JP4392371B2 - Method for producing particle-dispersed intermetallic compound - Google Patents
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Description
本発明は、マトリックスとなる金属間化合物相の中に、該金属間化合物よりも硬度の高い硬質化合物粒子が分散してなる粒子分散金属間化合物の製造方法に関するものである。 The present invention relates to a method for producing a particle-dispersed intermetallic compound in which hard compound particles having higher hardness than the intermetallic compound are dispersed in an intermetallic compound phase serving as a matrix.
鉄とアルミニウムとの金属間化合物である鉄アルミナイド基焼結合金は、高い硬度を備えていることが知られており、前記高い硬度に伴う優れた耐摩耗性により、各種摺動部材等に用いることが検討されている。 An iron aluminide-based sintered alloy, which is an intermetallic compound of iron and aluminum, is known to have high hardness, and is used for various sliding members due to the excellent wear resistance accompanying the high hardness. It is being considered.
従来、前記鉄アルミナイド基焼結合金として、鉄アルミナイド金属間化合物相の中に、ＦｅＣ化合物相が混在するものが知られている（例えば特許文献１参照）。前記鉄アルミナイド基焼結合金は、Ａｌ、Ｆｅ、Ｃの各粉末を所定の組成で混合してなる混合物を加圧成形して粉末成形体とし、該粉末成形体に通電プレス成形を施すことにより製造できるとされている。 Conventionally, as the iron aluminide-based sintered alloy, an iron aluminide intermetallic compound phase in which an FeC compound phase is mixed is known (for example, see Patent Document 1). The iron aluminide-based sintered alloy is obtained by press-molding a mixture formed by mixing Al, Fe, and C powders with a predetermined composition to form a powder compact, and subjecting the powder compact to electrical press molding. It is said that it can be manufactured.
一方、Ｆｅ−Ａｌ金属間化合物相の中に、ＴｉＣ粒子が分散された粒子分散金属間化合物も知られている（例えば特許文献２参照）。前記粒子分散金属間化合物は、Ｆｅ−Ａｌ金属間化合物の粉末と、ＴｉＣの粒子とを混合して、真空中で加熱することによりできるとされている。 On the other hand, a particle-dispersed intermetallic compound in which TiC particles are dispersed in an Fe—Al intermetallic compound phase is also known (see, for example, Patent Document 2). It is said that the particle-dispersed intermetallic compound can be obtained by mixing Fe—Al intermetallic compound powder and TiC particles and heating in a vacuum.
しかしながら、前記粒子分散金属間化合物は、Ｆｅ−Ａｌ金属間化合物の粉末と、ＴｉＣの粒子とを原料とするために、マトリックスとなるＦｅ−Ａｌ金属間化合物相とＴｉＣの粒子との親和性が低く、十分な硬度が得られないことがあるという不都合がある。
本発明は、かかる不都合を解消して、優れた硬度を備える粒子分散金属間化合物を得ることができる製造方法を提供することを目的とする。 An object of the present invention is to provide a production method capable of eliminating such inconvenience and obtaining a particle-dispersed intermetallic compound having excellent hardness.
かかる目的を達成するために、本発明は、マトリックスとなる金属間化合物相の中に、該金属間化合物よりも硬度の高い硬質化合物粒子が分散してなる粒子分散金属間化合物の製造方法であって、該硬質化合物粒子を形成する少なくとも２つの元素の粉末と、該金属間化合物を形成する少なくとも２つの元素の粉末とを混合し、成形して粉末成形体を得る工程と、得られた粉末成形体を加熱して溶融する工程と、該粉末成形体が溶融した後、冷却して凝固させる工程とを備え、該粉末成形体を加熱して溶融する工程において、該粉末成形体の溶融が開始される温度よりも５０〜１５０℃低い範囲の温度で一旦昇温を停止し、該温度に所定時間保持した後、昇温を再開して該粉末成形体を溶融することを特徴とする。
In order to achieve this object, the present invention is a method for producing a particle-dispersed intermetallic compound in which hard compound particles having a hardness higher than that of the intermetallic compound are dispersed in an intermetallic compound phase serving as a matrix. Mixing a powder of at least two elements forming the hard compound particles and a powder of at least two elements forming the intermetallic compound, and molding to obtain a powder compact, and the obtained powder a step of melting by heating the molded body, after the melted powder molded body, e Bei and coagulating by cooling, in the step of heating and melting the powder molded body, the melting of the powder molded body There temporarily stopped heating at a temperature of 50 to 150 ° C. range lower than the temperature that is initiated and, after holding for a predetermined time in the temperature, and characterized that you melt the powder molded body to resume heating To do.
本発明の製造方法では、目的とする粒子分散金属間化合物を構成する硬質化合物粒子と、金属間化合物とのそれぞれの原料となる各元素の粉末を混合し、成形して得られた粉末成形体を加熱する。このようにすると、温度が前記各元素の粉末のうち最も融点の低い元素の融点を超えると該元素の粉末が溶融し、溶融した元素の融液が毛管現象により他の元素の粉末の間隙に侵入するので、溶融した元素と他の元素の粉末との接触面積が急激に増大する。そして、溶融した元素と他の元素との間で化合物合成の発熱反応が連鎖的に起こり、反応温度が急上昇して、短時間のうちに前記各元素が溶融した融液が形成されるものと考えられる。 In the production method of the present invention, a powder molded body obtained by mixing and molding hard compound particles constituting the target particle-dispersed intermetallic compound and powders of respective elements as raw materials of the intermetallic compound Heat. In this case, when the temperature exceeds the melting point of the element having the lowest melting point among the powders of the respective elements, the powder of the element is melted, and the melt of the molten element enters the gaps between the powders of the other elements by capillary action. Since it penetrates, the contact area between the molten element and the powder of the other element increases rapidly. And, an exothermic reaction of compound synthesis occurs in a chain between the molten element and other elements, the reaction temperature rises rapidly, and a melt in which each element is melted is formed in a short time. Conceivable.
