JP2973152B2 - High melting point metal coated member and its manufacturing apparatus - Google Patents
High melting point metal coated member and its manufacturing apparatusInfo
- Publication number
- JP2973152B2 JP2973152B2 JP5232179A JP23217993A JP2973152B2 JP 2973152 B2 JP2973152 B2 JP 2973152B2 JP 5232179 A JP5232179 A JP 5232179A JP 23217993 A JP23217993 A JP 23217993A JP 2973152 B2 JP2973152 B2 JP 2973152B2
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- JP
- Japan
- Prior art keywords
- molybdenum
- melting point
- point metal
- coated member
- doped
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は，高温域において使用さ
れる金属耐熱材料及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant metal material used in a high temperature range and a method for producing the same.
【０００２】[0002]
【従来の技術】従来，この種の金属耐熱材料には，タン
グステン（Ｗ），モリブデン（Ｍｏ），タンタル（Ｔ
ａ）等の高融点金属を含む材料が利用されており，特に
加工性，材料価格，汎用性等の点からＭｏを含む材料
（以下，Ｍｏ材料と呼ぶ）が多用されている。2. Description of the Related Art Conventionally, such metal refractory materials include tungsten (W), molybdenum (Mo), tantalum (T
Materials containing a high melting point metal such as a) are used. In particular, materials containing Mo (hereinafter, referred to as Mo materials) are frequently used in terms of workability, material cost, versatility, and the like.
【０００３】また，Ｍｏ材料には，純Ｍｏ材料のほか，
純Ｍｏにランタンを添加した耐熱性モリブデン（東京タ
ングステン株式会社製／以下，「ＴＥＭ」と呼ぶ）や，
ＴＺＭ（チタンやジルコニウムの添加されたＭｏ基材料
／市販品）がある。上記したＭｏ材料の内，ＴＥＭ及び
ＴＺＭは高温における変形が少なく有利である。[0003] Mo materials include pure Mo materials,
Heat-resistant molybdenum obtained by adding lanthanum to pure Mo (manufactured by Tokyo Tungsten Co., Ltd .; hereinafter, referred to as "TEM");
There is TZM (Mo-based material to which titanium or zirconium is added / commercially available). Of the above Mo materials, TEM and TZM are advantageous because they have less deformation at high temperatures.
【０００４】まず，ここで，前述のＴＥＭについて説明
する。ＴＥＭの基本的内容については，特願昭６１−３
０１７８１号に開示されている。具体的に言えば，ＴＥ
Ｍは，ランタン又はランタン酸化物を含み，残部がモリ
ブデンである組成を有している。このようなＴＥＭか
ら，ＴＥＭ板を製作する場合，ＴＥＭのインゴットを８
０％以上の総加工率で加工し，焼結後のＭｏの平均粒径
が０．５〜１０ｍｍのランタン元素又はランタン酸化物
を０．１〜１ｗｔ％含有することにより，ＴＥＭ板材を
製作する。このＴＥＭ板は，純モリブデン或いは耐垂下
性に有効とされる市販のＴＺＭ材料に比べて下記の表１
及び下記の表２に示す通り，特に，高温での変形量が少
なく優れている。First, the TEM will be described. For the basic contents of TEM, refer to Japanese Patent Application No. Sho 61-3
No. 01781. Specifically, TE
M has a composition containing lanthanum or lanthanum oxide, with the balance being molybdenum. When manufacturing a TEM plate from such a TEM, the TEM ingot should be 8
A TEM plate is manufactured by processing at a total processing rate of 0% or more and containing 0.1 to 1 wt% of a lanthanum element or a lanthanum oxide having an average particle diameter of Mo of 0.5 to 10 mm after sintering. . This TEM plate is compared with pure molybdenum or a commercially available TZM material that is effective for drooping resistance, as shown in Table 1 below.
As shown in Table 2 below, the deformation amount at high temperature is particularly small and excellent.
【０００５】[0005]
【表１】 [Table 1]
【０００６】[0006]
【表２】 また，更に高温変形の少ない良く知られたＭｏ材料とし
て，Ｍｏにいくつかの添加物を含有させた所謂ドープモ
リブデン材料もある。この種のドープモリブデン材料
は，Ａｌ，Ｋ，Ｓｉの内の元素の少なくとも一種，特
に，Ｋ，Ｓｉのいずれか或いは，両方を添加したＭｏ材
料のインゴットに総加工率８０％以上，好ましくは，９
０％以上施すことによってＭｏにすることができる。こ
こで，このＭｏ板に，Ａｌ，Ｋ，Ｓｉは０．００５％〜
０．２ｗｔ％含有されており，結晶組織は板面方向に拡
がり，厚さに直角の断面観察では，積層組織を有してい
る場合が多い。[Table 2] Further, as a well-known Mo material with less high-temperature deformation, there is a so-called doped molybdenum material in which Mo contains some additives. This kind of doped molybdenum material can be used in an ingot of a Mo material to which at least one of the elements of Al, K, and Si, particularly, one or both of K and Si are added, and a total processing rate of 80% or more, preferably, 9
Mo can be obtained by applying 0% or more. Here, this Mo plate contains 0.005% of Al, K, and Si.
