JP7331447B2 - Ni--Nb laminated plate material and manufacturing method thereof, Ni--Nb alloy plate material and manufacturing method thereof - Google Patents
Ni--Nb laminated plate material and manufacturing method thereof, Ni--Nb alloy plate material and manufacturing method thereof Download PDFInfo
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Description
この発明は、Ｎｉ－Ｎｂ積層板材およびその製造方法、Ｎｉ－Ｎｂ合金板材およびその製造方法に関する。詳しくは、Ｎｉ系金属層およびＮｂ系金属層から構成されたＮｉ－Ｎｂ積層板材およびその製造方法、そのＮｉ－Ｎｂ積層板材を用いて製造可能なＮｉ－Ｎｂ合金板材およびその製造方法に関する。 The present invention relates to a Ni--Nb laminated sheet material and its manufacturing method, and a Ni--Nb alloy sheet material and its manufacturing method. More specifically, the present invention relates to a Ni--Nb laminated plate material composed of a Ni-based metal layer and an Nb-based metal layer, a method for producing the same, a Ni--Nb alloy plate material that can be produced using the Ni--Nb laminated plate material, and a method for producing the same.
従来、Ｎｉ（ニッケル）とＮｂ（ニオブ）を含む、Ｎｉ－Ｎｂ合金が知られている。 Ni—Nb alloys containing Ni (nickel) and Nb (niobium) are known.
図１はＮｉおよびＮｂの二元系状態図である。図１に示す状態図において、Ｎｉに対してＮｂが約２３．５ａｔ％（約３３質量％）以下の範囲にあるＮｉ－Ｎｂ合金は、金属ＮｉとＮｉ－Ｎｂ系の金属間化合物とが共存する。また、Ｎｉに対してＮｂが約５４ａｔ％（約６５質量％）以上の範囲にあるＮｉ－Ｎｂ合金は、金属ＮｂとＮｉ－Ｎｂ系の金属間化合物とが共存する。その中間、つまり、Ｎｉに対してＮｂが約２３．５ａｔ％（約３３質量％）を超えて約５４ａｔ％（約６５質量％）未満の範囲にあるＮｉ－Ｎｂ合金は、Ｎｉ－Ｎｂ系の金属間化合物によって構成される。その中でも、Ｎｉに対してＮｂが約２６．５ａｔ（約３６質量％）以上約５０ａｔ％（約６１質量％）以下の範囲にあるＮｉ－Ｎｂ合金は、Ｎｉ－Ｎｂ系の金属間化合物であるＮｉ３ＮｂとＮｉ６Ｎｂ７とが共存する。 FIG. 1 is a binary phase diagram of Ni and Nb. In the phase diagram shown in FIG. 1, the Ni—Nb alloy in which Nb is in the range of about 23.5 at% (about 33% by mass) or less with respect to Ni has a coexistence of metallic Ni and a Ni—Nb intermetallic compound. do. In addition, in a Ni—Nb alloy in which Nb is in the range of approximately 54 at % (approximately 65 mass %) or more with respect to Ni, metallic Nb and Ni—Nb intermetallic compounds coexist. Ni—Nb alloys in the middle, that is, in the range of more than about 23.5 at % (about 33 mass %) and less than about 54 at % (about 65 mass %) of Nb to Ni are Ni—Nb-based Composed of an intermetallic compound. Among them, Ni—Nb alloys in which Nb is in the range of about 26.5 at (about 36% by mass) to about 50 at% (about 61% by mass) or less with respect to Ni are Ni—Nb-based intermetallic compounds. Ni 3 Nb and Ni 6 Nb 7 coexist.
上記したように、Ｎｉ－Ｎｂ合金は、ＮｉとＮｂの配合比に応じて、組織形態が異なるものとなる。Ｎｉ－Ｎｂ合金は、上記した構成組織の特質が考慮され、Ｎｉ－Ｎｂ合金板材、Ｎｉ－Ｎｂ系の金属間化合物、あるいはＮｉ－Ｎｂ系の合金粉末などとして、実用化されている。例えば、特許文献１には、Ｎｉと６質量％以上３２質量％未満のＮｂを含むＮｉ－Ｎｂ合金によって構成された冷陰極放電管用電極が開示されている。この場合、Ｎｉ－Ｎｂ合金がＮｉ－Ｎｂ合金板材として用いられている。また、例えば、特許文献２には、Ｎｂ基材の表面がＮｉ－Ｎｂ系の金属間化合物（被覆材）で被覆された電解用不溶性電極が開示されている。この場合、Ｎｉ－Ｎｂ合金がＮｉ－Ｎｂ系の金属間化合物として用いられている。また、例えば、特許文献３には、Ｍｏ粉末に対してＮｉ６Ｎｂ７および／またはＮｉ３ＮｂからなるＮｉ－Ｎｂ系の合金粉末を混合し、次いで加圧焼結して製造されたＭｏ合金スパッタリングターゲット材が開示されている。この場合、Ｎｉ－Ｎｂ合金がＮｉ－Ｎｂ系の合金粉末として用いられている。 As described above, the Ni—Nb alloy has different structural forms depending on the mixing ratio of Ni and Nb. Ni--Nb alloys have been put to practical use as Ni--Nb alloy sheet materials, Ni--Nb intermetallic compounds, or Ni--Nb alloy powders, in consideration of the characteristics of the structure described above. For example, Patent Document 1 discloses a cold cathode discharge tube electrode made of a Ni—Nb alloy containing Ni and 6% by mass or more and less than 32% by mass of Nb. In this case, a Ni--Nb alloy is used as the Ni--Nb alloy plate material. Further, for example, Patent Document 2 discloses an insoluble electrode for electrolysis in which the surface of a Nb substrate is coated with a Ni—Nb-based intermetallic compound (coating material). In this case, a Ni--Nb alloy is used as the Ni--Nb intermetallic compound. Further, for example, in Patent Document 3, a Mo alloy produced by mixing Ni—Nb-based alloy powder consisting of Ni 6 Nb 7 and/or Ni 3 Nb with Mo powder and then sintering under pressure A sputtering target material is disclosed. In this case, a Ni--Nb alloy is used as the Ni--Nb alloy powder.
金属Ｎｉおよび金属Ｎｂは展延性が良い。Ｎｉ－Ｎｂ系の金属間化合物と展延性が良い金属Ｎｉとが共存するＮｉ－Ｎｂ合金は、展延性のよい金属Ｎｉが組織中に多く存在することによって、大変形を伴う圧延加工などによるＮｉ－Ｎｂ合金板材の製造が可能である。また、同様に、Ｎｉ－Ｎｂ系の金属間化合物と展延性が良い金属Ｎｂとが共存するＮｉ－Ｎｂ合金は、展延性のよい金属Ｎｂが組織中に多く存在することによって、プレス加工および圧延加工などの大変形を伴う塑性加工によるＮｉ－Ｎｂ合金板材の製造が可能である。こうしたＮｉ－Ｎｂ合金板材は、例えば、Ｎｉ源およびＮｂ源を同時に溶解・凝固させてインゴットを製造し、そのインゴットをプレスして厚板素材を製造し、その厚板素材を圧延して所定の厚さに形成する、などの方法で製造が可能である。 Metal Ni and metal Nb have good ductility. Ni—Nb alloys, in which Ni—Nb-based intermetallic compounds and highly malleable metallic Ni coexist, have a large amount of highly malleable metallic Ni present in the structure, resulting in Ni - It is possible to manufacture Nb alloy sheets. Similarly, a Ni—Nb alloy in which a Ni—Nb-based intermetallic compound and a highly malleable metal Nb coexist has a large amount of highly malleable metal Nb present in the structure, so that it is difficult to press and roll. It is possible to manufacture Ni—Nb alloy sheets by plastic working that involves large deformation such as working. Such a Ni—Nb alloy sheet material is produced, for example, by simultaneously melting and solidifying a Ni source and an Nb source to produce an ingot, pressing the ingot to produce a thick plate material, and rolling the thick plate material to a predetermined thickness. It can be manufactured by a method such as forming in thickness.
