JP2005330570A - Alloy with whistler structure and manufacturing method therefor - Google Patents
Alloy with whistler structure and manufacturing method therefor Download PDFInfo
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、ホイスラー構造の合金及びその製造方法等に関するものであり、更に詳しくは、機械的合金化法により合成した非平衡状態の合金粉末を用いて、焼結により平衡状態に遷移させて、長時間の熱処理を施すことなく効率的にホイスラー構造の合金を製造する方法、その製品及び用途に関するものである。本発明は、ホイスラー構造の合金及びその製造の技術分野において、従来の溶解法による合金の製造では、長時間の熱処理が必要であり、きわめて非効率であったこと、また、冷却過程において種々の非平衡状態の相が合成され、ホイスラー構造の相の割合が減少すること、更に、製造工程において低融点の金属が蒸発し、得られる合金の組成がホイスラー構造の合金の組成からずれること、等の問題があったことをふまえ、それらの問題を確実に解決して、高品質のホイスラー構造の合金を効率的に省エネルギーで製造することを可能とする新規ホイスラー構造の合金の製造方法及びその製品を開発し、提供することを目的としてなされたものである。本発明の方法により作製されたホイスラー構造の合金は、電子の状態密度において擬ギャップ構造が期待され、温度差を電圧に変換する温度計や熱を電気に変換する熱電変換材料として応用できるものとして有用である。 The present invention relates to an alloy having a Heusler structure, a manufacturing method thereof, and the like, and more specifically, using an alloy powder in a non-equilibrium state synthesized by a mechanical alloying method, transitioning to an equilibrium state by sintering, The present invention relates to a method for producing an alloy having a Heusler structure efficiently without performing a heat treatment for a long period of time, its product and use. In the technical field of Heusler-structured alloys and their production, the present invention requires a long heat treatment and is extremely inefficient in the production of alloys by the conventional melting method. A phase in a non-equilibrium state is synthesized, the proportion of the phase of the Heusler structure is reduced, a metal having a low melting point evaporates in the manufacturing process, and the composition of the obtained alloy deviates from the composition of the alloy of the Heusler structure, etc. New Heusler alloy manufacturing method and product capable of efficiently solving high-quality Heusler alloy with energy saving, based on the above problems It was made for the purpose of developing and providing. The Heusler structure alloy produced by the method of the present invention is expected to have a pseudogap structure in the density of states of electrons, and can be applied as a thermometer that converts a temperature difference into a voltage or a thermoelectric conversion material that converts heat into electricity. Useful.
ホイスラー構造を有するＦｅ、Ａｌ、Ｖ等の遷移金属で構成される合金は、Ｆｅ2 ＶＡｌなどの金属間化合物として知られており、例えば、先行文献において西野らが熱電材料としての有効性を公表している（非特許文献１参照）。このようなホイスラー構造の合金においては、合金を構成する元素が均質に分散している必要があり、従来、溶解法による合成が行われている。 Alloys composed of transition metals such as Fe, Al and V having a Heusler structure are known as intermetallic compounds such as Fe 2 VAl. For example, Nishino et al. Announced the effectiveness as thermoelectric materials in the prior literature. (See Non-Patent Document 1). In an alloy having such a Heusler structure, elements constituting the alloy need to be uniformly dispersed, and conventionally, synthesis by a melting method has been performed.
しかし、溶解法による合金の製造では、冷却過程において、さまざまな非平衡状態の相が合成され、熱を電気に変換できる相（ホイスラー）の割合が減少するという問題があった。また、これを解決するためには、溶解法で得られた合金を約１０００℃に加熱し、４８時間もの長期間にわたる熱処理を行う必要があり、きわめて非効率的な製造技術であった。更に、溶解法においては、合金を構成する金属元素の融点（Ｆｅは１５３５℃、Ｖは１８９０℃、及びＡｌは６６０℃）が大きく異なるため、製造工程において、低融点の金属が蒸発し、得られた合金の組成がホイスラー構造の合金の組成からずれるという問題があった。 However, the production of alloys by the melting method has a problem that various non-equilibrium phases are synthesized in the cooling process, and the proportion of phases (Heusler) that can convert heat into electricity is reduced. Further, in order to solve this, it is necessary to heat the alloy obtained by the melting method to about 1000 ° C. and to perform heat treatment for a long period of 48 hours, which is a very inefficient manufacturing technique. Furthermore, in the melting method, the melting points of the metal elements composing the alloy (Fe is 1535 ° C., V is 1890 ° C., and Al is 660 ° C.) are greatly different. There was a problem that the composition of the alloy obtained was deviated from the composition of the alloy having the Heusler structure.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、上記の問題点を解決することを可能とする新しい製造技術を開発することを目標として鋭意研究した結果、ホイスラー合金を構成する金属元素を出発原料として、機械的合金化法によりひずみを導入しながら合金粉末を合成し、これを焼結することによって熱処理なしにホイスラー構造の合金を作製できることを見出し、本発明を完成するに至った。すなわち、本発明は、機械的合金化法により容器やボールへの付着を防止しながら、均質な原子の分散を行うとともに、ひずみを導入することで加熱時に容易に目的の結晶構造へ相転移させること、それにより、熱を電気に変換できるホイスラー構造の合金を目的組成で効率的に製造することを可能とする新規なホイスラー構造の合金の製造方法及びその製品を提供することを目的とするものである。 