JP3354377B2 - Fabrication method of high corrosion resistance modified layer by laser spraying method - Google Patents
Fabrication method of high corrosion resistance modified layer by laser spraying methodInfo
- Publication number
- JP3354377B2 JP3354377B2 JP04715196A JP4715196A JP3354377B2 JP 3354377 B2 JP3354377 B2 JP 3354377B2 JP 04715196 A JP04715196 A JP 04715196A JP 4715196 A JP4715196 A JP 4715196A JP 3354377 B2 JP3354377 B2 JP 3354377B2
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- JP
- Japan
- Prior art keywords
- laser
- metal
- corrosion resistance
- metal substrate
- spraying
- 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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- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本内容は、レーザ溶射法を利
用し、金属表面、とくに鉄鋼の表面にクロム等を含む改
質層を形成し、材料の耐食性を著しく改善する方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a modified layer containing chromium or the like on a metal surface, particularly on a steel surface, by using a laser spraying method, thereby significantly improving the corrosion resistance of a material.
【０００２】[0002]
【従来の技術】鉄鋼材料表面の耐食性改善法としては、
耐食性の金属被膜を電気めっき、化学めっき等の方法に
よって形成するめっき法、めっきしたクロム等の表面に
レーザ照射し、金属基体と合金化する方法、金属粉末を
塗布した表画にレーザ照射し合金化する方法、金属粉末
をプラズマ溶射等の方法によって溶射して金属表面に溶
射層を形成する方法等が知られている。2. Description of the Related Art As a method for improving the corrosion resistance of the surface of a steel material,
Plating method for forming a corrosion-resistant metal film by electroplating, chemical plating, etc., laser irradiation on the surface of plated chromium, etc., and alloying with metal substrate, laser irradiation on metal powder coated surface And a method of spraying a metal powder by a method such as plasma spraying to form a sprayed layer on the metal surface.
【０００３】めっき法による耐食皮膜形成は簡便であり
古くから用いられている。しかしこの方法は厚膜の形成
には不向きであり、数十μｍ程度が限界である。また、
基体金属と金属被膜の間の密着性が小さく、また皮膜中
にピンホールが存在するため、基板金属を外界から完全
に遮断することは困難である。またクロムめっきの場
合、一般にクラックが生ずるため耐食性が不充分であっ
た。また、クロムめっきした鉄鋼材料にレーザ照射し、
基体の鉄鋼と合金化する方法は一般に改質層の厚さが５
０μｍ〜２５０μｍ程度と薄いため耐食性には限界があ
る。また、めっき工程、レーザ照射工程と２工程を要す
るという問題がある。 金属粉末をあらかじめ塗布して
レーザ照射する方法では粉末全体が溶融した後、基体金
属が溶融するために界面では合金層が形成されるが表面
は塗布した粉末と同一組成となり、基体金属との合金層
を厚さ方向の広い範囲に形成したり、均一組成の合金層
を形成することは困難である。また、その組成は局所的
にかなりのばらつきが見られ、さらに界面の合金層形成
が不十分であることが多いため、密着性に問題がある。[0003] The formation of a corrosion resistant film by plating is simple and has been used for a long time. However, this method is not suitable for forming a thick film, and its limit is about several tens μm. Also,
Since the adhesion between the base metal and the metal coating is low and the pinholes are present in the coating, it is difficult to completely block the substrate metal from the outside. In the case of chromium plating, cracks generally occur, and thus the corrosion resistance is insufficient. In addition, laser irradiation of chrome-plated steel material,
In general, the method of alloying with the base steel is such that the thickness of the modified layer is 5 mm.
Since it is as thin as about 0 μm to 250 μm, there is a limit in corrosion resistance. There is also a problem that two steps, a plating step and a laser irradiation step, are required. In the method in which the metal powder is applied in advance and the laser irradiation is performed, after the entire powder is melted, the base metal is melted and an alloy layer is formed at the interface, but the surface has the same composition as the applied powder, and the alloy with the base metal is formed. It is difficult to form a layer in a wide range in the thickness direction or to form an alloy layer having a uniform composition. Further, the composition has a considerable local variation, and the formation of an alloy layer at the interface is often insufficient, so that there is a problem in adhesion.