Ｎｉ－Ｎｂ系の金属間化合物は脆く、割れやすい。そのため、Ｎｉ－Ｎｂ系の金属間化合物からなり、展延性が良い金属Ｎｉまたは金属Ｎｂが共存しないＮｉ－Ｎｂ合金は、大変形を伴う圧延加工などによるＮｉ－Ｎｂ合金板材の製造が困難である。例えば、Ｎｉに対してＮｂが約２６．５ａｔ（約３６質量％）以上約５０ａｔ％（約６１質量％）以下の範囲にあって、Ｎｉ－Ｎｂ系の金属間化合物からなるＮｉ－Ｎｂ合金のインゴットを製造し、インゴットから厚板素材へのプレス加工、また、厚板素材から板材への圧延加工などの工程を経て、Ｎｉ－Ｎｂ合金板材を製造するのは困難と考えられる。こうした事情から、Ｎｉに対して約２６．５ａｔ（約３６質量％）以上約５０ａｔ％（約６１質量％）以下のＮｂを含む、Ｎｉ－Ｎｂ系の金属間化合物の共存組織を有するＮｉ－Ｎｂ合金から構成された、商用のＮｉ－Ｎｂ合金板材は市場に出ていない。 Ni—Nb based intermetallic compounds are brittle and easily cracked. Therefore, it is difficult to manufacture Ni-Nb alloy sheets by rolling with large deformation, etc., from Ni-Nb alloys that are composed of Ni-Nb intermetallic compounds and do not coexist with metallic Ni or metallic Nb with good ductility. . For example, a Ni—Nb alloy composed of a Ni—Nb intermetallic compound in which Nb is in the range of about 26.5 at (about 36% by mass) or more and about 50 at% (about 61% by mass) or less with respect to Ni It is considered difficult to manufacture a Ni—Nb alloy plate material by manufacturing an ingot, pressing the ingot into a thick plate material, and rolling the thick plate material into a plate material. Under these circumstances, Ni—Nb having a coexistence structure of Ni—Nb-based intermetallic compounds containing Nb of about 26.5 at (about 36% by mass) or more and about 50 at% (about 61% by mass) or less with respect to Ni There is no commercial Ni--Nb alloy sheet material made from the alloy on the market.
この発明の目的の１つは、Ｎｉ－Ｎｂ系の金属間化合物の共存組織を有するＮｉ－Ｎｂ合金板材の製造を可能にする板素材およびその製造方法を提供することである。また、この発明の目的の１つは、上記板素材から構成されたＮｉ－Ｎｂ合金板材およびその製造方法を提供することである。また、望ましくは、板厚が４ｍｍ以下のＮｉ－Ｎｂ合金板材の製造を可能とする、板厚が例えば４ｍｍ以下の板素材、およびその板素材から構成された板厚が４ｍｍ以下のＮｉ－Ｎｂ合金板材を提供する。 One of the objects of the present invention is to provide a sheet material and a method for manufacturing the same that enable the manufacture of a Ni--Nb alloy sheet material having a coexisting structure of Ni--Nb intermetallic compounds. Another object of the present invention is to provide a Ni--Nb alloy plate material made from the above plate material and a method for producing the same. Further, desirably, a plate material having a thickness of 4 mm or less, and a Ni-Nb plate material having a thickness of 4 mm or less composed of the plate material, which enables the production of a Ni-Nb alloy plate material having a thickness of 4 mm or less We provide alloy sheets.
本発明者は、展延性の良いＮｉ系金属板材と、展延性の良いＮｂ系金属板材とを、交互に積層した状態で圧延接合して積層板材を製造する、クラッド圧延工程と、クラッド圧延工程で製造された積層板材を拡散焼鈍してＮｉ－Ｎｂ系の金属間化合物を生成する拡散焼鈍工程と、を含む、製造方法によって、上記した課題が解決できることを見出し、この発明に想到することができた。 The present inventors have proposed a clad rolling process and a clad rolling process in which a Ni-based metal plate material with good ductility and a Nb-based metal plate material with good ductility are alternately laminated and roll-joined to produce a laminated plate material. and a diffusion annealing step of forming a Ni—Nb-based intermetallic compound by diffusion annealing the laminated plate material produced in (1). did it.
この発明の１つは、上記Ｎｉ－Ｎｂ積層板材から構成されたＮｉ－Ｎｂ合金板材およびその製造方法に関する。
すなわち、この発明に係るＮｉ－Ｎｂ合金板材は、ＮｉおよびＮｂからなる金属間化合物の共存組織を有し、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層されて構成されており、前記Ｎｉリッチ層および前記Ｎｂリッチ層の合計の層数が３以上である。
この発明において、Ｎｉ－Ｎｂ合金板材は、板厚が４ｍｍ以下であってよい。
One aspect of the present invention relates to a Ni--Nb alloy sheet material composed of the above-mentioned Ni--Nb laminated sheet material and a method for producing the same.
That is, the Ni—Nb alloy sheet material according to the present invention has a coexisting structure of intermetallic compounds composed of Ni and Nb, and is configured by alternately laminating Ni-rich layers and Nb-rich layers in the thickness direction. , the total number of layers of the Ni-rich layers and the Nb-rich layers is 3 or more.
In the present invention, the Ni—Nb alloy sheet may have a thickness of 4 mm or less.
この発明に係るＮｉ－Ｎｂ合金板材の製造方法は、純Ｎｉまたは７質量％以下のＮｂを含むＮｉ合金からなるＮｉ系金属板材と、純Ｎｂまたは１５質量％以下のＮｉを含むＮｂ合金からなるＮｂ系金属板材とを、厚さ方向に交互に積層し、前記Ｎｉ系金属板材および前記Ｎｂ系金属板材の合計の積層数を３以上とした状態で圧延接合することによって、Ｎｉ系金属層とＮｂ系金属層とが厚さ方向に交互に積層され、合計の積層数が３以上の積層板材を形成し、前記積層板材に対して拡散焼鈍を行うことによって、ＮｉおよびＮｂからなる金属間化合物の共存組織を有し、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層され、前記Ｎｉリッチ層および前記Ｎｂリッチ層の合計の積層数が３以上の合金板材を形成する。
この発明において、板厚を４ｍｍ以下に形成するＮｉ－Ｎｂ合金板材の製造方法であってよい。
A method for producing a Ni—Nb alloy sheet material according to the present invention consists of a Ni-based metal sheet material made of pure Ni or a Ni alloy containing 7% by mass or less of Nb, and an Nb alloy containing pure Nb or 15% by mass or less of Ni. The Nb-based metal plate materials are alternately laminated in the thickness direction, and roll-bonded in a state where the total number of layers of the Ni-based metal plate material and the Nb-based metal plate material is 3 or more, thereby forming the Ni-based metal layer and Nb-based metal layers are alternately laminated in the thickness direction to form a laminated plate material having a total number of laminated layers of 3 or more, and the laminated plate material is subjected to diffusion annealing to form an intermetallic compound composed of Ni and Nb. Ni-rich layers and Nb-rich layers are alternately laminated in the thickness direction, and the total number of laminated layers of the Ni-rich layers and the Nb - rich layers is 3 or more.
In the present invention, the method may be a method for producing a Ni—Nb alloy sheet having a thickness of 4 mm or less.
この発明によれば、Ｎｉ－Ｎｂ系の金属間化合物の共存組織を有するＮｉ－Ｎｂ合金板材を提供することができる。
また、板厚が４ｍｍ以下のＮｉ－Ｎｂ合金板材の製造を可能とすることができる。
According to the present invention, it is possible to provide a Ni--Nb alloy sheet having a coexisting structure of Ni--Nb intermetallic compounds.
In addition, it is possible to manufacture a Ni—Nb alloy sheet having a thickness of 4 mm or less.
まず、この発明に係るＮｉ－Ｎｂ積層板材およびその製造方法について説明する。
図２は、この発明に係るＮｉ－Ｎｂ積層板材の１つの実施形態であって、板厚方向に切断したＮｉ－Ｎｂ積層板材の断面（横断面）の観察写真である。図２に示すＮｉ－Ｎｂ積層板材は、Ｎｉ系金属層と、Ｎｂ系金属層と、Ｎｉ系金属層とが、この順に、厚さ方向（圧接方向）に交互に積層されて成る。このＮｉ－Ｎｂ積層板材はＮｉ系金属層およびＮｂ系金属層の合計の層数が３である。つまり、このＮｉ－Ｎｂ積層板材は３層構造のクラッド板材である。Ｎｉ系金属層とＮｂ系金属層とが、交互に３層以上積層されることによって、後の拡散焼鈍におけるＮｉおよびＮｂの相互拡散によるＮｉ－Ｎｂ合金化を十分に進めることができる。また、この発明に係るＮｉ－Ｎｂ積層板材は、板厚が４ｍｍ以下であってよく、板厚を構成するそれぞれの層の厚さは限定されない。例えば、図２に示すＮｉ－Ｎｂ積層板材は、板厚が約０．１ｍｍであり、板厚を構成するそれぞれの層の厚さ比率（Ｎｉ系金属層：Ｎｂ系金属層：Ｎｉ系金属層）は、およそ、１：２．５：１である。
First, a Ni—Nb laminated plate material and a method for manufacturing the same according to the present invention will be described.
