JP2857776B2 - Metal surface oxidation resistance imparting treatment method - Google Patents
Metal surface oxidation resistance imparting treatment methodInfo
- Publication number
- JP2857776B2 JP2857776B2 JP1237889A JP23788989A JP2857776B2 JP 2857776 B2 JP2857776 B2 JP 2857776B2 JP 1237889 A JP1237889 A JP 1237889A JP 23788989 A JP23788989 A JP 23788989A JP 2857776 B2 JP2857776 B2 JP 2857776B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- plating layer
- metal surface
- copper wire
- oxidation resistance
- 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 - Fee Related
Links
- 239000002184 metal Substances 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 13
- 238000010301 surface-oxidation reaction Methods 0.000 title claims 2
- 238000011282 treatment Methods 0.000 title description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 238000007747 plating Methods 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 229910000846 In alloy Inorganic materials 0.000 claims description 13
- YLZGECKKLOSBPL-UHFFFAOYSA-N indium nickel Chemical compound [Ni].[In] YLZGECKKLOSBPL-UHFFFAOYSA-N 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 21
- 239000010410 layer Substances 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 241000080590 Niso Species 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、金属の酸化腐食を防止するための表面処理
方法に関する。Description: TECHNICAL FIELD The present invention relates to a surface treatment method for preventing oxidative corrosion of a metal.
［従来の技術］ 金属に耐酸化腐食性を付与するための処理法として
は、金属表面への有機化合物の吸着により防錆処理やク
ロメート処理、樹脂被覆等の方法が知られている。しか
しながら、これらの方法によっては、500℃のような高
温でも処理された金属が充分な耐酸化腐食効果を示すよ
うにするということは期待できない。[Prior Art] As a treatment method for imparting oxidation corrosion resistance to a metal, there are known methods such as rust prevention treatment, chromate treatment, and resin coating by adsorption of an organic compound to a metal surface. However, depending on these methods, it cannot be expected that the metal treated at a high temperature such as 500 ° C. will exhibit a sufficient oxidation corrosion resistance.
一方、金属にニッケルメッキをすることによって、処
理された金属が500℃のような高温でも充分な酸化防止
効果を示すようにすることができるということは知られ
ている。しかしながら、この場合、メッキしたニッケル
の表面が酸化して黒色化し、美観が損われるばかりでな
く、これを高温下に長期間保持するとニッケルの酸化が
さらに進行し、遂にはメッキされた金属の折り曲げ等に
より金属表面にクラックが発生し、ニッケルメッキした
表面層が剥離脱落するようになる。On the other hand, it is known that by plating a metal with nickel, the treated metal can exhibit a sufficient antioxidant effect even at a high temperature such as 500 ° C. However, in this case, the surface of the plated nickel is oxidized and blackened, and not only the appearance is impaired, but also if it is kept at a high temperature for a long time, the oxidation of the nickel further progresses, and finally the plated metal is bent. Cracks occur on the metal surface due to the above-mentioned factors, and the nickel-plated surface layer peels off.
［発明が解決しようとする問題点］ そこで、500℃のような高温下においても、目的金属
の酸化腐食を充分に防止できると共に、処理後のものを
折り曲げても表面に形成したメッキ層等が剥離脱落する
ことのない金属表面の耐酸化処理方法を見い出すことが
必要となっていた。[Problems to be Solved by the Invention] Therefore, even at a high temperature such as 500 ° C., it is possible to sufficiently prevent oxidative corrosion of a target metal, and a plated layer or the like formed on a surface even after bending a treated metal is bent. It has been necessary to find an oxidation-resistant treatment method for a metal surface that does not peel off and fall off.
［問題点を解決するための手段］ 金属表面にニッケルメッキ層を形成した後、その上に
ニッケル−インジウム合金メッキ層を形成することによ
って、上記の問題点を解決することができた。この場合
のニッケル−インジウム合金メッキ層の厚さは0.05μｍ
〜５μｍの範囲とするのが適切であることが確認され
た。0.05μｍ未満の厚さでは合金メッキ層形成の効果が
実質的に評価できるほど顕著には表れず、一方、下引き
ニッケルメッキ層を施す場合、厚さが５μｍにも達する
とその効果はほとんど飽和してしまうため、それ以上厚
くしても単にコストを高となるに過ぎないからである。
尚、上記ニッケル−インジウム合金メッキ層の形成に先
立ち、金属表面上に予めニッケルメッキ層を形成する。
この下引きメッキ層の厚さは0.05μｍ〜５μｍの範囲の
厚さとするのが適切である。また、ニッケル−インジウ
ム合金メッキの合金組成は、インジウムの含有比率が10
〜80重量％となるような合金であればよい。この範囲の
組成でないと充分な耐酸化性が得られないからである。
インジウムの含有比率が40〜60重量％となるような合金
であれば特に好ましい。[Means for Solving the Problems] After a nickel plating layer was formed on a metal surface, a nickel-indium alloy plating layer was formed thereon to solve the above problems. In this case, the thickness of the nickel-indium alloy plating layer is 0.05 μm.
