JP2009249702A - Magnetic alloy powder, and method for producing the same - Google Patents
Magnetic alloy powder, and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、オゾン層の破壊や温室ガス排出により地球温暖化に悪影響をおよぼすフロンガスや代替フロンを使用する気体冷凍に代わる環境保全型の冷凍システムとして期待されている磁気冷凍技術に関するものである。磁気冷凍システムにおいては、外部の磁界変化に対して、磁性体内部で大きなエントロピー変化を示す磁気冷凍作業物質が必要である。本発明は、室温近傍で大きな磁気エントロピー変化を示す、Ｒ−ＴＭ−Ｍ−Ｈ系の磁性合金粉末およびその製造方法に関するものである。 The present invention relates to a magnetic refrigeration technology that is expected as an environment-conserving refrigeration system that replaces gas refrigeration using CFCs and CFCs that adversely affect global warming due to ozone layer destruction and greenhouse gas emissions. In a magnetic refrigeration system, a magnetic refrigeration working material that exhibits a large entropy change inside a magnetic body with respect to an external magnetic field change is required. The present invention relates to an R-TM-MH-based magnetic alloy powder that exhibits a large magnetic entropy change near room temperature and a method for producing the same.
現在世界規模で、オゾン層破壊および地球温暖化が深刻な社会問題となっている。オゾン層破壊の原因がエアコンや冷蔵庫などの冷凍機に使用されるフロンガスであることが指摘され、１９９２年モントリオールで開催された国際会議において特定フロンの全廃が定められた。しかし、特定フロンの代替として使用が認められている。
いわゆる代替フロンにおいても二酸化炭素の数千倍から数万倍の温暖化効果が確認されており１９９７年の地球温暖化防止京都会議において削減対象となった。欧州では、自動車への代替フロンの搭載を全廃することが決定されている。このような状況から、より環境負荷の低い冷凍技術の開発実用化が望まれている。このような背景から、気体冷凍に代わる環境に優しい冷凍空調技術として磁気冷凍技術が注目されている。磁気冷凍は極低温域における冷却技術としては既に利用されている。しかし常温域では作業物質の格子振動による熱容量が大きいこと、また磁気系の熱ゆう乱によるエネルギーが大きくなるため実用化が困難であった。常温での磁気冷凍材料としては、安価で大きな磁気熱量効果が得られる磁性材料が必要とされている。
Currently, ozone depletion and global warming are serious social problems on a global scale. It was pointed out that the cause of the ozone depletion was chlorofluorocarbon gas used in refrigerators such as air conditioners and refrigerators, and the abolition of specific chlorofluorocarbons was decided at an international conference held in Montreal in 1992. However, it is approved for use as a substitute for specific chlorofluorocarbons.
So-called CFC substitutes have been confirmed to have a warming effect that is several thousand to several tens of thousands times that of carbon dioxide, and was reduced at the Kyoto Conference on Global Warming Prevention in 1997. In Europe, it has been decided to completely eliminate the use of CFC substitutes in automobiles. Under such circumstances, development and practical use of a refrigeration technique with a lower environmental load is desired. From such a background, magnetic refrigeration technology has attracted attention as an environment-friendly refrigeration air conditioning technology that replaces gas refrigeration. Magnetic refrigeration has already been used as a cooling technique in a cryogenic region. However, in the normal temperature range, the heat capacity due to the lattice vibration of the work substance is large, and the energy due to the thermal disturbance of the magnetic system becomes large, making it difficult to put it into practical use. As a magnetic refrigeration material at room temperature, a magnetic material that is inexpensive and has a large magnetocaloric effect is required.
従来常温磁気冷凍材料として室温付近に磁気変態点（キュリー温度）を有するＧｄおよびＧｄ合金が知られているが、Ｇｄは希土類元素の中では比較的稀少で高価な金属であり、工業的に実用性の高い磁気冷凍材料ではない。近年、Ｇｄの代わる常温磁気冷凍材料として、常温近傍で一次相転移を示す磁性材料が注目されている。このような磁性材料は、キュリー点近傍の常磁性温度域で外部より磁界を印加することにより強磁性に磁気変態する磁性材料であり、比較的小さな外部磁界により大きな磁化変化に伴う大きなエントロピー変化（磁気熱量効果）が得られるという特長を有する。
このような磁性材料としては、Ｇｄ5Ｓｉ2Ｇｅ2系、Ｍｎ（Ａｓ-Ｓｂ）系、ＭｎＦｅ（Ｐ―Ａｓ）系、Ｌａ（Ｆｅ-Ｓｉ）Ｈ系などが検討されている。これら提案されている常温磁気冷凍作業物質の中では、原材料コスト、環境負荷、製造工程の中での安全性等を考慮すると、Ｌａ（Ｆｅ-Ｓｉ）Ｈ系合金が実用材料として最も有望な作業物質と考えられる。本磁気冷凍材料に関しては、大学が主体となり物性研究を中心に検討が行われている。（非特許文献１，２，３）
Conventionally, Gd and Gd alloys having a magnetic transformation point (Curie temperature) near room temperature are known as room temperature magnetic refrigeration materials, but Gd is a relatively rare and expensive metal among rare earth elements, and is practically used industrially. It is not a highly magnetic refrigeration material. In recent years, magnetic materials that exhibit a first-order phase transition near normal temperature have attracted attention as normal temperature magnetic refrigeration materials that replace Gd. Such a magnetic material is a magnetic material that undergoes magnetic transformation to ferromagnetism by applying a magnetic field from the outside in the paramagnetic temperature range near the Curie point, and a large entropy change (with a relatively large external magnetic field) The magnetocaloric effect is obtained.