【０００４】また、プラズマ溶射のような溶射による方
法は、供給した金属粉末をプラズマ中で溶融し、基体上
に被膜を形成する方法であるが、基体金属との合金化は
一般に不可能である。そのため、密着性に問題がある。
しかも、クロム溶射膜の場合、必ずクラックを生じ、耐
食性を保持できないので、封孔処理を行ったり、あるい
はクロムめっきに先だってニッケルの下地めっきを行う
必要があった。また、減圧プラズマ溶射にレーザ照射を
併用したレーザ・プラズマハイブリッド溶射により、母
材上に高性能摺動面を被着する方法が「トライポロジー
会議予稿集 福岡１９９１−１０」 Ｐ１７５〜Ｐ１７
８（特開平６−２６５７８６号公報）に記載されている
が、プラズマ溶射によって形成した被膜を併用したレー
ザによって溶融させて気孔等を消滅させたものであり、
プラズマ溶射とレーザ溶射の２種の装置を用いることが
必要であった。[0004] A thermal spraying method such as plasma spraying is a method in which a supplied metal powder is melted in plasma to form a film on a substrate, but alloying with a substrate metal is generally impossible. . Therefore, there is a problem in adhesion.
Moreover, in the case of the chromium sprayed film, cracks always occur and the corrosion resistance cannot be maintained. Therefore, it is necessary to perform a sealing treatment or a nickel base plating prior to the chromium plating. In addition, a method of depositing a high-performance sliding surface on a base material by laser-plasma hybrid spraying using laser irradiation in combination with reduced-pressure plasma spraying is described in "Trilogy Conference Proceedings Fukuoka 1991-10-10" P175-P17
8 (Japanese Patent Application Laid-Open No. 6-265786), in which pores and the like are eliminated by melting with a laser combined with a film formed by plasma spraying.
It was necessary to use two types of devices, plasma spraying and laser spraying.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、金属材料、
特に鉄鋼材料の表面に耐食性に優れ、基体金属との密着
性が大きな金属被膜を形成する方法を提供することを課
題とするものであり、とくに基体の金属材料と合金化を
した密着性が大きな緻密な金属被膜を形成する方法を提
供することを課題とするものである。SUMMARY OF THE INVENTION The present invention relates to a metal material,
In particular, it is an object of the present invention to provide a method of forming a metal film having excellent corrosion resistance on a surface of a steel material and having high adhesion to a base metal. An object of the present invention is to provide a method for forming a dense metal film.
【０００６】[0006]
【課題を解決するための手段】本発明は、金属基体上に
高耐食性改質層を形成する方法において、金属基体上に
金属基体表面を溶融することが可能な出力のレーザを照
射しながら、レーザの焦点の近傍に金属基体上に被覆形
成材料の粉末を注ぎ、被覆形成材料の粉末を溶融して金
属基体上の溶融した金属層に溶射することによって基体
金属との合金層を形成する高耐食性改質層の形成方法で
ある。According to the present invention, there is provided a method for forming a highly corrosion-resistant modified layer on a metal substrate, the method comprising irradiating the metal substrate with a laser having an output capable of melting the surface of the metal substrate. Pouring the powder of the coating material on the metal substrate near the focal point of the laser, melting the powder of the coating material and spraying the molten metal layer on the metal substrate to form an alloy layer with the base metal. This is a method for forming a corrosion resistance modified layer.
【０００７】[0007]
【発明の実施の形態】本発明の方法は、レーザの焦点位
置と金属基体との距離を調整し、金属基体の表面に金属
基体の表面を溶融することが可能なレーザを照射しなが
ら、レーザの焦点の近傍に金属基体上に被覆を形成する
材料の粉末を供給し、レーザによって溶融した金属基体
表面に、被覆材料を溶射するものであり、金属基体表面
に被覆材料との合金からなる改質層を形成するものであ
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention adjusts the distance between the focal position of a laser and a metal substrate, and irradiates the surface of the metal substrate with a laser capable of melting the surface of the metal substrate. A powder of a material for forming a coating on a metal substrate is supplied near the focal point of the metal substrate, and the coating material is sprayed on the surface of the metal substrate melted by a laser. To form a porous layer.
