JPH02138483A - Surface coating method - Google Patents
Surface coating methodInfo
- Publication number
- JPH02138483A JPH02138483A JP28961088A JP28961088A JPH02138483A JP H02138483 A JPH02138483 A JP H02138483A JP 28961088 A JP28961088 A JP 28961088A JP 28961088 A JP28961088 A JP 28961088A JP H02138483 A JPH02138483 A JP H02138483A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- film
- liquid phase
- temp
- layer
- 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.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 239000010410 layer Substances 0.000 claims abstract description 21
- 239000007791 liquid phase Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 9
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 31
- 238000005260 corrosion Methods 0.000 abstract description 31
- 230000007547 defect Effects 0.000 abstract description 17
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000011282 treatment 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］
本発明は被コーティング材の表面に緻密で、欠陥の無い
耐蝕性被膜を形成する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for forming a dense, defect-free, corrosion-resistant coating on the surface of a material to be coated.
材料の表面特性を改質する表面処理技術は古くから種々
の方法が知られていて、メツキ、はうろう、溶射等の表
面化成処理、或いは表面層のみを硬化する浸炭、窒化等
の表面硬化処理等が行なわれており、最近ではイオンブ
レーティング等の物理的蒸着法ＣＰＶＤ法）やイオン注
入法等も行なわれている。Various surface treatment techniques have been known for a long time to modify the surface properties of materials, including surface chemical conversion treatments such as plating, coating, and thermal spraying, and surface hardening methods such as carburizing and nitriding that harden only the surface layer. Recently, physical vapor deposition methods such as ion blating (CPVD method) and ion implantation methods have also been used.
而してこの様な表面改質が材料の耐蝕性向上を目的とす
る場合、特に素材の耐蝕性が余り良好でなく、且つ腐食
性の雰囲気や溶液中で使用される場合には、表面改質層
にピンホールや亀裂等の微細な欠陥が存在すると、これ
らの欠陥から腐食が進行して大事に到る場合があるので
、前記表面改質層は欠陥が皆無である様にする事が必要
である。Therefore, when the purpose of such surface modification is to improve the corrosion resistance of a material, especially when the material has poor corrosion resistance and is used in a corrosive atmosphere or solution, surface modification is necessary. If there are minute defects such as pinholes or cracks in the surface-modified layer, corrosion may progress from these defects and cause serious damage, so it is important to ensure that the surface-modified layer is completely free of defects. is necessary.
従来表面改質層に欠陥が無い様にする為には、素材表面
に耐蝕性下地メツキを施してから、目的とする改質層を
設ける方法、溶射等で比較的厚い被膜を設け、素材から
被膜表面迄貫通している欠陥を確率的に少なくする方法
、被膜表面にレーザーを照射して表面付近を局部的に溶
融し、欠陥を埋める方法等がとられていた。Conventionally, in order to ensure that there are no defects in the surface modified layer, there are methods such as applying a corrosion-resistant base plating to the material surface and then applying the desired modified layer, or applying a relatively thick coating by thermal spraying, etc. Methods have been used to stochastically reduce the number of defects penetrating to the surface of the coating, and methods of irradiating the coating surface with a laser to locally melt the vicinity of the surface to fill in the defects.
然しなから、前記耐蝕性下地メツキを施す方法において
は、メツキ自体にもピンホール等の欠陥が含まれており
、要求に合う下地メツキを施す事が出来る素材金属も限
られたものであった２□又溶射の様な厚肉被覆は最終の
製品表面として不都合である場合が多く、しかも被膜自
体に欠陥が含まれている為絶対の信顛性はないものであ
った。However, in the method of applying the corrosion-resistant base plating, the plating itself contains defects such as pinholes, and there are only a limited number of metal materials that can be used to apply the base plating that meets the requirements. 2□Also, thick coatings such as thermal spray coatings are often inconvenient for the final product surface, and furthermore, the coating itself contains defects, so it is not absolutely reliable.
更に被膜表面にレーザーを照射する方法においては、表
面付近の欠陥を埋める事は可能であるが、コスト高であ
り、処理能力も低いという問題があった。Furthermore, in the method of irradiating the surface of the coating with a laser, it is possible to fill in defects near the surface, but there are problems in that the cost is high and the processing capacity is low.