As such a magnetic material, Gd 5 Si 2 Ge 2 series, Mn (As—Sb) series, MnFe (P—As) series, La (Fe—Si) H series, and the like have been studied. Among these proposed room-temperature magnetic refrigeration working materials, La (Fe-Si) H-based alloys are the most promising work as practical materials, considering raw material costs, environmental impact, safety in the manufacturing process, etc. It is considered a substance. This magnetic refrigeration material is being studied mainly by physical properties research led by universities. (Non-patent documents 1, 2, 3)
また特許文献１には、Ｌａ（Ｆｅ１−ＸＭＸ）１３ＨＺ系合金（ＭはＳｉ、Ａｌから選択された１種または２種以上）の１００〜１５００μｍの粒子が磁気冷凍材料として有望であることが開示されている。 Also in Patent Document 1, as L a (Fe 1-X M X) 13 H Z alloy (M is Si, 1 kind or 2 or more selected from Al) magnetic refrigeration material particles are 100~1500μm of Promising is disclosed.
常温磁気冷凍材料であるＲ‐Ｆｅ‐Ｓｉ‐Ｈ系合金はＮａＺｎ13型結晶構造を有するＲ‐（Ｆｅ‐Ｓｉ）13結晶格子中に水素を侵入型で固溶させることにより結晶格子を膨張させキュリー温度を上昇させることにより常温近傍にキュリー温度を持つ磁気冷凍材料である。本材料の製造方法としては、アーク溶解や高周波溶解により得られた鋳造合金を不活性雰囲気あるいは真空中で、１０００℃以上で１００時間以上の長時間溶体化熱処理し得られた合金を機械粉砕で数百μｍの粉末とし、水素を含む雰囲気中で水素吸臓することにより製造されていた。（非特許文献４） The R-Fe-Si-H alloy, which is a room-temperature magnetic refrigeration material, expands the crystal lattice by dissolving hydrogen in an interstitial form in the R- (Fe-Si) 13 crystal lattice having the NaZn 13 type crystal structure. It is a magnetic refrigeration material having a Curie temperature near normal temperature by raising the Curie temperature. As a manufacturing method of this material, an alloy obtained by subjecting a cast alloy obtained by arc melting or high-frequency melting to a solution heat treatment at 1000 ° C. or higher for 100 hours or longer in an inert atmosphere or vacuum is mechanically pulverized. It was manufactured by making a powder of several hundred μm and absorbing hydrogen in an atmosphere containing hydrogen. (Non-Patent Document 4)
一方、特許文献２においては、１０００℃以上での溶体化を容易とするために、Ｌａ‐Ｆｅ‐Ｓｉ系合金溶湯を１０２℃/秒〜１０８℃/秒で急冷し、初晶として析出するα鉄を低減かつ微細に分散させた厚さ１０〜３００μｍの薄帯を得ることにより、９００〜１２００℃で比較的短時間で溶体化処理を可能とする技術が開示されている。 On the other hand, in Patent Document 2, in order to facilitate solution at 1000 ° C. or higher, the La—Fe—Si alloy melt is rapidly cooled at 10 2 ° C./second to 10 8 ° C./second to precipitate as primary crystals. A technology that enables solution treatment at 900 to 1200 ° C. in a relatively short time by obtaining a thin ribbon having a thickness of 10 to 300 μm in which α iron is reduced and finely dispersed is disclosed.
