JP2001288556A - Refractory-metal material with oxidation resistant layer, and manufacturing method - Google Patents
Refractory-metal material with oxidation resistant layer, and manufacturing methodInfo
- Publication number
- JP2001288556A JP2001288556A JP2000100552A JP2000100552A JP2001288556A JP 2001288556 A JP2001288556 A JP 2001288556A JP 2000100552 A JP2000100552 A JP 2000100552A JP 2000100552 A JP2000100552 A JP 2000100552A JP 2001288556 A JP2001288556 A JP 2001288556A
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- Japan
- Prior art keywords
- oxidation
- resistant layer
- metal material
- refractory
- molybdenum
- 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.)
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- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、モリブデン等の高
融点金属の表面に耐酸化層を有することによって，酸化
雰囲気中の高温で使用される耐酸化層を有する高融点金
属材料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 high melting point metal material having an oxidation resistant layer used at a high temperature in an oxidizing atmosphere by providing an oxidation resistant layer on the surface of a high melting point metal such as molybdenum, and a method of manufacturing the same About.
【０００２】[0002]
【従来の技術】従来，元素周期律表のＶａ，ＶＩａ族に
位置するニオブ、タンタル、クロム、モリブデン、タン
グステンは、高融点金属の代表とされ、その中でもタン
グステンやモリブデンは高温で使用される加熱炉の発熱
体、熱反射板、焼成用の坩堝、トレー，敷き板などの耐
熱構造材料部材として使用されている。2. Description of the Related Art Conventionally, niobium, tantalum, chromium, molybdenum and tungsten located in the Va and VIa groups of the Periodic Table of the Elements have been represented as high melting point metals. It is used as a heat-resistant structural material such as a heating element of a furnace, a heat reflecting plate, a crucible for firing, a tray, and a laying plate.
【０００３】しかし，モリブデンは耐酸化性に乏しい。
即ち、モリブデンにおいては空気中６００℃で酸化が顕
著になり，約７００℃では生成したＭｏＯ３が昇華し始
める。一酸化炭素中や一酸化炭素中では、それそれ１４
００℃および１２００℃以上で顕著に酸化する。上記の
ような現象を克服するために種々の耐酸化膜をモリブデ
ンの表面に生成，あるいは張り合わせることが試みられ
ている。[0003] However, molybdenum has poor oxidation resistance.
That is, in molybdenum, oxidation becomes remarkable at 600 ° C. in air, and at about 700 ° C., generated MoO 3 starts to sublime. In carbon monoxide and carbon monoxide,
Significantly oxidizes above 00 ° C and 1200 ° C. In order to overcome the above-mentioned phenomena, it has been attempted to form or bond various oxidation resistant films on the surface of molybdenum.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、プラズ
マ溶射法、ＣＶＤなどによって、モリブデンの表面に耐
酸化性のセラミックス材料の薄膜を被覆しても、生成さ
れた被覆薄膜は比較的粗密であったりして、酸素が薄膜
を通過して、基板であるモリブデンにまで到達してしま
うという事態は解消されない。However, even if the surface of molybdenum is coated with a thin film of an oxidation-resistant ceramic material by plasma spraying, CVD, or the like, the resulting coated thin film may be relatively coarse and dense. Thus, the situation where oxygen passes through the thin film and reaches molybdenum as the substrate is not solved.
