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JPH0811824B2 - Crucible and manufacturing method thereof - Google Patents

Crucible and manufacturing method thereof

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Publication number
JPH0811824B2
JPH0811824B2 JP18514292A JP18514292A JPH0811824B2 JP H0811824 B2 JPH0811824 B2 JP H0811824B2 JP 18514292 A JP18514292 A JP 18514292A JP 18514292 A JP18514292 A JP 18514292A JP H0811824 B2 JPH0811824 B2 JP H0811824B2
Authority
JP
Japan
Prior art keywords
crucible
molybdenum
peripheral surface
tungsten
tungsten film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP18514292A
Other languages
Japanese (ja)
Other versions
JPH0625855A (en
Inventor
晃 市田
重彦 高岡
Original Assignee
東京タングステン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東京タングステン株式会社 filed Critical 東京タングステン株式会社
Priority to JP18514292A priority Critical patent/JPH0811824B2/en
Publication of JPH0625855A publication Critical patent/JPH0625855A/en
Publication of JPH0811824B2 publication Critical patent/JPH0811824B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Chemical Vapour Deposition (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Crucibles And Fluidized-Bed Furnaces (AREA)

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は,金属モリブデンを含む
金属材料から形成されたルツボ(以下,モリブデンルツ
ボと呼ぶ)とその製造方法に関し,詳しくは,1800
℃以上の超高温での使用に適した高温強度の優れたモリ
ブデンルツボと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 crucible made of a metallic material containing metallic molybdenum (hereinafter referred to as molybdenum crucible) and a manufacturing method thereof.
TECHNICAL FIELD The present invention relates to a molybdenum crucible having excellent high-temperature strength suitable for use at an ultrahigh temperature of ℃ or more and a method for producing the same.

【0002】[0002]

【従来の技術】一般に金属又は金属酸化物等の高融点材
料は,ルツボ中で,不活性ガス或いは真空の雰囲気中で
溶解される。高融点金属溶解用のルツボとしては,金属
モリブデン又はモリブデン合金のように,金属モリブデ
ンを含むルツボ(以下,全てこの種のルツボをモリブデ
ンルツボと呼ぶ)が使用されている。
2. Description of the Related Art Generally, a high melting point material such as a metal or a metal oxide is melted in a crucible, an inert gas atmosphere or a vacuum atmosphere. As a crucible for melting a high melting point metal, a crucible containing molybdenum metal such as molybdenum metal or molybdenum alloy (hereinafter, this type of crucible is referred to as a molybdenum crucible) is used.

【0003】しかし,モリブデンルツボとして,純モリ
ブデン製のルツボを使用した場合,モリブデンの再結晶
温度が約1000℃であるため,使用温度が高くなるほ
ど,また,高温での使用時間が長くなるほど,ルツボを
構成するモリブデン結晶粒の粗大化が起こる。そのた
め,純モリブデン製のルツボは,結晶粒界の脆弱化によ
る粒界に割れ,又はひびが生じ,この部分からルツボ中
の被溶解物が漏れ出して使用不能となるという欠点を有
している。この欠点を解消するために,例えば,特願昭
62−1542号(以下,参考文献1と呼ぶ)に示され
た改良されたルツボが提案されている。この改良された
ルツボは,モリブデンにランタン又はランタン酸化物を
0.01〜1wt%を含有させた材料によって形成され
ており,鍛造における加工率を余り高くしないで加工す
ることで,加工が容易で,強度が高く優れているという
利点を有する。
However, when a molybdenum crucible made of pure molybdenum is used as the molybdenum crucible, the recrystallization temperature of molybdenum is about 1000 ° C. Therefore, the higher the operating temperature and the longer the operating time at a high temperature, the crucible. The coarsening of the molybdenum crystal grains that constitute Therefore, the crucible made of pure molybdenum has a drawback that the grain boundary is cracked or cracked due to the weakening of the crystal grain boundary, and the melted substance in the crucible leaks out from this portion to make it unusable. . In order to solve this drawback, for example, an improved crucible disclosed in Japanese Patent Application No. 62-1542 (hereinafter referred to as Reference Document 1) has been proposed. This improved crucible is made of molybdenum containing 0.01 to 1 wt% of lanthanum or lanthanum oxide, and can be easily processed by processing without increasing the processing rate in forging. , It has the advantage of high strength and excellent.