It is contained in an amount of 0.2 wt%, and the crystal structure spreads in the plate surface direction, and when observed in a cross section perpendicular to the thickness, it often has a laminated structure.
【０００７】さらに，他のドープモリブデン材料とし
て，Ｍｏに，Ａｌ，Ｓｉ，Ｋのうちの元素の少なくとも
一種を０．００５〜０．２ｗｔ％添加すると共に，Ｌ
ａ，Ｃｅ，Ｄｙ，Ｙ，Ｔｈ，Ｔｉ，Ｚｒ，Ｎｂ，Ｔａ，
Ｈｆ，Ｖ，Ｃｒ，Ｍｏ，Ｗ，Ｍｇの酸化物，炭化物，硼
化物あるいは，窒化物のうちの少なくとも一種を０．１
〜３％含むものも知られている。このドープモリブデン
材料に対しても，そのインゴットに，総加工率で８０％
以上，好ましくは，９５％以上施すことによりＭｏ板を
製作できる。このＭｏ板は，高温強度の特に優れた板材
として期待されている。Further, as another doped molybdenum material, at least one of the elements of Al, Si and K is added to Mo in an amount of 0.005 to 0.2 wt% and L is added.
a, Ce, Dy, Y, Th, Ti, Zr, Nb, Ta,
0.1% of at least one of oxides, carbides, borides or nitrides of Hf, V, Cr, Mo, W, Mg
Those containing 〜3% are also known. Even for this doped molybdenum material, the ingot has a total processing rate of 80%.
As described above, preferably, by applying 95% or more, a Mo plate can be manufactured. This Mo plate is expected as a plate material having particularly excellent high-temperature strength.
【０００８】[0008]
【発明が解決しようとする課題】一方，高温域での変形
が少ないとされるＭｏ材料については，上記したように
種々提案されているが，Ｍｏ自体の気化が考慮されるべ
き雰囲気で使用される場合には，従来のＭｏ材料では，
特性的に不十分であることが判明した。例えば，原子法
レーザーウラン濃縮における蒸発したウランの内，所望
の有効ウラン分を補集する板材（以下，コレクターと呼
ぶ）等としては，中面５００ｍｍ，長さ１０００〜２０
００ｍｍ程度の大型の板が使用されている。このコレク
ターとして，Ｗ材料を用いた場合，自重だけでも１０〜
２０ｋｇの重さとなり，取扱いが難しくなると共に，コ
レクター自身が変形してしまうため，望ましくない。そ
こで，Ｗ材料よりも比重の小さなＭｏ材料を選択するこ
とも考慮されているが，１８００℃以上，特に，２００
０℃を越える雰囲気では，Ｗ材料に比較して気化による
損失が著しいため，安定した特性が期待できず，また耐
久性においても劣るという欠点がある。更に，気化の速
度は表面積が増加する程，増加するため，大面積のコレ
クターにＭｏ材料を使用するには，問題がある。On the other hand, as described above, various proposals have been made for Mo materials which are considered to be less deformed in a high temperature range, but are used in an atmosphere in which the vaporization of Mo itself should be considered. In the case of conventional Mo material,
It turned out to be insufficient in characteristics. For example, among the evaporated uranium in the atomic method laser uranium enrichment, a plate material (hereinafter, referred to as a collector) for collecting a desired effective uranium portion is 500 mm in inner surface and 1000 to 20 mm in length.
A large plate of about 00 mm is used. When using W material as this collector, 10
The weight is 20 kg, which makes it difficult to handle and undesirably deforms the collector itself. Therefore, it has been considered to select a Mo material having a specific gravity smaller than that of the W material.
In an atmosphere exceeding 0 ° C., loss due to vaporization is remarkable as compared with the W material, so that stable characteristics cannot be expected and durability is poor. Furthermore, the use of Mo material for large area collectors is problematic because the rate of vaporization increases with increasing surface area.
【０００９】上記したように，コレクターを製作する場
合には，コレクター材料の高温域での変形に加えて気化
抑制も考慮したものである必要があるが，このような条
件にかなう材料の開発は未だ提案されていない。As described above, when manufacturing a collector, it is necessary to consider not only the deformation of the collector material in a high temperature range but also the suppression of vaporization. Not yet proposed.
【００１０】そこで，本発明の技術的課題は，モリブデ
ン材において，高温での使用に際して気化，揮散を抑制
するとともに，耐変形性能も合せ持つコレクター等に使
用する大面積の高融点被覆金属部材及びその製造装置を
提供することにある。Therefore, a technical problem of the present invention is to use a molybdenum material for a collector or the like which suppresses vaporization and volatilization when used at a high temperature and also has deformation resistance.
An object of the present invention is to provide a large-area high-melting-point coated metal member to be used and an apparatus for manufacturing the same.