従来のＲ‐Ｆｅ‐Ｓｉ‐Ｈ系合金の製造方法には、以下の課題がある。磁気冷凍材料としては、比較的小さな外部磁界の変化で大きな磁化変化（エントロピー変化）を示す物質が好ましい。そのためにはＲ‐Ｆｅ‐Ｓｉ合金中に出来るだけ均一に水素を固溶させる必要がある。合金中の水素濃度分布が不均一である場合には、Ｘ線回折図においては図４に示すように高水素固溶相と低水素固溶相に分離した回折線となり、このような合金の磁化の温度変化は、図７に示すように広い温度範囲で強磁性から常磁性に転移するため、磁気冷凍作業物質として大きな磁気エントロピー変化が得られないという問題点がある。この問題を改善する手段として、非特許文献５においては高圧水素中で水素吸臓処理を行い、一旦飽和量まで水素を吸蔵させた後、Ａｒ雰囲気中で脱水素熱処理を行うことにより水素固溶量を調整しキュリー温度を制御することが開示されている。しかしながら、この方法においては脱水素量が熱処理条件や試料の量により微妙に変化するため合金中の固溶水素量を所望の値に制御することは工業的には極めて難しく、安定に本材料を製造することが困難であるという問題がある。さらに、非特許文献５において合金の水素濃度をより容易に均一とする手段として、０．０２ＭＰａの密閉した低圧水素雰囲気中で長時間水素吸蔵反応を行うことにより、水素の拡散速度制御することが提案されているが、この方法でも水素を所望の濃度まで吸蔵させるために２０時間以上の長時間を要するため工業的に大量の合金を製造することが困難であるという問題点がある。
よって、本発明では合金中の水素量を均一に調整できる簡易な磁気冷凍材料用の磁性合金粉末の製造方法および高い効率で、大きなエントロピー変化を持つ磁性合金粉末を提供することを課題とする。
The conventional method for producing an R—Fe—Si—H alloy has the following problems. As the magnetic refrigeration material, a substance that exhibits a large magnetization change (entropy change) with a relatively small change in the external magnetic field is preferable. For this purpose, it is necessary to dissolve hydrogen in the R—Fe—Si alloy as uniformly as possible. When the hydrogen concentration distribution in the alloy is not uniform, the X-ray diffraction diagram shows a diffraction line separated into a high hydrogen solid solution phase and a low hydrogen solid solution phase as shown in FIG. As shown in FIG. 7, the temperature change of magnetization is changed from ferromagnetism to paramagnetism in a wide temperature range, so that there is a problem that a large magnetic entropy change cannot be obtained as a magnetic refrigeration material. As a means for improving this problem, in Non-Patent Document 5, hydrogen absorption treatment is performed in high-pressure hydrogen, and after hydrogen is absorbed to a saturated amount, dehydrogenation heat treatment is performed in an Ar atmosphere. Adjusting the amount and controlling the Curie temperature is disclosed. However, in this method, the amount of dehydrogenation changes slightly depending on the heat treatment conditions and the amount of the sample, so it is extremely difficult industrially to control the amount of dissolved hydrogen in the alloy to a desired value. There is a problem that it is difficult to manufacture. Furthermore, as a means of making the hydrogen concentration of the alloy more uniform in Non-Patent Document 5, the hydrogen diffusion rate can be controlled by performing a hydrogen storage reaction for a long time in a closed low-pressure hydrogen atmosphere of 0.02 MPa. Although proposed, this method has a problem that it is difficult to produce a large amount of an alloy industrially because it takes a long time of 20 hours or more to occlude hydrogen to a desired concentration.
Therefore, it is an object of the present invention to provide a simple method for producing a magnetic alloy powder for a magnetic refrigeration material capable of uniformly adjusting the amount of hydrogen in the alloy and a magnetic alloy powder having a large entropy change with high efficiency.
本発明は、実質的にＮａＺｎ13型結晶構造を有する化合物相により構成される磁気冷凍用の磁性合金粉末であって、厚さが３０μｍ以下の偏平状であることを特徴とする。厚さ（ｔ）と厚み方向と交差する面の長径（ｌ）の比率ｌ/ｔ（アスペクト比）が５以上であるものが好ましい。 The present invention is a magnetic alloy powder for magnetic refrigeration substantially composed of a compound phase having a NaZn 13 type crystal structure, and has a flat shape with a thickness of 30 μm or less. It is preferable that the ratio 1 / t (aspect ratio) of the major axis (l) of the surface intersecting the thickness (t) and the thickness direction is 5 or more.
本発明の磁性合金粉末は、組成式で、Ｒａ（ＴＭxＭ1-x）ｂ（但し、ＲはＬａを必須として必要によりＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ，Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙ、Ｌｕからなる希土類元素の１種以上を含み、ＴＭはＦｅを必須として必要によりＴｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎからなる遷移金属元素群より選択される１種以上を含み、ＭはＳｉを必須として必要によりＡｌ、Ｇａ、Ｇｅ、Ｓｎからなる元素群より選択される少なくとも１種以上を含み、かつ、原子％で５．５≦ａ≦７．５、９２．５≦ｂ≦９４．５、０．７５≦X≦０．９５であるものが好ましい。 The magnetic alloy powder of the present invention has a composition formula: R a (TM x M 1-x ) b (where R is essential to La, and if necessary, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, It contains one or more rare earth elements composed of Ho, Er, Tm, Y, and Lu, TM requires Fe as an essential element, and includes a transition metal element group composed of Ti, V, Cr, Mn, Co, Ni, Cu, and Zn as necessary. Including one or more selected, M including Si as an essential element, including at least one selected from the element group consisting of Al, Ga, Ge, and Sn if necessary, and 5.5% a ≦ atomic% Preferred are 7.5, 92.5 ≦ b ≦ 94.5, and 0.75 ≦ X ≦ 0.95.