Under such circumstances, the present inventors have conducted intensive research with the goal of developing a new manufacturing technology capable of solving the above-mentioned problems in view of the above-mentioned conventional technology. It was found that an alloy having a Heusler structure can be produced without heat treatment by synthesizing an alloy powder while introducing strain by a mechanical alloying method using a metal element constituting the starting material as a starting material and sintering it. It came to be completed. That is, according to the present invention, a homogeneous alloy is dispersed while preventing adhesion to a container or a ball by a mechanical alloying method, and a phase transition is easily made to a target crystal structure during heating by introducing strain. It is an object of the present invention to provide a novel Heusler-structured alloy manufacturing method and its product that can efficiently produce a Heusler-structured alloy capable of converting heat into electricity with a target composition. It is.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）ホイスラー構造の合金を長時間の熱処理を施すことなく効率的に合成する方法であって、１）出発原料として、鉄、アルミニウム及び鉄を除くバナジウム等の遷移金属を使用し、機械的合金化法で、鉄、アルミニウム、鉄を除くバナジウム等の遷移金属及び不可避的に含まれる元素より構成される非平衡状態の合金粉末を合成する、２）上記合金粉末を焼結することにより平衡状態に遷移させた規則構造のホイスラー合金を作製する、ことを特徴とするホイスラー構造の合金の製造方法。
（２）上記合金粉末を加圧焼結する、前記（１）に記載のホイスラー構造の合金の製造方法。
（３）上記合金粉末を通電加圧焼結する、前記（１）に記載のホイスラー構造の合金の製造方法。
（４）出発原料として、鉄とアルミニウムを含む合金粉末と、鉄粉末、アルミニウム粉末、鉄を除くバナジウム等の遷移金属粉末を使用し、機械的合金化法により合金粉末を合成し、上記合金粉末を焼結する、前記（１）に記載のホイスラー構造の合金の製造方法。
（５）上記合金粉末を加圧焼結することを特徴とする前記（４）に記載のホイスラー構造の合金の製造方法。
（６）上記合金粉末を通電加圧焼結する、前記（４）に記載のホイスラー構造の合金の製造方法。
（７）焼結前にセラミックス粒子を混合して焼結する、前記（１）から（６）のいずれかに記載のホイスラー構造の合金の製造方法。
（８）前記（１）から（７）のいずれかに記載の方法により作製された、平衡状態に遷移させた規則構造を有することを特徴とするホイスラー構造の合金。
（９）前記（８）に記載のホイスラー構造の合金からなり、熱を電気に変換する機能を有することを特徴とする熱電変換材料。
（１０）前記（９）に記載の熱電変換材料を構成要素として含むことを特徴とする熱電変換部材。
The present invention for solving the above-described problems comprises the following technical means.
(1) A method for efficiently synthesizing an alloy with a Heusler structure without subjecting it to heat treatment for a long time. 1) Using a transition metal such as iron, aluminum, and vanadium excluding iron as a starting material, mechanically An alloying method is used to synthesize a non-equilibrium alloy powder composed of transition metals such as iron, aluminum, vanadium excluding iron, and elements inevitably contained. 2) Equilibrium by sintering the alloy powder. A method for producing an alloy having a Heusler structure, characterized by producing an ordered structure Heusler alloy that has been changed to a state.
(2) The method for producing an alloy having a Heusler structure according to (1), wherein the alloy powder is subjected to pressure sintering.
(3) The method for producing an alloy having a Heusler structure according to (1), wherein the alloy powder is subjected to current-pressure compression sintering.
(4) Using alloy powder containing iron and aluminum as a starting material, transition metal powder such as iron powder, aluminum powder, vanadium excluding iron, etc., and synthesizing the alloy powder by mechanical alloying method, the above alloy powder The manufacturing method of the alloy of the Heusler structure as described in said (1) which sinters.
(5) The method for producing an alloy having a Heusler structure according to (4), wherein the alloy powder is subjected to pressure sintering.
(6) The method for producing an alloy having a Heusler structure according to (4), wherein the alloy powder is subjected to current-pressure sintering.
(7) The method for producing an alloy having a Heusler structure according to any one of (1) to (6), wherein ceramic particles are mixed and sintered before sintering.
(8) An alloy having a Heusler structure manufactured by the method according to any one of (1) to (7) above, having an ordered structure shifted to an equilibrium state.
(9) A thermoelectric conversion material comprising the Heusler structure alloy according to (8) and having a function of converting heat into electricity.
(10) A thermoelectric conversion member comprising the thermoelectric conversion material according to (9) as a constituent element.
次に、本発明について更に詳細に説明する。
本発明のホイスラー構造の合金の製造方法は、ホイスラー構造の合金を長時間の熱処理を施すことなく効率的に合成する方法であって、出発原料として、鉄、アルミニウム及び鉄を除くバナジウム等の遷移金属を使用し、機械的合金化法で、鉄、アルミニウム、鉄を除くバナジウム等の遷移金属及び不可避的に含まれる元素より構成される非平衡状態の合金粉末を合成すること、上記合金粉末を焼結することにより平衡状態に遷移させた規則構造のホイスラー合金を作製すること、を特徴とするものである。
Next, the present invention will be described in more detail.