本発明は上記の点に鑑み鋭意検討の結果なされたもので
あり、その目的とするところは、被コーティング材の表
面に緻密で、欠陥の無い耐蝕性被膜を形成する比較的筒
車で且つ効率の良い方法を提供する事である。The present invention has been made as a result of intensive studies in view of the above points, and its purpose is to form a corrosion-resistant coating on the surface of a material to be coated with a dense and defect-free coating in a relatively simple and efficient manner. The goal is to provide a good method for
本発明者等は、被コーティング材の表面に目的とする耐
蝕性被膜を形成し、更にその上に前記被コーティング材
や耐蝕性被膜よりも低温で液相を生成づる被膜を形成し
た後、この様にして得られた多層膜体を低温で熱処理し
、生成した液相、或いは生成した液相と耐蝕性被膜との
反応生成物によって当該耐蝕性被膜の欠陥部を埋める事
によって、緻密で、欠陥の無い耐蝕性被膜が得られる事
を見出して、本発明の完成に到ったものである。The present inventors formed a desired corrosion-resistant coating on the surface of a material to be coated, and further formed a coating that generates a liquid phase at a lower temperature than the material to be coated or the corrosion-resistant coating. The multilayer film obtained in the above manner is heat-treated at a low temperature, and the defects in the corrosion-resistant coating are filled with the generated liquid phase or a reaction product between the generated liquid phase and the corrosion-resistant coating, thereby creating a dense, The present invention was completed by discovering that a corrosion-resistant coating without defects can be obtained.
即ち本発明における請求項１の発明は、物理蒸着法（Ｐ
ＶＤ法）により被コーティング材表面に直接或いは下地
被覆層を介して、目的とする被膜を被覆した後、その表
面に直接或いは必要に応じて所定の被覆層を介して目的
とする被膜よりも低温で液相を生成する被膜（低融点層
）を被覆し、これを前記低融点層の液相生成温度（固相
線温度）以上で、被コーティング材及び目的とする被膜
の固相線温度未満の温度で熱処理する事を特徴とする表
面被覆方法である。又請求項２の発明は、被膜を熱処理
する際に同時に加圧する事を特徴とする請求項１記載の
表面被覆方法である。又請求項３の発明は、被膜を熱処
理後ＣＩＰで加圧し、再度熱処理を行なう事を特徴とす
る請求項１記載の表面被覆方法である。That is, the invention of claim 1 of the present invention is based on the physical vapor deposition method (P
After coating the target coating directly on the surface of the material to be coated (VD method) or through a base coating layer, apply the coating directly to the surface or, if necessary, through a predetermined coating layer at a lower temperature than the target coating. A coating that generates a liquid phase (low melting point layer) is coated with a coating that generates a liquid phase (low melting point layer), and this is heated at a temperature higher than the liquid phase generation temperature (solidus temperature) of the low melting point layer and lower than the solidus temperature of the material to be coated and the target coating. This is a surface coating method characterized by heat treatment at a temperature of . A second aspect of the invention is the surface coating method according to the first aspect, characterized in that pressure is applied at the same time as the coating is heat treated. A third aspect of the invention is the surface coating method according to the first aspect, characterized in that after the heat treatment, the coating is pressurized by CIP and then heat treated again.
本発明方法においては、被コーティング材表面に目的と
する耐蝕性被膜及び低融点層の被膜を被覆し、これを所
定温度で熱処理する際に、被コーティング材と耐蝕性被
膜との間で熱拡散が起こるのを防止する為、必要に応じ
て両者間に下地被覆層を介在させる事が望ましい。又目
的とする耐蝕性被膜と低融点層との間に、前記熱処理に
よって生成した液相の耐蝕性被膜への浸透、或いは生成
した液相と耐蝕性被膜との反応を促進する所定の被覆層
を必要に応じて介在させる事が望ましい。In the method of the present invention, when the surface of the material to be coated is coated with the intended corrosion-resistant film and the film of the low-melting point layer, and when this is heat-treated at a predetermined temperature, thermal diffusion occurs between the material to be coated and the corrosion-resistant film. In order to prevent this from occurring, it is desirable to interpose a base coating layer between the two as necessary. Further, a predetermined coating layer is provided between the desired corrosion-resistant coating and the low melting point layer to promote the penetration of the liquid phase generated by the heat treatment into the corrosion-resistant coating or the reaction between the generated liquid phase and the corrosion-resistant coating. It is desirable to intervene as necessary.
更に本発明方法においては、前記被膜の熱処理時に、同
時に加圧する事が望ましく、この様にする事によって目
的とする耐蝕性被膜中に存在するピンホールや亀裂等の
微細な欠陥を機械的に押しつぶすと共に、生成した液相
のこれら欠陥中への浸透を促進する事が可能である。Furthermore, in the method of the present invention, it is desirable to apply pressure at the same time as the heat treatment of the coating, and by doing so, minute defects such as pinholes and cracks existing in the target corrosion-resistant coating are mechanically crushed. At the same time, it is possible to promote the penetration of the generated liquid phase into these defects.