【０００５】そこで、本発明の技術的課題は、高温にお
いても耐酸化性を有するモリブデン材等の高融点金属材
料とその製造方法とを提供することにある。It is an object of the present invention to provide a refractory metal material such as a molybdenum material having oxidation resistance even at a high temperature and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、耐酸化性
被膜を有するモリブデン又はモリブデン合金材等の高融
点金属材料について鋭意検討した。その結果、モリブデ
ン材料等の表面に窒素、炭素量のそれぞれの値は、表面
よりも母材側が少なく、また、耐酸化層の厚さが５〜１
００μｍの範囲ににあり、耐酸化層と母材金属の界面が
喫状に結合されていることを見出だし、本発明をなすに
至ったものである。Means for Solving the Problems The present inventors have intensively studied a high melting point metal material such as molybdenum or a molybdenum alloy material having an oxidation resistant film. As a result, the respective values of the amounts of nitrogen and carbon on the surface of the molybdenum material or the like are smaller on the base material side than on the surface, and the thickness of the oxidation-resistant layer is 5 to 1
It was found that the thickness was in the range of 00 μm, and that the interface between the oxidation-resistant layer and the base metal was bonded in a zigzag manner, leading to the present invention.
【０００７】即ち、本発明によれば、モリブデン又はモ
リブデン合金からなる金属母材の表面に窒素と炭素を含
有した耐酸化層を有することを特徴とする耐酸化層を有
する高融点金属材料が得られる。That is, according to the present invention, there is provided a high melting point metal material having an oxidation resistant layer characterized by having an oxidation resistant layer containing nitrogen and carbon on the surface of a metal base material made of molybdenum or a molybdenum alloy. Can be
【０００８】また、本発明によれば、前記耐酸化層を有
する高融点金属材料において、前記耐酸化層の窒素及び
酸素の含有量は、表面から前記金属母材に向かって次第
に減少していることを特徴とする耐酸化層を有する高融
点金属材料が得られる。According to the present invention, in the refractory metal material having the oxidation-resistant layer, the contents of nitrogen and oxygen in the oxidation-resistant layer gradually decrease from the surface toward the metal base material. Thus, a high melting point metal material having an oxidation resistant layer is obtained.
【０００９】また、本発明によれば、前記いずれかの耐
酸化層を有する高融点金属材料において、前記耐酸化層
と前記金属母材との界面は、楔状に結合されていること
を特徴とする耐酸化層を有する高融点金属材料が得られ
る。According to the present invention, in the refractory metal material having any one of the oxidation-resistant layers, an interface between the oxidation-resistant layer and the metal base material is connected in a wedge shape. A refractory metal material having an oxidation-resistant layer is obtained.
【００１０】また、本発明によれば、前記耐酸化層を有
する高融点金属材料を製造する方法であって、前記金属
母材の表面に炭素供給源を塗布し、窒素雰囲気中で加熱
及び加圧処理することによって前記耐酸化層を形成する
ことを特徴とする耐酸化層を有する高融点金属材料の製
造方法が得られる。Further, according to the present invention, there is provided a method for producing a refractory metal material having the oxidation-resistant layer, comprising applying a carbon source to the surface of the metal base material, heating and heating in a nitrogen atmosphere. A method for producing a refractory metal material having an oxidation-resistant layer, wherein the oxidation-resistant layer is formed by pressure treatment.
【００１１】また、本発明によれば、前記耐酸化層を有
する高融点金属材料の製造方法において、前記加熱処理
は、１１００〜１４００℃の温度範囲内で行われること
を特徴とする耐酸化層を有する高融点金属材料の製造方
法が得られる。Further, according to the present invention, in the method for producing a refractory metal material having an oxidation resistant layer, the heat treatment is performed within a temperature range of 1100 to 1400 ° C. Is obtained.
【００１２】さらに、本発明によれば、前記いずれかの
耐酸化層を有する高融点金属材料の製造方法において、
前記加圧処理は、１ＭＰａ以上の窒素雰囲気中で行わ
れ、前記加熱及び加圧処理の時間は、１０分以上である
ことを特徴とする耐酸化層を有する高融点金属材料の製
造方法が得られる。Further, according to the present invention, in the method for producing a refractory metal material having any one of the oxidation-resistant layers,
The pressure treatment is performed in a nitrogen atmosphere of 1 MPa or more, and the time of the heating and pressure treatment is 10 minutes or more, whereby a method for producing a refractory metal material having an oxidation-resistant layer is obtained. Can be
【００１３】また、本発明において、母材金属と耐酸化
性膜との界面の結合状態は楔形であることが、好まし
い。その理由は、結合状態が平らなままでは、母材金属
と耐酸化性膜との結合状態が弱く、楔型とすることによ
ってより強固な結合となるからである。In the present invention, the bonding state of the interface between the base metal and the oxidation-resistant film is preferably a wedge shape. The reason is that if the bonding state is flat, the bonding state between the base metal and the oxidation-resistant film is weak, and the wedge shape results in a stronger connection.