FIG. 2 is one embodiment of the Ni—Nb laminated plate material according to the present invention, and is an observation photograph of a cross section (cross section) of the Ni—Nb laminated plate member cut in the plate thickness direction. The Ni—Nb laminated plate material shown in FIG. 2 is formed by alternately laminating a Ni-based metal layer, a Nb-based metal layer, and a Ni-based metal layer in this order in the thickness direction (pressing direction). This Ni—Nb laminated plate material has a total of three layers of Ni-based metal layers and Nb-based metal layers. In other words, this Ni--Nb laminated plate material is a clad plate material having a three-layer structure. By alternately laminating three or more layers of Ni-based metal layers and Nb-based metal layers, Ni—Nb alloying due to interdiffusion of Ni and Nb in the subsequent diffusion annealing can be sufficiently advanced. Further, the Ni—Nb laminated plate material according to the present invention may have a plate thickness of 4 mm or less, and the thickness of each layer constituting the plate thickness is not limited. For example, the Ni—Nb laminated plate material shown in FIG. ) is approximately 1:2.5:1.
この発明に係るＮｉ－Ｎｂ積層板材において、Ｎｉ系金属層は、純Ｎｉまたは７質量％以下のＮｂを含むＮｉ合金から成る。純ＮｉはＮｉを９９質量％以上含むものをいう。純Ｎｉまたは７質量％以下のＮｂを含むＮｉ合金は、後に、Ｎｉ－Ｎｂ系の金属間化合物を生成するためのＮｉ源となる。純Ｎｉは展延性が良く、７質量％（約４．５ａｔ％）以下のＮｂを含むＮｉ合金は展延性の良い金属Ｎｉが豊富に存在するため、大変形を伴う圧延接合を容易に行うことができる。また、純ＮｉからなるＮｉ板材、および例えば５質量％（約３．２ａｔ％）のＮｂを含むＮｉ合金板材（Ｎｉ－５Ｎｂ合金板材）は、入手が容易である。なお、図２に示すＮｉ－Ｎｂ積層板材を構成するＮｉ系金属層は、Ｎｉを９９質量％以上含む純Ｎｉから構成されている。 In the Ni--Nb laminated plate material according to the present invention, the Ni-based metal layer is made of pure Ni or a Ni alloy containing 7% by mass or less of Nb. Pure Ni refers to a material containing 99% by mass or more of Ni. Pure Ni or Ni alloys containing 7% by mass or less of Nb later serve as Ni sources for producing Ni—Nb-based intermetallic compounds. Pure Ni has good ductility, and Ni alloys containing 7% by mass (approximately 4.5 at%) or less of Nb are rich in metallic Ni with good ductility, so roll joining involving large deformation can be easily performed. can be done. Further, a Ni plate material made of pure Ni and a Ni alloy plate material (Ni-5Nb alloy plate material) containing, for example, 5 mass % (about 3.2 at %) of Nb are readily available. The Ni-based metal layer forming the Ni—Nb laminated plate shown in FIG. 2 is made of pure Ni containing 99% by mass or more of Ni.
この発明に係るＮｉ－Ｎｂ積層板材において、Ｎｂ系金属層は、純Ｎｂまたは１５質量％以下のＮｉを含むＮｂ合金から成る。純ＮｂはＮｂを９９質量％以上含むものをいう。純Ｎｂまたは１５質量％以下のＮｉを含むＮｂ合金は、後に、Ｎｉ－Ｎｂ系の金属間化合物を生成するためのＮｂ源となる。純Ｎｂは展延性が良く、１５質量％（約２２ａｔ％）以下のＮｉを含むＮｂ合金は展延性の良い金属Ｎｂが存在するため、大変形を伴う圧延接合を行うことができる。純ＮｂからなるＮｂ板材（Ｎｂ箔材）は入手が容易であり、好ましくは、純ＮｂからなるＮｂ系金属層とする。なお、図２に示すＮｉ－Ｎｂ積層板材を構成するＮｂ系金属層は、Ｎｂを９９質量％以上含む純Ｎｂから構成されている。 In the Ni—Nb laminated plate material according to the present invention, the Nb-based metal layer is made of pure Nb or an Nb alloy containing Ni in an amount of 15% by mass or less. Pure Nb means one containing 99% by mass or more of Nb. Pure Nb or an Nb alloy containing 15% by mass or less of Ni later becomes a Nb source for producing a Ni—Nb-based intermetallic compound. Pure Nb has good ductility, and an Nb alloy containing 15% by mass (approximately 22 at%) or less of Ni contains metal Nb with good ductility, so roll-joining with large deformation can be performed. An Nb plate material (Nb foil material) made of pure Nb is easily available, and an Nb-based metal layer made of pure Nb is preferably used. The Nb-based metal layer forming the Ni—Nb laminated plate shown in FIG. 2 is made of pure Nb containing 99% by mass or more of Nb.
図２に示すＮｉ－Ｎｂ積層板材は、この発明に係るＮｉ－Ｎｂ積層板材の製造方法によって、製造することができる。
この発明に係るＮｉ－Ｎｂ積層板材の製造方法では、まず、純Ｎｉまたは７質量％以下のＮｂを含むＮｉ合金からなるＮｉ系金属板材と、純Ｎｂまたは１５質量％以下のＮｉを含むＮｂ合金からなるＮｂ系金属板材とを、準備する。Ｎｉ系金属板材およびＮｂ系金属板材は、圧延接合の前に、必要十分な熱処理を行っておくのがよい。図２に示すＮｉ－Ｎｂ積層板材を製造する場合は、純Ｎｉからなる板厚が約０．３ｍｍのＮｉ系金属板材と、純Ｎｂからなる板厚が約０．３ｍｍのＮｂ系金属板材とを準備した。なお、Ｎｉ系金属板材およびＮｂ系金属板材に対して、圧延接合の前に、例えば７００℃以上１０５０℃以下の温度で１分間以上１０分間以下保持する熱処理を行ってもよい。
The Ni--Nb laminated plate material shown in FIG. 2 can be produced by the method for producing a Ni--Nb laminated plate material according to the present invention.
In the method for producing a Ni—Nb laminated plate material according to the present invention, first, a Ni-based metal plate material made of pure Ni or a Ni alloy containing 7% by mass or less of Nb, and an Nb alloy containing pure Nb or 15% by mass or less of Ni A Nb-based metal plate material consisting of is prepared. The Ni-based metal sheet material and the Nb-based metal sheet material are preferably subjected to necessary and sufficient heat treatment before rolling and joining. When manufacturing the Ni—Nb laminated plate material shown in FIG. 2, a Ni-based metal plate material made of pure Ni and having a plate thickness of about 0.3 mm and a Nb-based metal plate material made of pure Nb and having a plate thickness of about 0.3 mm are used. prepared. Note that the Ni-based metal sheet material and the Nb-based metal sheet material may be subjected to a heat treatment at a temperature of 700° C. or more and 1050° C. or less for 1 minute or more and 10 minutes or less before roll-bonding.
次に、この発明に係るＮｉ－Ｎｂ積層板材の製造方法では、Ｎｉ系金属板材と、Ｎｂ系金属板材と、Ｎｉ系金属板材とを、この順に、厚さ方向（圧接方向）に交互に積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を３以上とした状態で圧延接合を行う。こうした圧延接合によって、Ｎｉ系金属層とＮｂ系金属層とが厚さ方向に交互に積層され、合計の積層数が３以上の積層板材を形成することができる。なお、この発明において、上記した圧延接合の後に、必要に応じて熱処理を行ってもよい。この熱処理は、例えば７００℃以上９００℃以下の温度で約１分間以上５分間以下保持するものであってよい。図２に示すＮｉ－Ｎｂ積層板材を製造する場合は、Ｎｉ系金属板材と、Ｎｂ系金属板材と、Ｎｉ系金属板材とを、この順に、厚さ方向（圧接方向）に交互に積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を３とした状態で圧延接合を行っている。また、圧延接合の後、約８００℃で約３分間保持する熱処理を行っている。 Next, in the method for producing a Ni—Nb laminated plate material according to the present invention, a Ni-based metal plate material, a Nb-based metal plate material, and a Ni-based metal plate material are alternately laminated in this order in the thickness direction (pressure contact direction). Then, roll bonding is performed in a state in which the total number of laminated layers of the Ni-based metal plate material and the Nb-based metal plate material is set to 3 or more. By such roll bonding, the Ni-based metal layers and the Nb-based metal layers are alternately laminated in the thickness direction, and a laminated plate material having a total number of laminated layers of 3 or more can be formed. In addition, in the present invention, heat treatment may be performed as necessary after the roll bonding described above. This heat treatment may be carried out at a temperature of, for example, 700° C. or higher and 900° C. or lower for about 1 minute or longer and 5 minutes or shorter. When manufacturing the Ni—Nb laminated plate material shown in FIG. 2, the Ni-based metal plate material, the Nb-based metal plate material, and the Ni-based metal plate material are alternately laminated in this order in the thickness direction (pressure contact direction), Rolling bonding is performed in a state in which the total number of laminated layers of the Ni-based metal plate material and the Nb-based metal plate material is set to three. Further, after roll bonding, a heat treatment is performed at about 800° C. for about 3 minutes.