【００１１】[0011]
【課題を解決するための手段】本発明によれば，モリブ
デンが気化するような雰囲気で使用される大面積の金属
部材において，ドープモリブデン材によって形成された
基板と該基板表面に６００〜７００℃の成膜温度で形成
された被覆層とを備え，前記被覆層は前記基板を形成す
るドープモリブデン材よりも遅い気化速度を有し，且つ
実質的にタングステンからなることを特徴とする高融点
金属被覆部材が得られる。According to the present invention, in a large-area metal member used in an atmosphere in which molybdenum is vaporized, a substrate formed of a doped molybdenum material and a surface of the substrate at 600 to 700 ° C. A coating layer formed at a film formation temperature , wherein the coating layer has a lower vaporization rate than the doped molybdenum material forming the substrate, and is substantially made of tungsten. A covering member is obtained.
【００１２】[0012]
【００１３】即ち，本発明では，タングステンからなる
被覆層をモリブデン材に形成した高融点金属被覆材にお
いて，前記モリブデン材は高温における強度が向上した
ドープモリブデン材からなり，高温における耐変形性に
優れ，前記被覆膜は高温使用時におけるドープモリブデ
ン材中のモリブデン元素の外部への気化及び揮散を抑制
したものである。That is, according to the present invention, in a high melting point metal coating material in which a coating layer made of tungsten is formed on a molybdenum material, the molybdenum material is made of a doped molybdenum material having improved strength at high temperatures and has excellent deformation resistance at high temperatures. The coating film suppresses vaporization and volatilization of the molybdenum element in the doped molybdenum material to the outside when used at a high temperature.
【００１４】本発明によれば，前記高融点金属被覆部材
において，前記ドープモリブデン材は，モリブデン元素
又はモリブデン基合金にランタン元素又はランタン酸化
物を０．１〜１ｗｔ％含有することを特徴とする高融点
金属被覆部材が得られる。According to the invention, in the high-melting-point metal-coated member, the doped molybdenum material contains 0.1 to 1% by weight of a lanthanum element or a lanthanum oxide in a molybdenum element or a molybdenum-based alloy. A high melting point metal coated member is obtained.
【００１５】ここで，本発明の高融点金属被覆材におい
て，前記ドープモリブデン材は，少なくとも総加工率８
０％の鍛造，熱間圧延，冷間圧延のうちから選択された
少なくとも一種の機械加工が施されていることが好まし
い。Here, in the high melting point metal coating material of the present invention, the doped molybdenum material has a total processing rate of at least 8%.
Preferably, at least one type of machining selected from 0% forging, hot rolling and cold rolling is performed.
【００１６】また，本発明においては，前記タングステ
ンの被覆は，化学気相蒸着法（以下，ＣＶＤと呼ぶ）及
び溶射法から選択された少なくとも一種により行われる
ことが好ましい。これらの方法は，ドープモリブデン材
にポアの無い緻密なタングステン層が成膜でき，しかも
又，これらＭｏ板に対して，程々平坦な仕上がりとし得
る。In the present invention, the tungsten is preferably coated by at least one selected from a chemical vapor deposition method (hereinafter, referred to as CVD) and a thermal spraying method. These methods can form a dense tungsten layer having no pores in the doped molybdenum material, and can also provide a slightly flat finish to these Mo plates.
【００１７】また，本発明の高融点金属被覆部材におい
て，前記ドープモリブデン材は，（イ）モリブデン元素
又はモリブデン基合金にランタン元素またはランタン酸
化物を０．１〜１ｗｔ％含有すること，（ロ）モリブデ
ン元素又はモリブデン基合金にＡｌ，Ｋ，Ｓｉの内の少
なくとも一種を含むこと，（ハ）モリブデン元素又はモ
リブデン基合金にＡｌ，Ｓｉ，Ｋの内の少なくとも一種
を０．００５〜０．２ｗｔ％とＬａ，Ｃｅ，Ｄｙ，Ｙ，
Ｔｈ，Ｔｉ，Ｚｒ，Ｎｂ，Ｔａ，Ｈｆ，Ｖ，Ｃｒ，Ｍ
ｏ，Ｗ，Ｍｇの内から選択された少なくとも一種の金属
元素を酸化物，炭化物，硼素化合物，及び窒化物のうち
の少なくとも一種の状態で０．１〜３ｗｔ％とを含むこ
とのいずれかであることが好ましい。Further, in the high melting point metal-coated member of the present invention, the doped molybdenum material comprises: (a) a molybdenum element or a molybdenum-based alloy containing 0.1 to 1 wt% of a lanthanum element or a lanthanum oxide; ) The molybdenum element or the molybdenum-based alloy contains at least one of Al, K, and Si. (C) The molybdenum element or the molybdenum-based alloy contains at least one of Al, Si, and K in an amount of 0.005 to 0.2 wt. % And La, Ce, Dy, Y,
Th, Ti, Zr, Nb, Ta, Hf, V, Cr, M
at least one metal element selected from the group consisting of o, W, and Mg in the form of at least one of an oxide, a carbide, a boron compound, and a nitride; Preferably, there is.