【００１４】また、本発明において、加熱処理温度を１
１００〜１４００℃未満と限定したのは、１１００℃末
満では、耐酸化性膜の生成が見られず、一方、１４００
℃以上の温度になると母材金属劣化が起こるためであ
る。In the present invention, the heat treatment temperature is set at 1
The reason why the temperature is limited to 100 to less than 1400 ° C. is that no oxidation-resistant film is formed below 1100 ° C.
This is because when the temperature is higher than ° C., the base metal deteriorates.
【００１５】また、本発明において、加圧処理における
窒素圧を１ＭＰａ以上としたのは、１ＭＰａ未満では表
面に耐酸化性膜の形成が出来ないためである。In the present invention, the reason why the nitrogen pressure in the pressure treatment is set to 1 MPa or more is that if less than 1 MPa, an oxidation resistant film cannot be formed on the surface.
【００１６】さらに、本発明において、加熱及び加圧処
理の時間を１０分以上としたは、１０分未満では表面に
耐酸化性膜の形成が不十分であるためである。Further, in the present invention, the time of the heating and pressurizing treatment is set to 10 minutes or more because if less than 10 minutes, the formation of the oxidation resistant film on the surface is insufficient.
【００１７】[0017]
【発明の実施の形態】以下、本発明の実施の形態につい
て説明する。Embodiments of the present invention will be described below.
【００１８】厚さ３ｍｍのモリブデンの板を酸洗浄によ
り清浄化した後、カーボン粉末を有機溶剤で分散させた
ペーストを塗布し、乾燥後、下記表１に示した条件で表
面に耐酸化被膜を生成させた。After cleaning a 3 mm-thick molybdenum plate by acid washing, a paste in which carbon powder is dispersed with an organic solvent is applied, and after drying, an oxidation-resistant film is formed on the surface under the conditions shown in Table 1 below. Generated.
【００１９】[0019]
【表１】 [Table 1]
【００２０】得られた硬質層の厚さを走査型電子顕微鏡
（ＳＥＭ）、組成をＥＰＭＡで測定、定量した結果およ
び母材の組成分析を表２及び表３に示した。Tables 2 and 3 show the results of measuring and quantifying the thickness of the obtained hard layer with a scanning electron microscope (SEM) and the composition with EPMA, and analyzing the composition of the base material.
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【表３】 [Table 3]
【００２３】次に、本発明の実施の形態により得られた
本発明材６と比較材４の耐酸化試験を行った。条件とし
ては、大気中４００℃から８００℃で各３０分加熱、保
持した後、試料片の状態および重量の変化を調べた。そ
の結果を図１に示した。Next, an oxidation resistance test was performed on the inventive material 6 and the comparative material 4 obtained according to the embodiment of the present invention. The conditions were as follows: after heating and holding at 400 ° C. to 800 ° C. in the atmosphere for 30 minutes each, the state of the sample pieces and changes in weight were examined. The result is shown in FIG.
【００２４】図１の結果から、曲線１１で示される本発
明材６の方が曲線１１で示される比較材４よりも明らか
に、耐酸化性に優れていることが分かる。From the results shown in FIG. 1, it can be seen that the material 6 of the present invention shown by the curve 11 is clearly superior to the comparative material 4 shown by the curve 11 in oxidation resistance.