上記したように、図２に示す３層構造のＮｉ－Ｎｂ積層板材は、展延性の良いＮｉ系金属板材と、展延性の良いＮｂ系金属板材と、展延性の良いＮｉ系金属板材とを、厚さ方向（圧接方向）に交互に積層し、合計の積層数を３とした状態で圧延接合する、クラッド圧延によって、容易に製造することができる。こうしたクラッド圧延によって、Ｎｉ系金属層とＮｂ系金属層とが厚さ方向に交互に積層され、合計の積層数が３の図２に示すＮｉ－Ｎｂ積層板材を形成することができる。なお、図２に示すＮｉ－Ｎｂ積層板材は、板厚が約０．１ｍｍである。厚さ比率（Ｎｉ系金属層：Ｎｂ系金属層：Ｎｉ系金属層）は、およそ、１：２．５：１である。Ｎｉ系金属層は、それぞれの層の厚さが約２２μｍである。Ｎｂ系金属層は、層の厚さが約５６μｍである。 As described above, the Ni—Nb laminated plate material having a three-layer structure shown in FIG. It can be easily manufactured by clad rolling, in which layers are alternately laminated in the thickness direction (pressing direction) and the total number of layers is 3, and roll bonding is performed. By such clad rolling, the Ni-based metal layers and the Nb-based metal layers are alternately laminated in the thickness direction, and the total number of laminated layers is 3 to form the Ni--Nb laminated plate shown in FIG. The thickness of the Ni—Nb laminated plate material shown in FIG. 2 is approximately 0.1 mm. The thickness ratio (Ni-based metal layer:Nb-based metal layer:Ni-based metal layer) is approximately 1:2.5:1. The Ni-based metal layers each have a thickness of about 22 μm. The Nb-based metal layer has a layer thickness of about 56 μm.
この発明に係るＮｉ－Ｎｂ積層板材の別の実施形態について説明する。
図３は、この発明に係るＮｉ－Ｎｂ積層板材の１つの実施形態であって、板厚方向に切断したＮｉ－Ｎｂ積層板材の断面（横断面）の観察写真である。図３に示すＮｉ－Ｎｂ積層板材は、Ｎｉ系金属層およびＮｂ系金属層が厚さ方向（圧接方向）に交互に積層されて成る。このＮｉ－Ｎｂ積層板材はＮｉ系金属層およびＮｂ系金属層の合計の層数が１８である。つまり、このＮｉ－Ｎｂ積層板材は１８層構造のクラッド板材である。このＮｉ－Ｎｂ積層板材において、Ｎｉ系金属層はＮｉを９９質量％以上含む純Ｎｉから構成され、Ｎｂ系金属層はＮｂを９９質量％以上含む純Ｎｂから構成されている。このＮｉ－Ｎｂ積層板材は、板厚が約０．１ｍｍである。また、このＮｉ－Ｎｂ積層板材の横断面を、図３に示すように３つのエリア１～３に区分し、エリア１～３のそれぞれについてＥＤＳ（Ｅｎｅｒｇｙ Ｄｉｓｐｅｒｓｉｖｅ Ｓｐｅｃｔｒｏｓｃｏｐｙ）分析を行ったところ、エリア１～３の平均のＮｂ含有比は４９．６質量％（約３７．４ａｔ％）であった。
Another embodiment of the Ni—Nb laminated plate material according to the present invention will be described.
FIG. 3 is one embodiment of the Ni—Nb laminated plate material according to the present invention, and is an observation photograph of a cross section (cross section) of the Ni—Nb laminated plate member cut in the plate thickness direction. The Ni—Nb laminated plate material shown in FIG. 3 is formed by alternately laminating Ni-based metal layers and Nb-based metal layers in the thickness direction (pressure contact direction). This Ni—Nb laminated plate material has a total of 18 layers of Ni-based metal layers and Nb-based metal layers. In other words, this Ni—Nb laminated plate material is a clad plate material having an 18-layer structure. In this Ni—Nb laminated plate, the Ni-based metal layer is composed of pure Ni containing 99% by mass or more of Ni, and the Nb-based metal layer is composed of pure Nb containing 99% by mass or more of Nb. This Ni—Nb laminated plate material has a plate thickness of about 0.1 mm. In addition, the cross section of this Ni—Nb laminated plate material was divided into three areas 1 to 3 as shown in FIG. The average Nb content ratio of ∼3 was 49.6% by mass (about 37.4at%).
図４は、この発明に係るＮｉ－Ｎｂ積層板材の１つの実施形態であって、板厚方向に切断したＮｉ－Ｎｂ積層板材の断面（横断面）の観察写真である。図４に示すＮｉ－Ｎｂ積層板材は、Ｎｉ系金属層およびＮｂ系金属層が厚さ方向（圧接方向）に交互に積層されて成る。このＮｉ－Ｎｂ積層板材はＮｉ系金属層およびＮｂ系金属層の合計の層数が１８である。つまり、このＮｉ－Ｎｂ積層板材は１８層構造のクラッド板材である。このＮｉ－Ｎｂ積層板材において、Ｎｉ系金属層はＮｉに対してＮｂを５質量％含むＮｉ合金（Ｎｉ－５Ｎｂ）から構成され、Ｎｂ系金属層はＮｂを９９質量％以上含む純Ｎｂから構成されている。このＮｉ－Ｎｂ積層板材は、板厚が約０．１ｍｍである。また、このＮｉ－Ｎｂ積層板材の横断面を、図４に示すように３つのエリア１～３に区分し、エリア１～３のそれぞれについて、上記した図３に示すＮｉ－Ｎｂ積層板材の場合と同様に、ＥＤＳ分析を行ったところ、エリア１～３の平均のＮｂ比率は５５．３質量％（約４３．９ａｔ％）であった。 FIG. 4 is one embodiment of the Ni—Nb laminated plate material according to the present invention, and is an observation photograph of a cross section (cross section) of the Ni—Nb laminated plate member cut in the plate thickness direction. The Ni—Nb laminated plate material shown in FIG. 4 is formed by alternately laminating Ni-based metal layers and Nb-based metal layers in the thickness direction (pressure contact direction). This Ni—Nb laminated plate material has a total of 18 layers of Ni-based metal layers and Nb-based metal layers. In other words, this Ni—Nb laminated plate material is a clad plate material having an 18-layer structure. In this Ni—Nb laminated plate material, the Ni-based metal layer is composed of a Ni alloy (Ni-5Nb) containing 5% by mass of Nb relative to Ni, and the Nb-based metal layer is composed of pure Nb containing 99% by mass or more of Nb. It is This Ni—Nb laminated plate material has a plate thickness of about 0.1 mm. In addition, the cross section of this Ni—Nb laminated plate material is divided into three areas 1 to 3 as shown in FIG. EDS analysis was performed in the same manner as in , and the average Nb ratio in areas 1 to 3 was 55.3% by mass (approximately 43.9at%).