また、本発明の磁性合金粉末は、組成式でＲａ（ＴＭＸＭ１-Ｘ）bＨc（但し、ＲはＬａを必須として必要によりＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ，Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙ、Ｌｕからなる希土類元素の１種以上を含み、ＴＭはＦｅを必須として必要によりＴｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎからなる遷移金属元素群より選択される１種以上を含み、ＭはＳｉを必須としてＡｌ、Ｇａ、Ｇｅ、Ｓｎからなる元素群より選択される少なくとも１種以上を含み、かつ、原子％で５．５≦ａ≦７．５、８０．５≦ｂ≦９２．５、０＜ｃ≦１４、０．７５≦Ｘ≦０．９５）であるものが好ましい。この磁性合金粉末は、ＮａＺｎ13相のＸ線回折の（５３１）面に相当する回折線の半価幅が０．５度以下のものが得られる。 In addition, the magnetic alloy powder of the present invention has a composition formula of R a (TM X M 1-X ) b H c (where R is essential as La is required, and Ce, Pr, Nd, Sm, Eu, Gd, Tb if necessary. , Dy, Ho, Er, Tm, Y, Lu, including one or more rare earth elements, TM is an essential transition metal consisting of Ti, V, Cr, Mn, Co, Ni, Cu, Zn as required Including at least one selected from the element group, M including at least one selected from the element group consisting of Al, Ga, Ge, and Sn as essential elements of Si, and 5.5 ≦ a in atomic% ≦ 7.5, 80.5 ≦ b ≦ 92.5, 0 <c ≦ 14, 0.75 ≦ X ≦ 0.95) are preferable. As this magnetic alloy powder, a half-width of a diffraction line corresponding to the (531) plane of X-ray diffraction of NaZn 13 phase is 0.5 degrees or less.
また、本発明は、実質的にＮａＺｎ13型結晶構造を有する化合物相により構成される磁気冷凍用の磁性合金粉末の製造方法であって、厚さが３０μｍ以下の偏平状の磁性合金粉末を水素を含む雰囲気中で熱処理することを特徴とする。前記の偏平状の磁性合金粉末は、合金溶湯を回転する冷却ディスクに向けてガス噴霧することにより得ることができる。磁性合金粉末を水素雰囲気中で熱処理する前に、水素雰囲気以外の非酸素雰囲気中で１０００℃以上で溶体化熱処理することが好ましい。 The present invention also relates to a method for producing a magnetic alloy powder for magnetic refrigeration composed substantially of a compound phase having a NaZn 13 type crystal structure, wherein a flat magnetic alloy powder having a thickness of 30 μm or less is hydrogenated. It heat-processes in the atmosphere containing this. The flat magnetic alloy powder can be obtained by gas spraying the molten alloy toward a rotating cooling disk. Before the magnetic alloy powder is heat-treated in a hydrogen atmosphere, it is preferable to perform a solution heat treatment at 1000 ° C. or higher in a non-oxygen atmosphere other than the hydrogen atmosphere.
本発明による、厚さ３０μｍ以下の偏平状のＲａ（ＴＭＸＭ１−Ｘ）ｂ合金粉末に、水素を固溶させることにより、短時間の反応時間で大きなエントロピー変化を有するＲa（ＴＭxＭ1-x）bHc系磁気冷凍作業物質を安定に製造することが可能となる。 According to the invention, the R a (TM X M 1- X) b alloy powder thickness 30μm following flat, by solid solution hydrogen, Ra having a large entropy change in a short reaction time (TMxM1- it is possible to stably produce x) b H c based magnetic refrigeration working substance.
図１に示すような本発明のＮａＺｎ１３型結晶構造を有する偏平状のＲａ（ＴＭＸＭ１−Ｘ）ｂ合金粉末は、所望の組成に配合し原料を１３００℃以上の高温で溶融し、溶湯を高速で回転する円錐状のデイスク上に噴霧することにより得られる。本発明による偏平粉の製造装置を、図２に示す。溶湯を噴霧するガスの圧力、ノズル径、デイスクの回転速度、ノズルとデイスク間の距離を変化させることなどにより粉末の厚さやアスペクト比を制御することが可能である。噴霧圧力を３ＭＰａ以上、ノズル径３ｍｍ以下、デイスク回転数を５００ｒ.ｐ.ｍ.以上とすることで偏平粉末の厚さを３０μｍ以下とすることが可能である。得られた偏平粉末を、１０００℃以上で溶体化熱処理することにより、α-Ｆe相が５ｖｏｌ％以下で実質的にＮａＺｎ13単相のＲａ（ＴＭＸＭ１−Ｘ）ｂ合金粉末が得られる。この偏平粉末を、水素を含む反応ガス雰囲気中で２００〜３５０℃で０．５〜２時間熱処理することにより水素濃度分布が粉末全体で均一な磁気冷凍作業物質を得ることが可能である。反応ガスとしては、水素、水素とアルゴンの混合ガス、アンモニアガス、などを使用することが可能である。３０μｍ以下の偏平粉末を用いることにより、反応速度を向上し水素拡散時の表面と内部の濃度差を低減することが可能となり、水素濃度分布が粉末全体で均一な磁気冷凍作業物質が得られる。本製造方法によると、水素吸蔵反応後の熱処理が不要となり製造プロセスも簡略化できる。 The flat R a (TM X M 1-X ) b alloy powder having the NaZn 13 type crystal structure of the present invention as shown in FIG. 1 is blended into a desired composition and the raw material is melted at a high temperature of 1300 ° C. or higher. It is obtained by spraying the molten metal on a conical disk rotating at high speed. An apparatus for producing flat powder according to the present invention is shown in FIG. The thickness and aspect ratio of the powder can be controlled by changing the pressure of the gas for spraying the molten metal, the nozzle diameter, the rotational speed of the disk, and the distance between the nozzle and the disk. By setting the spray pressure to 3 MPa or more, the nozzle diameter to 3 mm or less, and the disk rotation speed to 500 rpm or more, the thickness of the flat powder can be made 30 μm or less. The obtained flat powder is subjected to a solution heat treatment at 1000 ° C. or higher to obtain an Ra (TM X M 1-X ) b alloy powder having an α-Fe phase of 5 vol% or less and a substantially NaZn 13 single phase. It is done. By heat-treating the flat powder at 200 to 350 ° C. for 0.5 to 2 hours in a reaction gas atmosphere containing hydrogen, it is possible to obtain a magnetic refrigeration working material having a uniform hydrogen concentration distribution throughout the powder. As the reaction gas, hydrogen, a mixed gas of hydrogen and argon, ammonia gas, or the like can be used. By using a flat powder of 30 μm or less, it becomes possible to improve the reaction rate and reduce the concentration difference between the surface and the inside during hydrogen diffusion, and a magnetic refrigeration working substance having a uniform hydrogen concentration distribution throughout the powder can be obtained. According to this production method, the heat treatment after the hydrogen storage reaction is not required, and the production process can be simplified.
