JPH0261055A - Method for coating iron base material with metal - Google Patents
Method for coating iron base material with metalInfo
- Publication number
- JPH0261055A JPH0261055A JP21165388A JP21165388A JPH0261055A JP H0261055 A JPH0261055 A JP H0261055A JP 21165388 A JP21165388 A JP 21165388A JP 21165388 A JP21165388 A JP 21165388A JP H0261055 A JPH0261055 A JP H0261055A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- metal
- iron base
- coating
- powder
- 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.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 14
- 238000009792 diffusion process Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002002 slurry Substances 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- -1 e.g. Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、軟鋼などの鉄基材上へ、銅その他の一般的に
コーチインクか困難な金属をコーティングする方法に関
するものであり、さらに詳しくは、車両のエンジンやミ
ッション、軸受部等て面圧が高く耐摩耗性を必要とする
部品、タービンブレードのように高耐酸化性が要求され
る部品、または高導電性金属のコーティングにより電気
関連分野の部品に適用するのに好適な鉄基材上への金属
コーティング方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for coating copper and other metals that are generally difficult to coat onto ferrous substrates such as mild steel, and more specifically relates to is used for parts that are subject to high surface pressure and require wear resistance such as vehicle engines, transmissions, and bearings, parts that require high oxidation resistance such as turbine blades, or electrically related parts that are coated with highly conductive metal. The present invention relates to a method for coating metals on iron substrates suitable for application to parts in the field.
［従来の技術］
鉄基材上への金属コーティング方法としては、電気メツ
キ法、真空蒸着法、溶射、ＣＶＤまたはＰＶＤ、あるい
はスパッタリンクなどがある。[Prior Art] Methods for coating metals on iron substrates include electroplating, vacuum evaporation, thermal spraying, CVD or PVD, and sputter linking.
しかしながら、例えば、銅のような金属は、鉄基材の上
に直接コーチインクすることが困難てあり、たとえ電気
メツキ等によって被着できるとしても、両者の害着強度
か非常に弱く、また厚いコーティング層を得ることはで
きない、さらに、高真空状態でコーティングする蒸着、
スパッタリンク、ＣＶＤ、あるいはＰＶＤでは、皮膜そ
のものの性能は優れているが、大型部品へのコーチイン
クや、大量生産がてきないという問題がある。However, for example, it is difficult to coat metals such as copper directly onto the iron base material, and even if it can be coated by electroplating, the adhesion strength of both is very weak, and it is thick. Furthermore, the coating layer cannot be obtained by vapor deposition, which is coated in high vacuum conditions.
Sputterlink, CVD, or PVD have excellent film performance, but there are problems with coach ink for large parts and the inability to mass produce them.
また１局部的に微小領域へ金属をコーティングしようと
する場合、マスキングが必要となり、無駄な労力を必要
とする。Furthermore, when attempting to locally coat a minute area with metal, masking is required, which requires wasted effort.
このような問題は、金や銀等のコーチインクを行う場合
も同様である。これは、コーティングに際して両者の金
属間に拡散層が形成されないことに起因する。This problem also occurs when using gold, silver, or other coach inks. This is due to the fact that no diffusion layer is formed between the two metals during coating.
［発明か解決しようとする問題点］
本発明者は、このような鉄に対する密着強度か劣る金属
を、高真空状態ての処理を必要とすることなく、拡散層
を介して高い密着強度でコーチインクすべく、鋭意研究
を重ねた結果、助剤としてレーザー吸収性においてすぐ
れたＢＮを用い、その存在下において高出力レーザーの
照射によるコーチインクを行うと、特殊な拡散層の形成
により極めてすぐれた密着強度のコーテイング膜か得ら
れることを確かめ、本発明をなすに至ったものである。[Problem to be solved by the invention] The present inventor has developed a method for coating metals with poor adhesion strength to iron with high adhesion strength through a diffusion layer without requiring treatment in a high vacuum state. As a result of intensive research, we found that when BN, which has excellent laser absorption properties, is used as an auxiliary agent, and when coach ink is performed by irradiation with a high-power laser in the presence of BN, it is extremely effective due to the formation of a special diffusion layer. It was confirmed that a coating film with good adhesion strength could be obtained, and the present invention was completed.
従って、本発明の目的は、本来鉄基材の表面にコーティ
ングし難い金属を、簡単な手段ですぐれた密着強度をも
たせてコーチインク可能にすることにある。Therefore, an object of the present invention is to provide a coatable ink with a metal that is originally difficult to coat on the surface of an iron base material by providing excellent adhesion strength with a simple means.