【００１８】また，本発明によれば，前記高融点金属被
覆部材によって形成されたことを特徴とするコレクター
が得られる。According to the present invention, there is provided a collector characterized by being formed by the high-melting-point metal-coated member.
【００１９】本発明によれば，ドープモリブデン板材を
加熱するヒータと，前記ドープモリブデン板材にフッ化
タングステンを含むガスを吹き付けるノズルとを反応槽
内に備え，前記ドープモリブデン板材に実質的にタング
ステンからなる被覆層を形成する高融点金属被膜形成装
置において，前記ドープモリブデン板材は大面積を有す
るとともに固定されており，前記ノズルは，前記ドープ
モリブデン板材面に対して回転するように構成され，前
記被覆層を前記ドープモリブデン板材表面に６００〜７
００℃の成膜温度で形成することを特徴とする高融点金
属部材製造装置が得られる。According to the present invention, a heater for heating the doped molybdenum plate and a nozzle for spraying a gas containing tungsten fluoride to the doped molybdenum plate are provided in the reaction tank , and the tongue is substantially attached to the doped molybdenum plate.
In refractory metal film forming apparatus for forming a coating layer made of stainless, the doped molybdenum plate is fixed and has a large area, the nozzle is configured to rotate relative to the doped molybdenum plate surface ,Previous
The coating layer is formed on the surface of the doped molybdenum plate material by 600 to 7
A refractory metal member manufacturing apparatus characterized by being formed at a film forming temperature of 00 ° C. is obtained.
【００２０】更に，詳細に本発明を説明する。Further, the present invention will be described in detail.
【００２１】本発明に用いられるＣＶＤ−Ｗ成膜におい
てのファクターは，成膜温度，広範囲領域の成膜方法及
び製造される板材でのサイド（端部）での密着性であ
る。本発明において，ＣＶＤ−Ｗ成膜は，成膜温度を有
する工程によって製造される。Factors in the CVD-W film formation used in the present invention are a film formation temperature, a film formation method in a wide range, and adhesion at a side (end) of a manufactured plate material. In the present invention, the CVD-W film is manufactured by a process having a film forming temperature.
【００２２】この成膜温度は，５００℃以上，好ましく
は７００℃での成膜が密着強度としては優れている。Ｃ
ＶＤプロセスの一般概念では，低温化指向があるが，本
発明の温度では，基板いわゆるＭｏへの成膜であり，高
温による弊害等はなく，むしろ，実際の使用温度，即ち
２０００℃あるいはそれ以上の高温では，Ｗ被膜とＭｏ
基材との境界にＷ／Ｍｏ固溶相も生成し，その結果，密
着信頼性が向上する。The film forming temperature of 500 ° C. or higher, preferably 700 ° C., is excellent in adhesion strength. C
The general concept of the VD process is to lower the temperature, but at the temperature of the present invention, the film is formed on a substrate, so-called Mo, and there is no adverse effect due to the high temperature. At high temperatures, W coating and Mo
A W / Mo solid solution phase is also formed at the boundary with the substrate, and as a result, the adhesion reliability is improved.
【００２３】本発明において，広範囲領域の成膜法にお
いて，使用するＷＦ6 ガス自体の密度が大きい，その
為，キャリアガスで希釈しすぎると，成膜速度が低下し
てしまう。しかし，本発明の方法においては，従来の成
膜限界とされた直径２００ｍｍ位の範囲は，十分にカバ
ーできる。そこで，本発明において，成膜方法について
更に，検討した。その結果，被処理物が平面でしかも盤
面が広い為，被処理物を連続的には移動せず，ガス供給
ノズルを回転させ，厚みの均一な成膜を可能にした。In the present invention, the WF 6 gas itself has a high density in a film forming method in a wide range. Therefore, if the WF 6 gas is excessively diluted with a carrier gas, the film forming rate is reduced. However, the method of the present invention can sufficiently cover the range of about 200 mm in diameter, which has been conventionally regarded as the film forming limit. Therefore, in the present invention, the film forming method was further studied. As a result, since the object to be processed was flat and the board surface was wide, the object to be processed was not continuously moved, and the gas supply nozzle was rotated to enable uniform film thickness.
【００２４】次に，モリブデン基板への長手方向の残り
の部分の成膜は，上述と同じ機能を持つノズルにより行
うか，あるいは，同時にガスを供し行ってもよい。Next, the formation of the remaining portion in the longitudinal direction on the molybdenum substrate may be performed by a nozzle having the same function as described above, or may be performed by simultaneously supplying gas.
【００２５】本発明におけるモリブデン板端部での密着
性であるが，使用されたモリブデン板材は，０．５〜３
ｍｍ程度であり，矩形のままの端部では，カバレッジの
良いＣＶＤと言えども剥離不安が残る為，矩形コーナー
にアール（Ｒ）付けを施した。０．２〜０．３Ｒでも十
分であり，設計上問題なければ，０．５Ｒでも良い。The adhesion at the end of the molybdenum plate according to the present invention is as follows.
mm, and the end of the rectangular shape is round (R) at the corner of the rectangular shape, because even though it is a CVD with good coverage, there is still anxiety about peeling. 0.2 to 0.3R is sufficient, and if there is no problem in design, 0.5R may be used.
