JPS624466B2 - - Google Patents
Info
- Publication number
- JPS624466B2 JPS624466B2 JP58211152A JP21115283A JPS624466B2 JP S624466 B2 JPS624466 B2 JP S624466B2 JP 58211152 A JP58211152 A JP 58211152A JP 21115283 A JP21115283 A JP 21115283A JP S624466 B2 JPS624466 B2 JP S624466B2
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- weight
- earth element
- pack
- metal article
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Description
〔産業上の利用分野〕
本発明は、金属物品表面に対する希土類元素拡
散処理方法に関し、更に詳細には、耐熱性金属物
品の表面に希土類元素を拡散させ、金属物品の耐
酸化性、耐腐食性を更に向上させるための表面処
理方法に関する。
〔従来技術〕
耐熱鋳鉄、耐熱鋼、Ni基合金、高Si鋳鉄などの
耐熱材料に合金元素としてLa、Ceなどの希土類
元素を添加すると耐熱材料の耐酸化性が向上する
ことはよく知られている。これは希土類元素が表
面の酸化皮膜の剥離を抑制するためである。しか
し、このような耐熱材料を希土類元素を多量に添
加すると、材料の熱間加工性を低下させてしまう
という欠点がある。
ところで、耐熱材料中に添加された希土類元素
のうち、耐熱材料の耐酸化性すなわち酸化皮膜の
剥離抑制に寄与する希土類元素は材料表面近傍に
存在するものだけである。したがつて耐熱材料で
つくられた金属物品すなわち熱間加工後の最終製
品の表面層にのみ希土類元素を含有させることが
できれば、上記熱間加工性の問題ならびに耐酸化
性の向上という課題を一挙に解決することができ
る。
〔発明の目的〕
したがつて本発明の目的は、耐熱鋳鉄、耐熱
鋼、Ni基合金、高Si鋳鉄などの耐熱材料、すなわ
ちアルミニウム、珪素、クロムの少くとも一種を
含む金属物品の耐酸化性、耐腐食性を更に向上さ
せることができる方法を提供することである。
〔発明の構成〕
本発明者は、希土類元素含有粉末を含む処理粉
末中で上記金属物品を処理することにより、上記
目的が達成されることを見出し本発明を完成する
に至つた。
すなわち本発明は、アルミニウム、珪素および
クロムの少くとも一種を含む金属物品を、希土類
元素を70重量％以上含有する粉末を0.5〜15重量
％と、ハロゲン化物を２〜４重量％と、残部不活
性担体粉末とを含むパツク剤中に埋設し、非酸化
性雰囲気中で加熱し、希土類元素を金属物品表面
に拡散させることを特徴とする希土類元素拡散処
理方法である。
以下本発明を詳細に説明する。
本発明方法の被処理物は、アルミニウム、珪
素、クロムの少くとも一種を含む金属物品であ
る。一般にアルミニウムは１〜７重量％、珪素は
１〜７重量％、クロムは１〜30重量％の範囲で含
まれていることが望ましい。これらの金属の含有
量が上記範囲より少いと十分な酸化皮膜の形成が
行われなくなり、また上記範囲を越えるとσ相が
生成してもろくなるので、好ましくない。
本発明方法に使用するパツク剤は、希土類元素
含有粉末と不活性担体粉末とハロゲン化物とを含
んでいる。その配合割合は、希土類元素含有粉末
0.5〜15重量％、ハロゲン化物２〜４重量％、不
活性担体粉末残部から成る。
本願明細書中、「希土類元素含有粉末」とは、
希土類元素単独から成る粉末、希土類元素と他の
金属、たとえばアルミニウム、鉄、ニツケルなど
との合金粉末、希土類元素のハロゲン化物粉末、
またはこれらの２種以上の混合物を意味するもの
である。希土類元素としてはスカンジウム
（Sc）、イツトリウム（Ｙ）、ランタン（La）、セ
リウム（Ce）、プラセオジム（Pr）、ネオジム
（Nd）、プロメチウム（Pm）、サマリウム
（Sm）、ユーロピウム（Eu）、ガドリニウム
（Gd）、テルビウム（Tb）、ジスプロシウム
（Dy）、ホルミウム（Ho）、エルビウム（Er）、ツ
リウム（Tm）、イツテルビウム（Yb）、ルテチウ
ム（Lu）、およびこれらの２種以上の混合物を使
用することができる。またミツユメタル（Mm）
（La22〜38％、Ce48〜56％、その他Nd、Pr、Ｙ
および少量のFl、Alを含む、希土類元素95重量
％以上の混合物）も本発明の希土類元素として使
用することができる。
希土類元素含有粉末中の希土類元素含有量は、
70重量％以上とする。たとえば、パツク剤の全重
量に対して希土類元素0.5〜15重量％、アルミニ
ウム0.15〜4.5重量％の割合の合金粉末を使用す
ることができる。
本発明に使用するハロゲン化物は、パツク剤中
の希土類元素が被処理金属物表面に拡散浸透する
のを促進するものであり、具体的にはNH4Cl、
NH4F、NaCl、NaFなどのハロゲン化物が使用さ
れる。希土類元素含有粉末として希土類元素のハ
ロゲン化物を使用する場合には、特別にNH4Cl等
のハロゲン化物を添加する必要がないことはいう
までもない。また、不活性担体粉末は、溶融した
合金粉末粒子が相互に接触しないように働くもの
であり、たとえばアルミナが使用される。
上記パツク剤を用いて希土類元素拡散処理を行
うにはたとえば次のようにすればよい。
まずパツク剤中に被処理金属物品を埋設し、非
酸化性雰囲気、たとえばH2またはAf雰囲気中、
700〜900℃で0.5〜2.0時間パツク処理を行う。次
に被処理物をパツク剤の中から取り出し、H2、
H2またはArのような非酸化性雰囲気中、900〜
1100℃で0.5〜4.0時間拡散処理を行えばよい。
〔発明の効果〕
本発明によれば、耐熱材料でつくられた金属物
品にすぐれた耐酸化性を付与することができる。
〔実施例〕
次に実施例により本発明を更に詳細に説明す
る。
実施例 １
次の組成を有するNi Resist鋳鉄から25mm×40
mm×５mmの試料を作成した。
[Industrial Application Field] The present invention relates to a rare earth element diffusion treatment method for the surface of a metal article, and more specifically, the present invention relates to a rare earth element diffusion treatment method for the surface of a metal article, and more specifically, it diffuses a rare earth element on the surface of a heat-resistant metal article to improve the oxidation resistance and corrosion resistance of the metal article. The present invention relates to a surface