［問題点を解決するための手段］
上記目的を達成するための本発明の方法は、鉄基材上に
、助剤としてのＢＮと、コーチインクすべき金属の粉末
とを塗着し、その表面に高出力レーザーを照射すること
により、鉄基材表面にＦｅ２Ｂを主体とするコーティン
グ金属の拡散層を形成させて上記金属のコーチインクを
行うことを特徴とするものである。[Means for Solving the Problems] The method of the present invention for achieving the above object is to apply BN as an auxiliary agent and powder of a metal to be coach inked onto an iron base material, This method is characterized in that a diffusion layer of a coating metal mainly composed of Fe2B is formed on the surface of an iron base material by irradiating the surface with a high-power laser, and the above-mentioned metal coach ink is performed.
本発明の金属コーティング方法をさらに具体的に説明す
ると、本発明の方法は、特に鉄基材に対してコーティン
グか困難な金属を対象とし、そのコーティングに際して
は、助剤としてレーザー吸収剤であるＢＮを用い、それ
に上記金属粉末を混合し、エチルアルコール等の揮発性
液体と共に混練して泥状にしたものを鉄基材上に塗着す
る。To explain the metal coating method of the present invention more specifically, the method of the present invention targets metals that are difficult to coat, especially on iron base materials, and in coating, BN, which is a laser absorber, is used as an auxiliary agent. The metal powder is mixed therewith and kneaded with a volatile liquid such as ethyl alcohol to form a slurry, which is applied onto an iron base material.
金属粉末に対するＢＮの混合比は、２５〜５０ ｖｏ１
％が望ましく、特に、 ３０ｖｏ１％程度か最も望まし
い。この混合比率か少なくても、また逆に多くても被膜
生成は阻害される。また、ＢＮの粒度は、光エネルギ吸
収性がよい３〜１０用のものか被膜の生成を助長する。The mixing ratio of BN to metal powder is 25 to 50 vol.
% is desirable, and in particular, about 30vo1% is most desirable. Even if this mixing ratio is low or high, film formation is inhibited. Moreover, the particle size of BN is 3 to 10, which has good light energy absorption properties, and promotes the formation of a film.
上記鉄基材上への金属粉末及び助剤の塗着は。Coating the metal powder and auxiliary agent onto the above-mentioned iron base material.
上述した泥状のものを適宜手段て塗布することにより行
うことがてき１例えば鉄基材をそのまま泥状液の中に浸
漬してもよい。また、最初に鉄基材表面に助剤であるＢ
Ｎをスプレーし、その上に金属粉末を重ね、さらにその
上にＢＮをスプレーその他の方法で被着するなどの方法
によることもできる。This can be done by applying the above-mentioned slurry by appropriate means. For example, the iron base material may be immersed as it is in the slurry. In addition, B, which is an auxiliary agent, is first applied to the surface of the iron base material.
It is also possible to use a method such as spraying N, layering metal powder thereon, and then depositing BN on top of it by spraying or other methods.
このようにして金属粉末及び助剤を塗着した鉄基材は、
電気炉等において乾燥させるが、前述した脱脂・洗浄が
不十分てあれば、ここで塗布膜の剥離か生起する。この
乾燥後に、鉄基材の塗布膜上に高出力レーザーを照射す
ると、瞬時に上記金属のコーテイング膜か形成される。The iron base material coated with metal powder and auxiliary agents in this way is
It is dried in an electric oven or the like, but if the degreasing and cleaning described above are insufficient, the coating film may peel off. After this drying, when a high-power laser is irradiated onto the coating film of the iron base material, a coating film of the above-mentioned metal is instantly formed.
その際、接合界面にａｇｍのＦｅ２Ｂを主体とするＣｕ
拡散層か形成され、それによって密着強度の高いコーチ
インク膜か形成される。At that time, Cu mainly composed of agm Fe2B is used at the bonding interface.
A diffusion layer is formed, thereby forming a coach ink film with high adhesion strength.
上記接合界面の拡散層を形成するＦｅ、Ｂは、それ自体
、比較的脆い材料であるが、拡散層か非常に薄いもので
あるため、表面的に脆さか生しるようなことはなく、む
しろすぐれた破断強度を示すため、コーチインク膜の密
着強度か非常に高くなって、１０ｋｇ／＋＋＋ｌ１２ま
たはそれ以上にも達し、簡単に剥離することがないばか
りてなく、その膜の被着面に機械加工を施すこともてき
る。The Fe and B that form the diffusion layer at the bonding interface are themselves relatively brittle materials, but since the diffusion layer is very thin, there is no appearance of brittleness on the surface. In fact, because it shows excellent breaking strength, the adhesion strength of the coach ink film is extremely high, reaching 10 kg/+++l12 or more, and not only does it not peel off easily, but it also adheres to the surface it adheres to. It can also be machined.