The method for producing an alloy having a Heusler structure according to the present invention is a method for efficiently synthesizing an alloy having a Heusler structure without subjecting it to heat treatment for a long time. Using a metal and mechanical alloying method, synthesizing a non-equilibrium alloy powder composed of transition metals such as iron, aluminum, vanadium excluding iron and elements inevitably contained, It is characterized by producing a Heusler alloy having a regular structure which is shifted to an equilibrium state by sintering.
本発明では、出発原料として、鉄、アルミニウム、及び鉄を除くバナジウム等の遷移金属が用いられるが、これらは、粉末状のものを用いる。これは、本発明においては、機械的合金化法により合金を形成するため、その合金化が効率的に行われるために必要なものである。ただ、それぞれの粉末は、純金属から構成される必要性はなく、鉄とアルミニウムの合金粉末などを利用することも可能である。純金属を機械的合金化法の出発原料として用いた場合には、合金化条件によって機械的合金化に用いられる粉砕ボールや容器への付着が増加することが一般に知られており、合金粉末を用いることによりその効率が改善される場合が多い。機械的合金化処理時の効率が低下すると、目的の合金粉末が得られるまでの処理時間が長くなり、粉砕ボールや容器からの汚染量が増加する。本発明の機械的合金化処理で得られたホイスラー合金組成の粉末は、合金を構成する元素が微細で均質に混合された状態であり、ひずみも大量に導入されているため、溶解法で作製される合金に比べて、Ｘ線回折パターンが幅広くなっているという特徴を有している。 In the present invention, iron, aluminum, and transition metals such as vanadium excluding iron are used as starting materials, and these are in powder form. In the present invention, the alloy is formed by the mechanical alloying method, which is necessary for the efficient alloying. However, each powder does not have to be made of pure metal, and an alloy powder of iron and aluminum can be used. When pure metal is used as a starting material for mechanical alloying, it is generally known that adhesion to pulverized balls and containers used for mechanical alloying increases depending on the alloying conditions. In many cases, the efficiency is improved by using it. If the efficiency at the time of mechanical alloying treatment decreases, the treatment time until the target alloy powder is obtained becomes longer, and the amount of contamination from the pulverized balls and containers increases. The powder of Heusler alloy composition obtained by the mechanical alloying treatment of the present invention is a state in which the elements constituting the alloy are finely and homogeneously mixed, and a large amount of strain is introduced, so it is produced by a melting method. Compared to alloys, the X-ray diffraction pattern is wide.
機械的合金化処理に用いる容器やボールの材質は、特に指定しないが、一般的には、ステンレス鋼や超硬合金、セラミックスなどが用いられる。また、機械的合金化処理時に粉末が容器やボールへ付着することを防止するために、アルコール系あるいは油脂系などの潤滑剤を適量添加しても問題ない。また、固体潤滑剤を少量添加してもよい。これらの潤滑剤は、１質量％以下が好ましく、機械的合金化処理後は不純物として粉末に取り込まれる場合が多い。なお、ホイスラー構造の合金は、合金の組成に依存するため、処理した粉末の９０質量％以上の粉末を回収しなくてはならない。そのためには、粉末とボールの重量比率、容器の大きさ、機械的合金化処理条件などを適切に選択する必要がある。特に、粉末回収量の改善には、合金粉末を用いることや潤滑剤を用いることが有効であり、合金粉末の組成に影響を与えないためには、合金粉末を利用することが効果的である。これは、純金属粉末より高硬度の合金粉末を混合することで、容器やボールに付着した粉末を削りとるものと考えられる。 The material of the container or ball used for the mechanical alloying treatment is not particularly specified, but in general, stainless steel, cemented carbide, ceramics or the like is used. Moreover, in order to prevent the powder from adhering to the container or ball during the mechanical alloying treatment, there is no problem even if an appropriate amount of a lubricant such as alcohol or oil is added. A small amount of solid lubricant may be added. These lubricants are preferably 1% by mass or less, and are often taken into the powder as impurities after the mechanical alloying treatment. In addition, since the alloy of the Heusler structure depends on the composition of the alloy, it is necessary to recover 90% by mass or more of the processed powder. For this purpose, it is necessary to appropriately select the weight ratio between the powder and the ball, the size of the container, the mechanical alloying treatment conditions, and the like. In particular, it is effective to use an alloy powder or a lubricant to improve the amount of recovered powder. In order not to affect the composition of the alloy powder, it is effective to use the alloy powder. . This is considered that the powder adhering to the container or the ball is scraped off by mixing an alloy powder having a hardness higher than that of the pure metal powder.