例えば、融点１４５３℃のニッケルと、融点６６０℃のアルミニウムとから両者の金属間化合物であるニッケルアルミナイドを合成するときには、ニッケル粉末とアルミニウム粉末とを混合して加熱すると、温度が６６０℃を超えた時点でアルミニウム粉末が溶融し、その融液が毛管現象によりニッケル粉末の間隙に侵入する。すると、アルミニウム融液とニッケル粉末との接触面積が急増し、これを引き金にニッケルアルミナイド生成の発熱反応が起きる。この結果、反応温度は約２５００℃もの高温に僅か数秒で上昇する。 For example, when synthesizing nickel aluminide, which is an intermetallic compound, from nickel having a melting point of 1453 ° C. and aluminum having a melting point of 660 ° C., the temperature exceeded 660 ° C. when the nickel powder and the aluminum powder were mixed and heated. At that time, the aluminum powder melts, and the melt enters the gap between the nickel powders by capillary action. Then, the contact area between the aluminum melt and the nickel powder increases rapidly, and this causes the exothermic reaction to generate nickel aluminide. As a result, the reaction temperature rises to as high as about 2500 ° C. in just a few seconds.
前記の例は、金属間化合物を生成する２種の元素の粉末についてのみ述べているが、前記金属間化合物を生成する元素の粉末に、さらに前記硬質化合物粒子を生成する元素の粉末が含まれる場合にも同様のメカニズムにより反応温度の急上昇が起き、短時間のうちに前記各元素が溶融した融液が形成される。 In the above example, only the powders of the two elements that generate the intermetallic compound are described. However, the powder of the element that generates the hard compound particles is further included in the powder of the element that generates the intermetallic compound. Even in such a case, the reaction temperature rapidly rises by the same mechanism, and a melt in which each element is melted is formed in a short time.
次に、前記融液を冷却すると、まず、前記融液中、融点の高い化合物として前記硬質化合物粒子が形成され、次いで該硬質化合物粒子の間隙に残った未凝固融液から前記金属間化合物が形成されるものと考えられる。この結果、マトリックスとなる金属間化合物相の中に、該金属間化合物よりも硬度の高い硬質化合物粒子が分散してなる粒子分散金属間化合物が形成される。 Next, when the melt is cooled, first, the hard compound particles are formed as a compound having a high melting point in the melt, and then the intermetallic compound is formed from the unsolidified melt remaining in the gaps between the hard compound particles. It is thought that it is formed. As a result, a particle-dispersed intermetallic compound is formed in which hard compound particles having a hardness higher than that of the intermetallic compound are dispersed in the intermetallic compound phase serving as a matrix.
かかる本発明の製造方法によれば、前記粒子分散金属間化合物をその構成元素から形成するので、前記金属間化合物と前記質化合物粒子との親和性が高くなり、優れた硬度を備える粒子分散金属間化合物を得ることができる。 According to the production method of the present invention, since the particle-dispersed intermetallic compound is formed from its constituent elements, the affinity between the intermetallic compound and the quality compound particles is increased, and the particle-dispersed metal having excellent hardness Intermetallic compounds can be obtained.
ところで、前述のようにして粒子分散金属間化合物を形成するときには、生成する粒子分散金属間化合物の微細組織、例えば前記硬質化合物粒子の粒子径を制御することが難しいという問題がある。前記微細組織は、前記粒子分散金属間化合物の機械的強度等の材料物性を支配する重要な因子である。 By the way, when the particle-dispersed intermetallic compound is formed as described above, there is a problem that it is difficult to control the fine structure of the particle-dispersed intermetallic compound to be generated, for example, the particle diameter of the hard compound particles. The microstructure is an important factor governing material properties such as mechanical strength of the particle-dispersed intermetallic compound.
前記問題は、前述のように溶融した元素と他の元素との間で化合物合成の発熱反応が連鎖的に起きたときに、反応速度や反応熱を制御することが難しいことによるものである。即ち、前記反応温度は、反応前の各元素の粉末の顕熱、生成物の生成エンタルピー、生成物の融解エンタルピー等の反応系に固有の物理量により決定されてしまい、外部からは制御することができない。 The problem is due to the difficulty in controlling the reaction rate and the heat of reaction when an exothermic reaction of compound synthesis occurs in a chain between the molten element and other elements as described above. That is, the reaction temperature is determined by physical quantities inherent to the reaction system such as sensible heat of each element powder before reaction, product formation enthalpy, product melting enthalpy, and can be controlled from the outside. Can not.
また、前述のようにして前記粒子分散金属間化合物を形成するときには、該粒子分散金属間化合物の内部に多量の気孔が残存してしまうおそれもある。前記気孔は、複数の元素の粉末を反応させる際に粉末間に空隙が残存することにより形成され、あるいは前記粉末表面に吸着されている水分が反応時の高温で気化することにより形成されるものと考えられる。 Further, when the particle-dispersed intermetallic compound is formed as described above, a large amount of pores may remain in the particle-dispersed intermetallic compound. The pores are formed by leaving voids between powders when reacting a plurality of elemental powders, or formed by vaporizing moisture adsorbed on the powder surface at a high temperature during the reaction. it is conceivable that.