磁性粉末の均一性は粉末Ｘ線回折の特定回折線の半価幅と、磁化曲線の温度変化を測定することにより判定することが可能である。すなわち水素の濃度分布が不均一な場合は格子定数の異なる相が連続的に存在するため半価幅が広くなる。このような磁性合金粉末の温度変化は、磁性相のキュリー温度が局所的に異なり、一定の分布を持つため相変化に伴う磁化曲線の温度変化の傾きが小さくなり、磁気冷凍性能は著しく低下する。本発明の磁性合金は、良好な磁気冷凍性能を有し、ＮａＺｎ１３相のＸ線回折の（５３１）面に相当する回折線の半価幅が０．５度（ラジアン）以下とすることができる。 The uniformity of the magnetic powder can be determined by measuring the half-value width of a specific diffraction line of powder X-ray diffraction and the temperature change of the magnetization curve. That is, when the concentration distribution of hydrogen is non-uniform, the half-value width is wide since phases having different lattice constants are continuously present. The temperature change of such a magnetic alloy powder is such that the Curie temperature of the magnetic phase is locally different and has a constant distribution, so the slope of the temperature change of the magnetization curve accompanying the phase change is small, and the magnetic refrigeration performance is significantly reduced. . The magnetic alloy of the present invention has good magnetic refrigeration performance, and the half width of the diffraction line corresponding to the (531) plane of the X-ray diffraction of the NaZn 13 phase is 0.5 degrees (radian) or less. it can.
本発明における、Ｘ線回折による半価幅は以下のように定義する。Ｃｕをターゲットとして加速電圧５０ｋV、加速電流２００ｍAにて測定した粉末Ｘ線回折（図４）において、Ｌａ（Ｆｅ・Ｓｉ）13相のメインピークのひとつである、４７度近傍に観察される（５３１）面の回折線の基線からの高さの１／２の位置における回折線の幅を半価幅として求めた。また磁化曲線の最大傾きは、印加磁界７９６ｋＡ／ｍ（１kOe）で測定した磁化−温度曲線においてＬａ（Ｆｅ・Ｓｉ）13相の磁気変態に伴い、磁化が急激に変化する領域での最大傾きを図６のように求めた。磁性体内でキュリー温度の分布（揺らぎ）が存在すると、この傾きは小さくなる。また強磁性のＦｅ-Ｓｉ相が多量に存在するとこの傾きが小さくなり好ましくない。 The half width by X-ray diffraction in the present invention is defined as follows. In powder X-ray diffraction (FIG. 4) measured at an acceleration voltage of 50 kV and an acceleration current of 200 mA using Cu as a target, it is observed at around 47 degrees, which is one of the main peaks of the La (Fe · Si) 13 phase (531). ) The width of the diffraction line at a position half the height from the base line of the diffraction line on the surface was determined as the half-value width. The maximum slope of the magnetization curve is the maximum slope in the region where the magnetization changes suddenly due to the magnetic transformation of the La (Fe · Si) 13 phase in the magnetization-temperature curve measured with an applied magnetic field of 796 kA / m (1 kOe). It calculated | required like FIG. If there is a Curie temperature distribution (fluctuation) in the magnetic body, this slope becomes smaller. In addition, when a large amount of ferromagnetic Fe—Si phase is present, this inclination is undesirably small.