機械的合金化処理の雰囲気は、金属粉末の酸化などを防止するために、不活性ガス雰囲気や減圧雰囲気が望ましい。ただ、真空度が高い状態で機械的合金化処理を行うと、粉末の混合が均一にならず、長時間の処理が必要となるので好ましくない。機械的合金化処理には、例えば、遊星型ボールミルや振動型ボールミル、転動型ボールミルなどの一般的な粉砕器を利用することができる。処理時間は、機械的合金化処理を行う装置のメカニズムに依存するが、例えば、遊星型ボールミルにおいては、５０時間から２００時間程度で本発明に好適な粉末を作製することができる。 The atmosphere for the mechanical alloying treatment is preferably an inert gas atmosphere or a reduced pressure atmosphere in order to prevent oxidation of the metal powder. However, it is not preferable to perform the mechanical alloying process in a state where the degree of vacuum is high, because the powder mixing is not uniform and a long-time process is required. For the mechanical alloying treatment, for example, a general pulverizer such as a planetary ball mill, a vibration ball mill, or a rolling ball mill can be used. The treatment time depends on the mechanism of the apparatus for performing the mechanical alloying treatment. For example, in a planetary ball mill, a powder suitable for the present invention can be produced in about 50 to 200 hours.
機械的合金化処理で合成された合金は、粉末であり、本発明では、これを工業的な利用に供するために、粉末を固化成形する。粉末の固化成形には、一般的な焼結技術が利用できる。機械的合金化法で合成された粉末は、ひずみが大量に導入された非平衡状態の粉末である。そのため、この粉末は、焼結により容易に平衡状態の結晶相へ変化させることができる。機械的合金化処理で合成した粉末が加熱時に平衡状態に遷移する温度は、約８００℃と推定される。この粉末を、焼結時にその温度以上に加熱することで規則構造のホイスラー合金とすることができる。溶解法で合成されたホイスラー合金においては、凝固時に発生する組成の揺らぎに起因する準安定相が生成するため、得られた合金を、長時間、高温で加熱処理を行わないと平衡相を得ることができないが、機械的合金化法で得られた合金粉末においては、低温で平衡相を作製することができる。 The alloy synthesized by the mechanical alloying treatment is a powder, and in the present invention, the powder is solidified and formed in order to be used for industrial use. A general sintering technique can be used for solidifying and forming the powder. The powder synthesized by the mechanical alloying method is a non-equilibrium powder in which a large amount of strain is introduced. Therefore, this powder can be easily changed to an equilibrium crystal phase by sintering. The temperature at which the powder synthesized by mechanical alloying transitions to an equilibrium state when heated is estimated to be about 800 ° C. By heating this powder to a temperature higher than that during sintering, an ordered structure Heusler alloy can be obtained. In the Heusler alloy synthesized by the melting method, a metastable phase is generated due to fluctuations in the composition that occurs during solidification. Therefore, if the obtained alloy is not heat-treated at high temperature for a long time, an equilibrium phase is obtained. However, in the alloy powder obtained by the mechanical alloying method, an equilibrium phase can be produced at a low temperature.
一般に、焼結は、合金の融点の８０〜９０％程度の加熱で行われており、ホイスラー合金においては、焼結温度が約１３００℃と推定され、焼結時の加熱によって平衡相を得ることが可能である。本発明において、焼結温度は、７００〜１３００℃であり、より好ましくは９５０〜１１５０℃である。なお、焼結時に加圧を行うことで、より緻密な成形体を作製することが可能であり、特に、ホイスラー合金の導電性を利用して通電しながら加圧することで、より低温において緻密な成形体を作製することができる。したがって、本発明では、焼結方法としては、通電焼結が好適な方法として例示されるが、これに限定されるものではない。 Generally, sintering is performed by heating at about 80 to 90% of the melting point of the alloy. In the Heusler alloy, the sintering temperature is estimated to be about 1300 ° C., and an equilibrium phase is obtained by heating during sintering. Is possible. In this invention, sintering temperature is 700-1300 degreeC, More preferably, it is 950-1150 degreeC. In addition, it is possible to produce a denser molded body by applying pressure at the time of sintering, and in particular, by applying pressure while applying current using the conductivity of Heusler alloy, it becomes denser at a lower temperature. A molded body can be produced. Therefore, in the present invention, as a sintering method, electric current sintering is exemplified as a suitable method, but it is not limited to this.
粉末の成形には、一般的な焼結方法が利用できる。焼結の雰囲気については、金属粉末の酸化を防止するという観点から、真空あるいは不活性ガス雰囲気が望ましいが、特に、限定されるものではない。また、焼結時に使用する型やジグについても、特に指定しないが、例えば、黒鉛やセラミックス、超硬合金などの材料が好適に利用できる。更に、焼結時に加圧する際の加圧力発生機構についても、特に限定しないが、一般には、油圧や空圧、機械的な加圧などを利用できる。焼結時の圧力条件としては、黒鉛型を用いた場合、５０ＭＰａ前後が例示されるが、これに限定されるものではない。 A general sintering method can be used for forming the powder. The sintering atmosphere is preferably a vacuum or an inert gas atmosphere from the viewpoint of preventing oxidation of the metal powder, but is not particularly limited. Further, although the die and jig used at the time of sintering are not particularly specified, for example, materials such as graphite, ceramics and cemented carbide can be suitably used. Further, the pressurizing mechanism for pressurizing during sintering is not particularly limited, but generally, hydraulic pressure, pneumatic pressure, mechanical pressurization, or the like can be used. As a pressure condition at the time of sintering, when a graphite mold is used, about 50 MPa is exemplified, but is not limited thereto.