本発明者は、前記粒子分散金属間化合物における前記微細組織を制御する方法と、該粒子分散金属間化合物の全体積に対する気孔率を低減する方法について検討した。この結果、本発明者は、本発明の製造方法において、前記粉末成形体が溶融した後、冷却して凝固させる工程が前記微細組織の形成と前記気孔の形成とに影響することを見出した。また、本発明者は、本発明の製造方法の前記粉末成形体を加熱して溶融する工程において、該粉末成形体の溶融が開始される前に、所定温度で一旦昇温を停止し、該温度に所定時間保持することにより、該粉末成形体が溶融した後、冷却して凝固させる工程における温度を制御できることを見出した。 The present inventor studied a method for controlling the microstructure in the particle-dispersed intermetallic compound and a method for reducing the porosity with respect to the total volume of the particle-dispersed intermetallic compound. As a result, the present inventors have found that, in the production method of the present invention, the step of cooling and solidifying after the powder compact has melted affects the formation of the microstructure and the formation of the pores. Further, in the step of heating and melting the powder molded body of the production method of the present invention, the inventor temporarily stops the temperature rise at a predetermined temperature before the melting of the powder molded body is started, It has been found that by maintaining the temperature for a predetermined time, the temperature in the step of cooling and solidifying after the powder compact has melted can be controlled.
そこで、本発明の製造方法は、前記粉末成形体を加熱して溶融する工程において、該粉末成形体の溶融が開始される前の所定温度で一旦昇温を停止し、該温度に所定時間保持した後、昇温を再開して該粉末成形体の溶融することが好ましい。 Therefore, the production method of the present invention stops heating at a predetermined temperature before the melting of the powder molded body is started and maintains the temperature for a predetermined time in the step of heating and melting the powder molded body. After that, it is preferable to resume the temperature rise and melt the powder compact.
このようにするときには、前記所定温度に所定時間保持している間に、元素同士が固体状態で緩やかに反応し、異種元素の粉末間の境界に反応生成物の膜が形成する。この後、昇温を再開して、前記粉末成形体中の未反応粉末を溶融すると、反応熱の放出が少ないばかりか、前記所定温度に所定時間保持している間に生成した反応生成物により熱が吸収される。この結果、前記粉末成形体が溶融する際の最高温度を低下させ、前記粉末成形体が溶融した後、冷却して凝固させる工程における冷却速度を増大させることができるので、生成される粒子分散金属間化合物に含まれる硬質化合物粒子の粒子径を小さくすることができると共に、該粒子分散金属間化合物の全体積に対する気孔率を低減することができる。 In doing so, the elements react slowly in a solid state while being held at the predetermined temperature for a predetermined time, and a reaction product film is formed at the boundary between the powders of different elements. After this, when the temperature rise is resumed and the unreacted powder in the powder compact is melted, not only is the reaction heat released, but also by the reaction product generated while holding at the predetermined temperature for a predetermined time. Heat is absorbed. As a result, it is possible to reduce the maximum temperature when the powder compact is melted, and to increase the cooling rate in the step of cooling and solidifying after the powder compact is melted. The particle diameter of the hard compound particles contained in the intermetallic compound can be reduced, and the porosity with respect to the total volume of the particle-dispersed intermetallic compound can be reduced.
前記粉末成形体の溶融が開始される前に、所定温度で一旦昇温を停止するときに、前記昇温を停止する温度は、前記粉末成形体の溶融が開始される温度よりも５０〜１５０℃低い範囲の温度であることが好ましい。前記昇温を停止する温度が前記粉末成形体の溶融が開始される温度よりも５０℃未満の低さである場合（粉末成形体の溶融が開始される温度−昇温を停止する温度＜５０℃）には、昇温を停止する温度に所定時間保持している間に前記元素同士の反応が過度に進行することがある。一方、前記昇温を停止する温度が前記粉末成形体の溶融が開始される温度よりも１５０℃を超える低さである場合（粉末成形体の溶融が開始される温度−昇温を停止する温度＞１５０℃）には、前記元素同士の反応が不十分になることがある。
本発明の製造方法では、前記硬質化合物粒子は、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｓｉからなる群から選択される１種以上の元素と、Ｃ、Ｂからなる群から選択される１種以上の元素とから形成される。また、前記金属間化合物は、Ｆｅ、Ｃｏ、Ｎｉ、Ｔｉ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗからなる群から選択され前記硬質化合物粒子を形成する元素とは異なる１種以上の元素と、Ａｌ、Ｓｉからなる群から選択され前記硬質化合物粒子を形成する元素とは異なる１種以上の元素とから形成される。
前記硬質化合物粒子と前記金属間化合物との組み合わせとしては、例えば、前記硬質化合物粒子はＴｉとＣまたはＢとから形成され、前記金属間化合物はＦｅとＡｌとから形成されるものを挙げることができる。
When the temperature rise is temporarily stopped at a predetermined temperature before the melting of the powder compact is started, the temperature at which the temperature rise is stopped is 50 to 150 than the temperature at which the powder compact is started to melt. It is preferable that the temperature be in the range of ℃. When the temperature at which the temperature rise is stopped is lower than the temperature at which the melting of the powder compact starts to be less than 50 ° C. (the temperature at which the powder compact begins to be melted−the temperature at which the temperature rise is stopped <50 (° C.), the reaction between the elements may proceed excessively while the temperature is kept at a temperature at which the temperature rise is stopped for a predetermined time. On the other hand, when the temperature at which the temperature rise is stopped is lower than 150 ° C. than the temperature at which the melting of the powder compact is started (temperature at which the melting of the powder compact is started−temperature at which the temperature rise is stopped) > 150 ° C.), the reaction between the elements may be insufficient.
