 25 vol% (remaining argon gas). With respect to these CaMg 2 alloys, the dissolution yield and chemical composition were measured by the methods (1) and (2) above, and the results are also shown in Table 1. From these results, it can be seen that when the helium gas concentration exceeds 50 vol% (Invention Examples 2 and 3), the dissolution yield is as high as about 98%, and the target alloy composition can be obtained with high accuracy. On the other hand, when the helium gas concentration is 25 vol% (Invention Example 4), the dissolution yield and alloy composition are inferior to those of Invention Examples 1 to 3, but the dissolution yield is higher than that when no helium gas is contained (Comparative Example 1). In addition, the accuracy of the alloy composition is improved, and the effect of introducing helium gas can be confirmed.
FIG. 1 shows the relationship between the helium gas concentration and the dissolution yield obtained from the results of Invention Examples 1 to 4 and Comparative Example 1. FIG. 1 shows that the dissolution yield is improved as the helium gas concentration increases.
Further, the CaMg 2 alloy obtained in Invention Example 1 and Comparative Example 1 was measured for X-ray diffraction intensity to confirm whether the alloy and the compound had a target single-phase structure. The results are shown in FIG. From FIG. 2, the CaMg 2 alloy of Invention Example 1 is a CaMg 2 phase single-phase structure alloy, but the alloy of Comparative Example 1 is an alloy having a structure in which two phases of CaMg 2 phase and Ca phase are mixed. You can see that
As can be seen from Table 1, FIG. 1 and FIG. 2, according to the method of the present invention, it is possible to produce a single-phase alloy having a desired composition without variation. On the other hand, in the method of the comparative example, the evaporation loss of the raw material cannot be controlled, greatly deviating from the target composition, and the alloy composition varies.
(Invention Example 5)
A CaAl 2 alloy was produced in the same manner as in Invention Example 1 except that Ca and Al were used as alloy raw materials. The obtained CaMg 2 alloy was dissolved by the methods (1) and (2) above. The chemical components were measured, and the results are also shown in Table 1. From this result, it can be seen that in Example 5 of the present invention, the dissolution yield is as high as about 98%, and the target alloy is obtained with high accuracy within ± 1% with respect to the target Al composition.
(Invention Example 6)
An MgNi 2 alloy was prepared in the same manner as in Invention Example 1 except that Mg and Ni were used as alloy raw materials. The obtained MgNi 2 alloy was dissolved by the methods (1) and (2) above. The chemical components were measured, and the results are also shown in Table 1. From this result, it can be seen that in Example 6 of the present invention, the dissolution yield is as high as about 98%, and the target alloy is obtained with high accuracy within ± 2% with respect to the target Ni composition ratio.
(Invention Example 7)
A CaNi 2 alloy was produced in the same manner as in Experimental Example 1 except that Ca and Ni were used as alloy raw materials, and the obtained CaNi 2 alloy was dissolved by the methods (1) and (2) above. The chemical components were measured, and the results are also shown in Table 1. From this result, it can be seen that in Example 7 of the present invention, the dissolution yield is as high as about 98%, and the target alloy is obtained with high accuracy within ± 2% with respect to the target Ni composition ratio.
(Invention Example 8 and Comparative Example 2)
In accordance with the present invention, a La—Ni-based hydrogen storage alloy (Invention Example 8) prepared by dissolution in an atmosphere of 100 vol% helium gas and a La—Ni-based hydrogen storage alloy of the same chemical composition prepared by dissolution in an atmosphere of 100 vol% argon gas ( For Comparative Example 2), a pressure composition isotherm was measured, and the results are shown in FIG. From FIG. 3, the alloy of Invention Example 8 has a flat and wide plateau region as compared with the alloy of Comparative Example 2, and the alloy of Invention Example 8 that is rapidly solidified by helium gas has excellent homogeneity. It turns out that it is an alloy.