It has been confirmed that it is appropriate to set the range to ５5 μm. When the thickness is less than 0.05 μm, the effect of forming the alloy plating layer does not appear so remarkably that it can be substantially evaluated. On the other hand, when the undercoating nickel plating layer is applied, the effect is almost saturated when the thickness reaches 5 μm. This is because, even if the thickness is further increased, the cost simply increases.
Prior to the formation of the nickel-indium alloy plating layer, a nickel plating layer is formed on the metal surface in advance.
It is appropriate that the thickness of the undercoat plating layer is in the range of 0.05 μm to 5 μm. Further, the alloy composition of the nickel-indium alloy plating is such that the indium content ratio is 10%.
Any alloy may be used so as to be up to 80% by weight. If the composition is not in this range, sufficient oxidation resistance cannot be obtained.
Particularly preferred is an alloy having an indium content ratio of 40 to 60% by weight.
本発明で金属表面に形成する合金メッキ層は、実施例
に示すようなメッキ浴を用いてニッケルとインジウムと
を同時に電着させて合金化することによって形成できる
が、予め用意した所定の組成の溶融合金中に浸漬する方
法によって形成してもよい。下引きメッキ層を形成する
場合も、電解メッキ、上記の浸漬する方法のいずれによ
ってもよい。The alloy plating layer formed on the metal surface in the present invention can be formed by simultaneously electrodepositing and alloying nickel and indium using a plating bath as shown in Examples, but having a predetermined composition prepared in advance. It may be formed by a method of dipping in a molten alloy. Also when forming an undercoat plating layer, any of electrolytic plating and the above-mentioned immersion method may be used.
［作 用］ 本発明により金属表面上にニッケル属を介して形成さ
れたニッケル−インジウム合金メッキ層は、ニッケルと
インジウムとを同時に電卓させて合金化させたメッキ層
であるために、ニッケル単独のメッキ層よりも改善され
た耐酸化性を示す。また、インジウムは156.6℃という
低い融点を持つ金属であるが、ニッケルと合金化された
ことによって、600℃の温度下においても溶解しない安
定なニッケル−インジウム合金メッキ層を形成して母材
金属を保護している。[Operation] The nickel-indium alloy plating layer formed on the metal surface via the nickel genus according to the present invention is a plating layer in which nickel and indium are simultaneously calculated and alloyed, so that nickel alone is used. It shows improved oxidation resistance over the plating layer. Indium is a metal having a low melting point of 156.6 ° C, but is alloyed with nickel to form a stable nickel-indium alloy plating layer that does not dissolve even at a temperature of 600 ° C to form a base metal. Protected.
［実施例］ 直径5mmの銅線に電気メッキ法で厚さ２μｍのニッケ
ルメッキ層を形成した後、下記の基本組成を持つニッケ
ル−イミジウム合金メッキ浴中で、電気メッキを行うこ
とにより、厚さ１μｍのニッケル−インジウム合金メッ
キ層を形成して本発明の被覆銅線を製造した。ニッケル−インジウム合金メッキ浴の基本組成 NiSO4 1 mol/ NiCl2 0.2 mol/ In2（SO4）３ 0.05mol/ H3BO3 0.5 mol/ pH 2.3 この場合の合金メッキ条件は、電流密度4Adm-2、浴温
50℃であった。また、得られたニッケル−インジウム合
金メッキ層の組成はNi55重量％−In45重量％であった。[Example] After a nickel plating layer having a thickness of 2 μm was formed on a copper wire having a diameter of 5 mm by an electroplating method, electroplating was performed in a nickel-imidium alloy plating bath having the following basic composition. A coated copper wire of the present invention was manufactured by forming a 1 μm nickel-indium alloy plating layer. Basic composition of nickel-indium alloy plating bath NiSO 4 1 mol / NiCl 2 0.2 mol / In 2 (SO 4 ) 3 0.05 mol / H 3 BO 3 0.5 mol / pH 2.3 In this case, the alloy plating condition is a current density of 4 Adm − 2 , bath temperature
50 ° C. The composition of the obtained nickel-indium alloy plating layer was 55% by weight of Ni-45% by weight of In.
一方、上記と同じ直径5mmの銅線に通常のワット浴か
ら電気メッキすることにより、厚さ３μｍのニッケルメ
ッキ層を形成して、比較対照用のニッケル被覆銅線を製
造した。On the other hand, a nickel-plated copper wire having a thickness of 3 μm was formed by electroplating the same copper wire having a diameter of 5 mm from an ordinary watt bath to produce a nickel-coated copper wire for comparison.