In the production method of the present invention, the hard compound particles are composed of one or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, and Si, and C and B. And one or more elements selected from the group consisting of: In addition, the intermetallic compound is selected from the group consisting of Fe, Co, Ni, Ti, Nb, Ta, Cr, Mo, W, and one or more elements different from the elements that form the hard compound particles, and Al And one or more elements selected from the group consisting of Si and different from the elements forming the hard compound particles.
As a combination of the hard compound particles and the intermetallic compound, for example, the hard compound particles are formed from Ti and C or B, and the intermetallic compound is formed from Fe and Al. it can.
また、前記範囲の温度に保持する時間は、１０〜６０分間の範囲であることが好ましい。前記範囲の温度に保持する時間が１０分間未満である場合には、前記元素同士の反応が不十分になることがある。一方、前記範囲の温度に保持する時間が６０分間を超える場合には、前記元素同士の反応が過度に進行することがある。 Moreover, it is preferable that the time hold | maintained at the temperature of the said range is the range for 10 to 60 minutes. When the time for maintaining the temperature in the above range is less than 10 minutes, the reaction between the elements may be insufficient. On the other hand, when the time for maintaining the temperature in the above range exceeds 60 minutes, the reaction between the elements may proceed excessively.
次に、添付の図面を参照しながら本発明の実施の形態についてさらに詳しく説明する。図１は第１の実施形態の製造方法における反応温度の経時変化を示すグラフ、図２は粒子分散金属間化合物のマトリックスとなる金属間化合物のＸ線回折角度と強度との関係を示すグラフ、図３乃至図５は粒子分散金属間化合物のＸ線回折角度と強度との関係を示すグラフ、図６は粒子分散金属間化合物に分散している硬質化合物粒子のＸ線回折角度と強度との関係を示すグラフ、図７は粒子分散金属間化合物に含まれる硬質化合物粒子の割合と、該粒子分散金属間化合物の硬度との関係を示すグラフである。また、図８は第２の実施形態の製造方法における反応温度の経時変化を示すグラフである。 Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is a graph showing the change over time of the reaction temperature in the production method of the first embodiment, and FIG. 2 is a graph showing the relationship between the X-ray diffraction angle and the intensity of an intermetallic compound that is a matrix of a particle-dispersed intermetallic compound, 3 to 5 are graphs showing the relationship between the X-ray diffraction angle and intensity of the particle-dispersed intermetallic compound, and FIG. 6 is a graph showing the relationship between the X-ray diffraction angle and intensity of the hard compound particles dispersed in the particle-dispersed intermetallic compound. FIG. 7 is a graph showing the relationship between the ratio of hard compound particles contained in the particle-dispersed intermetallic compound and the hardness of the particle-dispersed intermetallic compound. FIG. 8 is a graph showing the change over time in the reaction temperature in the production method of the second embodiment.
次に、第１の実施形態の粒子分散金属間化合物の製造方法について説明する。本実施形態で製造する粒子分散金属間化合物は、マトリックスとなる金属間化合物相の中に、硬質化合物粒子が分散されているものである。 Next, the manufacturing method of the particle-dispersed intermetallic compound of 1st Embodiment is demonstrated. The particle-dispersed intermetallic compound produced in this embodiment is one in which hard compound particles are dispersed in an intermetallic compound phase that serves as a matrix.
本実施形態の製造方法では、まず、前記硬質化合物粒子を形成する元素の粉末と、前記金属間化合物を形成する元素の粉末とを所定の割合で混合する。 In the manufacturing method of this embodiment, first, the powder of the element forming the hard compound particles and the powder of the element forming the intermetallic compound are mixed at a predetermined ratio.
前記硬質化合物粒子は、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｓｉからなる群から選択される１種以上の第１の元素と、Ｃ、Ｂからなる群から選択される１種以上の第２の元素とから形成される。従って、前記第２の元素がＣであるときには、前記硬質化合物粒子は前記第１の元素の炭化物となり、前記第２の元素がＢであるときには、前記硬質化合物粒子は前記第１の元素のホウ化物となる。このような硬質化合物粒子として、例えばＴｉＣ、ＴｉＢ２を挙げることができる。 The hard compound particles are selected from the group consisting of one or more first elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Si, and C, B And one or more second elements. Accordingly, when the second element is C, the hard compound particles are carbides of the first element, and when the second element is B, the hard compound particles are boronized with the first element. It becomes a monster. Such hard compound particles may include, for example, TiC, and TiB 2.