照射する高出力レーザーとしては、高出力エネルギか広
領域て取り出せる炭酸ガスレーザーか適し、それを広領
域に照射するには、多数の分割されたミラーによって所
要の位置に集光するインテグレーションミラーや、ポリ
ゴンミラーを使用し、鉄基材に適当な送りを与えるとか
、あるいは、レーザーによって鉄基材の表面をスキャニ
ングするなどの手段により、鉄基材における所要の表面
に照射する。また、局部的な微小望域に被膜を生成させ
る場合には、集光レンズを用いて集光することかでき、
適当なスポット光を用いて加工テーブルをＮＣ化するこ
とにより、直線状、曲線状、あるいはそれらを複合化し
た各種図形、模様状に金属をコーティングすることもで
きる。The suitable high-power laser to irradiate is either a high-power energy or a carbon dioxide laser that can be extracted over a wide area.In order to irradiate a wide area, an integration mirror that focuses the light on the desired position using many divided mirrors, Irradiation is applied to a desired surface of the iron base material by using a polygon mirror to give an appropriate feed to the iron base material, or by scanning the surface of the iron base material with a laser. In addition, when producing a film in a local minute viewing area, it is possible to condense the light using a condensing lens.
By NC processing the processing table using an appropriate spot light, metal can be coated in various shapes and patterns such as straight lines, curved lines, or a combination thereof.
高出力レーザーのパワーは、諸条件に対応して適切に設
定される。The power of the high-output laser is appropriately set according to various conditions.
第 １ 表
第１表に各金属のコーティングに用いるレーザー出力及
び鉄基材の送り速度の一例を示す。Table 1 Table 1 shows an example of the laser power used for coating each metal and the feed rate of the iron base material.
レーザー照射の後、鉄基材上に残留する未溶着粉末は、
必要に応じて、有機溶剤による洗浄、あるいは鉄基材に
振動を与えることにより除去する。After laser irradiation, the unwelded powder remaining on the iron base material is
If necessary, it is removed by cleaning with an organic solvent or by applying vibration to the iron base material.
上述したところにより得られるコーチインク膜は、コー
ティング条件の適切な設定により比較的厚くすることも
容易であり、また鉄基材の表面に塗着する際にＢＮの量
を多くすると、コーテイング膜の内部にＢＮが残留して
複合被膜を形成し、そのＢＮか潤滑性を有していて、固
体潤滑材として作用するのて、潤滑性複合被膜を形成す
ることかできる。この複合被膜を潤滑材料として使用す
るには、複合被膜中にＢＮが少なくとも２０ Ｖｏ１％
あることが望ましい。The coach ink film obtained as described above can be made relatively thick by appropriately setting the coating conditions, and if the amount of BN is increased when coating on the surface of the iron base material, the thickness of the coating film will be increased. BN remains inside to form a composite film, and since the BN has lubricating properties and acts as a solid lubricant, a lubricious composite film can be formed. To use this composite coating as a lubricating material, the composite coating must contain at least 20 Vo1% of BN.
It is desirable that there be.
このような潤滑性被膜を形成する場合において、ＢＮは
そのままでは熱を加えても分解しないか、溶融金属に触
れると分解する特性を有し、そのため比較的大量に添加
しないと内部に残留しない。また、ＢＮはＣｕ等に比し
て比重か小さく、金属か溶融したときにその表面に浮上
するためＢＮをコーチインク膜の内部に残留させる場合
には、この点も考慮して大量に添加する必要かある。When forming such a lubricating film, BN has the property that it does not decompose as it is even when heated or decomposes when it comes into contact with molten metal, so it will not remain inside unless it is added in a relatively large amount. In addition, BN has a lower specific gravity than Cu, etc., and floats to the surface of the metal when it melts, so if BN is to remain inside the coach ink film, it should be added in large quantities with this point in mind. Is it necessary?
［実施例］
高出力レーザーを利用し密着性のよいコーチインク膜を
作るのか極めて困難といわれている鉄基材上への銅のコ
ーティングについて実験を行った。[Example] An experiment was conducted on coating copper on an iron base material, which is said to be extremely difficult to create a coach ink film with good adhesion using a high-power laser.
実験方法には、 ６９ｘ １７ｘ １４ｍｍのＳＳ４１
材の試験片を用い、この試験片上にエチルアルコールに
分散した粒径約３０トｌの銅粉末を塗着した試料。The experimental method includes 69x 17x 14mm SS41
This is a sample in which a copper powder with a particle size of approximately 30 torr dispersed in ethyl alcohol is applied onto the test piece.