【００２６】尚，本発明をコレクターとして利用する場
合，ウランとの反応を抑制するため，イットッリア（Ｙ
2 Ｏ3 ）を外表皮に被覆するのも有効である。When the present invention is used as a collector, in order to suppress the reaction with uranium, yttria (Y
It is also effective to coat 2 O 3 ) on the outer epidermis.
【００２７】[0027]
【実施例】以下，本発明の実施例について説明する。Embodiments of the present invention will be described below.
【００２８】図１は本発明の実施例に係る高融点金属被
覆部材の製造装置の構成を概略的に示す図である。図１
で示すように，製造装置は，反応槽内１０に設けられた
円錐形のガス供給ノズル１と，モリブデン（Ｍｏ）基板
２を載せるためのボード状のヒーター３とを備えてい
る。このガス供給ノズル１には，ニッケル（Ｎｉ）製
で，外部から反応ガス導入するための反応ガス導入管４
が設けられている。このノズル１から噴き出される反応
ガスによって，直径２００ｍｍ位の範囲が十分にカバー
される。この装置では，被処理物が平面でしかも盤面が
広い為，被処理物を連続的には移動させず，ガス供給ノ
ズル１を回転させる構造が採用されている。ガス供給ノ
ズル１を回転させるために，ノズル１を基板２からなる
べくはなれた所に，ノズル１の摺り合わせ部６が設けら
れており，これによって，反応ガス導入管４をノズル１
とを連絡し，ノズル１側が回転できるような構造になっ
ている。この構造を用いてガス供給ノズル１を回転させ
ることで，厚みの均一な成膜が可能となった。FIG. 1 is a view schematically showing a configuration of a manufacturing apparatus of a high melting point metal-coated member according to an embodiment of the present invention. FIG.
As shown in FIG. 1, the manufacturing apparatus includes a conical gas supply nozzle 1 provided in a reaction tank 10 and a board-shaped heater 3 for mounting a molybdenum (Mo) substrate 2 thereon. The gas supply nozzle 1 has a reaction gas introduction pipe 4 made of nickel (Ni) for introducing a reaction gas from outside.
Is provided. The reaction gas blown out from the nozzle 1 sufficiently covers a range of about 200 mm in diameter. This apparatus employs a structure in which the gas supply nozzle 1 is rotated without continuously moving the workpiece because the workpiece is flat and the board surface is wide. In order to rotate the gas supply nozzle 1, a sliding portion 6 of the nozzle 1 is provided at a place where the nozzle 1 is separated from the substrate 2 as much as possible, whereby the reaction gas introduction pipe 4 is connected to the nozzle 1.
And the nozzle 1 side can be rotated. By rotating the gas supply nozzle 1 using this structure, a film having a uniform thickness can be formed.
【００２９】また，Ｍｏ基板２の長手方向の残りの成膜
は，上述と同じ機能を持つノズル１により行うか，ある
いは，同時にガスを供給し行ってもよい。The remaining film in the longitudinal direction of the Mo substrate 2 may be formed by the nozzle 1 having the same function as described above, or may be supplied with gas at the same time.
【００３０】以下，上記装置を用いた製造の具体例につ
いて説明する。 （実施例１）酸化ランタン（Ｌａ2 Ｏ3 ）を０．３ｗｔ
％添加し，通常の還元雰囲気で還元されたモリブデン粉
末をプレス成形した後，１８００℃で１０時間焼結する
ことにより，総厚３０ｍｍのインゴットを得た。つい
で，熱間，冷間圧延を繰り返し行うことにより，厚さ１
ｍｍの５００×１０００ｍｍの平板にし，矩形の端部を
グラインダーによりおおよそＲ０．５に加工して，Ｌａ
2 Ｏ3 添加のＭｏ板を得た。Hereinafter, a specific example of manufacturing using the above-described apparatus will be described. (Example 1) 0.3 wt% of lanthanum oxide (La 2 O 3 )
%, And press-molded molybdenum powder reduced in a normal reducing atmosphere, followed by sintering at 1800 ° C. for 10 hours to obtain an ingot having a total thickness of 30 mm. Then, hot and cold rolling are repeated to obtain a thickness of 1 mm.
mm × 500 mm flat plate, and the end of the rectangle is processed to approximately R0.5 with a grinder to obtain La
A Mo plate to which 2 O 3 was added was obtained.
【００３１】次いで，図１で示すように，ＣＶＤ反応槽
内１０に，Ｌａ2 Ｏ3 添加Ｍｏ基板（ＴＥＭ材）２を，
加熱用のヒーター３上にセットした。Next, as shown in FIG. 1, a La 2 O 3 -added Mo substrate (TEM material) 2 is placed in a CVD reactor 10.