また、前記金属間化合物は、Ｆｅ、Ｃｏ、Ｎｉ、Ｔｉ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗからなる群から選択され前記硬質化合物粒子を形成する元素とは異なる１種以上の第３の元素と、Ａｌ、Ｓｉからなる群から選択され前記硬質化合物粒子を形成する元素とは異なる１種以上の第４の元素とから形成される。従って、前記第４の元素がＡｌであるときには、前記金属間化合物は前記第３の元素とのアルミナイドとなり、前記第４の元素がＳｉであるときには、前記金属間化合物は前記第３の元素とのシリサイドとなる。このような金属間化合物として、例えばＦｅＡｌ金属間化合物（鉄アルミナイド）を挙げることができる。 The intermetallic compound is one or more third elements selected from the group consisting of Fe, Co, Ni, Ti, Nb, Ta, Cr, Mo, W and different from the element forming the hard compound particles And one or more fourth elements selected from the group consisting of Al and Si and different from the elements forming the hard compound particles. Therefore, when the fourth element is Al, the intermetallic compound is an aluminide with the third element, and when the fourth element is Si, the intermetallic compound is the third element. It becomes a silicide. Examples of such intermetallic compounds include FeAl intermetallic compounds (iron aluminides).
本実施形態では、ＦｅＡｌ金属間化合物相をマトリックスとして、該ＦｅＡｌ金属間化合物相中にＴｉＣ粒子が分散している粒子分散金属間化合物を例として説明する。 In the present embodiment, a particle-dispersed intermetallic compound in which TiC particles are dispersed in the FeAl intermetallic compound phase using the FeAl intermetallic compound phase as a matrix will be described as an example.
前記ＦｅＡｌ金属間化合物相中にＴｉＣ粒子が分散している粒子分散金属間化合物を製造する場合には、Ｆｅ粉末、Ａｌ粉末、Ｔｉ粉末、Ｃ粉末を、所定の割合で混合し、成形して得られた粉末成形体を、例えば、７００〜７５０℃の範囲の温度に加熱する。前記粉末成形体を前記範囲の温度に加熱すると、図１に示すように、該粉末成形体の温度（反応温度）が次第に上昇して行くが、前記４種の元素の中で最も融点の低いＡｌの融点（６６０℃）に達した後、反応温度が急激な上昇を示す。 When manufacturing a particle-dispersed intermetallic compound in which TiC particles are dispersed in the FeAl intermetallic compound phase, Fe powder, Al powder, Ti powder, and C powder are mixed at a predetermined ratio and molded. The obtained powder compact is heated to a temperature in the range of 700 to 750 ° C., for example. When the powder compact is heated to a temperature within the above range, the temperature (reaction temperature) of the powder compact gradually increases as shown in FIG. 1, but the melting point is the lowest among the four elements. After reaching the melting point of Al (660 ° C.), the reaction temperature increases rapidly.
これは、Ａｌが溶融することにより、Ａｌの融液と他の３種の元素との接触面積が大きくなり、Ａｌと他の３種の元素との間で化合物合成の発熱反応が連鎖的に起こるためと考えられる。この結果、前記粉末成形体の温度は短時間のうちに非常な高温に達し、Ｆｅ、Ａｌ、Ｔｉ、Ｃの４元系融液が生成する。このときの最高温度は、図１に示す測定結果では約１７００℃程度であるが、測定に用いた熱電対及びアルミナ保護管による熱の消費を考慮すれば、さらに数百度高い温度に達したものと推察される。 This is because when Al melts, the contact area between the Al melt and the other three elements increases, and the exothermic reaction of compound synthesis is chained between Al and the other three elements. It is thought to happen. As a result, the temperature of the powder compact reaches a very high temperature within a short time, and a quaternary melt of Fe, Al, Ti, and C is generated. The maximum temperature at this time is about 1700 ° C. in the measurement results shown in FIG. 1. However, when the heat consumption by the thermocouple and the alumina protective tube used in the measurement is taken into consideration, the maximum temperature is several hundred degrees higher. It is guessed.
前記反応温度は前記最高温度に達した後は下降に転じ、前記融液が冷却される。すると、まず、融点の高い化合物であるＴｉＣの硬質化合物粒子が形成され、次いでＴｉＣ粒子の間隙に残った未凝固融液からＦｅＡｌ金属間化合物が形成されるものと考えられる。この結果、前記融液が凝固し、ＦｅＡｌ金属間化合物相中にＴｉＣ粒子が分散している粒子分散金属間化合物の成形体が形成される。 After the reaction temperature reaches the maximum temperature, the reaction temperature starts to decrease, and the melt is cooled. Then, it is considered that TiC hard compound particles having a high melting point are first formed, and then an FeAl intermetallic compound is formed from the unsolidified melt remaining in the gaps between the TiC particles. As a result, the melt is solidified to form a particle-dispersed intermetallic compound compact in which TiC particles are dispersed in the FeAl intermetallic phase.
尚、図１は、Ｆｅ、Ａｌ、Ｔｉ、Ｃの各粉末をそれぞれ２５モル％ずつ混合して、成形した粉末成形体を加熱する場合の反応温度の経時変化を示すものであり、この場合にはＦｅＡｌ金属間化合物相中に５０体積％のＴｉＣ粒子が分散している粒子分散金属間化合物の成形体が形成される。 FIG. 1 shows the change over time in the reaction temperature when each of the Fe, Al, Ti, and C powders is mixed by 25 mol% and the molded powder compact is heated. Forms a particle-dispersed intermetallic compound compact in which 50% by volume of TiC particles are dispersed in the FeAl intermetallic phase.