【0004】[0004]

【発明が解決しようとする課題】しかしながら,このモ
リブデンルツボは,外部から加熱するように使用される
ので,ルツボ外壁の熱による亀裂等の損傷に対しては十
分とはいえなかった。このため,被溶解物の粒界への溶
入を避けることができなかった。そこで,モリブデンル
ツボに代えて更に高温強度の優れたルツボ材料として,
注目されるのが,純金属タングステン又はタングステン
合金等の金属タングステンを含む材料(以下,単にタン
グステンと呼ぶ)である。
However, since this molybdenum crucible is used so as to be heated from the outside, it cannot be said that the molybdenum crucible is sufficiently protected against damage such as cracks due to heat on the outer wall of the crucible. For this reason, it was impossible to avoid infiltration of the material to be melted into the grain boundaries. Therefore, instead of the molybdenum crucible, as a crucible material with superior high temperature strength,
Attention is focused on a material containing metallic tungsten such as pure metallic tungsten or a tungsten alloy (hereinafter, simply referred to as tungsten).

【0005】しかし,現実に必要とされるルツボは,直
径で60〜220mm程度,高さが30〜100mm程
度とかなり大型のものであり,現在のタングステン加工
技術では,このような大型のタングステンルツボを加工
することは実際上困難である。
However, the crucible actually required is quite large, having a diameter of about 60 to 220 mm and a height of about 30 to 100 mm. In the present tungsten processing technology, such a large size crucible is used. Is difficult to process in practice.

【0006】そこで,本発明の技術的課題は,タングス
テンの高温強度を備えたモリブデンルツボとその製造方
法を提供することにある。
Therefore, a technical object of the present invention is to provide a molybdenum crucible having high-temperature strength of tungsten and a method for manufacturing the same.

【0007】[0007]

【課題を解決するための手段】本発明では,CVD法又
は溶射法によって,微細で且つ緻密なタングステン材料
からなる膜を作製することによって,上記課題を解決し
たものである。
The present invention has solved the above-mentioned problems by forming a film made of a fine and dense tungsten material by a CVD method or a thermal spraying method.

【0008】本発明によれば,高融点金属又は高融点金
属酸化物の溶解に用いるモリブデンからなるルツボであ
って,少なくとも外周面にタングステン膜を有すること
を特徴とするモリブデンルツボが得られる。
According to the present invention, there is provided a molybdenum crucible which is used for melting a refractory metal or a refractory metal oxide and has a tungsten film on at least the outer peripheral surface.

【0009】ここで,本発明において,タングステンと
は,少なくとも金属タングステンを含む金属材料を呼
び,純金属タングステン,タングステン合金等を含む。
Here, in the present invention, the term "tungsten" refers to a metallic material containing at least metallic tungsten, and includes pure metallic tungsten, a tungsten alloy and the like.

【0010】本発明者の実験によれば,タングステン膜
でモリブデンルツボを被覆することによって,実質的に
タングステンの特性を具備したルツボが得られることが
判明した。
According to the experiments conducted by the present inventor, it was found that by coating a molybdenum crucible with a tungsten film, a crucible having substantially the characteristics of tungsten can be obtained.

【0011】ここで,本発明において,タングステン膜
は,熱又は機械的衝撃に対する剥離強度を考慮して,5
0〜100μmより大とすることが好ましい。また,
ングステン膜を形成する方法としては,CVD法及び溶
射法のいずれかまたは両方を併用してもよいが,低廉で
使用温度の著しく高くないものについては,溶射法のみ
によって被覆しても,CVD法によるタングステン膜と
同等の特性が得られる。
In the present invention, the tungsten film has a peel strength of 5 in consideration of the peel strength against heat or mechanical impact.
It is preferable that it is larger than 0 to 100 μm. In addition, data
As a method for forming a tungsten film, a CVD method and a melting method are used.
Either or both of archery may be used together, but for those not significantly higher use temperatures inexpensive, be coated only by the spraying method, Ru obtained tungsten film characteristics equivalent by CVD.

