JPH07292491A - High corrosion resistant plating film and plating liquid - Google Patents
High corrosion resistant plating film and plating liquidInfo
- Publication number
- JPH07292491A JPH07292491A JP8333894A JP8333894A JPH07292491A JP H07292491 A JPH07292491 A JP H07292491A JP 8333894 A JP8333894 A JP 8333894A JP 8333894 A JP8333894 A JP 8333894A JP H07292491 A JPH07292491 A JP H07292491A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- plating film
- tungstate
- molybdate
- corrosion 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.)
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- Electroplating And Plating Baths Therefor (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高耐食性めっき皮膜およ
びめっき液に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly corrosion resistant plating film and a plating solution.
【０００２】[0002]
【従来の技術】わずかな処理、例えばめっき、クラッド
等で金属材料を高耐食化することは、耐食性の要求され
る腐食環境下での使用を可能にし、有益である。2. Description of the Related Art Making a metallic material highly corrosion-resistant by a small amount of treatment, such as plating and cladding, is advantageous because it enables use in a corrosive environment where corrosion resistance is required.
【０００３】高耐食性皮膜としてはステンレス鋼の圧延
薄膜などが一般的であるが、ステンレス鋼は最も薄いも
のでも厚さが２０μｍ以上あり、しかも他の材料へ密着
させようとしても、接合性が極めて悪い。他方、銅合金
材等の上にステンレス鋼を圧接させた、いわゆるクラッ
ド材が生産されているが、ステンレス鋼が厚く且つ比較
的硬くて加工性が悪いため微細加工や深しぼり加工など
が困難である。As a high corrosion resistant film, a rolled thin film of stainless steel is generally used, but even the thinnest stainless steel has a thickness of 20 μm or more, and even if it is attempted to adhere to other materials, the bondability is extremely high. bad. On the other hand, a so-called clad material, which is produced by pressing stainless steel onto a copper alloy material or the like, is produced, but since stainless steel is thick and relatively hard and has poor workability, it is difficult to perform fine processing or deep drawing processing. is there.
【０００４】そのため、母材を他の加工しやすい材料で
成形した後、その上に高耐食性皮膜を種々の方法で設け
る技術がある。この種の耐食性皮膜としてはニッケル系
めっき皮膜が一般的であり、例えばＮｉ−Ｐ、Ｎｉ−Ｍ
ｏ、Ｎｉ−Ｗなどがある。またこれらの耐食性皮膜を設
ける方法としては、電解めっき、無電解めっき、蒸着
法、スパッタリング法などがある。Therefore, there is a technique in which a base material is formed from another easily workable material and then a high corrosion resistant film is provided thereon by various methods. A nickel-based plating film is generally used as this type of corrosion-resistant film, for example, Ni-P and Ni-M.
o, Ni-W, etc. Further, as a method of providing these corrosion resistant coatings, there are electrolytic plating, electroless plating, vapor deposition method, sputtering method and the like.
【０００５】しかしこれらの合金めっき皮膜の耐食性
は、オーステナイト系ステンレス鋼のＳＵＳ３０４より
も劣ることが知られている。However, it is known that the corrosion resistance of these alloy plating films is inferior to that of austenitic stainless steel SUS304.
【０００６】また、金属材料の耐食性は、材料の結晶構
造に影響され、結晶質構造を持つものは、格子欠陥、粒
界が存在し、そしてそこが活性点となって腐食反応が進
行するという難点がある。Further, the corrosion resistance of a metal material is affected by the crystal structure of the material, and those having a crystalline structure have lattice defects and grain boundaries, and these become active points to promote the corrosion reaction. There are difficulties.
【０００７】[0007]
【発明が解決しようとする課題】本発明はかかる点に立
って為されたものであって、その目的とするところは前
記した従来技術の欠点を解消し、任意の形状に加工した
導電性母材上に形成でき且つＳＵＳ３０４よりも耐食性
が優れた耐食性めっき皮膜およびそのめっき液を提供す
ることにある。SUMMARY OF THE INVENTION The present invention has been made in view of such a point, and its purpose is to solve the above-mentioned drawbacks of the prior art and to form a conductive mother into an arbitrary shape. It is intended to provide a corrosion-resistant plating film which can be formed on a material and is superior in corrosion resistance to SUS304, and a plating solution thereof.
【０００８】[0008]
【課題を解決するための手段】本発明の要旨とするとこ
ろは、Ｎｉ−Ｍｏ−Ｗの３元合金の非晶質めっき皮膜
から成る高耐食性めっき皮膜、硫酸ニッケル、モリブ
デン酸塩、タングステン酸塩およびクエン酸から成るこ
とを特徴とするめっき液の２点にある。The gist of the present invention is to provide a highly corrosion resistant plating film composed of an amorphous plating film of a ternary alloy of Ni-Mo-W, nickel sulfate, molybdate and tungstate. And the plating solution characterized by being composed of citric acid.