（厚さとアスペクト比）
本発明による偏平粉末の厚さが、３０μｍ超である場合は粉末内での水素濃度分布の均一性が低下するため好ましくない。水素濃度分布の均一性は、水素吸蔵後の合金粉末のＸ線回折線図の半価幅により判定することが出来る。水素濃度分布が不均一な場合は、図５に示すような（５３１）面に相当する半価幅の大きい回折線となる。粉末厚さに対するアスペクト比（ｌ/ｔ）は、図２に示すデイスクの傾斜角度やノズル径、噴霧圧力を変えることにより変化させることが可能である。水素吸蔵の反応時間を短くするためには、アスペクト比はより大きい方が好ましい。
(Thickness and aspect ratio)
When the thickness of the flat powder according to the present invention exceeds 30 μm, the uniformity of the hydrogen concentration distribution in the powder is not preferable. The uniformity of the hydrogen concentration distribution can be determined by the half width of the X-ray diffraction diagram of the alloy powder after hydrogen storage. When the hydrogen concentration distribution is not uniform, a diffraction line having a large half width corresponding to the (531) plane as shown in FIG. 5 is obtained. The aspect ratio (l / t) with respect to the powder thickness can be changed by changing the tilt angle, nozzle diameter, and spray pressure of the disk shown in FIG. In order to shorten the reaction time of hydrogen storage, a larger aspect ratio is preferable.
（組成の限定理由）
本発明による合金粉末は、組成式で、Ｒａ（ＴＭxＭ1-x）ｂ（但し、ＲはＬａを必須として必要によりＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ，Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙ、Ｌｕからなる希土類元素の１種以上を含み、ＴＭはＦｅを必須として必要によりＴｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎからなる遷移金属元素群より選択される１種以上を含み、ＭはＳｉを必須として必要によりＡｌ、Ｇａ、Ｇｅ、Ｓｎからなる元素群より選択される少なくとも１種以上を含み、かつ、原子％で５．５≦ａ≦７．５、９２．５≦ｂ≦９４．５、０．７５≦X≦０．９５で表記されるものが好ましい。この磁性合金は液体窒素温度においては強磁性を示し、常温では水素と窒素の固溶量により、強磁性あるいは常磁性を示す。ここで、実質的に結晶構造がＮａＺｎ１３単相からなる、とは組織の９５％以上がＮａＺｎ１３相で構成されることを示す。
(Reason for limitation of composition)
The alloy powder according to the present invention has a composition formula: R a (TM x M 1-x ) b (wherein R is essential and Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho as required. Including one or more rare earth elements consisting of Er, Tm, Y, and Lu, and TM is selected from a transition metal element group consisting of Ti, V, Cr, Mn, Co, Ni, Cu, and Zn if necessary, with Fe as an essential element M includes at least one selected from the group of elements consisting of Al, Ga, Ge, and Sn as required, and includes 5.5 ≦ a ≦ 7 in atomic%. .5, 92.5 ≦ b ≦ 94.5, 0.75 ≦ X ≦ 0.95 are preferred, and this magnetic alloy exhibits ferromagnetism at liquid nitrogen temperature, and hydrogen and nitrogen at room temperature. Depending on the amount of solid solution, it exhibits ferromagnetism or paramagnetism, where The fact that the crystal structure is substantially composed of a NaZn 13 single phase means that 95% or more of the structure is composed of the NaZn 13 phase.
希土類量ａが５.５原子％未満あるいはｂが９４．５原子％超では、希土類元素が不足し反応生成物中に強磁性のＦｅ-Ｓｉ相が析出するため好ましくない。またａが７.５原子％超あるいはｂが９２．５原子％未満では、希土類元素が過剰となり合金中にＲ２ＴＭ３やＲＴＭ２などの希土類リッチな非磁性相あるいは希土類酸化物等が生成されるため水素吸蔵後の磁気熱量効果を低下させる。 If the rare earth amount a is less than 5.5 atomic% or b exceeds 94.5 atomic%, the rare earth element is insufficient and a ferromagnetic Fe—Si phase is precipitated in the reaction product, which is not preferable. If a is more than 7.5 atomic% or b is less than 92.5 atomic%, the rare earth element becomes excessive and a rare earth-rich nonmagnetic phase such as R 2 TM 3 or RTM 2 or a rare earth oxide is generated in the alloy. Therefore, the magnetocaloric effect after hydrogen storage is reduced.
Ｒ元素の内、Ｌａは５０原子％以下とすることが好ましい。Ｌａが５０原子％を超えるとＲ元素を含む異相が析出し、実質的にＮａＺｎ１３相単相とならないため好ましくない。Ｌａの一部を５０原子％以下の範囲で置換することにより、磁気変態温度（キュリー温度）を意図的に変えることが可能となる。
また、Ｆｅの一部をＴｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎより選択される１種または１種以上で置換することにより、α鉄の析出を抑制したり、キュリー温度を制御したり、粉末の耐食性を改善したりすることが可能である。Ｆｅ量が少ないと磁気特性（飽和磁化）が低下するため、Ｆｅ量は８０原子％以上が好ましい。
Of the R elements, La is preferably 50 atomic% or less. When La exceeds 50 atomic%, a heterogeneous phase containing an R element is precipitated, and the NaZn 13 phase single phase is not substantially formed. By substituting a part of La in a range of 50 atomic% or less, the magnetic transformation temperature (Curie temperature) can be changed intentionally.
In addition, by replacing a part of Fe with one or more selected from Ti, V, Cr, Mn, Co, Ni, Cu, and Zn, precipitation of α iron can be suppressed, or the Curie temperature can be reduced. It is possible to control or improve the corrosion resistance of the powder. If the Fe content is small, the magnetic properties (saturation magnetization) are lowered, so the Fe content is preferably 80 atomic% or more.