本発明の技術は、ＭｇやＣａ，ＺｎおよびＬｉ等に代表される低融点、低沸点でかつ蒸気圧が高い金属を含む合金の大量生産技術として利用されるだけでなく、それら金属を単体で溶解する場合や、ガリウム−ヒ素の如き半導体等に用いられる化合物やその他の化合物の溶解にも適用することができる。さらに、本発明の技術は、次世代において用いられる軽量金属や合金からなる構造材料や機能性材料や半導体化合物、その他の化合物の溶解技術にも適用が可能である。 The technology of the present invention is not only used as a mass production technology of an alloy containing a metal having a low melting point, a low boiling point, and a high vapor pressure typified by Mg, Ca, Zn, and Li, but these metals are used alone. It can also be applied to the dissolution of a compound used in a semiconductor such as gallium-arsenic or other compounds. Furthermore, the technology of the present invention can also be applied to a melting material for structural materials, functional materials, semiconductor compounds, and other compounds made of lightweight metals and alloys used in the next generation.
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| PCT/JP2006/304525 WO2006093334A1 (en) | 2005-03-02 | 2006-03-02 | Method of melting alloy containing high-vapor-pressure metal |
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| CN106978557A (en) * | 2017-05-11 | 2017-07-25 | 江苏理工学院 | A kind of magnesium lithium alloy and preparation method thereof |
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| US3845805A (en) * | 1972-11-14 | 1974-11-05 | Allied Chem | Liquid quenching of free jet spun metal filaments |
| US4375371A (en) * | 1981-06-12 | 1983-03-01 | Allegheny Ludlum Steel Corporation | Method for induction melting |
| JPS6217144A (en) * | 1985-07-15 | 1987-01-26 | Alum Funmatsu Yakin Gijutsu Kenkyu Kumiai | Manufacture of al-li alloy |
| US4948423A (en) * | 1989-07-21 | 1990-08-14 | Energy Conversion Devices, Inc. | Alloy preparation of hydrogen storage materials |
| JPH0611889B2 (en) * | 1989-10-06 | 1994-02-16 | 住友軽金属工業株式会社 | Method for melting A1-Li alloy |
| JPH08120365A (en) * | 1994-10-19 | 1996-05-14 | Sanyo Electric Co Ltd | Hydrogen storage alloy and its production |
| JPH08158043A (en) * | 1994-12-05 | 1996-06-18 | Nisshin Steel Co Ltd | Supply of mg to evaporation vessel |
| FR2746112B1 (en) * | 1996-03-13 | 1998-06-05 | METHOD OF CONTINUOUS HEAT TREATMENT OF METAL STRIPS IN ATMOSPHERES OF DIFFERENT NATURE | |
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| AT2420U1 (en) * | 1997-11-24 | 1998-10-27 | Unitech Ag | METHOD FOR THE OPERATION OF OVEN PLANTS FOR MAGNESIUM ALLOYS |
| JP2000239769A (en) * | 1998-12-22 | 2000-09-05 | Shin Etsu Chem Co Ltd | Rare earth hydrogen storage alloy and electrode using it |
| JP2003113430A (en) * | 2001-10-03 | 2003-04-18 | Sumitomo Metal Ind Ltd | Melting and casting method for magnesium and magnesium alloy |
| CN1296502C (en) * | 2001-12-14 | 2007-01-24 | 松下电器产业株式会社 | Magnesium alloy sectional stocks, their continuous casting method and device |
| JP4294947B2 (en) * | 2001-12-14 | 2009-07-15 | パナソニック株式会社 | Magnesium alloy shape casting method |
| JP4183959B2 (en) * | 2002-03-22 | 2008-11-19 | 株式会社日本製鋼所 | Method for producing hydrogen storage alloy |
| JP2004195527A (en) * | 2002-12-20 | 2004-07-15 | Seiko Epson Corp | Material melting apparatus and injection molding machine with the apparatus installed therein |
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| Publication number | Publication date |
|---|---|
| EP1875978A4 (en) | 2008-11-05 |
| US20090007728A1 (en) | 2009-01-08 |
| WO2006093334A1 (en) | 2006-09-08 |
| KR20070107757A (en) | 2007-11-07 |
| CN101132871A (en) | 2008-02-27 |
| JP4956826B2 (en) | 2012-06-20 |
| EP1875978B1 (en) | 2019-05-08 |
| CN101132871B (en) | 2011-04-20 |
| EP1875978A1 (en) | 2008-01-09 |
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