本発明では、機械的合金化法で合成された粉末に、セラミックス粒子などを混合して、焼結することもできる。機械的合金化法で合成された粉末は、低温で焼結できるため、セラミックス粒子との反応がほとんどなく、ホイスラー構造の合金の中にセラミックス粒子が分散した複合材料を容易に作製することが可能となる。粉末に混合するセラミックス粒子としては、例えば、アルミナ、イットリア、ジルコニア、チタニア、窒化ホウ素、炭化ケイ素、窒化ケイ素が例示されるが、これらに制限されるものではない。セラミックス粒子の混合方法は、特に指定しないが、例えば、湿式混合や乳鉢混合などの低いエネルギーでの混合が好ましい。これにより、ウィスカー繊維強化ホイスラー合金、カーボンナノチューブ分散ホイスラー合金等の複合材料を作製し、提供することができる。 In the present invention, ceramic particles or the like can be mixed with powder synthesized by a mechanical alloying method and sintered. Powders synthesized by mechanical alloying can be sintered at low temperatures, so there is almost no reaction with ceramic particles, and composite materials in which ceramic particles are dispersed in a Heusler alloy can be easily produced. It becomes. Examples of the ceramic particles mixed with the powder include, but are not limited to, alumina, yttria, zirconia, titania, boron nitride, silicon carbide, and silicon nitride. The method for mixing the ceramic particles is not particularly specified, but for example, mixing with low energy such as wet mixing or mortar mixing is preferable. Thereby, composite materials, such as a whisker fiber reinforced Heusler alloy and a carbon nanotube dispersed Heusler alloy, can be produced and provided.
本発明では、従来、溶解法により長時間の熱処理を施して合成されていたホイスラー構造の合金を、機械的合金化法によりひずみを導入しながら非平衡状態の合金粉末を合成すること、次いで、これを焼結することにより平衡状態に遷移させた規則構造のホイスラー合金を作製すること、により、長時間の熱処理をする必要がなく、また、製造工程において、低融点の金属が蒸発してホイスラー合金の組成がずれることがなく、低温焼結で、省エネルギーで、短時間に所定のホイスラー組成及び構造を有する高品質のホイスラー構造の合金を作製することが実現できるが、これらは、後記する実施例に示すように、格別の実験をしてはじめてその有効性が実証されたものであり、特に、製造工程において、熱を電気に変換できるホイスラー相の割合が減少するという従来技術の問題点を確実に解消することを可能にしたことに高い技術的意義を有するものである。 In the present invention, a Heusler-structured alloy that has been conventionally synthesized by a long-time heat treatment by a melting method, a non-equilibrium alloy powder is synthesized while introducing strain by a mechanical alloying method, By producing a Heusler alloy having an ordered structure that has been transitioned to an equilibrium state by sintering this, it is not necessary to perform heat treatment for a long time, and in the manufacturing process, the low melting point metal evaporates and Heusler It is possible to produce a high-quality Heusler alloy having a predetermined Heusler composition and structure in a short period of time by low-temperature sintering, energy saving, and low-temperature sintering. As shown in the example, its effectiveness was demonstrated only after a special experiment, especially in the manufacturing process, a Heusler phase that can convert heat into electricity. Ratio and has a high technical significance that made it possible to reliably solve the problems of the prior art of reducing.
本発明により、（１）本発明のホイスラー構造の合金を用いて、熱を電気に変換する素子を提供することが可能となる、（２）これまで、ホイスラー合金は、溶解法で作製されてきているが、凝固時の組成の揺らぎによる準安定相の生成のため、長時間、高温での熱処理が不可欠であるという問題があったのに対し、本発明では、粉末を非平衡化することにより均質な粉末を作製し、その後の焼結過程において安定なホイスラー構造の結晶を低温で短時間に合成することを可能としている、（３）そのため、セラミックス粒子などとの複合化も実現でき、熱電変換素子を容易に構成することもできる、（４）また、従来の熱電発電素子には、少なからず人体に有害な元素が含まれていたが、ホイスラー構造の合金には、人体に有害な元素がほとんど含まれておらず、環境にやさしい熱電発電素子を提供することが可能となり、生活に密着した熱源（例えば、自動車の廃熱や生活廃水など）から電気を安心して抽出することが可能となる、という格別の効果が奏される。 According to the present invention, (1) it is possible to provide an element that converts heat into electricity using the alloy of the Heusler structure of the present invention. (2) Until now, Heusler alloys have been produced by a melting method. However, there is a problem that heat treatment at a high temperature for a long time is indispensable for the generation of a metastable phase due to fluctuations in the composition during solidification. This makes it possible to produce a homogeneous powder and to synthesize a stable Heusler crystal in a subsequent sintering process at a low temperature in a short time. (3) Therefore, it can be combined with ceramic particles. The thermoelectric conversion element can also be easily constructed. (4) In addition, the conventional thermoelectric power generation element contains elements that are harmful to the human body, but the Heusler structure alloy is harmful to the human body. Elemental It is possible to provide a thermoelectric power generation element that is not contained and is environmentally friendly, and it is possible to extract electricity with peace of mind from heat sources closely related to daily life (for example, waste heat from automobiles and domestic wastewater). The special effect of becoming.
次に、実施例に基づいて本発明を具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.