【0012】[0012]

【作用】本発明においては,モリブデンルツボ本体の少
なくとも外周面に,タングステン膜を設けることで,タ
ングステンの高温強度を備えたルツボが得られる。
In the present invention, by providing the tungsten film on at least the outer peripheral surface of the molybdenum crucible body, the crucible having the high temperature strength of tungsten can be obtained.

【0013】[0013]

【実施例】以下に,本発明の実施例について,図面を参
照して説明する。
Embodiments of the present invention will be described below with reference to the drawings.

【0014】図1は,本発明のルツボの一例を示す図で
ある。図1において,ルツボ10は,モリブデンルツボ
本体1と,タングステン膜を備えている。
FIG. 1 is a diagram showing an example of the crucible of the present invention. In FIG. 1, a crucible 10 includes a molybdenum crucible body 1 and a tungsten film.

【0015】モリブデンルツボ本体1は,モリブデン材
料から切削加工されており,内周面12,外周面14,
縁面16,内底面17及び外底面18とによって,構成
されている。
The molybdenum crucible body 1 is machined from a molybdenum material, and has an inner peripheral surface 12, an outer peripheral surface 14,
It is constituted by the edge surface 16, the inner bottom surface 17 and the outer bottom surface 18.

【0016】内周面12と内底面17及び外周面14と
外底面18との境界部は,曲率を持つように形成されて
いる。タングステン膜2は,縁面16の略中央部から外
周面14及び凹部に渡って施されている。
The boundary between the inner peripheral surface 12 and the inner bottom surface 17 and the outer peripheral surface 14 and the outer bottom surface 18 is formed to have a curvature. The tungsten film 2 is applied from the substantially central portion of the edge surface 16 to the outer peripheral surface 14 and the recess.

【0017】図2は,本発明のルツボの他の例を示す図
である。図1のルツボ10との相違点は,図2で示すル
ツボ20は,タングステン膜2´が,モリブデンルツボ
本体1の縁面16全体を覆い,更に内底面17及び内周
面12にも施されている点である。このように外周面1
4だけでなく,内底面17及び内周面12をもタングス
テン膜2´によって,覆うことによって,溶解した液に
よる粒界への侵入を防止するに適し,図1のルツボ10
よりも高温強度が高いルツボを得ることができる。
FIG. 2 is a diagram showing another example of the crucible of the present invention. The difference from the crucible 10 of FIG. 1 is that the crucible 20 shown in FIG. 2 has a tungsten film 2 ′ that covers the entire edge surface 16 of the molybdenum crucible body 1, and is also applied to the inner bottom surface 17 and the inner peripheral surface 12. That is the point. Thus, the outer peripheral surface 1
4, not only the inner bottom surface 17 and the inner peripheral surface 12 are covered with the tungsten film 2 ′, which is suitable for preventing the melted liquid from entering the grain boundaries.
It is possible to obtain a crucible having a higher high temperature strength than that.

【0018】図3は,本発明のルツボの更に他の例を示
す図である。図2のルツボ20との相違点は,図3のル
ツボ30は,タングステン膜2''が外底面18にも施さ
れている点である。このルツボ30は,2300〜24
00℃の超高温で使用した場合においても,モリブデン
ルツボ粒界に発生する外壁の亀裂は見られなかった。
FIG. 3 is a diagram showing still another example of the crucible of the present invention. The difference from the crucible 20 of FIG. 2 is that the crucible 30 of FIG. 3 has the tungsten film 2 ″ also provided on the outer bottom surface 18. This crucible 30 is 2300-24
Even when used at an ultrahigh temperature of 00 ° C., no cracks on the outer wall occurred at the molybdenum crucible grain boundaries.

【0019】また,外底面18に施すことで,更に高温
強度を高め,寿命を長くすることができる。
Further, by applying to the outer bottom surface 18, the high temperature strength can be further enhanced and the life can be extended.

【0020】以下,上記したルツボの具体的方法を実施
例として説明する。
A specific method of the above crucible will be described below as an embodiment.