It was set on a heater 3 for heating.
【００３２】この状態で，一旦槽内１０を減圧した後，
槽内１０に水素を所定圧力まで導入した。その後，ガス
供給ノズル１より水素を単独で供給しつつ，ヒーター３
によりＭｏ基板２を７００℃まで昇温させた。次に，同
じガス供給ノズル１にＷＦ6ガスを導入混合させ，ＷＦ
6 ：Ｈ2 ＝１：３に調節しながら，Ｍｏ基板２上にＷ被
覆層５を成膜した。ガス供給ノズル１を１回／分の割合
で回転させながら，成膜した所，１６０μｍ／時間の割
合で一表面上にＷ被覆層５が形成された。続いてＭｏ基
板２をＷ被覆層５と共に裏返し，再び成膜することで，
Ｍｏ基板２の裏面に２００μｍの厚さのＷ被覆層５を全
域に渡り成膜できた。そして，Ｗ被覆層５の端部のバリ
を取り，表面の若干の凹凸を修正し仕上げた。Ｗ被覆層
５をＭｏ基板２上に被覆した高融点金属部材の垂下特性
を評価するために表１及び表２では，Ｗ被覆前のＭｏ基
板（ＴＥＭ材）２の耐垂下性を純Ｍｏ材料及びＴＺＭ材
料の耐垂下性を比較して示している。表１は１０時間後
の垂下量と温度との関係を示しており，表１から明らか
なように，市販のＴＺＭ材と比較した所，２０７３Ｋ
（１８００℃），ＴＺＭ材が１２〜１７ｍｍに対し，本
発明で使用されるＴＥＭ材では，４ｍｍ以下にとどまっ
ていた。また，表２は，１６００℃の温度における耐垂
下量を時間の経過と共に示したものであり，ＴＥＭ材の
垂下量は長時間経過後も極めて少ないことがわかる。In this state, once the pressure in the tank 10 is reduced,
Hydrogen was introduced into the tank 10 to a predetermined pressure. Then, while supplying hydrogen alone from the gas supply nozzle 1, the heater 3
As a result, the temperature of the Mo substrate 2 was increased to 700 ° C. Next, WF 6 gas is introduced and mixed into the same gas supply nozzle 1 and WF 6 gas is mixed.
The W coating layer 5 was formed on the Mo substrate 2 while adjusting the ratio of 6 : H 2 = 1: 3. When the film was formed while rotating the gas supply nozzle 1 at a rate of once / min, a W coating layer 5 was formed on one surface at a rate of 160 μm / hour. Subsequently, the Mo substrate 2 is turned over together with the W coating layer 5 and formed again to form a film.
On the back surface of the Mo substrate 2, a W coating layer 5 having a thickness of 200 μm was formed over the entire area. Then, burrs were removed from the ends of the W coating layer 5, and slight irregularities on the surface were corrected and finished. In order to evaluate the drooping characteristics of the refractory metal member in which the W coating layer 5 is coated on the Mo substrate 2, Tables 1 and 2 show that the droop resistance of the Mo substrate (TEM material) 2 before W coating is determined by using pure Mo material. 2 shows the sag resistance of the TZM material. Table 1 shows the relationship between the amount of droop after 10 hours and the temperature. As is clear from Table 1, when compared with the commercially available TZM material, 2073K was obtained.
(1800 ° C.), whereas the TZM material was 12 to 17 mm, the TEM material used in the present invention was 4 mm or less. In addition, Table 2 shows the amount of droop resistance at a temperature of 1600 ° C. with the passage of time. It can be seen that the amount of droop of the TEM material is extremely small even after a long time.
【００３３】次に，Ｍｏ材料とＷ材料との気化速度を比
較するために，エル・ベカテリニコフ，エス・エヌ・バ
シルイコフ，ゼ・ゲ・ガリアクバロフ，ア・イ・カシタ
ノフ共著，「超高融点材料便覧」，第４５頁，日ソ通信
社，昭和５２年２月２５日発行から引用した図を図２と
して提示する。図２に示す通り，Ｍｏ材料は，２０００
℃（２２７３Ｋ）を越える高温領域において，Ｗ材料に
比較して非常に高い速度を有していることがわかる。し
たがって，Ｍｏ基板２の表面をＷ被覆膜５で覆った本発
明の金属被覆部材は，高温領域において，気化速度を著
しく遅くすることができ，結果として気化揮散を抑制で
きる。Next, in order to compare the vaporization rates of the Mo material and the W material, see "Ultra-high melting point material handbook", co-authored by El Bekatelinnikov, S. N. Basiliykov, Ze Ge Galiacbarov, and A. I. Kashitanov. FIG. 2, page 45, quoted from Nisso Tsushinsha, published on February 25, 1977, is presented as FIG. As shown in FIG. 2, the Mo material was 2000
It can be seen that in the high temperature region exceeding ℃ (2273K), the material has a very high speed as compared with the W material. Therefore, the metal-coated member of the present invention in which the surface of the Mo substrate 2 is covered with the W coating film 5 can significantly reduce the vaporization rate in a high-temperature region, and as a result, can suppress vaporization and volatilization.