【０００８】本発明を図面を参照して説明する。図１
は、本発明に用いるレーザ溶射装置を説明する図であ
る。真空室１に設けた試料を任意の方向に移動すること
ができる試料載置台２に金属基体３が載置されており、
炭酸ガスレーザ等によって発生させたレーザビーム４を
Ｚｎ−Ｓｅレンズからなる焦点調節レンズ５が設けられ
ており、Ｚｎ−Ｓｅ窓６を通じて真空室内に照射するよ
うに構成されている。金属基体と焦点との距離を試料載
置台の位置と焦点調節レンズによって調整し、金属基体
表面を溶融する条件に設定し、真空室内に保護ガス供給
口７からアルゴン等の保護ガスを供給しながらレーザビ
ームを金属基体に照射し、被覆材料粉末８をキャリアー
ガス９によってレーザビームの焦点位置１０の近傍に供
給すると被覆材料は瞬時に溶融し、レーザービームによ
って表面が溶融した金属基体上に溶射する。金属基体の
表面と溶射する金属が共に溶融状態であるので、広範な
成分範囲の合金が得られる。また、試料載置装置を移動
しながら、溶射することによって金属基体の所望の部分
に被膜を形成することができる。The present invention will be described with reference to the drawings. FIG.
FIG. 2 is a diagram illustrating a laser spraying apparatus used in the present invention. A metal base 3 is mounted on a sample mounting table 2 that can move a sample provided in a vacuum chamber 1 in an arbitrary direction.
A focus adjusting lens 5 made of a Zn-Se lens is provided to irradiate a laser beam 4 generated by a carbon dioxide laser or the like through a Zn-Se window 6 into a vacuum chamber. The distance between the metal substrate and the focal point is adjusted by the position of the sample mounting table and the focus adjusting lens, the conditions for melting the surface of the metal substrate are set, and a protective gas such as argon is supplied from the protective gas supply port 7 into the vacuum chamber. When the laser beam is applied to the metal substrate and the coating material powder 8 is supplied to the vicinity of the focal position 10 of the laser beam by the carrier gas 9, the coating material is instantaneously melted and sprayed onto the metal substrate whose surface is melted by the laser beam. . Since both the surface of the metal substrate and the metal to be sprayed are in a molten state, an alloy having a wide component range can be obtained. In addition, a coating can be formed on a desired portion of the metal substrate by performing thermal spraying while moving the sample mounting device.
【０００９】本発明には、各種の金属基体を用いること
ができるが、軟鋼、ステンレス等を用いることが好まし
い。また、金属基体上に形成する被膜材料には、クロ
ム、モリブデン、タングステン、ニッケル、コバルト、
ケイ素等の金属を単独、もしくはそれらの合金を用いる
ことができ、鉄鋼とニッケル、クロム、モリブデン等と
の金属との合金化の結果、ステンレスと同様の合金の被
膜が得られる。また、鉄鋼材料にタングステンの被膜を
形成した場合には、Ｆｅ2Ｗ 等の超硬質合金の被膜を形
成することができ、ステンレスの表面にケイ素の被膜を
形成するとステンレス基材の耐酸性を向上することがで
きる。Although various metal substrates can be used in the present invention, it is preferable to use mild steel, stainless steel or the like. The coating materials formed on the metal substrate include chromium, molybdenum, tungsten, nickel, cobalt,
A metal such as silicon alone or an alloy thereof can be used. As a result of alloying iron and steel with a metal such as nickel, chromium, and molybdenum, a film of an alloy similar to stainless steel can be obtained. In addition, when a tungsten film is formed on a steel material, a super-hard alloy film such as Fe 2 W can be formed. When a silicon film is formed on a stainless steel surface, the acid resistance of the stainless steel substrate is improved. can do.