図３および図４に示すような１８層構造のＮｉ－Ｎｂ積層板材は、例えば、展延性の良いＮｉ系金属板材と展延性の良いＮｂ系金属板材とを交互に積層した状態で圧延接合する、クラッド圧延を繰り返すことによって、製造することができる。具体的には、例えば、１回目のクラッド圧延（第１クラッド圧延）工程において、展延性の良いＮｉ系金属板材と展延性の良いＮｂ系金属板材とを積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を２とした状態で圧延接合することによって、２層構造のＮｉ－Ｎｂ積層板材を製造することができる。２回目のクラッド圧延（第２クラッド圧延）工程において、２層構造のＮｉ－Ｎｂ積層板材を３枚積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を６とした状態で圧延接合することによって、６層構造のＮｉ－Ｎｂ積層板材を製造することができる。３回目のクラッド圧延（第３クラッド圧延）工程において、６層構造のＮｉ－Ｎｂ積層板材を３枚積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を１８とした状態で圧延接合することによって、１８層構造のＮｉ－Ｎｂ積層板材を製造することができる。なお、こうしたクラッド圧延を繰り返す場合、上記した１８層構造のＮｉ－Ｎｂ積層板材に限らず、クラッド圧延の繰り返し回数は限定されないし、クラッド圧延は１回であってもよい。 An 18-layer Ni—Nb laminated plate material as shown in FIGS. 3 and 4 is rolled and joined, for example, in a state in which a highly malleable Ni-based metal plate material and a highly malleable Nb-based metal plate material are alternately laminated. , can be manufactured by repeating clad rolling. Specifically, for example, in the first clad rolling (first clad rolling) step, a Ni-based metal plate material with good ductility and an Nb-based metal plate material with good ductility are laminated, and the Ni-based metal plate material and the Nb-based metal plate material are laminated. A Ni—Nb laminated plate material having a two-layer structure can be manufactured by rolling and joining the metal plate materials in a state in which the total number of laminated layers is two. In the second clad rolling (second clad rolling) step, three Ni—Nb laminated plate materials having a two-layer structure are laminated, and the total number of laminated layers of the Ni-based metal plate material and the Nb-based metal plate material is set to 6. By joining, a Ni--Nb laminated plate material having a six-layer structure can be manufactured. In the third clad rolling (third clad rolling) step, three Ni—Nb laminated plate materials having a six-layer structure are laminated, and the total number of laminated layers of the Ni-based metal plate material and the Nb-based metal plate material is set to 18. By joining, an 18-layer structure Ni--Nb laminated plate material can be manufactured. When such clad rolling is repeated, the number of repetitions of clad rolling is not limited to the Ni—Nb laminated plate material having the 18-layer structure described above, and the clad rolling may be repeated once.
上記したように、例えばクラッド圧延を繰り返すことによって、展延性の良いＮｉ系金属板材および展延性の良いＮｂ系金属板材から構成された、図３および図４に示すような１８層構造のＮｉ－Ｎｂ積層板材を、製造することができる。なお、この発明に係るＮｉ－Ｎｂ積層板材は、後に、この発明に係るＮｉ－Ｎｂ合金板材の製造を容易にするために、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数が３以上であればよい。また、上記したようにクラッド圧延を繰り返す場合の途中のクラッド圧延におけるＮｉ系金属板材およびＮｂ系金属板材の合計の積層数は限定されない。 As described above, for example, by repeating clad rolling, Ni- having an 18-layer structure as shown in FIGS. Nb laminates can be produced. Note that the Ni—Nb laminated plate material according to the present invention has a total number of laminations of 3 or more of the Ni-based metal plate material and the Nb-based metal plate material in order to facilitate the production of the Ni—Nb alloy plate material according to the present invention later. If it is Further, as described above, when the clad rolling is repeated, the total number of laminated layers of the Ni-based metal sheet material and the Nb-based metal sheet material in the intermediate clad rolling is not limited.
以下、図３および図４に示すような１８層構造のＮｉ－Ｎｂ積層板材の製造方法について詳述する。
＜Ｎｉ系金属板材、Ｎｂ系金属板材＞
Ｎｉ系金属板材およびＮｂ系金属板材を準備する。Ｎｉ系金属板材は、図３に示すＮｉ－Ｎｂ積層板材を製造する場合は純Ｎｉからなる板厚が約０．３ｍｍのものを準備し、図４に示すＮｉ－Ｎｂ積層板材を製造する場合はＮｉに対してＮｂを５質量％含む板厚が約０．３ｍｍのものを準備する。また、Ｎｂ系金属板材は、図３および図４に示すいずれのＮｉ－Ｎｂ積層板材を製造する場合においても、純Ｎｂからなる板厚が約０．３ｍｍのものを準備する。なお、Ｎｉ系金属板材およびＮｂ系金属板材に対して、圧延接合の前に、例えば７００℃以上１０５０℃以下の温度で１分間以上１０分間以下保持する熱処理を行ってもよい。図３および図４に示すいずれのＮｉ－Ｎｂ積層板材を製造する場合においても、Ｎｉ系金属板材に対しては約９００℃で約５分間保持する熱処理を行い、Ｎｂ系金属板材に対しては約１０００℃で約５分間保持する熱処理を行っている。
A method of manufacturing the 18-layer Ni—Nb laminated plate material as shown in FIGS. 3 and 4 will be described in detail below.
<Ni-based metal plate material, Nb-based metal plate material>
A Ni-based metal plate material and an Nb-based metal plate material are prepared. For the Ni-based metal plate material, when manufacturing the Ni—Nb laminated plate material shown in FIG. A plate containing 5% by mass of Nb with respect to Ni and having a thickness of about 0.3 mm is prepared. Also, the Nb-based metal plate material is made of pure Nb and has a plate thickness of about 0.3 mm when any of the Ni—Nb laminated plate materials shown in FIGS. 3 and 4 is manufactured. Note that the Ni-based metal sheet material and the Nb-based metal sheet material may be subjected to a heat treatment at a temperature of 700° C. or more and 1050° C. or less for 1 minute or more and 10 minutes or less before roll-bonding. In the case of manufacturing any of the Ni—Nb laminated plate materials shown in FIGS. 3 and 4, the Ni-based metal plate material is heat-treated at about 900° C. for about 5 minutes, and the Nb-based metal plate material is A heat treatment is performed at about 1000° C. for about 5 minutes.
＜第１クラッド圧延＞
Ｎｉ系金属板材およびＮｂ系金属板材を用いて、２層構造のＮｉ－Ｎｂ積層板材を製造する、第１クラッド圧延を行う。第１クラッド圧延においては、Ｎｉ系金属板材とＮｂ系金属板材とを厚さ方向（圧接方向）に積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を２とした状態で圧延接合する。これにより、２層構造のＮｉ－Ｎｂ積層板材を製造することができる。この２層構造のＮｉ－Ｎｂ積層板材は、板厚が例えば０．１ｍｍ以上０．３ｍｍ以下であってよい。なお、クラッド圧延のパス数は必要に応じて設定してよい。また、２層構造のＮｉ－Ｎｂ積層板材に対して、必要に応じて、例えば７００℃以上９００℃以下の温度で約１分間以上５分間以下保持する熱処理を行うことができる。図３および図４に示すいずれのＮｉ－Ｎｂ積層板材を製造する場合においても、２層構造のＮｉ－Ｎｂ積層板材に対して、約８００℃で約３分間保持する熱処理を行っている。
<First clad rolling>
A first clad rolling is performed to manufacture a two-layer structure Ni--Nb laminated plate material using the Ni-based metal plate material and the Nb-based metal plate material. In the first clad rolling, the Ni-based metal plate material and the Nb-based metal plate material are laminated in the thickness direction (pressure contact direction), and the total number of laminated layers of the Ni-based metal plate material and the Nb-based metal plate material is set to 2. Join. As a result, a Ni--Nb laminate having a two-layer structure can be manufactured. The thickness of the two-layered Ni--Nb laminated plate may be, for example, 0.1 mm or more and 0.3 mm or less. The number of passes for clad rolling may be set as required. Further, the two-layer structure Ni--Nb laminated plate material can be subjected to heat treatment by holding at a temperature of 700° C. or higher and 900° C. or lower for about 1 minute or longer and 5 minutes or shorter, if necessary. In the production of any of the Ni--Nb laminated plate materials shown in FIGS. 3 and 4, the two-layered Ni--Nb laminated plate material is subjected to heat treatment at about 800.degree. C. for about 3 minutes.