【0021】(実施例1)純モリブデン材と,この純モ
リブデン材に結晶粒界の脆弱防止に添加されたランタン
を含む化合物とを含むモリブデン材を最終的に切削加工
することによって,ルツボ形状に加工し,モリブデンル
ツボ本体1を得た。充分にAr置換して,その後,減圧
された反応槽に,H2 を500cc/min,WF6
50cc/minを夫々導入した。モリブデンルツボ本
体1を高周波電源等によって,400℃に加熱し,水素
還元CVD法によって,このモリブデンルツボ本体1表
面に,純タングステン膜2を被覆した。被覆後,約40
分経過後,ルツボを取り出したところ,図1で示すよう
に外周面に85μmの厚さのタングステン膜2を有する
ルツボ10が得られた。
Example 1 A molybdenum material containing a pure molybdenum material and a compound containing lanthanum added to the pure molybdenum material to prevent fragility of crystal grain boundaries is finally cut into a crucible shape. By processing, a molybdenum crucible body 1 was obtained. After sufficiently replacing with Ar, 500 cc / min of H 2 and 50 cc / min of WF 6 were introduced into the depressurized reaction tank. The molybdenum crucible body 1 was heated to 400 ° C. by a high frequency power source or the like, and the surface of the molybdenum crucible body 1 was coated with a pure tungsten film 2 by a hydrogen reduction CVD method. About 40 after coating
After a lapse of minutes, the crucible was taken out to obtain a crucible 10 having a tungsten film 2 having a thickness of 85 μm on the outer peripheral surface as shown in FIG.

【0022】(実施例2) 実施例1と同様に切削加工を施したモリブデンルツボ本
体1を,アルミナ粒にてブラスト処理した。市販の溶射
用造粒W粉(メテコ社製,No.61)を65V,50
0Aのパワー,Ar流速7kg/cm,H流速3.
5kg/cmで噴霧速度12l(エル)bs/H(ポ
ンド/時間)で,溶射を行った。この溶射に用いたガン
は,40m/min送りで,加工物であるモリブデンル
ツボ本体1との距離を100mmとして溶射を行った。
数回溶射し,約300μmの純タングステン層を形成
し,図1で示すようなルツボ10が得られた。
(Example 2) The molybdenum crucible body 1 that was cut in the same manner as in Example 1 was blasted with alumina grains. Commercially available thermal spray granulated W powder (Metco, No. 61) at 65V, 50
Power of 0 A, Ar flow rate of 7 kg / cm 2 , H 2 flow rate of 3.
Thermal spraying was performed at 5 kg / cm 2 with a spray rate of 12 1 (ell) bs / H (pounds / hour). The gun used for this thermal spraying was carried out at a feed rate of 40 m / min, with the distance from the molybdenum crucible body 1 being the workpiece being 100 mm.
Thermal spraying was performed several times to form a pure tungsten layer of about 300 μm, and the crucible 10 as shown in FIG. 1 was obtained.

【0023】実施例2に係るW粉の溶射による被覆方法
は,使用状態において過酷さを求められないルツボに
は,適用することができる。この方法は,実施例1で示
したCVD法よりも操作,取扱いが容易であるととも
に,上記実施例1で示したようなWF6 等の有害ガスを
使用しないで済むという利点も兼ね備えている。
The coating method by thermal spraying of W powder according to the second embodiment can be applied to a crucible which is not required to be harsh in use. This method is easier to operate and handle than the CVD method shown in the first embodiment, and also has the advantage that no harmful gas such as WF 6 is used as shown in the first embodiment.

【0024】しかし,実施例2で説明した溶射法では,
何回か繰り返し溶射しないと,1回当り2〜3%の空孔
が残るので,この空孔を塞ぐには,減圧溶射を繰り返す
ことが好ましい。
However, in the thermal spraying method described in the second embodiment,
If the thermal spraying is not repeated several times, 2-3% of the pores remain, so it is preferable to repeat the reduced pressure spraying to close the pores.