【００１０】被膜材料として用いる粉末の粒子の形状
は、供給する際に流れやすい球形もしくは楕円形状のも
のが好ましい。また、粒子の大きさは０．５μｍ以上と
することが好ましい。粒子の大きさがあまりに小さくな
ると凝集が起こり取り扱いが困難となる。本発明の方法
では、基体金属と被膜形成材料から形成される合金は、
一定の組成のものとすることも、焦点位置と金属基体と
の距離の調整によって組成を変化させることも可能であ
る。また、金属基体上に形成する被覆の厚さは、任意の
厚さのものを形成することができるが、とくに１ｍｍ以
上の膜厚の大きな被膜を容易に形成することができる。[0010] The shape of the particles of the powder used as the coating material is preferably spherical or elliptical, which easily flows when supplied. The size of the particles is preferably 0.5 μm or more. If the particle size is too small, agglomeration occurs and handling becomes difficult. In the method of the present invention, the alloy formed from the base metal and the film forming material is:
The composition can be constant, or the composition can be changed by adjusting the distance between the focal position and the metal substrate. The thickness of the coating formed on the metal substrate can be any thickness, but a coating having a thickness of 1 mm or more can be easily formed.
【００１１】本発明に用いるレーザは、炭酸ガスレー
ザ、ＹＡＧレーザ等の比較的大きな出力を得られるもの
であれば任意のものを用いることができ、レーザの焦点
位置と金属基体との距離は、レーザの出力、金属基体の
種類、形成すべき被膜の厚み等の条件によって適宜調整
することができる。本発明の方法によって金属基体上に
形成された被膜は、基体の金属と完全に一体化してお
り、強固な密着性を有するとともに合金化によって優れ
た耐食性を有するものが得られる。As the laser used in the present invention, any laser can be used as long as it can obtain a relatively large output, such as a carbon dioxide gas laser or a YAG laser. Can be appropriately adjusted depending on conditions such as the output of the metal substrate, the type of metal substrate, and the thickness of the film to be formed. The coating formed on the metal substrate by the method of the present invention is completely integrated with the metal of the substrate, has strong adhesion, and has excellent corrosion resistance due to alloying.
【００１２】[0012]
【実施例】以下に本発明の実施例を示し、本発明をさら
に詳細に説明する。 実施例１ 真空室内に１７×１５×７０ｍｍの大きさの軟鋼を金属
基体とし、真空室内を溶射操作の前に４Ｐａまで排気
し、保護気体として窒素を５ｄｍ3／分 の流量で供給
し、２ｋＷの炭酸ガスレーザを用い、焦点位置と基板と
の距離を５〜２５ｍｍに変化させながら溶射中の真空室
内は、２×１０3Ｐａ の圧力として、平均直径１０μｍ
のクロム粉末を、２ｄｍ3／分 の流量の窒素をキャリア
ー気体として４ｇ／分の速度でレーザの焦点位置に供給
し、金属基体を５５ｍｍ／秒で移動させながらレーザ溶
射を行い厚さ０．５ないし１ｍｍの被膜を有する４個の
試料を作製した。試料の作製条件を表１に示す。The present invention will be described in more detail with reference to the following examples. Example 1 A mild steel having a size of 17 × 15 × 70 mm was used as a metal base in a vacuum chamber, and the vacuum chamber was evacuated to 4 Pa before the spraying operation. Nitrogen was supplied as a protective gas at a flow rate of 5 dm 3 / min. The vacuum chamber during thermal spraying was set to a pressure of 2 × 10 3 Pa and the average diameter was 10 μm while changing the distance between the focal position and the substrate to 5 to 25 mm using a carbon dioxide gas laser.
Chromium powder is supplied as a carrier gas with nitrogen at a flow rate of 2 dm 3 / min to the focal position of the laser at a rate of 4 g / min, and laser-sprayed while moving the metal substrate at 55 mm / sec to a thickness of 0.5 mm. Four samples with coatings of な い し 1 mm were made. Table 1 shows the conditions for preparing the sample.