或いは被膜の熱処理と加圧を同時に行なわないで、当該
被膜を熱処理後ＣＩ Ｐで加圧し、その後再度熱処理を
行なっても良く、この様に冷間で加圧する事によっても
目的とする被膜中に存在する欠陥を機械的に押しつぶす
事が可能である。Alternatively, instead of heat-treating and pressurizing the film at the same time, the film may be heat-treated and then pressurized using CI P, and then heat-treated again. It is possible to mechanically crush existing defects.
本発明方法においては、被コーティング材の表面に目的
とする耐蝕性被膜を形成し、さらにそのを上に前記被コ
ーティング材や耐蝕性被膜よりも低温で液相を生成する
被膜を形成した後、この様にして得られた多層膜体を低
温で熱処理しているので、生成した液相、或いは生成し
た液相と耐蝕性被膜との反応生成物によって当該耐蝕性
被膜の欠陥部が埋められ、緻密で、欠陥の無い耐蝕性被
膜が得られる。In the method of the present invention, a desired corrosion-resistant coating is formed on the surface of the material to be coated, and a coating that generates a liquid phase at a lower temperature than the material to be coated or the corrosion-resistant coating is formed on top of the coating, and then, Since the multilayer film obtained in this manner is heat-treated at a low temperature, defects in the corrosion-resistant coating are filled with the generated liquid phase or a reaction product between the generated liquid phase and the corrosion-resistant coating. A dense, defect-free, corrosion-resistant coating can be obtained.
〔実施例１〕
次に本発明を実施例により更に具体的に説明するー
被コーティング材として厚さ１ｍｍ、３０ｍｍ角（正方
形）の鏡面に研磨したＦｅ仮を用い、この表面に高周波
マグネトロンスパッタにより、目的とする耐蝕性被膜と
して厚さ３μｍのＮｂ被膜を形成した。更にこの上に厚
さ１μｍのＣｕ被膜を介して、低融点層として厚さ２μ
ｍのＳｎ被膜をスパッタリングした。[Example 1] Next, the present invention will be explained in more detail with reference to an example. As the material to be coated, a mirror-polished Fe temporary of 1 mm thickness and 30 mm square (square) was used, and this surface was coated with high-frequency magnetron sputtering. A Nb coating with a thickness of 3 μm was formed as the intended corrosion-resistant coating. Furthermore, a 2 μm thick low melting point layer is placed on top of this via a 1 μm thick Cu film.
A Sn film of m was sputtered.
この様にして得られたサンプルを、真空中で６５０°Ｃ
Ｘ４ ｈ ｒ熱処理したところ、表面はブロンズ色を呈
しており、断面をＸ線マイクロアナライザーで観察した
ところ、Ｎｂ層の上にＮｂ−Ｓｎ化合物層が形成され、
最外層はＳ ｎ −Ｃｕ合金層となっていた。The sample thus obtained was heated to 650°C in vacuum.
After X4 hr heat treatment, the surface had a bronze color, and when the cross section was observed with an X-ray microanalyzer, an Nb-Sn compound layer was formed on the Nb layer.
The outermost layer was a Sn-Cu alloy layer.
この試料のコーティング面以外をエポキシ系樹脂接着剤
でマスキングし、室温の塩酸に浸漬したところ、表面Ｓ
ｎ層は溶解するものの、表面分析では鉄分は検出されず
、下地は完全に保護されていた。即ち熱処理により生成
した液相や、生成した液相とＮｂ被膜との反応生成物（
Ｎｂ−Ｓｎ化合物層）によってＮｂ被膜中のピンホール
等の欠陥が埋められ、被コーティング材から被膜表面に
到る貫通孔が皆無になったものと考えられる。When this sample was masked with an epoxy resin adhesive and immersed in hydrochloric acid at room temperature, the surface S
Although the n-layer dissolved, no iron was detected in surface analysis, and the underlying layer was completely protected. That is, the liquid phase generated by heat treatment and the reaction product between the generated liquid phase and the Nb coating (
It is considered that defects such as pinholes in the Nb film were filled by the Nb-Sn compound layer, and that there were no through holes from the material to be coated to the surface of the film.