treatment method for further improving. [Prior art] It is well known that adding rare earth elements such as La and Ce as alloying elements to heat-resistant materials such as heat-resistant cast iron, heat-resistant steel, Ni-based alloys, and high-Si cast iron improves the oxidation resistance of the heat-resistant materials. There is. This is because the rare earth elements suppress the peeling of the oxide film on the surface. However, when a large amount of rare earth elements are added to such a heat-resistant material, there is a drawback that the hot workability of the material is reduced. By the way, among the rare earth elements added to the heat-resistant material, the rare earth elements that contribute to the oxidation resistance of the heat-resistant material, that is, to suppress the peeling of the oxide film, are only those present near the surface of the material. Therefore, if rare earth elements can be contained only in the surface layer of metal articles made of heat-resistant materials, that is, the final product after hot working, the problem of hot workability and the problem of improving oxidation resistance can be solved all at once. can be solved. [Object of the Invention] Therefore, the object of the present invention is to improve the oxidation resistance of heat-resistant materials such as heat-resistant cast iron, heat-resistant steel, Ni-based alloys, and high-Si cast iron, that is, metal articles containing at least one of aluminum, silicon, and chromium. The object of the present invention is to provide a method that can further improve corrosion resistance. [Structure of the Invention] The present inventor has completed the present invention by discovering that the above object can be achieved by treating the metal article in a treated powder containing rare earth element-containing powder. That is, the present invention provides a metal article containing at least one of aluminum, silicon, and chromium, with powder containing 70% or more of rare earth elements in an amount of 0.5 to 15% by weight, a halide in an amount of 2 to 4% by weight, and the balance being free. This rare earth element diffusion treatment method is characterized by embedding the rare earth element in a pack containing active carrier powder and heating it in a non-oxidizing atmosphere to diffuse the rare earth element onto the surface of the metal article. The present invention will be explained in detail below. The object to be treated in the method of the present invention is a metal article containing at least one of aluminum, silicon, and chromium. Generally, it is desirable that aluminum be contained in a range of 1 to 7% by weight, silicon in a range of 1 to 7% by weight, and chromium to be contained in a range of 1 to 30% by weight. If the content of these metals is less than the above range, a sufficient oxide film will not be formed, and if it exceeds the above range, a σ phase will be formed and the film will become brittle, which is not preferable. The pack agent used in the method of the present invention contains a rare earth element-containing powder, an inert carrier powder, and a halide. The blending ratio is powder containing rare earth elements.