【００２５】以上説明した本発明の実施の形態において
は、モリブデン材についてのみ説明下が、モリブデン合
金においても、本発明が適用できることは明らかであ
る。In the embodiment of the present invention described above, only the molybdenum material will be described. However, it is clear that the present invention can be applied to a molybdenum alloy.
【００２６】[0026]
【発明の効果】以上説明したように、本発明によれば、
高温においても耐酸化性を有するモリブデン材等の高融
点金属材料とその製造方法とを提供することができる。As described above, according to the present invention,
A high melting point metal material such as a molybdenum material having oxidation resistance even at a high temperature and a method for manufacturing the same can be provided.
【図１】本発明の実施の形態による本発明材６と比較材
４の高温における耐酸化試験結果を示す図である。FIG. 1 is a view showing the results of an oxidation resistance test at a high temperature of a material 6 of the present invention and a comparative material 4 according to an embodiment of the present invention.
１１ 本発明材６の耐酸化性を示す曲線 １２ 比較材４の耐酸化性を示す曲線 11 Curve showing oxidation resistance of material 6 of the present invention 12 Curve showing oxidation resistance of comparative material 4
───────────────────────────────────────────────────── フロントページの続き (72)発明者 瀧田 朋広 富山県富山市岩瀬古志町２番地 東京タン グステン株式会社富山製作所内 (72)発明者 五十嵐 廉 富山県富山市岩瀬古志町２番地 東京タン グステン株式会社富山製作所内 (72)発明者 土井 良彦 東京都台東区東上野五丁目24番８号 東京 タングステン株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tomohiro Takita 2nd Iwase Koshicho, Toyama City, Toyama Prefecture Tokyo Tan Gusten Co., Ltd. Toyama Works (72) Inventor Ren Igarashi 2nd Iwase Koshimachi Toyama City, Toyama Prefecture Tokyo Tan Gusten (72) Inventor Yoshihiko Doi Tokyo Tungsten Co., Ltd. 5--24-8 Higashi Ueno, Taito-ku, Tokyo
Claims (6)
金属母材の表面に窒素と炭素を含有した耐酸化層を有す
ることを特徴とする耐酸化層を有する高融点金属材料。1. A refractory metal material having an oxidation-resistant layer, characterized by having an oxidation-resistant layer containing nitrogen and carbon on the surface of a metal base material made of molybdenum or a molybdenum alloy.
金属材料において、前記耐酸化層の窒素及び酸素の含有
量は、表面から前記金属母材に向かって次第に減少して
いることを特徴とする耐酸化層を有する高融点金属材
料。2. The refractory metal material having an oxidation-resistant layer according to claim 1, wherein the content of nitrogen and oxygen in the oxidation-resistant layer gradually decreases from the surface toward the metal base material. A high melting point metal material having a characteristic oxidation resistant layer.
高融点金属材料において、前記耐酸化層と前記金属母材
との界面は、楔状に結合されていることを特徴とする耐
酸化層を有する高融点金属材料。3. The oxidation-resistant metal material having an oxidation-resistant layer according to claim 1, wherein an interface between the oxidation-resistant layer and the metal base material is wedge-shaped. Refractory metal material having a layer.
金属材料を製造する方法であって、前記金属母材の表面
に炭素供給源を塗布し、窒素雰囲気中で加熱及び加圧処
理することによって前記耐酸化層を形成することを特徴
とする耐酸化層を有する高融点金属材料の製造方法。4. A method for producing a refractory metal material having an oxidation-resistant layer according to claim 1, wherein a carbon supply source is applied to the surface of the metal base material, and heating and pressing are performed in a nitrogen atmosphere. Forming the oxidation-resistant layer by performing the method described above.
金属材料の製造方法において、前記加熱処理は、１１０
０〜１４００℃の温度範囲内で行われることを特徴とす
る耐酸化層を有する高融点金属材料の製造方法。5. The method for producing a high-melting metal material having an oxidation-resistant layer according to claim 4, wherein the heat treatment is performed at a temperature of 110.