〔比較例１〕
実施例１と同様なＦ ｅ板上に、実施例１と同様な方法
で厚さ３μｍのＮｂ被膜を形成した。しかる後実施例１
と同様な塩Ｍ浸漬試験を行なったところ、直ちにＮｂ被
膜面に浸食箇所が発生した。[Comparative Example 1] A 3 μm thick Nb film was formed on the same Fe plate as in Example 1 in the same manner as in Example 1. After that, Example 1
When a salt M immersion test similar to the above was conducted, corrosion spots were immediately generated on the Nb coating surface.
〔実施例２〕
実施例１と同様なＦｅ板上に、高周波マグネトロンスパ
ッタにより、Ｎ ｂ ｙ Ｓ ｎターゲットを用いて厚
さ５μｍのＮｂ、Ｓｎｌ膜を形成し、この上に厚さ２μ
ｍのＳｎ被膜をスパッタリングした。[Example 2] On the same Fe plate as in Example 1, a 5 μm thick Nb, Snl film was formed using a N by S n target by high frequency magnetron sputtering, and a 2 μm thick Nb and Snl film was formed on this.
A Sn film of m was sputtered.
この様にして得られたサンプルを、真空中で６００℃Ｘ
５ｈｒ熱処理した後、実施例１と同様な塩酸浸漬試験を
行なったところ、表面Ｓｎ層は溶解するものの、表面分
析では鉄分は検出されず、下地は完全に保護されていた
。The sample obtained in this way was heated to 600°C in a vacuum.
After heat treatment for 5 hours, a hydrochloric acid immersion test similar to that in Example 1 was conducted, and although the surface Sn layer was dissolved, no iron was detected in surface analysis, and the base was completely protected.
〔比較例２〕
実施例１と同様なＦｅ板上に、実施例２と同様な方法で
厚さ５μｍのＮｂｔＳｎ被膜を形成した。[Comparative Example 2] On the same Fe plate as in Example 1, a 5 μm thick NbtSn coating was formed in the same manner as in Example 2.
しかる後実施例１と同様な塩酸浸漬試験を行なったとこ
ろ、直ちにＮ ｂ ｓ Ｓ ｎ被膜面に浸食箇所が発生
した。Thereafter, when a hydrochloric acid immersion test similar to that in Example 1 was conducted, erosion spots were immediately generated on the N b s S n coating surface.
本発明方法によれば、被コーティング材の表面に緻密で
、欠陥の無い耐蝕性被膜を比較的簡単に、且つ効率良く
形成する事が出来、工業上顕著な効果を奏するものであ
る。According to the method of the present invention, a dense, defect-free corrosion-resistant coating can be formed relatively easily and efficiently on the surface of a material to be coated, and it has a significant industrial effect.
特許出願人 古河電気工業株式会社Patent applicant: Furukawa Electric Co., Ltd.
Claims (3)
表面に直接或いは下地被覆層を介して、目的とする被膜
を被覆した後、その表面に直接或いは必要に応じて所定
の被覆層を介して目的とする被膜よりも低温で液相を生
成する被膜（低融点層）を被覆し、これを前記低融点層
の液相生成温度（固相線温度）以上で、被コーティング
材及び目的とする被膜の固相線温度未満の温度で熱処理
する事を特徴とする表面被覆方法。(1) After coating the target coating directly on the surface of the material to be coated using the physical vapor deposition method (PVD method) or via a base coating layer, apply the desired coating directly to the surface or via a predetermined coating layer as necessary. Coat a film (low melting point layer) that generates a liquid phase at a lower temperature than the target film, and use this as the material to be coated and the target at a temperature higher than the liquid phase formation temperature (solidus temperature) of the low melting point layer. A surface coating method characterized by heat treatment at a temperature below the solidus temperature of the coating.
する請求項１記載の表面被覆方法。(2) The surface coating method according to claim 1, wherein the coating is pressurized at the same time as the heat treatment.
なう事を特徴とする請求項１記載の表面被覆方法。(3) The surface coating method according to claim 1, characterized in that after the heat treatment, the film is pressurized by CIP and then heat treated again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28961088A JPH02138483A (en) | 1988-11-16 | 1988-11-16 | Surface coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28961088A JPH02138483A (en) | 1988-11-16 | 1988-11-16 | Surface coating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02138483A true JPH02138483A (en) | 1990-05-28 |
Family
ID=17745469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28961088A Pending JPH02138483A (en) | 1988-11-16 | 1988-11-16 | Surface coating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02138483A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241373A (en) * | 2018-03-09 | 2019-09-17 | 三菱重工业株式会社 | The manufacturing method of metal formed article |
-
1988
- 1988-11-16 JP JP28961088A patent/JPH02138483A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241373A (en) * | 2018-03-09 | 2019-09-17 | 三菱重工业株式会社 | The manufacturing method of metal formed article |
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