【００１３】[0013]
【表１】 [Table 1]
【００１４】次いで、各試料について、銅ターゲットＸ
線管と回折ビームモノクロメーターを備えたＸ線回折装
置（日本電子製 ＪＴＸ３５３０）を用いて、Ｘ線回折
角を測定し、軟鋼についてのデータと共にその結果を図
２に示す。金属基体と焦点位置との距離によって生成す
る合金の組成が変化していることを示しており、試料４
では金属基体との合金化が進んでおらず、クロムから形
成された層が生成していることを示している。また、エ
ネルギー分散型Ｘ線分析装置（エリオニクス製 ＥＲＡ
−８０００ＥＤＳ）によって、試料１および試料２につ
いて、厚さ方向のクロムの分布を測定し、その結果を金
属基体からの表面からの距離に対するクロムの存在量を
図３に示す。生成条件の違いによって、被膜の組成を均
一にすること、あるいは組成を連続的に変化させること
が可能であることを示している。 軟鋼、試料１および
試料２を、２５℃１規定硫酸中に、３０分間浸漬処理の
後、飽和甘汞電極を参照電極として、−１．０Ｖの電位
に５分間、陰分極した後に、３０分間の浸漬処理をし、
次いで腐食電流を測定し、その結果を図４に示す。軟鋼
は、０．８Ｖと１．６Ｖの間で不働態化したが、試料１
および試料２は、−０．３Ｖと１．０Ｖの間で不働態化
した。試料１および試料２の不働態領域での電流密度
は、軟鋼に比べて５０〜１００分の１であった。この値
は、Ｆｅ−２５Ｃｒの１規定硫酸中の値と同様であり、
軟鋼上の被膜は大きな耐食性を示していた。Next, for each sample, a copper target X
The X-ray diffraction angle was measured using an X-ray diffractometer (JTX3530 manufactured by JEOL Ltd.) equipped with a ray tube and a diffraction beam monochromator, and the results are shown in FIG. 2 together with data on mild steel. Sample 4 shows that the composition of the alloy formed varies depending on the distance between the metal substrate and the focal position.
Shows that alloying with the metal substrate has not progressed, and that a layer formed from chromium has been formed. In addition, an energy dispersive X-ray analyzer (ERA manufactured by Elionix)
-8000 EDS), the distribution of chromium in the thickness direction was measured for Sample 1 and Sample 2, and the results are shown in FIG. 3 for the chromium abundance with respect to the distance from the metal substrate to the surface. This shows that it is possible to make the composition of the coating uniform or to continuously change the composition by changing the formation conditions. The mild steel, sample 1 and sample 2 were immersed in 25 ° C. 1N sulfuric acid for 30 minutes, and then negatively polarized at a potential of −1.0 V for 5 minutes using a saturated calomel electrode as a reference electrode, followed by 30 minutes. Immersion treatment,
Next, the corrosion current was measured, and the results are shown in FIG. Mild steel was passivated between 0.8 V and 1.6 V, but sample 1
And sample 2 was passivated between -0.3V and 1.0V. The current density in the passive region of Sample 1 and Sample 2 was 50 to 100 times lower than that of mild steel. This value is similar to the value in 1N sulfuric acid of Fe-25Cr,
The coating on mild steel showed great corrosion resistance.
【００１５】[0015]
【発明の効果】本発明の方法は、レーザ溶射のみによ
り、軟鋼表面にクロムをはじめとする金属が軟鋼と合金
化した、密着性が大きな厚みの厚い緻密な被膜を形成す
ることができるので、従来のクロム溶射膜、ステンレス
めっき等を行った軟鋼の耐食性の問題点を解決すること
が可能となった。According to the method of the present invention, it is possible to form a thick and dense coating film having a large adhesion and a large thickness on the surface of mild steel by alloying chromium and other metals with mild steel only by laser spraying. It has become possible to solve the problem of corrosion resistance of mild steel which has been subjected to conventional chromium spray coating, stainless plating, and the like.
【図１】本発明のレーザ溶射装置の一例を説明する図で
ある。FIG. 1 is a diagram illustrating an example of a laser spraying apparatus according to the present invention.
【図２】本発明の実施例で得られた試料と軟鋼のＸ線回
折を説明する図である。FIG. 2 is a diagram illustrating X-ray diffraction of a sample and mild steel obtained in an example of the present invention.
【図３】本発明の実施例で得られた厚さ方向のクロムの
分布を説明する図である。FIG. 3 is a diagram illustrating a distribution of chromium in a thickness direction obtained in an example of the present invention.
【図４】本発明の実施例で得られた試料と軟鋼の腐食電
流を説明する図である。FIG. 4 is a diagram illustrating the corrosion current of a sample and mild steel obtained in an example of the present invention.