及び上記銅粉末と３０ｖｏ１％のＢＮの混合粉末をそれ
ぞれ塗着した試料を作成し、インテグレーションミラー
を使用してレーザーを照射した。照射面積は１２．５Ｘ
１２．５ｍ＋ｎ、レーザー出力は３〜５ｋｖｊ、試料
の送り速度は０．５〜１．５ｍ／ｍｉｎとした。Samples were prepared by applying the above-mentioned copper powder and a mixed powder of 30 vol 1% BN, respectively, and irradiated with a laser using an integration mirror. Irradiation area is 12.5X
12.5 m+n, laser output was 3 to 5 kvj, and sample feeding speed was 0.5 to 1.5 m/min.
実験の結果、 Ｃｕ粉末のみてのコーティングは、この
実験条件の範囲で実現できなかった。As a result of the experiment, coating using only Cu powder could not be realized within the range of the experimental conditions.
一方、 Ｃｕ−ＢＮ 混合粉末の場合については、４ｋ
Ｗのパワーて、試験片送り速度０．５ｍ／ｆｆ１ｉｎの
条件で行ったとき、最良のコーチインクか得られた。形
成されたＣｕ層の厚さは約１８０ｇｍである。また、Ｅ
Ｐ Ｍ Ａ （ｅｌｅｃｔｒｏｎ ｐｒｏｂｅ ｍ１
ｃｒｏ ａｎａｌｙｚｅｒ）分析の結果、Ｃｕ層表面に
ＢＮ濃度か高く、深さ方向に濃度は減少し、ｌ０ｇｍ以
上深いとＢＮは殆ど検出されなかった。第１図に、接合
界面をＥＰＭＡ線分析した結果を示しているか、約３ｇ
ｍのＦｅ、Ｂを主体とするＣｕ拡散層が形成されている
ことかわかった。On the other hand, in the case of Cu-BN mixed powder, 4k
The best coach ink was obtained when the test was conducted under the conditions of W power and a test piece feed rate of 0.5 m/ff1 inch. The thickness of the formed Cu layer is approximately 180 gm. Also, E
PMA (electron probe m1
As a result of the cro analyzer) analysis, the BN concentration was high on the surface of the Cu layer, and the concentration decreased in the depth direction, and almost no BN was detected at depths of 10 gm or more. Figure 1 shows the results of EPMA line analysis of the bonding interface, approximately 3g
It was found that a Cu diffusion layer mainly composed of Fe and B was formed.
［発明の効果コ
以上に詳述したように、本発明の金属コーチインク方法
によれば、今まで難しいと考えられていた鉄基材上への
Ｃｕ等のコーティングを容易に行うことかてき、しかも
比較的簡単な手段て短時間にすぐれた密着強度をもつコ
ーティング層を得ることができる。[Effects of the Invention] As detailed above, according to the metal coach ink method of the present invention, coating of Cu or the like on an iron base material, which has been thought to be difficult until now, can be easily performed. Moreover, a coating layer with excellent adhesion strength can be obtained in a short time using relatively simple means.
第１図は本発明の方法によるコーテイング膜の接合界面
をＥＰＭＡ線分析した結果を示す線図である。FIG. 1 is a diagram showing the results of EPMA line analysis of the bonding interface of the coating film according to the method of the present invention.
Claims (1)
塗着し、その表面に高出力レーザーを照射することによ
り、鉄基材表面にＦｅ＿２Ｂを主体とするコーティング
金属の拡散層を形成させて、上記金属のコーティングを
行うことを特徴とする鉄基材上への金属コーティング方
法。1. By applying BN and powder of the metal to be coated on the iron base material and irradiating the surface with a high-power laser, a diffusion layer of the coating metal mainly composed of Fe_2B is formed on the surface of the iron base material. A method for coating a metal on an iron base material, the method comprising: coating the metal as described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21165388A JPH0240737B2 (en) | 1988-08-26 | 1988-08-26 | TETSUKIZAIJOHENOKINZOKUKOOTEINGUHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21165388A JPH0240737B2 (en) | 1988-08-26 | 1988-08-26 | TETSUKIZAIJOHENOKINZOKUKOOTEINGUHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0261055A true JPH0261055A (en) | 1990-03-01 |
| JPH0240737B2 JPH0240737B2 (en) | 1990-09-13 |
Family
ID=16609359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21165388A Expired - Lifetime JPH0240737B2 (en) | 1988-08-26 | 1988-08-26 | TETSUKIZAIJOHENOKINZOKUKOOTEINGUHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0240737B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010185098A (en) * | 2009-02-10 | 2010-08-26 | Mitsubishi Electric Corp | Iron-based material and surface treatment method for iron-based material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3016362U (en) * | 1995-03-30 | 1995-10-03 | 船井電機株式会社 | Paper jam clearing mechanism in printer |
-
1988
- 1988-08-26 JP JP21165388A patent/JPH0240737B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010185098A (en) * | 2009-02-10 | 2010-08-26 | Mitsubishi Electric Corp | Iron-based material and surface treatment method for iron-based material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0240737B2 (en) | 1990-09-13 |
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