鉄−２４．４質量％アルミニウム合金粉末、鉄粉末（アトマイズ鉄粉末、９９．９質量％鉄）、アルミニウム粉末（高純度科学研究所（株）製試薬、９９．９質量％アルミニウム）及びバナジウム粉末（高純度科学研究所（株）製試薬、９９．９質量％バナジウム）を出発原料として、遊星型ボールミルによる２００時間の機械的合金化処理により、Ｆｅ−２５ａｔ％Ｖ−２５ａｔ％Ａｌ組成の合金粉末を合成した。得られた粉末は、配合重量の９５質量％であり、図１に示したように、ブロードなＸ線回折パターンを示す非平衡状態の１０ミクロン程度の粉末であった。この粉末は、図２に熱分析曲線（ＤＴＡ）を示すように、８００℃で平衡相へ転移した。 Iron-24.4 mass% aluminum alloy powder, iron powder (atomized iron powder, 99.9 mass% iron), aluminum powder (reagent manufactured by High Purity Science Laboratory Co., Ltd., 99.9 mass% aluminum) and vanadium powder An alloy having a composition of Fe-25 at% V-25 at% Al by a mechanical alloying treatment for 200 hours with a planetary ball mill using a reagent (99.9 mass% vanadium manufactured by High Purity Science Laboratory Co., Ltd.) as a starting material A powder was synthesized. The obtained powder was 95% by mass of the blended weight, and as shown in FIG. 1, it was a non-equilibrium state powder of about 10 microns showing a broad X-ray diffraction pattern. This powder transitioned to the equilibrium phase at 800 ° C. as shown in the thermal analysis curve (DTA) in FIG.
得られた粉末２ｇを、外径３０ｍｍ、内径１０ｍｍ、高さ３０ｍｍの黒鉛製の型に充填し、５０ＭＰａの加圧力にてパルス状の電流を流しながら通電加熱を行った。焼結の雰囲気は１０Ｐａ程度の真空中にて行い、１１００℃まで加熱して固化成形した。 2 g of the obtained powder was filled in a graphite mold having an outer diameter of 30 mm, an inner diameter of 10 mm, and a height of 30 mm, and energized and heated while flowing a pulsed current at a pressure of 50 MPa. The sintering atmosphere was performed in a vacuum of about 10 Pa and heated to 1100 ° C. for solidification molding.
得られた焼結体のＸ線回折パターンは、図３のように、ホイスラー構造特有の回折パターン（２θ＝２６ｄｅｇ．付近で回折ピーク（１１１）が観察されることが特徴）を示した。焼結体の結晶粒は、０．５ミクロン程度と非常に細かく、通常の溶解法で合成された合金の５００分の１程度であった。 As shown in FIG. 3, the X-ray diffraction pattern of the obtained sintered body showed a diffraction pattern peculiar to the Heusler structure (characterized by a diffraction peak (111) observed in the vicinity of 2θ = 26 deg.). The crystal grains of the sintered body were very fine, about 0.5 microns, which was about 1/500 of an alloy synthesized by a normal melting method.
鉄−２４．４質量％アルミニウム合金粉末、鉄粉末（アトマイズ鉄粉末、９９．９質量％鉄）、アルミニウム粉末（高純度科学研究所（株）製試薬、９９．９質量％アルミニウム）及びバナジウム粉末（高純度科学研究所（株）製試薬、９９．９質量％バナジウム）を出発原料として、遊星型ボールミルによる２００時間の機械的合金化処理により、Ｆｅ−２５ａｔ％Ｖ−２５ａｔ％Ａｌ組成の合金粉末を合成した。 Iron-24.4 mass% aluminum alloy powder, iron powder (atomized iron powder, 99.9 mass% iron), aluminum powder (reagent manufactured by High Purity Science Laboratory Co., Ltd., 99.9 mass% aluminum) and vanadium powder An alloy having a composition of Fe-25 at% V-25 at% Al by a mechanical alloying treatment for 200 hours with a planetary ball mill using a reagent (99.9 mass% vanadium manufactured by High Purity Science Laboratory Co., Ltd.) as a starting material A powder was synthesized.
得られた粉末２ｇを、外径３０ｍｍ、内径１０ｍｍ、高さ３０ｍｍの超硬合金製の型に充填し、２５０ＭＰａの加圧力にて室温で成形した。この成形体を真空炉にて焼結した。雰囲気は１×１０-3Ｐａ程度の真空中にて行い、１２００℃まで加熱して１時間保持することにより固化成形した。 2 g of the obtained powder was filled into a cemented carbide mold having an outer diameter of 30 mm, an inner diameter of 10 mm, and a height of 30 mm, and molded at room temperature with a pressure of 250 MPa. This compact was sintered in a vacuum furnace. The atmosphere was set in a vacuum of about 1 × 10 −3 Pa, heated to 1200 ° C. and held for 1 hour for solidification molding.
得られた焼結体のＸ線回折パターンは、ホイスラー構造特有の回折パターンを示した。焼結体の結晶粒は、１０ミクロン程度であり、通電焼結により作製した焼結体に比べて、大きな結晶粒径となった。 The X-ray diffraction pattern of the obtained sintered body showed a diffraction pattern peculiar to the Heusler structure. The crystal grains of the sintered body were about 10 microns, and the crystal grain size was larger than that of the sintered body produced by current sintering.