１…真空室、２…試料載置台、３…金属基体、４…レー
ザビーム、５…焦点調節レンズ、６…Ｚｎ−Ｓｅ窓、７
…保護ガス供給口、８…被覆材料粉末、９…キャリアー
ガス、１０…焦点位置DESCRIPTION OF SYMBOLS 1 ... Vacuum chamber, 2 ... Sample mounting table, 3 ... Metal substrate, 4 ... Laser beam, 5 ... Focusing lens, 6 ... Zn-Se window, 7
... Protective gas supply port, 8 ... Coating material powder, 9 ... Carrier gas, 10 ... Focal position
Claims (2)
製する方法において、金属基体上に金属基体表面を溶融
することが可能な出力のレーザを照射しながら、レーザ
の焦点位置の近傍に被覆形成材料の粉末を注ぎ、レーザ
によって被覆形成材料の粉末を溶融して金属基体上の溶
融金属層に溶射することによって基体金属との合金層を
形成することを特徴とするレーザ溶射法による高耐食性
改質層の作製方法。In a method for producing a high corrosion resistance modified layer by a laser spraying method, a laser is applied to a metal substrate in the vicinity of a focal position of the laser while irradiating the laser with an output capable of melting the surface of the metal substrate. High corrosion resistance by laser spraying, characterized by forming an alloy layer with the base metal by pouring the powder of the forming material and melting the powder of the coating forming material with a laser and spraying it on the molten metal layer on the metal base Method for forming a modified layer.
クロム、モリブデン、ニッケル、コバルト、タングステ
ン、ケイ素の少なくとも１種を含むことを特徴とする請
求項１記載のレーザ溶射法による高耐食性改質層の作製
方法。2. The high corrosion resistance improvement by a laser spraying method according to claim 1, wherein the metal substrate is mild steel, and the film forming material contains at least one of chromium, molybdenum, nickel, cobalt, tungsten and silicon. Method of forming a porous layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04715196A JP3354377B2 (en) | 1996-03-05 | 1996-03-05 | Fabrication method of high corrosion resistance modified layer by laser spraying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04715196A JP3354377B2 (en) | 1996-03-05 | 1996-03-05 | Fabrication method of high corrosion resistance modified layer by laser spraying method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09241863A JPH09241863A (en) | 1997-09-16 |
| JP3354377B2 true JP3354377B2 (en) | 2002-12-09 |
Family
ID=12767103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04715196A Expired - Fee Related JP3354377B2 (en) | 1996-03-05 | 1996-03-05 | Fabrication method of high corrosion resistance modified layer by laser spraying method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3354377B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE518807C2 (en) * | 1999-11-09 | 2002-11-26 | Koncentra Verkst S Ab | Method and apparatus for coating a piston ring blank with a layer and piston ring provided with a heated coating layer |
| DE10154093B4 (en) * | 2001-11-02 | 2006-02-02 | Daimlerchrysler Ag | Process for surface treatment by a powder material using a laser beam and apparatus for carrying out the method |
| KR100931664B1 (en) * | 2007-12-21 | 2009-12-14 | 주식회사 포스코 | Abrasion resistant scale brake work roll |
| EP2534702A1 (en) * | 2010-02-10 | 2012-12-19 | Tata Steel Nederland Technology BV | Layered system for producing a solar cell on a metal substrate, method for producing said layered system |
| DE102011000984A1 (en) * | 2011-03-01 | 2012-09-06 | Rasselstein Gmbh | Process for refining a metallic coating on a steel strip |
| KR101535117B1 (en) * | 2013-10-28 | 2015-07-08 | 주식회사 포스코 | Method for forming cladding on sink roll shaft in hot dip galvanizing pot |
| CN103691949B (en) * | 2014-01-09 | 2015-08-19 | 湖北工业大学 | A kind of laser forming method of WC-metallic composite structural member |
| CN112226722B (en) * | 2020-10-15 | 2021-11-12 | 西安特种设备检验检测院 | Laser alloying surface strengthening treatment method for pipeline steel |
-
1996
- 1996-03-05 JP JP04715196A patent/JP3354377B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09241863A (en) | 1997-09-16 |
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