＜第２クラッド圧延＞
２層構造のＮｉ－Ｎｂ積層板材を用いて、６層構造のＮｉ－Ｎｂ積層板材を製造する、第２クラッド圧延を行う。第２クラッド圧延においては、２層構造のＮｉ－Ｎｂ積層板材を厚さ方向（圧接方向）に３枚積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を６とした状態で圧延接合する。これにより、６層構造のＮｉ－Ｎｂ積層板材を製造することができる。この２層構造のＮｉ－Ｎｂ積層板材は、板厚が例えば０．２ｍｍ以上０．４ｍｍ以下であってよい。なお、クラッド圧延のパス数は必要に応じて設定してよい。また、６層構造のＮｉ－Ｎｂ積層板材に対して、必要に応じて、例えば７００℃以上９００℃以下の温度で約１分間以上５分間以下保持する熱処理を行うことができる。図３および図４に示すいずれのＮｉ－Ｎｂ積層板材を製造する場合においても、６層構造のＮｉ－Ｎｂ積層板材に対して、約８００℃で約３分間保持する熱処理を行っている。
<Second clad rolling>
A second clad rolling is performed to produce a six-layer Ni--Nb laminated plate using the two-layered Ni--Nb laminated plate. In the second clad rolling, three Ni-Nb laminated plate materials having a two-layer structure are laminated in the thickness direction (pressure contact direction), and the total number of laminated layers of the Ni-based metal plate material and the Nb-based metal plate material is set to 6. Roll joint. As a result, a Ni—Nb laminated plate material having a six-layer structure can be manufactured. The thickness of the two-layered Ni--Nb laminated plate may be, for example, 0.2 mm or more and 0.4 mm or less. The number of passes for clad rolling may be set as required. Further, the six-layered Ni--Nb laminated plate material can be subjected to heat treatment at a temperature of 700° C. or higher and 900° C. or lower for about 1 minute or longer and 5 minutes or shorter, if necessary. 3 and 4, the six-layer structure Ni--Nb laminated plate is heat-treated at about 800.degree. C. for about 3 minutes.
＜第３クラッド圧延＞
６層構造のＮｉ－Ｎｂ積層板材を用いて、１８層構造のＮｉ－Ｎｂ積層板材を製造する、第３クラッド圧延を行う。この第３クラッド圧延は、図３および図４に示すＮｉ－Ｎｂ積層板材を製造する場合の最終のクラッド圧延になる。第３クラッド圧延においては、６層構造のＮｉ－Ｎｂ積層板材を厚さ方向（圧接方向）に３枚積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を１８とした状態で圧延接合する。これにより、１８層構造のＮｉ－Ｎｂ積層板材を製造することができる。この１８層構造のＮｉ－Ｎｂ積層板材は、最終圧接の後に行った圧延により、板厚が約０．１ｍｍに形成されている。なお、クラッド圧延のパス数は必要に応じて設定してよい。また、６層構造のＮｉ－Ｎｂ積層板材に対して、必要に応じて、例えば７００℃以上９００℃以下の温度で約１分間以上５分間以下保持する熱処理を行うことができる。図３および図４に示すいずれのＮｉ－Ｎｂ積層板材を製造する場合においても、６層構造のＮｉ－Ｎｂ積層板材に対して、約８００℃で約３分間保持する熱処理を行っている。
<Third clad rolling>
The 6-layer Ni--Nb laminated plate is used to perform the third clad rolling for manufacturing the 18-layered Ni--Nb laminated plate. This third clad rolling is the final clad rolling in the case of manufacturing the Ni--Nb laminated plate material shown in FIGS. In the third clad rolling, three Ni—Nb laminated plate materials having a six-layer structure are laminated in the thickness direction (pressure contact direction), and the total number of laminated layers of the Ni-based metal plate material and the Nb-based metal plate material is set to 18. Roll joint. As a result, an 18-layer structure Ni--Nb laminate can be manufactured. This 18-layer structure Ni--Nb laminated plate material is formed to have a plate thickness of about 0.1 mm by rolling after the final pressure welding. The number of passes for clad rolling may be set as required. Further, the six-layered Ni--Nb laminated plate material can be subjected to heat treatment at a temperature of 700° C. or higher and 900° C. or lower for about 1 minute or longer and 5 minutes or shorter, if necessary. 3 and 4, the six-layer structure Ni--Nb laminated plate is heat-treated at about 800.degree. C. for about 3 minutes.
上記したように、例えば３回のクラッド圧延を繰り返すことによって、展延性の良いＮｉ系金属板材および展延性の良いＮｂ系金属板材から構成された、図３および図４に示すような１８層構造のＮｉ－Ｎｂ積層板材を、製造することができる。なお、この発明に係るＮｉ－Ｎｂ積層板材は、後に、この発明に係るＮｉ－Ｎｂ合金板材の製造を容易にするために、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数が３以上であればよい。また、上記したようにクラッド圧延を繰り返す場合の途中のクラッド圧延におけるＮｉ系金属板材およびＮｂ系金属板材の合計の積層数は限定されない。 As described above, for example, by repeating the clad rolling three times, an 18-layer structure as shown in FIGS. of Ni—Nb laminates can be produced. Note that the Ni—Nb laminated plate material according to the present invention has a total number of laminations of 3 or more of the Ni-based metal plate material and the Nb-based metal plate material in order to facilitate the production of the Ni—Nb alloy plate material according to the present invention later. If it is Further, as described above, when the clad rolling is repeated, the total number of laminated layers of the Ni-based metal sheet material and the Nb-based metal sheet material in the intermediate clad rolling is not limited.
次に、この発明に係るＮｉ－Ｎｂ合金板材およびその製造方法について説明する。
この発明に係るＮｉ－Ｎｂ合金板材は、この発明に係る上記したＮｉ－Ｎｂ積層板材から構成されたものである。詳しくは、上記したＮｉ－Ｎｂ積層板材に対して適切な条件で行った拡散焼鈍によって製造されたものである。この発明に係るＮｉ－Ｎｂ合金板材は、ＮｉおよびＮｂからなる金属間化合物の共存組織を有し、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層されて構成されており、Ｎｉリッチ層およびＮｂリッチ層の合計の層数が３以上である。なお、Ｎｉリッチ層とは、ＮｂよりもＮｉの含有比が大きい層状の組織を意図する。また、Ｎｂリッチ層とは、ＮｉよりもＮｂの含有比が大きい層状の組織を意図する。
Next, a Ni—Nb alloy sheet material and a method for manufacturing the same according to the present invention will be described.
A Ni--Nb alloy sheet material according to the present invention is composed of the above-described Ni--Nb laminated sheet material according to the present invention. Specifically, it is produced by diffusion annealing of the above Ni—Nb laminated plate material under appropriate conditions. A Ni—Nb alloy sheet material according to the present invention has a coexisting structure of intermetallic compounds composed of Ni and Nb, and is configured by alternately stacking Ni-rich layers and Nb-rich layers in the thickness direction. The total number of rich layers and Nb-rich layers is 3 or more. In addition, the Ni-rich layer intends a layered structure in which the content ratio of Ni is higher than that of Nb. Moreover, the Nb-rich layer intends a layered structure in which the content ratio of Nb is higher than that of Ni.
図５は、この発明に係るＮｉ－Ｎｂ合金板材の１つの実施形態であって、板厚方向に切断したＮｉ－Ｎｂ合金板材の断面（横断面）の観察写真である。図５に示すＮｉ－Ｎｂ合金板材は、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層されて構成され、Ｎｉリッチ層およびＮｂリッチ層の合計の層数が１８である。つまり、このＮｉ－Ｎｂ合金板材は、合金組織がＮｉリッチ層およびＮｂリッチ層による多層構造の形態になっている。このＮｉ－Ｎｂ合金板材は、板厚が約０．１ｍｍであり、板厚を構成するＮｉリッチ層およびＮｂリッチ層のそれぞれの厚さは一定ではなく、うねり模様を呈している。このＮｉ－Ｎｂ合金板材の横断面を、図５に示すように３つのエリア１～３に区分し、エリア１～３のそれぞれについて、上記したＮｉ－Ｎｂ積層板材の場合と同様に、ＥＤＳ分析を行ったところ、エリア１～３の平均のＮｂ含有比は４６．４質量％（約３５．４ａｔ％）であった。 FIG. 5 is one embodiment of the Ni--Nb alloy sheet material according to the present invention, and is an observation photograph of a cross section (transverse section) of the Ni--Nb alloy sheet material cut in the thickness direction. The Ni—Nb alloy plate material shown in FIG. 5 is configured by alternately laminating Ni-rich layers and Nb-rich layers in the thickness direction, and the total number of Ni-rich layers and Nb-rich layers is 18. In other words, this Ni--Nb alloy sheet material has an alloy structure in the form of a multi-layered structure of Ni-rich layers and Nb-rich layers. This Ni—Nb alloy sheet material has a thickness of about 0.1 mm, and the thicknesses of the Ni-rich layer and the Nb-rich layer that constitute the sheet thickness are not uniform, and exhibit an undulating pattern. The cross section of this Ni—Nb alloy plate material is divided into three areas 1 to 3 as shown in FIG. As a result, the average Nb content ratio of areas 1 to 3 was 46.4% by mass (approximately 35.4at%).