次に、Ｆｅ粉末、Ａｌ粉末、Ｔｉ粉末、Ｃ粉末の割合を変えた以外は、前述の製造方法と全く同一にして、ＦｅＡｌ金属間化合物のみからなる成形体Ａ、ＦｅＡｌ金属間化合物に３０体積％のＴｉＣ粒子が分散している粒子分散金属間化合物の成形体Ｂ、ＦｅＡｌ金属間化合物に５０体積％のＴｉＣ粒子が分散している粒子分散金属間化合物の成形体Ｃ、ＦｅＡｌ金属間化合物に７０体積％のＴｉＣ粒子が分散している粒子分散金属間化合物の成形体Ｄ、ＴｉＣのみからなる成形体Ｅを形成し、成形体Ａ〜ＥのＸ線回折角度と強度とを測定した。成形体Ａ〜ＥのＸ線回折角度と強度とを、それぞれ図２〜６に示す。 Next, except that the proportions of Fe powder, Al powder, Ti powder, and C powder were changed, it was exactly the same as the above-described manufacturing method, and compact 30A consisting of only FeAl intermetallic compound and 30 volumes of FeAl intermetallic compound. % Of particle-dispersed intermetallic compound B in which TiC particles are dispersed, and particle dispersed intermetallic compound compact C in which 50% by volume of TiC particles are dispersed in FeAl intermetallic compound. A compact D of a particle-dispersed intermetallic compound in which 70% by volume of TiC particles are dispersed and a compact E composed of only TiC were formed, and the X-ray diffraction angles and strengths of the compacts A to E were measured. The X-ray diffraction angles and intensities of the molded bodies A to E are shown in FIGS.
図２、図６がそれぞれＦｅＡｌ金属間化合物のみ、ＴｉＣのみに対するピークを示しているのに対し、図３〜５はＦｅＡｌ金属間化合物とＴｉＣとの両方のピークを示しており、成形体Ｂ〜Ｄは、ＦｅＡｌ金属間化合物相中にＴｉＣ粒子が分散している粒子分散金属間化合物であることが明らかである。 2 and FIG. 6 show peaks for only FeAl intermetallic compound and TiC, respectively, whereas FIGS. 3 to 5 show peaks for both FeAl intermetallic compound and TiC. It is clear that D is a particle-dispersed intermetallic compound in which TiC particles are dispersed in the FeAl intermetallic compound phase.
次に、Ｆｅ粉末、Ａｌ粉末、Ｔｉ粉末、Ｃ粉末の割合を変えた以外は、前述の製造方法と全く同一にして、分散しているＴｉＣ粒子の割合（体積％）がそれぞれ異なる成形体を形成し、各成形体のヴィッカース硬度を測定した。結果を図７に示す。 Next, except that the proportions of Fe powder, Al powder, Ti powder, and C powder were changed, the molded products were different from each other in the proportion (volume%) of the dispersed TiC particles exactly the same as the above-described manufacturing method. The Vickers hardness of each molded body was measured. The results are shown in FIG.
図７から、本実施形態の製造方法で得られた粒子分散金属間化合物は、ＦｅＡｌ金属間化合物のみからなる成形体よりも硬く、７００〜２５００（Ｈｖ）の範囲の優れた硬度を備えていることが明らかである。 From FIG. 7, the particle-dispersed intermetallic compound obtained by the production method of the present embodiment is harder than a molded body made of only FeAl intermetallic compound, and has excellent hardness in the range of 700 to 2500 (Hv). It is clear.
本実施形態では、ＦｅＡｌ金属間化合物相中にＴｉＣ粒子が分散している４元系の粒子分散金属間化合物について説明しているが、前記第１〜４の元素はそれぞれ複数の元素を用いてもよく、得られる粒子分散金属間化合物の諸物性を変えることができる。 In the present embodiment, a quaternary particle-dispersed intermetallic compound in which TiC particles are dispersed in the FeAl intermetallic compound phase has been described, but each of the first to fourth elements uses a plurality of elements. In addition, various physical properties of the obtained particle-dispersed intermetallic compound can be changed.
また、前記粉末成形体の加熱を、鉄基、ニッケル基、チタン基等の合金基材の表面で行うと、形成される粒子分散金属間化合物を該合金基材に接合することができる。 Further, when the powder compact is heated on the surface of an alloy base such as an iron group, nickel group, or titanium group, the formed particle-dispersed intermetallic compound can be bonded to the alloy base.
また、前記粉末成形体内の位置によって各元素の割合、元素の種類を徐々に変えると、傾斜組成を備える粒子分散金属間化合物を形成することができる。 Moreover, when the ratio of each element and the kind of element are gradually changed depending on the position in the powder molded body, a particle-dispersed intermetallic compound having a gradient composition can be formed.
尚、前記第２の元素がＣである場合、前記粉末成形体の加熱を窒素雰囲気中で行うと、前記硬質化合物粒子を前記第１の元素の炭窒化物とすることができる。ここで、前記第２の元素を全く使用しないときには、前記粉末成形体の加熱を窒素雰囲気中で行うことにより、前記硬質化合物粒子を前記第１の元素の窒化物とすることができる。 When the second element is C, the hard compound particles can be made into the carbonitride of the first element by heating the powder compact in a nitrogen atmosphere. Here, when the second element is not used at all, the hard compound particles can be made nitride of the first element by heating the powder compact in a nitrogen atmosphere.
次に、第２の実施形態の粒子分散金属間化合物の製造方法について説明する。第２の実施形態の製造方法は、前記硬質化合物粒子を形成する元素の粉末と、前記金属間化合物を形成する元素の粉末とを混合して得られた粉末成形体を加熱して溶融する際に、該粉末成形体の溶融が開始される前の所定温度で一旦昇温を停止し、該温度に所定時間保持した後、昇温を再開して該粉末成形体の溶融すること以外は、前記第１の実施形態の製造方法と全く同一である。 Next, the manufacturing method of the particle-dispersed intermetallic compound of 2nd Embodiment is demonstrated. In the manufacturing method of the second embodiment, a powder compact obtained by mixing the powder of the element forming the hard compound particles and the powder of the element forming the intermetallic compound is heated and melted. In addition, once the temperature rise is stopped at a predetermined temperature before the melting of the powder molded body is started, and held at the temperature for a predetermined time, the temperature rise is restarted to melt the powder molded body, This is exactly the same as the manufacturing method of the first embodiment.