A method for producing a refractory metal material having an oxidation-resistant layer, which is performed in a temperature range of 0 to 1400 ° C.
高融点金属材料の製造方法において、前記加圧処理は、
１ＭＰａ以上の窒素雰囲気中で行われ、前記加熱及び加
圧処理の時間は、１０分以上であることを特徴とする耐
酸化層を有する高融点金属材料の製造方法。6. The method for producing a refractory metal material having an oxidation-resistant layer according to claim 4 or 5, wherein the pressure treatment comprises:
The method for producing a refractory metal material having an oxidation-resistant layer, wherein the method is performed in a nitrogen atmosphere of 1 MPa or more and the time of the heating and pressure treatment is 10 minutes or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000100552A JP4684383B2 (en) | 2000-04-03 | 2000-04-03 | Refractory metal material having oxidation resistant layer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000100552A JP4684383B2 (en) | 2000-04-03 | 2000-04-03 | Refractory metal material having oxidation resistant layer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001288556A true JP2001288556A (en) | 2001-10-19 |
| JP4684383B2 JP4684383B2 (en) | 2011-05-18 |
Family
ID=18614733
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001295023A (en) * | 2000-04-06 | 2001-10-26 | Allied Material Corp | High melting point metallic material having surface hardened layer and its producing method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5117132A (en) * | 1974-08-01 | 1976-02-10 | Tokyo Shibaura Electric Co | DAIKASUTOYOTAINETSUSHOKETSUGOKIN |
| JPS54116313A (en) * | 1978-03-02 | 1979-09-10 | Nat Res Inst Metals | Production of molybdenum material or sintered molybdenum material with excellent low temperature tenacity |
| JPS5757867A (en) * | 1980-09-26 | 1982-04-07 | Hitachi Ltd | Surface hardening method of titanium and titanium alloy |
| JPS59208066A (en) * | 1983-05-13 | 1984-11-26 | Toshiba Corp | Method for working internally nitrided molybdenum-zirconium alloy |
| JPS6233756A (en) * | 1985-08-07 | 1987-02-13 | Mazda Motor Corp | Carburizing and nitriding method |
| JPH04232247A (en) * | 1990-07-04 | 1992-08-20 | Degussa Ag | Method for applying nitride layer to member composed of titanium and titanium alloy |
| JPH0543982A (en) * | 1991-08-12 | 1993-02-23 | Sumitomo Metal Ind Ltd | Cold rolled steel sheet for deep drawing and its production |
-
2000
- 2000-04-03 JP JP2000100552A patent/JP4684383B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5117132A (en) * | 1974-08-01 | 1976-02-10 | Tokyo Shibaura Electric Co | DAIKASUTOYOTAINETSUSHOKETSUGOKIN |
| JPS54116313A (en) * | 1978-03-02 | 1979-09-10 | Nat Res Inst Metals | Production of molybdenum material or sintered molybdenum material with excellent low temperature tenacity |
| JPS5757867A (en) * | 1980-09-26 | 1982-04-07 | Hitachi Ltd | Surface hardening method of titanium and titanium alloy |
| JPS59208066A (en) * | 1983-05-13 | 1984-11-26 | Toshiba Corp | Method for working internally nitrided molybdenum-zirconium alloy |
| JPS6233756A (en) * | 1985-08-07 | 1987-02-13 | Mazda Motor Corp | Carburizing and nitriding method |
| JPH04232247A (en) * | 1990-07-04 | 1992-08-20 | Degussa Ag | Method for applying nitride layer to member composed of titanium and titanium alloy |
| JPH0543982A (en) * | 1991-08-12 | 1993-02-23 | Sumitomo Metal Ind Ltd | Cold rolled steel sheet for deep drawing and its production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001295023A (en) * | 2000-04-06 | 2001-10-26 | Allied Material Corp | High melting point metallic material having surface hardened layer and its producing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4684383B2 (en) | 2011-05-18 |
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