また、本発明による水素吸蔵を行った合金粉末は、組成式でＲａ（ＴＭＸＭ１-Ｘ）bＨc（但し、ＲはＬａを必須として必要によりＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ，Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙ、Ｌｕからなる希土類元素の１種以上を含み、ＴＭはＦｅを必須としてＴｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎからなる遷移金属元素群より選択される１種以上を含み、ＭはＳｉを必須として必要によりＡｌ、Ｇａ、Ｇｅ、Ｓｎからなる元素群より選択される少なくとも１種以上を含み、かつ、原子％で５．５≦ａ≦７．５、８０．５≦ｂ≦９２．５、０＜ｃ≦１４、０．７５≦Ｘ≦０．９５）で表記されるものが好ましい。Ｒ量、遷移金属のｂ量の上限、下限の限定理由は前記した理由と同じである。 Further, the alloy powder subjected to hydrogen storage according to the present invention has a composition formula of R a (TM X M 1-X ) b H c (where R is essential to La, and Ce, Pr, Nd, Sm, Eu as necessary. Including one or more rare earth elements composed of Gd, Tb, Dy, Ho, Er, Tm, Y, and Lu, and TM is composed of Ti, V, Cr, Mn, Co, Ni, Cu, Zn with Fe as an essential element Including at least one selected from the group of transition metal elements, M including at least one selected from the group of elements consisting of Al, Ga, Ge, and Sn if necessary, and 5 in atomic%. 0.5 ≦ a ≦ 7.5, 80.5 ≦ b ≦ 92.5, 0 <c ≦ 14, 0.75 ≦ X ≦ 0.95) are preferable. The reasons for limiting the upper limit and the lower limit of the R amount and the b amount of the transition metal are the same as described above.
水素量ｃは磁気熱量効果そのものには直接影響を及ぼさないが、ｃが増加すると結晶格子が膨張し磁気変態温度が上昇する。ｃの量を１４原子％以下の範囲に制御することによりキュリー温度を２４５〜３３０Ｋの温度域で制御することが可能である。 The amount of hydrogen c does not directly affect the magnetocaloric effect itself, but when c increases, the crystal lattice expands and the magnetic transformation temperature rises. It is possible to control the Curie temperature in the temperature range of 245 to 330K by controlling the amount of c to be in the range of 14 atomic% or less.
また、水素の一部が窒素に置換されてても良い。水素と窒素が共存する雰囲気ガス中で、適正な反応温度と反応時間、水素濃度を選択することにより、短時間で所定の水素量が固溶した均一な合金が得られる。水素および窒素を含む反応ガス中５５０〜７００Kで、０．５〜５時間、好ましくは１〜３時間熱処理することにより、水素および窒素吸収分布が均一な磁性粉末を得ることが可能である。反応ガスとしては、水素と窒素の混合ガス、水素とアンモニアの混合ガス、アンモニアガスなどが使用できる。合金組成中の窒素は、原子％で０．０７≦ｄ＜５．０の範囲にすることが好ましい。 Further, part of hydrogen may be replaced with nitrogen. By selecting an appropriate reaction temperature, reaction time, and hydrogen concentration in an atmosphere gas in which hydrogen and nitrogen coexist, a uniform alloy in which a predetermined amount of hydrogen is dissolved in a short time can be obtained. A magnetic powder having a uniform hydrogen and nitrogen absorption distribution can be obtained by heat treatment at 550 to 700 K in a reaction gas containing hydrogen and nitrogen for 0.5 to 5 hours, preferably 1 to 3 hours. As the reaction gas, a mixed gas of hydrogen and nitrogen, a mixed gas of hydrogen and ammonia, ammonia gas, or the like can be used. Nitrogen in the alloy composition is preferably in the range of 0.07 ≦ d <5.0 in atomic percent.
以下実施例により、本発明の効果を説明するが、本発明の効果はこれに限定されるものではない。 The effects of the present invention will be described below with reference to examples, but the effects of the present invention are not limited thereto.