【0025】以上の実施例1,2においては,図1で示
すように,外周面のみにタングステン膜2を施したが,
施行する配置を考えると,図2で示すようなルツボ20
も形成することができる。また,実施例1及び2で述べ
た方法を,複数回行うと,図3で示すルツボ30を得る
ことができる。図2又は図3で示すルツボ20,30
は,ルツボ本体1の内壁部12に至るタングステン膜2
´,2''を施すと,中味の溶融物のモリブデンルツボの
粒界への侵入も抑制できる。
In Examples 1 and 2 described above, the tungsten film 2 was applied only to the outer peripheral surface as shown in FIG.
Considering the arrangement to be applied, the crucible 20 as shown in FIG.
Can also be formed. Further, the crucible 30 shown in FIG. 3 can be obtained by performing the method described in the first and second embodiments a plurality of times. Crucible 20, 30 shown in FIG. 2 or FIG.
Is the tungsten film 2 reaching the inner wall 12 of the crucible body 1.
By applying ′, 2 ″, it is also possible to suppress the intrusion of the molten material into the grain boundary of the molybdenum crucible.

【0026】ただし,ルツボ30の場合,実施例2で示
すノズルの施工においては2度に分けて行う必要があ
り,1800℃以上の高温とはいえ,寿命と経費とのバ
ランスを考慮しながら適用することが必要とされる。
However, in the case of the crucible 30, it is necessary to perform the nozzle construction shown in Example 2 in two steps. Even though the temperature is higher than 1800 ° C., the crucible 30 is applied while considering the balance between life and cost. Required to do.

【0027】[0027]

【発明の効果】以上,説明したように,本発明によれ
ば,タングステンの高温強度を備えたモリブデンルツボ
とその製造方法を提供することができる。
As described above, according to the present invention, it is possible to provide a molybdenum crucible having high-temperature strength of tungsten and a method for manufacturing the same.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明のルツボの一例を示す図である。FIG. 1 is a diagram showing an example of a crucible of the present invention.

【図2】本発明のルツボの他の例を示す図である。FIG. 2 is a diagram showing another example of the crucible of the present invention.

【図3】本発明のルツボの更に他の例を示す図である。FIG. 3 is a view showing still another example of the crucible of the present invention.

【符号の説明】[Explanation of symbols]

1 モリブデンルツボ本体 2,2′,2’’タングステン膜 10 モリブデンルツボ 1 内周面 14 外周面 16 縁面 17 内底面 18 外底面1 molybdenum crucible body 2, 2 ', 2''tungsten film 10 molybdenum crucible 1 within inner 2 peripheral surface 14 outer peripheral surface 16 edge surface 17 bottom surface 18 outer bottom face

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 内周面及び外周面を有するモリブデン本
体と, 少なくとも外周面に形成されたタングステン膜とを有す
ることを特徴とするルツボ。
1. A crucible having a molybdenum body having an inner peripheral surface and an outer peripheral surface, and a tungsten film formed on at least the outer peripheral surface.
【請求項2】 内周面及び外周面を有するモリブデンル
ツボ本体を製作した後,前記モリブデンルツボ本体の少
なくとも外周面に,CVD法及び溶射法のうちの少なく
とも一種の方法によって,タングステン膜を形成するこ
とを特徴とするルツボの製造方法。
2. After manufacturing a molybdenum crucible body having an inner peripheral surface and an outer peripheral surface, at least the outer peripheral surface of the molybdenum crucible main body is subjected to at least one of a CVD method and a thermal spraying method.
A method for manufacturing a crucible, characterized in that a tungsten film is formed by a kind of method.
JP18514292A 1992-07-13 1992-07-13 Crucible and manufacturing method thereof Expired - Lifetime JPH0811824B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP18514292A JPH0811824B2 (en) 1992-07-13 1992-07-13 Crucible and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP18514292A JPH0811824B2 (en) 1992-07-13 1992-07-13 Crucible and manufacturing method thereof

Publications (2)

Publication Number Publication Date
JPH0625855A JPH0625855A (en) 1994-02-01
JPH0811824B2 true JPH0811824B2 (en) 1996-02-07

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JPH0811824B2 (en)

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US20150128849A1 (en) * 2012-04-17 2015-05-14 Plansee Se Crucible for the manufacture of oxide ceramic single crystals
US9457405B2 (en) 2012-05-29 2016-10-04 H.C. Starck, Inc. Metallic crucibles and methods of forming the same
WO2014050585A1 (en) * 2012-09-28 2014-04-03 株式会社アライドマテリアル Crucible for growing sapphire single crystal, and method for producing crucible for growing sapphire single crystal
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