0.5-15% by weight, 2-4% by weight of halide, balance inert carrier powder. In the specification of this application, "rare earth element-containing powder" means
Powders consisting of rare earth elements alone, alloy powders of rare earth elements and other metals such as aluminum, iron, nickel, etc., halide powders of rare earth elements,
Or it means a mixture of two or more of these. Rare earth elements include scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), and gadolinium. (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and mixtures of two or more of these are used. can do. Also Mitsuyu Metal (Mm)
(La22~38%, Ce48~56%, other Nd, Pr, Y
A mixture containing 95% by weight or more of rare earth elements, including small amounts of Fl and Al) can also be used as the rare earth element in the present invention. The rare earth element content in the rare earth element-containing powder is
70% by weight or more. For example, alloy powders can be used in proportions of 0.5 to 15% by weight of rare earth elements and 0.15 to 4.5% by weight of aluminum, based on the total weight of the pack. The halides used in the present invention promote the diffusion and penetration of rare earth elements in the pack agent into the surface of the metal object to be treated, and specifically include NH 4 Cl,
Halides such as NH4F , NaCl, NaF are used. It goes without saying that when a halide of a rare earth element is used as the rare earth element-containing powder, there is no need to specifically add a halide such as NH 4 Cl. Further, the inert carrier powder acts to prevent the molten alloy powder particles from coming into contact with each other, and for example, alumina is used. In order to carry out the rare earth element diffusion treatment using the above-mentioned pack agent, for example, the following procedure may be performed. First, the metal article to be treated is embedded in a pack agent, and then heated in a non-oxidizing atmosphere, such as H 2 or Af atmosphere.
Pack treatment is performed at 700-900°C for 0.5-2.0 hours. Next, the object to be treated is taken out from the pack agent, and H 2 ,
In a non-oxidizing atmosphere like H2 or Ar, 900~
Diffusion treatment may be performed at 1100°C for 0.5 to 4.0 hours. [Effects of the Invention] According to the present invention, excellent oxidation resistance can be imparted to a metal article made of a heat-resistant material. [Example] Next, the present invention will be explained in more detail with reference to Examples. Example 1 25mm x 40 pieces of Ni Resist cast iron with the following composition
A sample of mm x 5 mm was prepared.
【表】
この試料を次の組成を有するパツク剤中に埋設
し、H2雰囲気中、750℃で1.0時間パツク処理を行
い、次にパツク剤の中から取り出し、N2雰囲気
中、950℃で3.0時間拡散処理を行つた。[Table] This sample was buried in a pack agent having the following composition, subjected to pack treatment at 750℃ in an H2 atmosphere for 1.0 hour, then taken out from the pack agent, and heated at 950℃ in an N2 atmosphere. Diffusion treatment was performed for 3.0 hours.
【表】
このようにして得られた各試料について、次の
ように耐酸化性試験を行つた。
1000℃に保つた大気炉中に上記試料を45分間保
持し、次に試料を炉から取り出して空気中で15分
間自然冷却する。これを１サイクル（60分）とし
て、所定のサイクル繰り返した後、試験前後の重
量変化および試験後の表面性状により、被膜の耐
酸化性を評価した。
第１図に示すように、ミツシユメタルの添加量
を0.1〜16重量％まで変化させ、その効果を確認
したところ、0.1〜15重量％の範囲で耐酸化性が
向上した。これは、希土類元素により、試料表面
に生成したAl2O3、SiO2、NiO、CrOなどの酸化
皮膜の脱落が抑制されるためである。
第２図には、ミツシユメタル５重量％を添加し
たパツク剤によりパツク処理した試料の酸化によ
る重量変化を調べた結果を、パツク処理しないも
のと比較して示す。この図から明らかなように、
パツク処理をしない場合は一旦、酸化皮膜を形成
して酸化増量を示すが、加熱冷却回数が15回を過
ぎるころから、次第に酸化膜剥離による重量の減
少を示すようになる。これに対して、ミツシユメ
タルを含むパツク剤により処理したものは、酸化
膜を安定に保持し続けていることがわかる。
実施例 ２
次の組成を有するステンレス鋼から、実施例１
と同じ寸法の試料を作成し、アルミナ粉末93重量
％、ミツシユメタル５重量％、NH4Cl ２重量％
から成るパツク剤中で、実施例１と同様にパツク
処理を行つた。[Table] For each sample thus obtained, an oxidation resistance test was conducted as follows. The sample is kept in an atmospheric furnace maintained at 1000° C. for 45 minutes, then taken out of the furnace and allowed to cool naturally in air for 15 minutes. This was regarded as one cycle (60 minutes), and after repeating a predetermined cycle, the oxidation resistance of the film was evaluated based on the weight change before and after the test and the surface texture after the test. As shown in FIG. 1, when the amount of Mitsushi Metal added was varied from 0.1 to 16% by weight and the effect was confirmed, oxidation resistance improved in the range of 0.1 to 15% by weight. This is because rare earth elements suppress the falling off of oxide films such as Al 2 O 3 , SiO 2 , NiO, and CrO formed on the surface of the sample. FIG. 2 shows the results of examining the weight change due to oxidation of a sample treated with a pack agent containing 5% by weight of Mitsushimetal in comparison with a sample without pack treatment. As is clear from this figure,
When no pack treatment is applied, an oxide film is formed and the weight increases due to oxidation, but after 15 heating and cooling cycles, the weight gradually begins to decrease due to peeling of the oxide film. On the other hand, it can be seen that those treated with a pack agent containing Mitsushimetal continue to maintain the oxide film stably. Example 2 From stainless steel having the following composition, Example 1
Prepare a sample with the same dimensions as 93% by weight of alumina powder, 5% by weight of Mitsushi Metal, and 2% by weight of NH 4 Cl.