（実施例１）
原子％で、Ｌａ７．３％、Ｆｅ８０．０％、Ｓｉ１０．９％、Ａｌ１．８％の組成比の合金をアルミナ坩堝中で高周波溶解し、１４５０℃でノズル径２ｍｍのノズルより出湯し、ガス圧６ＭＰａで溶湯を噴霧し、回転数２０００ｒｐｍで回転する傾斜角４５度のＣｕ製デイスク上で急冷凝固させ、厚さ１０μｍの偏平上のＬａ−Ｆｅ−Ｓｉ−Ａｌ粉末を得た。この粉末をＡｒ雰囲気中１０５０℃で２時間溶体化熱処理し、実質的にＮａＺｎ１３単相の常磁性粉末とした。この粉末を、２７０℃で２時間水素分圧７５％の水素とアルゴン混合ガス中で熱処理し水素を固溶させた。
水素固溶後の、合金粉末の磁化曲線およびＸ線回折図を図３および図４に示す。Ｘ線回折図の（５３１）面に相当する回折線の半価幅は、０．４２度であり、図３の磁化-温度変化で磁気変態点近傍で急峻な磁化変化を示すことより、粉末中に均一に水素が固溶されていることがわかる。
Example 1
An alloy having a composition ratio of La 7.3%, Fe 80.0%, Si 10.9%, Al 1.8% in an atomic% is melted by high frequency in an alumina crucible, discharged from a nozzle having a nozzle diameter of 2 mm at 1450 ° C., and gas The molten metal was sprayed at a pressure of 6 MPa, and rapidly cooled and solidified on a Cu disk having an inclination angle of 45 degrees rotating at a rotation speed of 2000 rpm, to obtain a flat La-Fe-Si-Al powder having a thickness of 10 μm. This powder was solution heat-treated in an Ar atmosphere at 1050 ° C. for 2 hours to obtain a substantially NaZn 13 single-phase paramagnetic powder. This powder was heat-treated at 270 ° C. for 2 hours in a mixed gas of hydrogen and argon having a hydrogen partial pressure of 75% to dissolve hydrogen into a solid solution.
3 and 4 show the magnetization curve and X-ray diffraction pattern of the alloy powder after hydrogen solid solution. The half-value width of the diffraction line corresponding to the (531) plane of the X-ray diffraction diagram is 0.42 degrees, and since the magnetization-temperature change in FIG. 3 shows a steep magnetization change near the magnetic transformation point, It can be seen that hydrogen is uniformly dissolved therein.
（実施例２）
原子％で、Ｌａ７．３％、Ｆｅ８０．０％、Ｓｉ１０．９％、Ａｌ１．８％の組成比の合金粉末を実施例１と同様に溶製し、１４５０℃でノズル径２ｍｍのノズルより、ガス圧６ＭＰａで溶湯を噴霧し、回転する傾斜角４５度のＣｕ製デイスク上で急冷凝固させた。デイスクの回転数を、３０００〜２００ｒｐｍと変化させることにより、偏平粉末の厚さを８μｍ〜２５μｍまで変化させた。これらの粉末を実施例１と同様の条件で溶体化処理した後、２７０℃で１時間水素分圧２５％の水素とアルゴン混合ガス中で熱処理した。水素吸蔵粉末の磁化測定およびＸ線回折により得られた結果を表１に示す。
(Example 2)
An alloy powder having a composition ratio of La 7.3%, Fe 80.0%, Si 10.9%, and Al 1.8% in atomic% was melted in the same manner as in Example 1, and from a nozzle having a nozzle diameter of 2 mm at 1450 ° C., The molten metal was sprayed at a gas pressure of 6 MPa and rapidly solidified on a rotating Cu disk having an inclination angle of 45 degrees. By changing the rotational speed of the disk from 3000 to 200 rpm, the thickness of the flat powder was changed from 8 μm to 25 μm. These powders were subjected to a solution treatment under the same conditions as in Example 1, followed by heat treatment at 270 ° C. for 1 hour in a hydrogen / argon mixed gas having a hydrogen partial pressure of 25%. The results obtained by the magnetization measurement and X-ray diffraction of the hydrogen storage powder are shown in Table 1.
原子％で、Ｌａ７．３％、Ｆｅ８０．０％、Ｓｉ１０．９％、Ａｌ１．８％の組成比の合金粉末を実施例１と同様に溶製し、溶湯を１４５０℃でノズル径を１．５ｍｍ〜４ｍｍ、噴霧ガス圧を２〜６ＭＰａ、回転数を５００〜３０００ｒ.ｐ.ｍ変えて、傾斜角４５度のＣｕ製デイスク上で急冷凝固させ、偏平粉末の厚さを７μｍ〜３８μｍの間で変化させた。これらの粉末を実施例１と同様１０５０℃アルゴン中で溶体化処理した後、２７０℃で１時間水素分圧２５％の水素とアルゴン混合ガス中で熱処理した。水素吸蔵粉末の磁化測定およびＸ線回折により測定した結果を表２に示す。 An alloy powder having an atomic% of La 7.3%, Fe 80.0%, Si 10.9%, and Al 1.8% was melted in the same manner as in Example 1. The molten metal was melted at 1450 ° C. and the nozzle diameter was 1. 5 mm to 4 mm, spray gas pressure is changed to 2 to 6 MPa, rotation speed is changed to 500 to 3000 rpm and rapidly solidified on a Cu disk having an inclination angle of 45 degrees, and the thickness of the flat powder is between 7 μm and 38 μm. It was changed with. These powders were solution-treated in argon at 1050 ° C. in the same manner as in Example 1, and then heat-treated at 270 ° C. for 1 hour in a hydrogen / argon mixed gas having a hydrogen partial pressure of 25%. Table 2 shows the results of measurement by magnetization measurement and X-ray diffraction of the hydrogen storage powder.
Claims (8)
The magnetic alloy powder according to claim 6 or 7, wherein solution heat treatment is performed at 1000 ° C or higher in a non-oxygen atmosphere not containing hydrogen before the magnetic alloy powder is heat-treated in a hydrogen atmosphere. Method.
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