鉄−２４．４質量％アルミニウム合金粉末、鉄粉末（アトマイズ鉄粉末、９９．９質量％鉄）、アルミニウム粉末（高純度科学研究所（株）製試薬、９９．９質量％アルミニウム）及びバナジウム粉末（高純度科学研究所（株）製試薬、９９．９質量％バナジウム）を出発原料として、遊星型ボールミルによる２００時間の機械的合金化処理により、Ｆｅ−２５ａｔ％Ｖ−２５ａｔ％Ａｌ組成の合金粉末を合成した。得られた粉末に、アルミナ粒子が１０体積％となるように配合し、乳鉢にて１０分間混合した。 Iron-24.4 mass% aluminum alloy powder, iron powder (atomized iron powder, 99.9 mass% iron), aluminum powder (reagent manufactured by High Purity Science Laboratory Co., Ltd., 99.9 mass% aluminum) and vanadium powder An alloy having a composition of Fe-25 at% V-25 at% Al by a mechanical alloying treatment for 200 hours with a planetary ball mill using a reagent (99.9 mass% vanadium manufactured by High Purity Science Laboratory Co., Ltd.) as a starting material A powder was synthesized. The obtained powder was blended so that the alumina particles were 10% by volume and mixed for 10 minutes in a mortar.
混合粉末２ｇを、外径３０ｍｍ、内径１０ｍｍ、高さ３０ｍｍの黒鉛製の型に充填し、５０ＭＰａの加圧力にてパルス状の電流を流しながら通電加熱を行った。焼結は１０Ｐａ程度の真空雰囲気中にて行い、１１００℃まで加熱して固化成形した。 2 g of the mixed powder was filled in a graphite mold having an outer diameter of 30 mm, an inner diameter of 10 mm, and a height of 30 mm, and energized and heated while flowing a pulsed current at a pressure of 50 MPa. Sintering was performed in a vacuum atmosphere of about 10 Pa, and solidified by heating to 1100 ° C.
得られた焼結体のＸ線回折パターンは、図４に示したように、ホイスラー構造のピークとアルミナのピークのみを示しており、両者の反応生成物は観察されなかった。 As shown in FIG. 4, the X-ray diffraction pattern of the obtained sintered body showed only the peak of the Heusler structure and the peak of alumina, and the reaction product of both was not observed.
鉄−２４．４質量％アルミニウム合金粉末、鉄粉末（アトマイズ鉄粉末、９９．９質量％鉄）、アルミニウム粉末（高純度科学研究所（株）製試薬、９９．９質量％アルミニウム）及びバナジウム粉末（高純度科学研究所（株）製試薬、９９．９質量％バナジウム）を出発原料として、遊星型ボールミルによる２００時間の機械的合金化処理により、Ｆｅ−２５ａｔ％Ｖ−２５ａｔ％Ａｌ組成の合金粉末を合成した。鉄−２４．４質量％アルミニウム合金粉末を用いた場合の粉末回収率は、９５％であり、アルミニウム粉末を用いた場合の３５％より非常に高い回収率となった。 Iron-24.4 mass% aluminum alloy powder, iron powder (atomized iron powder, 99.9 mass% iron), aluminum powder (reagent manufactured by High Purity Science Laboratory Co., Ltd., 99.9 mass% aluminum) and vanadium powder An alloy having a composition of Fe-25 at% V-25 at% Al by a mechanical alloying treatment for 200 hours with a planetary ball mill using a reagent (99.9 mass% vanadium manufactured by High Purity Science Laboratory Co., Ltd.) as a starting material A powder was synthesized. The powder recovery rate when using iron-24.4 mass% aluminum alloy powder was 95%, which was much higher than 35% when aluminum powder was used.
得られた粉末２ｇを、外径３０ｍｍ、内径１０ｍｍ、高さ３０ｍｍの黒鉛製の型に充填し、５０ＭＰａの加圧力にてパルス状の電流を流しながら通電加熱を行った。焼結は１０Ｐａ程度の真空雰囲気中にて行い、１１００℃まで加熱して固化成形した。 2 g of the obtained powder was filled in a graphite mold having an outer diameter of 30 mm, an inner diameter of 10 mm, and a height of 30 mm, and energized and heated while flowing a pulsed current at a pressure of 50 MPa. Sintering was performed in a vacuum atmosphere of about 10 Pa, and solidified by heating to 1100 ° C.
ＥＰＭＡを用いて組成分析をしたところ、アルミニウム粉末を用いて作製した焼結体は、目的組成よりアルミニウムの含有量が２〜３％低いことが分かった。これは、アルミニウム粉末の展伸性のため、機械的合金化処理中に容器あるいはボールに固着するためである。一方、鉄−２４．４質量％アルミニウム合金粉末を用いた場合、配合組成とのずれが±０．３％以内であった。 As a result of composition analysis using EPMA, it was found that the sintered body produced using aluminum powder had an aluminum content that was 2-3% lower than the target composition. This is due to the extensibility of the aluminum powder so that it adheres to the container or ball during the mechanical alloying process. On the other hand, when iron-24.4 mass% aluminum alloy powder was used, the deviation from the blending composition was within ± 0.3%.