【００３４】また，図３で示す通り，図１の装置では，
ポアの無い緻密なＷ被覆層を成膜でき，しかも，Ｗ被覆
層は平坦な表面を有していた。そして，２０００℃（２
２７３Ｋ）以上での垂下や変形に対して，大幅な向上が
期待されるいわゆる２０００℃を越える高温で変形が少
なくしかも材料気化の少ない大型板材として極めて有効
な高融点金属被覆部材が得られた。As shown in FIG. 3, in the apparatus shown in FIG.
A dense W coating layer without pores could be formed, and the W coating layer had a flat surface. And 2000 ° C (2
A high melting point metal-coated member which is extremely effective as a large plate material with little deformation at high temperatures exceeding 2000 ° C., which is expected to drastically improve drooping and deformation at 273 K) or higher, and little material vaporization is obtained.
【００３５】[0035]
【００３６】[0036]
【発明の効果】以上，説明したように，本発明において
は，耐変形性に優れるドープモリブデン材からなるＭｏ
材に，例えば，ＣＶＤによりＷ被覆を施し，耐変形性に
ついてはもちろん，高温用大面積構造物などに適用する
場合，高温変形性が少なく，再結晶後の高温変形も少な
いので，母材のＭｏ材と同等，もしくは，それ以上の優
れた材料を提供することができる。しかも，また，この
高融点金属被覆部材は，２０００℃（２２７３Ｋ）を越
える高温領域での気化量を基材のＭｏ材より大幅に低下
させることができ，Ｍｏ材において気化，及び揮散を抑
制することができる。また，本発明においては，厚さ
が，例えば，２００μｍ以上で且つポアがなく緻密なタ
ングステン被膜を備えた高温用大面積構造材料としての
高融点金属被覆部材とその製造装置とを提供することが
できる。さらに，本発明においては，ドープモリブデン
基材に対して，密着性の良好で，２０００℃を越える温
度領域においても，剥離や割れを生じない高融点金属被
覆部材を提供することができ，これはコレクター用の材
料に適している。 As described above, according to the present invention, Mo made of a doped molybdenum material having excellent deformation resistance is used.
Apply W coating to the material by , for example, CVD, and apply it not only to deformation resistance but also to large area structures for high temperature
Low deformation at high temperature and low deformation after recrystallization
In Ino, it can provide equivalent Mo material of the base material, or, a more excellent material. In addition, this high-melting-point metal-coated member can significantly reduce the amount of vaporization in a high-temperature region exceeding 2000 ° C. (2273K) as compared with the Mo material as the base material, and suppresses vaporization and volatilization in the Mo material. be able to. In the present invention, the thickness
However, for example, if the thickness is 200 μm or more,
As a large area structural material for high temperature with tungsten coating
It is possible to provide a high melting point metal coated member and an apparatus for manufacturing the same.
it can. Further, in the present invention, doped molybdenum
Good adhesion to substrate, temperature over 2000 ℃
High melting point metal coating that does not peel or crack
A covering member can be provided, which is a material for the collector.
Suitable for the fee.
【図１】本発明の実施例に係る高融点金属被覆材の製造
装置の構成を概略的に示す図である。FIG. 1 is a view schematically showing a configuration of an apparatus for producing a high-melting metal coating material according to an embodiment of the present invention.
【図２】タングステン元素及びモリブデン元素の各温度
に対する気化速度を示す図である。FIG. 2 is a diagram showing vaporization rates of tungsten element and molybdenum element with respect to respective temperatures.
【図３】本発明の実施例に係る高融点金属被覆の金属組
織を示す電子顕微鏡写真である。FIG. 3 is an electron micrograph showing a metal structure of a high melting point metal coating according to an example of the present invention.
１ ガス供給ノズル ２ Ｍｏ基板 ３ ヒーター ４ 導入管 ５ Ｗ被覆層 Reference Signs List 1 gas supply nozzle 2 Mo substrate 3 heater 4 introduction pipe 5 W coating layer
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−111932（ＪＰ，Ａ) 特開 昭63−157832（ＪＰ，Ａ) 特開 平５−25641（ＪＰ，Ａ) 堂山昌男 外１名編「材料テクノロジ ー９材料のプロセス技術［１］（Ｓ62− 11−30）東京大学出版会 ｐ．148 ────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-59-111932 (JP, A) JP-A-63-157832 (JP, A) JP-A-5-25641 (JP, A) Masao Doyama “Material Technology 9 Material Process Technology [1]” (S62-11-30) University of Tokyo Press p.148
Claims (6)
用される大面積の金属部材において，ドープモリブデン
材によって形成された基板と該基板表面に６００〜７０
０℃の成膜温度で形成された被覆層とを備え，前記被覆
層は前記基板を形成するドープモリブデン材よりも遅い
気化速度を有し，且つ実質的にタングステンからなるこ
とを特徴とする高融点金属被覆部材。1. A metal member having a large area which molybdenum is used in an atmosphere such as vaporizing, the substrate and the substrate surface formed by the doped molybdenum material 600-70
A coating layer formed at a deposition temperature of 0 ° C. , wherein the coating layer has a lower vaporization rate than the doped molybdenum material forming the substrate and is substantially made of tungsten. Melting point metal coated member.