A pack treatment was carried out in the same manner as in Example 1 in a pack consisting of:
【表】
得られた試料を1100℃に保つた大気炉中に20時
間保持した後、室温で冷却した。この耐酸化性試
験の結果を次に示す。[Table] The obtained sample was kept in an atmospheric furnace kept at 1100°C for 20 hours, and then cooled to room temperature. The results of this oxidation resistance test are shown below.
【表】
SUS 310S、SUS 430ともミツシユメタルを含
むパツク剤でパツク処理することにより耐酸化性
が向上することがわかる。[Table] It can be seen that the oxidation resistance of both SUS 310S and SUS 430 is improved by treating them with a pack agent containing Mitsushi Metal.
第１図は、ミツシユメタル添加量と耐酸化性と
の関係を示すグラフであり、第２図は、本発明方
法によりパツク処理した金属物品の耐酸化性向上
効果を、パツク処理しないものと比較して示すグ
ラフである。
Figure 1 is a graph showing the relationship between the amount of Mitsushi metal added and oxidation resistance, and Figure 2 is a graph comparing the oxidation resistance improvement effect of metal articles treated with a pack according to the method of the present invention with those not treated with a pack. This is a graph showing
Claims (1)
一種を含む金属物品を、希土類元素を70重量％以
上含有する粉末を0.5〜15重量％と、ハロゲン化
物を２〜４重量％と、残部不活性担体粉末とを含
むパツク剤中に埋設し、非酸化性雰囲気中で加熱
し、希土類元素を金属物品表面に拡散させること
を特徴とする希土類元素拡散処理方法。1 A metal article containing at least one of aluminum, silicon, and chromium is mixed with 0.5 to 15% by weight of a powder containing 70% or more of rare earth elements, 2 to 4% by weight of a halide, and the remainder an inert carrier powder. 1. A rare earth element diffusion treatment method, which comprises embedding the rare earth element in a pack agent containing the metal article and heating it in a non-oxidizing atmosphere to diffuse the rare earth element onto the surface of the metal article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21115283A JPS60103175A (en) | 1983-11-10 | 1983-11-10 | Method for diffusing rare earth element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21115283A JPS60103175A (en) | 1983-11-10 | 1983-11-10 | Method for diffusing rare earth element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60103175A JPS60103175A (en) | 1985-06-07 |
| JPS624466B2 true JPS624466B2 (en) | 1987-01-30 |
Family
ID=16601241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21115283A Granted JPS60103175A (en) | 1983-11-10 | 1983-11-10 | Method for diffusing rare earth element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60103175A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01123773U (en) * | 1988-02-12 | 1989-08-23 | ||
| JPH03111364U (en) * | 1990-02-28 | 1991-11-14 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5118947B2 (en) * | 2006-11-21 | 2013-01-16 | 株式会社アキタファインブランキング | Nano surface modification method with enhanced high-temperature durability, metal member subjected to nano surface modification method, and exhaust guide assembly in VGS type turbocharger to which this member is applied |
| US20100170593A1 (en) * | 2007-01-15 | 2010-07-08 | Toshio Narita | Oxidation resistant alloy coating film, method of producing an oxidation resistant alloy coating film, and heat resistant metal member |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5120449A (en) * | 1974-08-12 | 1976-02-18 | Fujita Corp | Kozobutsuniokeru taishinkako |
| JPS5687661A (en) * | 1979-12-19 | 1981-07-16 | Hitachi Ltd | Metal article coating method |
-
1983
- 1983-11-10 JP JP21115283A patent/JPS60103175A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01123773U (en) * | 1988-02-12 | 1989-08-23 | ||
| JPH03111364U (en) * | 1990-02-28 | 1991-11-14 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60103175A (en) | 1985-06-07 |
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