前記昇温を停止する温度は、粉末成形体の溶融が開始される温度、即ち前記粉末成形体を構成する元素の内の最も融点の低い元素の融点よりも５０〜１５０℃低い範囲の温度である。また、前記昇温を停止した温度に保持する時間は、１０〜６０分間の範囲である。 The temperature at which the temperature increase is stopped is a temperature at which melting of the powder compact starts, that is, a temperature in the range of 50 to 150 ° C. lower than the melting point of the lowest melting element among the elements constituting the powder compact. is there. Moreover, the time which hold | maintains the said temperature rise at the temperature which stopped is the range for 10 to 60 minutes.
本実施形態に用いる前記硬質化合物粒子を形成する元素と、前記金属間化合物を形成する元素としては、前記第１の実施形態の場合と全く同一の元素を挙げることができる。 Examples of the element forming the hard compound particles used in the present embodiment and the element forming the intermetallic compound include the same elements as those in the first embodiment.
本実施形態では、ＦｅＡｌ金属間化合物相をマトリックスとして、該ＦｅＡｌ金属間化合物相中にＴｉＢ２粒子が分散している粒子分散金属間化合物を例として説明する。 In the present embodiment, a description will be given by taking, as an example, a particle-dispersed intermetallic compound in which TiB 2 particles are dispersed in the FeAl intermetallic compound phase using the FeAl intermetallic compound phase as a matrix.
本実施形態の製造方法では、前記ＦｅＡｌ金属間化合物相中にＴｉＢ２粒子が分散している粒子分散金属間化合物を製造する場合、まず、Ｆｅ粉末、Ａｌ粉末、Ｔｉ粉末、Ｂ粉末を、所定の割合で混合し、成形して得られた粉末成形体を、例えば、７００〜７５０℃の範囲の温度に加熱する。前記粉末成形体を前記範囲の温度に加熱すると、図８（ａ）に示すように、該粉末成形体の温度（反応温度）が次第に上昇して行くが、本実施形態では前記４種の元素の中で最も融点の低いＡｌの融点（６６０℃）に達する前に、５５０℃に達した時点で一旦昇温を停止する。そして、前記昇温を停止した５５０℃の温度に、３０分間保持する。 In the manufacturing method of the present embodiment, when manufacturing a particle-dispersed intermetallic compound in which TiB 2 particles are dispersed in the FeAl intermetallic compound phase, first, Fe powder, Al powder, Ti powder, and B powder are predetermined. The powder compact obtained by mixing and molding at a ratio of, for example, is heated to a temperature in the range of 700 to 750 ° C. When the powder compact is heated to a temperature within the above range, the temperature (reaction temperature) of the powder compact gradually increases as shown in FIG. 8A. In this embodiment, the four elements are used. Before reaching the melting point (660 ° C.) of Al, which has the lowest melting point, the temperature rise is stopped once it reaches 550 ° C. And it hold | maintains for 30 minutes at the temperature of 550 degreeC which stopped the said temperature rising.
次に、前記保持時間経過後、再び７００〜７５０℃の範囲の温度に加熱して、昇温を開始する。このようにすると、図８（ｂ）に示すように、前記４種の元素の中で最も融点の低いＡｌの融点（６６０℃）に達した後、反応温度が急激な上昇を示す。 Next, after the holding time has elapsed, the temperature is again heated to a temperature in the range of 700 to 750 ° C., and the temperature rise is started. If it does in this way, as shown in FIG.8 (b), after reaching melting | fusing point (660 degreeC) of Al with the lowest melting | fusing point among the said 4 types of elements, reaction temperature will show a rapid rise.
これは、前記第１の実施形態の場合と同様に、Ａｌが溶融することにより、Ａｌの融液と他の３種の元素との接触面積が大きくなり、Ａｌと他の３種の元素との間で化合物合成の発熱反応が連鎖的に起こるためと考えられる。この結果、前記粉末成形体の温度は短時間のうちに非常な高温に達し、Ｆｅ、Ａｌ、Ｔｉ、Ｂの４元系融液が生成する。 As in the case of the first embodiment, when Al melts, the contact area between the Al melt and the other three elements increases, and Al and the other three elements This is probably because the exothermic reaction of compound synthesis occurs in a chain. As a result, the temperature of the powder compact reaches a very high temperature within a short time, and a quaternary melt of Fe, Al, Ti, and B is generated.
このときの最高温度は、図８（ｂ）に示すように約１５００℃であった。一方、第１の実施形態の製造方法に従って、途中で昇温を停止することなく加熱を続けた場合の反応温度の経時変化のうち、該反応温度がＡｌの融点（６６０℃）に達した後の経時変化を、図８（ｂ）に破線で示す。第１の実施形態の製造方法に従った場合の反応温度の最高温度は、前述のように約１７００℃であり、第２の実施形態の製造方法に従うことにより、反応温度の最高温度が低下することが明らかである。 The maximum temperature at this time was about 1500 ° C. as shown in FIG. On the other hand, after the reaction temperature reached the melting point of Al (660 ° C.) in the change over time of the reaction temperature when heating was continued without stopping the temperature increase in the middle according to the manufacturing method of the first embodiment, The change with time is shown by a broken line in FIG. The maximum reaction temperature when the production method of the first embodiment is followed is about 1700 ° C. as described above, and the maximum reaction temperature is lowered by following the production method of the second embodiment. It is clear.