鉄−２４．４質量％アルミニウム合金粉末、鉄粉末（アトマイズ鉄粉末、９９．９質量％鉄）、チタン粉末（高純度科学研究所（株）製試薬、９９．９質量％チタン）及びモリブデン粉末を出発原料として、遊星型ボールミルによる２００時間の機械的合金化処理により、Ｆｅ−２５ａｔ％Ｖ−２５ａｔ％Ａｌ組成の合金粉末を合成した。 Iron-24.4 mass% aluminum alloy powder, iron powder (atomized iron powder, 99.9 mass% iron), titanium powder (reagent manufactured by High Purity Science Laboratory Co., Ltd., 99.9 mass% titanium) and molybdenum powder As a starting material, an alloy powder having a composition of Fe-25 at% V-25 at% Al was synthesized by mechanical alloying treatment for 200 hours using a planetary ball mill.
得られた粉末２ｇを、外径３０ｍｍ、内径１０ｍｍ、高さ３０ｍｍの黒鉛製の型に充填し、５０ＭＰａの加圧力にてパルス状の電流を流しながら通電加熱を行った。焼結は１０Ｐａ程度の真空雰囲気中にて行い、１１００℃まで加熱して固化成形した。 2 g of the obtained powder was filled in a graphite mold having an outer diameter of 30 mm, an inner diameter of 10 mm, and a height of 30 mm, and energized and heated while flowing a pulsed current at a pressure of 50 MPa. Sintering was performed in a vacuum atmosphere of about 10 Pa, and solidified by heating to 1100 ° C.
得られた焼結体のＸ線回折パターンは、ホイスラー構造特有の回折パターンを示した。 The X-ray diffraction pattern of the obtained sintered body showed a diffraction pattern peculiar to the Heusler structure.
以上詳述したように、本発明は、ホイスラー構造の合金及びその製造方法に係るものであり、本発明により、粉末を非平衡化することにより均質な粉末を作製し、その後の焼結過程において安定なホイスラー構造の結晶を低温で短時間に合成し、提供することができる。従来の熱電発電素子には、少なからず人体に有害な元素が含まれていたが、本発明のホイスラー構造の合金には、人体に有害な元素がほとんど含まれておらず、環境にやさしい熱電発電素子を提供することが可能となり、生活に密着した熱源（例えば、自動車の廃熱や生活廃水など）から電気を安心して抽出することができる。 As described above in detail, the present invention relates to an alloy having a Heusler structure and a method for producing the same, and according to the present invention, a homogeneous powder is produced by non-equilibrium of the powder, and in the subsequent sintering process. A stable Heusler crystal can be synthesized and provided at a low temperature in a short time. Conventional thermoelectric power generation elements contain not a little harmful elements to the human body, but the Heusler structure alloy of the present invention contains almost no elements harmful to the human body and is friendly to the environment. An element can be provided, and electricity can be extracted with peace of mind from a heat source (for example, waste heat from automobiles or waste water from daily life) that is closely related to daily life.
Claims (10)
A thermoelectric conversion member comprising the thermoelectric conversion material according to claim 9 as a constituent element.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008021982A (en) * | 2006-06-15 | 2008-01-31 | Toyota Central Res & Dev Lab Inc | Thermoelectric material, and method for manufacturing it |
| JP2010157686A (en) * | 2008-12-30 | 2010-07-15 | Ind Technol Res Inst | Composite material of complex alloy and generation method thereof, thermoelectric device and thermoelectric module |
| WO2013093967A1 (en) * | 2011-12-21 | 2013-06-27 | 株式会社日立製作所 | Thermoelectric conversion element and thermoelectric conversion module using same |
| JPWO2013093967A1 (en) * | 2011-12-21 | 2015-04-27 | 株式会社日立製作所 | Thermoelectric conversion element and thermoelectric conversion module using the same |
| CN104611621A (en) * | 2015-02-12 | 2015-05-13 | 广西玉柴机器股份有限公司 | High-strength engine cylinder cover |
| JP2015192084A (en) * | 2014-03-28 | 2015-11-02 | 国立研究開発法人産業技術総合研究所 | Green compact for thermoelectric conversion material, sintered compact, and manufacturing method thereof |
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2004
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008021982A (en) * | 2006-06-15 | 2008-01-31 | Toyota Central Res & Dev Lab Inc | Thermoelectric material, and method for manufacturing it |
| JP2010157686A (en) * | 2008-12-30 | 2010-07-15 | Ind Technol Res Inst | Composite material of complex alloy and generation method thereof, thermoelectric device and thermoelectric module |
| WO2013093967A1 (en) * | 2011-12-21 | 2013-06-27 | 株式会社日立製作所 | Thermoelectric conversion element and thermoelectric conversion module using same |
| JPWO2013093967A1 (en) * | 2011-12-21 | 2015-04-27 | 株式会社日立製作所 | Thermoelectric conversion element and thermoelectric conversion module using the same |
| JP2015192084A (en) * | 2014-03-28 | 2015-11-02 | 国立研究開発法人産業技術総合研究所 | Green compact for thermoelectric conversion material, sintered compact, and manufacturing method thereof |
| CN104611621A (en) * | 2015-02-12 | 2015-05-13 | 广西玉柴机器股份有限公司 | High-strength engine cylinder cover |
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