図６は、この発明に係るＮｉ－Ｎｂ合金板材の１つの実施形態であって、板厚方向に切断したＮｉ－Ｎｂ合金板材の断面（横断面）の観察写真である。図６に示すＮｉ－Ｎｂ合金板材は、図５に示すＮｉ－Ｎｂ合金板材と同様に、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層されて構成され、Ｎｉリッチ層およびＮｂリッチ層の合計の層数が１８である。つまり、図６に示すＮｉ－Ｎｂ合金板材も図５に示すＮｉ－Ｎｂ合金板材と同様に、合金組織がＮｉリッチ層およびＮｂリッチ層による多層構造の形態になっている。このＮｉ－Ｎｂ合金板材は、板厚が約０．１ｍｍであり、板厚を構成するＮｉリッチ層およびＮｂリッチ層のそれぞれの厚さは一定ではなく、図５に示すＮｉ－Ｎｂ合金板材と同様に、うねり模様を呈している。このＮｉ－Ｎｂ合金板材の横断面を、図６に示すように３つのエリア１～３に区分し、エリア１～３のそれぞれについて、上記した図５に示すＮｉ－Ｎｂ合金板材の場合と同様に、ＸＰＳ分析を行ったところ、エリア１～３の平均のＮｂ含有比は４８．４質量％（約３７．２ａｔ％）であった。 FIG. 6 is one embodiment of the Ni—Nb alloy plate material according to the present invention, and is an observation photograph of a cross section (cross section) of the Ni—Nb alloy plate material cut in the plate thickness direction. The Ni—Nb alloy plate material shown in FIG. 6 is configured by alternately stacking Ni-rich layers and Nb-rich layers in the thickness direction in the same manner as the Ni—Nb alloy plate material shown in FIG. The total number of rich layers is 18. That is, the Ni--Nb alloy sheet material shown in FIG. 6 also has an alloy structure of a multi-layered structure of Ni-rich layers and Nb-rich layers, like the Ni--Nb alloy sheet material shown in FIG. This Ni—Nb alloy plate material has a plate thickness of about 0.1 mm, and the thicknesses of the Ni-rich layer and the Nb-rich layer constituting the plate thickness are not constant, and the Ni—Nb alloy plate material shown in FIG. Similarly, it has an undulating pattern. The cross section of this Ni—Nb alloy plate material is divided into three areas 1 to 3 as shown in FIG. Furthermore, when XPS analysis was performed, the average Nb content ratio of areas 1 to 3 was 48.4% by mass (about 37.2 at%).
この発明に係るＮｉ－Ｎｂ合金板材は、Ｎｉリッチ層およびＮｂリッチ層の合計の層数が３以上であればよく、図５および図６に示す１８層構造のＮｉ－Ｎｂ合金板材に限定されない。また、この発明に係るＮｉ－Ｎｂ合金板材は、板厚が４ｍｍ以下であってよく、板厚を構成するそれぞれの層の厚さは限定されない。例えば、この発明に係るＮｉ－Ｎｂ合金板材の実施形態である図５および図６に示すＮｉ－Ｎｂ合金板材は、板厚が約０．１ｍｍである。 The Ni—Nb alloy sheet material according to the present invention may have a total number of Ni-rich layers and Nb-rich layers of 3 or more, and is not limited to the Ni—Nb alloy sheet material having the 18-layer structure shown in FIGS. . Further, the Ni—Nb alloy sheet material according to the present invention may have a sheet thickness of 4 mm or less, and the thickness of each layer constituting the sheet thickness is not limited. For example, the Ni--Nb alloy sheet material shown in FIGS. 5 and 6, which is an embodiment of the Ni--Nb alloy sheet material according to the present invention, has a thickness of about 0.1 mm.
Ｎｉリッチ層およびＮｂリッチ層の合計の積層数が３以上のＮｉ－Ｎｂ合金板材は、例えば、図５および図６に示すような１８層構造のＮｉ－Ｎｂ合金板材は、この発明に係る上記したＮｉ－Ｎｂ積層板材を用いて、容易に製造することができる。具体的には、このＮｉ－Ｎｂ合金板材は、純Ｎｉまたは７質量％以下のＮｂを含むＮｉ合金からなるＮｉ系金属板材と、純Ｎｂまたは１５質量％以下のＮｉを含むＮｂ合金からなるＮｂ系金属板材とを、厚さ方向に交互に積層し、Ｎｉ系金属板材およびＮｂ系金属板材の合計の積層数を３以上とした状態で圧延接合することによって、Ｎｉ系金属層とＮｂ系金属層とが厚さ方向に交互に積層され、合計の積層数が３以上の積層板材を形成する、積層板材の製造工程の後に、その積層板材に対して拡散焼鈍を行うことによって、ＮｉおよびＮｂからなる金属間化合物の共存組織を有し、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層され、Ｎｉリッチ層およびＮｂリッチ層の合計の積層数が３以上の合金板材を形成する、拡散焼鈍工程を経ることによって、容易に製造することができる。 Ni--Nb alloy sheet materials having a total number of laminated layers of Ni-rich layers and Nb-rich layers of 3 or more, for example, Ni--Nb alloy sheet materials having an 18-layer structure as shown in FIGS. It can be easily manufactured by using the Ni—Nb laminated plate material. Specifically, the Ni—Nb alloy sheet material includes a Ni-based metal sheet material made of pure Ni or a Ni alloy containing 7% by mass or less of Nb, and a Nb alloy made of pure Nb or an Nb alloy containing 15% by mass or less of Ni. The Ni-based metal plate material and the Nb-based metal plate material are alternately laminated in the thickness direction, and rolled and joined in a state where the total number of laminated layers of the Ni-based metal plate material and the Nb-based metal plate material is 3 or more. layers are alternately laminated in the thickness direction to form a laminated plate having a total number of laminations of 3 or more. Ni-rich layers and Nb-rich layers are alternately laminated in the thickness direction, and the total number of laminated Ni-rich layers and Nb - rich layers is 3 or more. It can be easily manufactured by going through a diffusion annealing process.
この発明に係る上記したＮｉ－Ｎｂ合金板材の製造方法において、積層板材の製造工程は、この発明に係る上記したＮｉ－Ｎｂ積層板材の製造方法と同等である。つまり、この発明に係る上記したＮｉ－Ｎｂ積層板材に対して、上記した拡散焼鈍工程を行うことによって、ＮｉおよびＮｂからなる金属間化合物の共存組織を有し、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層され、Ｎｉリッチ層およびＮｂリッチ層の合計の積層数が３以上である、この発明に係るＮｉ－Ｎｂ合金板材を製造することができる。 In the method for manufacturing the Ni--Nb alloy sheet according to the present invention, the manufacturing process of the laminated sheet is the same as the method for manufacturing the Ni--Nb laminated sheet according to the present invention. That is, by performing the diffusion annealing process on the Ni—Nb laminated plate material according to the present invention, the intermetallic compound composed of Ni and Nb has a coexistent structure, and a Ni-rich layer and an Nb-rich layer are formed. are alternately laminated in the thickness direction, and the total number of laminated Ni-rich layers and Nb-rich layers is 3 or more.
例えば、図５に示すＮｉ－Ｎｂ合金板材は、図３に示すＮｉ－Ｎｂ積層板材に対して、約１１００℃の温度で約１時間、アルゴンガス雰囲気中で保持する拡散焼鈍を行うことによって、製造したものである。また、例えば、図６に示すＮｉ－Ｎｂ合金板材は、図４に示すＮｉ－Ｎｂ積層板材に対して、約１１００℃の温度で約１時間、アルゴンガス雰囲気中で保持する拡散焼鈍を行うことによって、製造したものである。なお、図５および図６に示すＮｉ－Ｎｂ合金板材のいずれにおいても、相対的に、濃い灰色に見える部分がＮｉリッチ層であり、薄い灰色に見える部分がＮｂリッチ層である。また、黒点状に見える部分は微細孔であって、拡散焼鈍で加熱された際のＮｉとＮｂとの拡散速度の差によって発生したと考えられるカーケンダルボイドである。こうした微細孔は、例えば、ＨＩＰ（Ｈｏｔ Ｉｓｏｓｔａｔｉｃ Ｐｒｅｓｓｉｎｇ）を行うことによって押し潰し、実質的に消滅させることが可能である。 For example, the Ni—Nb alloy plate material shown in FIG. 5 is obtained by subjecting the Ni—Nb laminated plate material shown in FIG. It is manufactured. Further, for example, the Ni—Nb alloy plate material shown in FIG. 6 is subjected to diffusion annealing by holding the Ni—Nb laminated plate material shown in FIG. 4 at a temperature of about 1100° C. for about 1 hour in an argon gas atmosphere. It is manufactured by In both of the Ni--Nb alloy sheets shown in FIGS. 5 and 6, the dark gray portion is the Ni-rich layer, and the light gray portion is the Nb-rich layer. Also, the portions that look like black dots are micropores, which are Kirkendall voids that are considered to have been generated due to the difference in diffusion speed between Ni and Nb when heated in diffusion annealing. Such micropores can be crushed and substantially eliminated by, for example, HIP (Hot Isostatic Pressing).