上記２種の互いに異なる表面処理をした銅線について
耐酸化性評価のための試験を行った結果は第１図に示す
通りであった。すなわち、各銅線試料を大気中に550℃
の温度で、それぞれ５日間、10日間、15日間および20日
保持した後に測定した各銅線試料10cm当りの重量増加量
は図示の通りであり、ニッケル−インジウム合金メッキ
層を形成した本発明の被覆銅線は、ニッケルメッキした
だけの比較対照用被覆銅線に比し、重量増加量が小さ
く、酸化される速度が小さいことがわかる。また、550
℃で20日間保持した後、銅線試料を折り曲げてみたとこ
ろ、本発明の方法で処理したものは剥離が生じなかった
が、比較対照用の被覆銅線試料は折り曲げにより表面の
一部が剥離した。FIG. 1 shows the results of a test for evaluating the oxidation resistance of the two types of copper wires having different surface treatments. That is, each copper wire sample was placed at 550 ° C in air.
At the temperature of 5 days, 10 days, 15 days and 20 days, respectively, the amount of weight increase per 10 cm of each copper wire sample measured was as shown in the figure, and the nickel-indium alloy plating layer of the present invention was formed. It can be seen that the coated copper wire has a smaller weight increase and a lower oxidation rate than the control coated copper wire which is only nickel-plated. Also, 550
After holding at 20 ° C for 20 days, when the copper wire sample was bent, the one treated by the method of the present invention did not peel off, but the coated copper wire sample for comparison used a part of the surface due to bending. did.
また、大気雰囲気中550℃でそれぞれ５日間、10日
間、15日間および20日間保持した後に測定した各銅線試
料の抵抗値の変化の模様は第２図に示す通りであり、本
発明の方法で処理した被覆銅線試料は比較対照用の被覆
銅線試料に比し、抵抗の増加が小さく、銅線の耐酸化性
が向上していることが明らかである。尚、第２図におい
て、抵抗値は550℃の雰囲気に入れる前の抵抗値を100％
とする相対値で示した。また抵抗値は550℃の雰囲気中
に保持した後、25℃中の雰囲気において測定したもので
ある。The pattern of the change in the resistance value of each copper wire sample measured after holding at 550 ° C. for 5 days, 10 days, 15 days and 20 days in the air atmosphere is as shown in FIG. It is clear that the coated copper wire sample treated with has a smaller increase in resistance and an improved oxidation resistance of the copper wire as compared with the coated copper wire sample for comparison and control. In FIG. 2, the resistance value is 100% of the resistance value before entering the atmosphere at 550 ° C.
The relative values are shown below. The resistance value was measured in an atmosphere at 25 ° C. after holding in an atmosphere at 550 ° C.
上記の比較試験の結果は、本発明方法で表面処理した
銅線は抵抗の増加が小さく、銅線に耐酸化性があること
を明らかに示している。The results of the above comparative test clearly show that the copper wire surface-treated by the method of the present invention has a small increase in resistance and has an oxidation resistance.
第１図は、銅線試料を550℃の大気雰囲気中に保持した
日数と、銅線の重量増加との関係を示すグラフである。 第２図は、銅線試料を550℃の大気雰囲気中に保持した
日数と銅線の抵抗値との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the number of days that a copper wire sample was kept in an air atmosphere at 550 ° C. and the weight increase of the copper wire. FIG. 2 is a graph showing the relationship between the number of days when a copper wire sample was kept in an air atmosphere at 550 ° C. and the resistance value of the copper wire.
Claims (2)
後、その上にニッケル−インジウムの合金メッキ層を形
成することからなる金属表面耐酸化性付与処理方法。A method for imparting oxidation resistance to a metal surface, comprising forming a nickel plating layer on a metal surface and then forming a nickel-indium alloy plating layer thereon.
厚みが0.05μｍ〜５μｍの範囲の厚みであり、かつニッ
ケル−インジウム合金メッキ層の合金組成がインジウム
10〜80重量％で残部がニッケルおよび不可避不純物であ
る請求項１に記載の金属表面耐酸化性付与処理方法。2. The nickel-indium alloy plating layer has a thickness in the range of 0.05 μm to 5 μm, and the nickel-indium alloy plating layer has an alloy composition of indium.
The metal surface oxidation resistance imparting method according to claim 1, wherein the balance is nickel and unavoidable impurities at 10 to 80% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1237889A JP2857776B2 (en) | 1989-09-13 | 1989-09-13 | Metal surface oxidation resistance imparting treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1237889A JP2857776B2 (en) | 1989-09-13 | 1989-09-13 | Metal surface oxidation resistance imparting treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03100196A JPH03100196A (en) | 1991-04-25 |
| JP2857776B2 true JP2857776B2 (en) | 1999-02-17 |
Family
ID=17021927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1237889A Expired - Fee Related JP2857776B2 (en) | 1989-09-13 | 1989-09-13 | Metal surface oxidation resistance imparting treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2857776B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITUA20162023A1 (en) | 2016-03-25 | 2017-09-25 | Giulio Properzi | PROCEDURE FOR TRANSFORMING VERGELLA OF NON-FERROUS METALS AND THEIR ALLOYS IN HIGH-STRETCH WIRE AND IN THE RICOTTO STATE. |
-
1989
- 1989-09-13 JP JP1237889A patent/JP2857776B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03100196A (en) | 1991-04-25 |
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| Date | Code | Title | Description |
|---|---|---|---|
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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