いて，前記ドープモリブデン材は，モリブデン元素又は
モリブデン基合金にランタン元素又はランタン酸化物を
０．１〜１ｗｔ％含有することを特徴とする高融点金属
被覆部材。2. The high-melting-point metal-coated member according to claim 1, wherein the doped molybdenum material contains 0.1 to 1 wt% of a lanthanum element or a lanthanum oxide in a molybdenum element or a molybdenum-based alloy. High melting point metal coated member.
いて，前記ドープモリブデン材は，モリブデン元素又は
モリブデン基合金にＡｌ，Ｋ，Ｓｉの内の少なくとも一
種を含むことを特徴とする高融点金属被覆部材。3. The high melting point metal coated member according to claim 1, wherein said doped molybdenum material contains at least one of Al, K, and Si in a molybdenum element or a molybdenum-based alloy. Covering member.
いて，前記ドープモリブデン材は，モリブデン元素又は
モリブデン基合金にＡｌ，Ｓｉ，Ｋの内の少なくとも一
種を０．００５〜０．２ｗｔ％を含むと共に，Ｌａ，Ｃ
ｅ，Ｄｙ，Ｙ，Ｔｈ，Ｔｉ，Ｚｒ，Ｎｂ，Ｔａ，Ｈｆ，
Ｖ，Ｃｒ，Ｍｏ，Ｗ，Ｍｇの内から選択された少なくと
も一種の金属元素を酸化物，炭化物，硼素化合物，及び
窒化物のうちの少なくとも一種の状態で０．１〜３ｗｔ
％とを含むことを特徴とする高融点金属被覆部材。4. The high-melting point metal coated member according to claim 1, wherein the doped molybdenum material contains at least one of Al, Si, and K in an amount of 0.005 to 0.2 wt% of a molybdenum element or a molybdenum-based alloy. Including La, C
e, Dy, Y, Th, Ti, Zr, Nb, Ta, Hf,
At least one metal element selected from V, Cr, Mo, W, and Mg in an oxide, carbide, boron compound, and nitride state in a state of 0.1 to 3 wt.
% Of the metal-coated member having a high melting point.
高融点金属被覆部材によって形成されたことを特徴とす
るコレクター。5. A collector formed by the high-melting-point metal-coated member according to any one of claims 1 to 4.
と，前記ドープモリブデン板材にフッ化タングステンを
含むガスを吹き付けるノズルとを反応槽内に備え，前記
ドープモリブデン板材に実質的にタングステンからなる
被覆層を形成する高融点金属被膜形成装置において，前
記ドープモリブデン板材は大面積を有するとともに固定
されており，前記ノズルは，前記ドープモリブデン板材
面に対して回転するように構成され，前記被覆層を前記
ドープモリブデン板材表面に６００〜７００℃の成膜温
度で形成することを特徴とする高融点金属部材製造装
置。A heater for heating the 6. doped molybdenum plate, and a nozzle for blowing a gas containing tungsten hexafluoride into the reaction vessel to the dope molybdenum plate, the
Substantially tungsten in doped molybdenum plate
In refractory metal film forming apparatus for forming a coating layer, said doped molybdenum plate is fixed and has a large area, the nozzle is configured to rotate relative to the doped molybdenum plate surface, said coating Layer
Deposition temperature of 600 to 700 ° C on the surface of the doped molybdenum plate
An apparatus for manufacturing a high melting point metal member, wherein the apparatus is formed at a predetermined temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5232179A JP2973152B2 (en) | 1993-08-26 | 1993-08-26 | High melting point metal coated member and its manufacturing apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5232179A JP2973152B2 (en) | 1993-08-26 | 1993-08-26 | High melting point metal coated member and its manufacturing apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0762538A JPH0762538A (en) | 1995-03-07 |
| JP2973152B2 true JP2973152B2 (en) | 1999-11-08 |
Family
ID=16935253
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5232179A Expired - Lifetime JP2973152B2 (en) | 1993-08-26 | 1993-08-26 | High melting point metal coated member and its manufacturing apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2973152B2 (en) |
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| CN105849322B (en) * | 2013-12-26 | 2018-09-28 | 联合材料公司 | The manufacturing method of sapphire single-crystal culture crucible, sapphire single-crystal cultural method and sapphire single-crystal culture crucible |
-
1993
- 1993-08-26 JP JP5232179A patent/JP2973152B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 堂山昌男 外１名編「材料テクノロジー９材料のプロセス技術［１］（Ｓ６２−１１−３０）東京大学出版会 ｐ．１４８ |
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| Publication number | Publication date |
|---|---|
| JPH0762538A (en) | 1995-03-07 |
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