図５および図６に示すＮｉ－Ｎｂ合金板材の他部位から別のサンプルを切り出し、Ｎｉリッチ層およびＮｂリッチ層と考えられる幾つかの層を対象として、ＥＤＳ分析によって、ＮｉおよびＮｂの含有比を調べた。図５に示すＮｉ－Ｎｂ合金板材に対応するサンプルおよび測定点を図７に示し、図６に示すＮｉ－Ｎｂ合金板材に対応するサンプルおよび測定点を図８に示す。表１は、調べたＮｉおよびＮｂの含有比である。 Another sample was cut out from another part of the Ni—Nb alloy plate material shown in FIGS. examined. Samples and measurement points corresponding to the Ni--Nb alloy sheet shown in FIG. 5 are shown in FIG. 7, and samples and measurement points corresponding to the Ni--Nb alloy sheet shown in FIG. 6 are shown in FIG. Table 1 shows the investigated Ni and Nb content ratios.
表１に示すＮｉおよびＮｂの含有比と、図７および図８に示すＮｉ－Ｎｂ合金板材の観察像とから、図７および図８に示すＮｉ－Ｎｂ合金板材は、含有比を質量％で表した場合、相対的に、図中の薄い灰色に見える部分（測定位置番号１～３および１６～１８）がＮｂリッチ層であり、図中の濃い灰色に見える部分（測定位置番号４～６および１９～２１）がＮｉリッチ層であることが確認された。また、図７および図８に示すＮｉ－Ｎｂ合金板材は、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層されて構成されており、Ｎｉリッチ層およびＮｂリッチ層の合計の層数が、およそ１８であることが確認された。また、図７および図８に示すＮｉ－Ｎｂ合金板材は、含有比を質量％で表した場合、Ｎｉリッチ層はＮｉ含有比（平均）が約６６質量％（約７６ａｔ％）でＮｂ含有比が約３４質量％（約２４ａｔ％）であり、Ｎｂリッチ層はＮｉ含有比（平均）が約４２質量％（約５３ａｔ％）でＮｂ含有比（平均）が約５８質量％（約４７ａｔ％）であることが確認された。これより、図７および図８に示すＮｉ－Ｎｂ合金板材は、ＮｉリッチのＮｉ－Ｎｂ合金部分とＮｂリッチのＮｉ－Ｎｂ合金部分とが厚さ方向に交互に積層されて構成された多層構造のＮｉ－Ｎｂ合金板材（Ｎｉ－Ｎｂ合金クラッド板材）であることが確認された。 From the Ni and Nb content ratios shown in Table 1 and the observed images of the Ni—Nb alloy plate materials shown in FIGS. 7 and 8, the Ni—Nb alloy plate materials shown in FIGS. Relatively speaking, the light gray parts in the figure (measurement position numbers 1 to 3 and 16 to 18) are the Nb-rich layers, and the dark gray parts in the figure (measurement position numbers 4 to 6 and 19-21) were confirmed to be Ni-rich layers. The Ni—Nb alloy plate shown in FIGS. 7 and 8 is configured by alternately laminating Ni-rich layers and Nb-rich layers in the thickness direction, and the total layer of the Ni-rich layers and the Nb-rich layers The number was confirmed to be approximately eighteen. 7 and 8, when the content ratio is represented by mass%, the Ni-rich layer has a Ni content ratio (average) of about 66 mass% (about 76 at%) and an Nb content ratio of is about 34 mass% (about 24at%), and the Nb-rich layer has a Ni content ratio (average) of about 42 mass% (about 53at%) and an Nb content ratio (average) of about 58 mass% (about 47at%). It was confirmed that Thus, the Ni—Nb alloy plate material shown in FIGS. 7 and 8 has a multilayer structure in which Ni-rich Ni—Nb alloy portions and Nb-rich Ni—Nb alloy portions are alternately laminated in the thickness direction. Ni--Nb alloy sheet material (Ni--Nb alloy clad sheet material).
図１に示すＮｉおよびＮｂの二元系状態図に基づけば、ＮｂリッチのＮｉ－Ｎｂ合金部分は、すなわち、Ｎｉに対してＮｂの含有比が約４７ａｔ％（約５８質量％）であるＮｉ－Ｎｂ合金部分は、Ｎｉ－Ｎｂ系の金属間化合物であるＮｉ３ＮｂとＮｉ６Ｎｂ７とが共存し、金属Ｎｉまたは金属Ｎｂが共存しない組織形態を成すことが解かる。また、ＮｉリッチのＮｉ－Ｎｂ合金部分は、すなわち、Ｎｉに対してＮｂの含有比が約２４ａｔ％（約３４質量％）であるＮｉ－Ｎｂ合金部分は、Ｎｉ－Ｎｂ系の金属間化合物であるＮｉ３Ｎｂが存在し、金属Ｎｉまたは金属Ｎｂが共存しない組織形態を成すことが解かる。こうした金属Ｎｉまたは金属Ｎｂが共存せず、Ｎｉ－Ｎｂ系の金属間化合物のみから成るＮｉ－Ｎｂ合金は脆く、割れやすいが、上記した製造方法によって、Ｎｉ－Ｎｂ合金板材を提供することができた。
Based on the binary system phase diagram of Ni and Nb shown in FIG. It can be seen that the -Nb alloy portion has a structure in which Ni-Nb intermetallic compounds, Ni 3 Nb and Ni 6 Nb 7 coexist , but neither metallic Ni nor metallic Nb coexist. In addition, the Ni-rich Ni—Nb alloy portion, that is, the Ni—Nb alloy portion in which the content ratio of Nb to Ni is about 24 at% (about 34% by mass) is a Ni—Nb intermetallic compound. It can be seen that a certain Ni 3 Nb is present and the structure forms a structure in which metallic Ni or metallic Nb does not coexist. Ni—Nb alloys composed only of Ni—Nb-based intermetallic compounds without the coexistence of metallic Ni or metallic Nb are brittle and easily cracked, but the above-described manufacturing method can provide Ni—Nb alloy sheet materials. Ta.
Claims (2)
前記積層板材に対して拡散焼鈍を行うことによって、ＮｉおよびＮｂからなる金属間化合物の共存組織を有し、Ｎｉリッチ層とＮｂリッチ層とが厚さ方向に交互に積層され、前記Ｎｉリッチ層および前記Ｎｂリッチ層の合計の積層数が３以上の合金板材を形成する、Ｎｉ－Ｎｂ合金板材の製造方法。 A Ni-based metal plate made of pure Ni or a Ni alloy containing 7% by mass or less of Nb and an Nb-based metal plate made of pure Nb or an Nb alloy containing 15% by mass or less of Ni are alternately laminated in the thickness direction. Then, the Ni-based metal layer and the Nb-based metal layer are laminated alternately in the thickness direction by roll-bonding in a state where the total number of laminated layers of the Ni-based metal sheet material and the Nb-based metal sheet material is set to 3 or more. , forming a laminated plate material with a total number of laminations of 3 or more,
By performing diffusion annealing on the laminated sheet material, an intermetallic compound composed of Ni and Nb has a coexistence structure, and the Ni-rich layer and the Nb-rich layer are alternately laminated in the thickness direction, and the Ni-rich layer and a method for producing a Ni—Nb alloy sheet, wherein the total number of laminated Nb-rich layers is 3 or more.
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| JP2004034125A (en) | 2002-07-05 | 2004-02-05 | Toyo Kohan Co Ltd | Metal sheet joint body, laminate body using the metal sheet joint body, and component using the laminate body |
| WO2006132166A1 (en) | 2005-06-08 | 2006-12-14 | Neomax Materials Co., Ltd. | Cladding material for discharge electrode, process for producing the same and discharge electrode |
| US20150170887A1 (en) | 2012-02-14 | 2015-06-18 | Tosoh Smd, Inc. | Low deflection sputtering target assembly and methods of making same |
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