ただし、これらの測定温度は、測定に用いた熱電対がアルミナ製保護管で覆われているため、試料温度が急速に昇温する場合、該熱電対の温度がこれに追随できず、最高温度が過小評価されている可能性がある。 However, because these measurement temperatures are covered with an alumina protective tube, the temperature of the thermocouple cannot follow the maximum temperature because the thermocouple used for measurement is covered with a protective tube made of alumina. May be underestimated.
前記反応温度は前記最高温度に達した後は下降に転じ、前記融液が冷却される。そして、第１の実施形態と同様のメカニズムにより前記融液が凝固して、ＦｅＡｌ金属間化合物相中にＴｉＢ２粒子が分散している粒子分散金属間化合物の成形体が形成される。但し、第２の実施形態の製造方法では、前述のように、反応温度の最高温度が低くなっているため、前記融液の冷却速度が大きくなる。この結果、第２の実施形態の製造方法によれば、ＴｉＢ２粒子の粒子径を小さくできると共に、全体積に対する気孔率が低減された粒子分散金属間化合物を得ることができる。 After the reaction temperature reaches the maximum temperature, the reaction temperature starts to decrease, and the melt is cooled. Then, the melt is solidified by a mechanism similar to that of the first embodiment, and a compact of a particle-dispersed intermetallic compound in which TiB 2 particles are dispersed in the FeAl intermetallic compound phase is formed. However, in the production method of the second embodiment, as described above, the maximum reaction temperature is low, and thus the cooling rate of the melt is increased. As a result, according to the manufacturing method of the second embodiment, it is possible to obtain a particle-dispersed intermetallic compound in which the particle diameter of TiB 2 particles can be reduced and the porosity with respect to the total volume is reduced.
次に、第１の実施形態の製造方法に従って、途中で昇温を停止することなく加熱を続けることにより得られた粒子分散金属間化合物を切断して微細組織を観察したところ、ＴｉＢ２粒子の粒子径は１０〜２０μｍの範囲であり、粒子分散金属間化合物全体積に対する気孔率は２０体積％であった。これに対して、第２の実施形態で得られた粒子分散金属間化合物を切断して微細組織を観察したところ、ＴｉＢ２粒子の粒子径は０．５〜３μｍの範囲であり、粒子分散金属間化合物全体積に対する気孔率は４体積％であった。 Next, according to the manufacturing method of the first embodiment, when the fine particle structure was observed by cutting the particle-dispersed intermetallic compound obtained by continuing the heating without stopping the temperature increase in the middle, the TiB 2 particles The particle diameter was in the range of 10-20 μm, and the porosity with respect to the total volume of the particle-dispersed intermetallic compound was 20% by volume. In contrast, when the fine particle structure was observed by cutting the particle-dispersed intermetallic compound obtained in the second embodiment, the particle diameter of the TiB 2 particles was in the range of 0.5 to 3 μm, and the particle-dispersed metal The porosity with respect to the total volume of the intermetallic compound was 4% by volume.
従って、第２の実施形態の製造方法によれば、第１の実施形態の製造方法に比較して、ＴｉＢ２粒子の粒子径が小さくなると共に、前記粒子分散金属間化合物の全体積に対する気孔率が低減されることが明らかである。 Therefore, according to the manufacturing method of the second embodiment, the particle diameter of TiB 2 particles is smaller than that of the manufacturing method of the first embodiment, and the porosity with respect to the total volume of the particle-dispersed intermetallic compound is reduced. Is clearly reduced.
符号なし。 No sign.
Claims (5)
該硬質化合物粒子を形成する少なくとも２つの元素の粉末と、該金属間化合物を形成する少なくとも２つの元素の粉末とを混合し、成形して粉末成形体を得る工程と、
得られた粉末成形体を加熱して溶融する工程と、
該粉末成形体が溶融した後、冷却して凝固させる工程とを備え、
該粉末成形体を加熱して溶融する工程において、該粉末成形体の溶融が開始される温度よりも５０〜１５０℃低い範囲の温度で一旦昇温を停止し、該温度に所定時間保持した後、昇温を再開して該粉末成形体を溶融することを特徴とする粒子分散金属間化合物の製造方法。 A method for producing a particle-dispersed intermetallic compound in which hard compound particles having higher hardness than the intermetallic compound are dispersed in an intermetallic compound phase serving as a matrix,
Mixing a powder of at least two elements forming the hard compound particles and a powder of at least two elements forming the intermetallic compound, and molding to obtain a powder compact;
Heating and melting the obtained powder compact, and
After the powder molded body is melted, e Bei and coagulating by cooling,
In the step of heating and melting the powder compact, once the temperature rise is temporarily stopped at a temperature in the range of 50 to 150 ° C. lower than the temperature at which the melting of the powder compact starts, the temperature is maintained for a predetermined time. the method of particle dispersion intermetallic compound characterized that you melt the powder molded body to resume heating.
The method for producing a particle-dispersed intermetallic compound according to any one of claims 1 to 4, wherein the time for maintaining the temperature in the range is in the range of 10 to 60 minutes .
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