【０００９】本発明においてＮｉ−Ｍｏ−Ｗ合金めっき
の浴成分は、金属塩として硫酸ニッケル（ＮｉＳＯ4 ・
６Ｈ2 Ｏ）、モリブデン酸ナトリウム（Ｎａ2 ＭｏＯ4
・２Ｈ2 Ｏ）、タングステン酸ナトリウム（Ｎａ2 ＷＯ
4 ・２Ｈ2 Ｏ）を用い、また錯化剤としてクエン酸（Ｃ
6 Ｈ8 Ｏ7 ・Ｈ2 Ｏ）を用いる。[0009] bath components of Ni-Mo-W alloy plating in the present invention, nickel sulfate as a metal salt (NiSO 4 ·
6H 2 O), sodium molybdate (Na 2 MoO 4
・ 2H 2 O), sodium tungstate (Na 2 WO
4 · 2H 2 O) used, also citric acid as a complexing agent (C
6 H 8 O 7 · H 2 O) is used.
【００１０】浴中の金属塩濃度は、溶解度および析出特
性を考慮し、硫酸ニッケル；１３〜６０ｇ／Ｌ、モリブ
デン酸ナトリウム；１５〜５０ｇ／Ｌ、タングステン酸
ナトリウム；２５〜６５ｇ／Ｌの範囲が望ましい。錯化
剤としてのクエン酸は７０〜１１０ｇ／Ｌが望ましい。The metal salt concentration in the bath is in the range of nickel sulfate: 13-60 g / L, sodium molybdate: 15-50 g / L, sodium tungstate: 25-65 g / L in consideration of solubility and precipitation characteristics. desirable. The citric acid as a complexing agent is preferably 70 to 110 g / L.
【００１１】本発明において非晶質めっき皮膜は、これ
ら金属塩の濃度範囲において、モリブデン酸塩とタング
ステン酸塩のめっき液中での濃度比（例えばモリブデン
酸ナトリウム／タングステン酸ナトリウム）が０．２〜
５．０の場合にのみめっきすることができる。ここにお
いて錯化剤としてのクエン酸を７０〜１１０ｇ／Ｌとし
たのはクエン酸濃度が７０ｇ／Ｌより少ないと錯化効果
が弱いため、析出するめっき皮膜が目的の組成になりに
くく、逆に１１０ｇ／Ｌより多いと溶解しにくいためで
ある。In the present invention, the amorphous plating film has a concentration ratio (for example, sodium molybdate / sodium tungstate) of 0.2 in the plating solution in the concentration range of these metal salts. ~
It can be plated only at 5.0. Here, the citric acid as the complexing agent is set to 70 to 110 g / L because the complexing effect is weak when the citric acid concentration is less than 70 g / L, and thus the deposited plating film is unlikely to have the desired composition. This is because if it exceeds 110 g / L, it is difficult to dissolve.
【００１２】本発明においてめっき液はｐＨを調整する
ことがよく、そのｐＨ調整剤としてはアンモニア水（Ｎ
Ｈ4 ＯＨ）を用いる。めっき液のｐＨが１．０未満では
強酸性のため、水素ガスが発生しやすく、その結果析出
効率が極めて悪くなって良好なめっき皮膜が得られな
い。ｐＨが１．５〜２．０において結晶質めっき皮膜が
得られ、そしてｐＨ２．５〜４．０において非晶質めっ
き皮膜が得られる。ｐＨが４．０を超えると、アンモニ
ア水の添加量が多くなるため、クエン酸錯体として安定
化しているニッケルが、ニッケルクエン酸アンミン混合
錯体となり、その結果析出電位が卑に移行するため、ニ
ッケルの析出よりも水素発生反応が起こりやすくなって
析出効率が著しく低下する。In the present invention, the plating solution is preferably adjusted in pH, and the pH adjusting agent is ammonia water (N
H 4 OH) is used. When the pH of the plating solution is less than 1.0, hydrogen gas is likely to be generated because of strong acidity, and as a result, the deposition efficiency is extremely deteriorated and a good plating film cannot be obtained. A crystalline plating film is obtained at a pH of 1.5 to 2.0, and an amorphous plating film is obtained at a pH of 2.5 to 4.0. When the pH exceeds 4.0, the amount of ammonia water added becomes large, so that nickel stabilized as a citric acid complex becomes a nickel citrate ammine mixed complex, and as a result, the deposition potential shifts to base, so The hydrogen generation reaction is more likely to occur than the precipitation of, and the precipitation efficiency is significantly reduced.
【００１３】めっき液の浴温は、室温から４０℃程度ま
での範囲が望ましい。高温にすると析出効率はやや上が
るが、昇温コストがかかるため経済的に不利な上、５０
℃以上ではめっき皮膜が粗れて均一なめっき皮膜が得ら
れない。The bath temperature of the plating solution is preferably in the range of room temperature to about 40 ° C. Precipitation efficiency increases a little at high temperature, but it is economically disadvantageous because of the temperature rise cost.
If the temperature is higher than ℃, the plating film will be rough and a uniform plating film cannot be obtained.
【００１４】析出時の電流密度は２〜１０Ａ／dm2 が良
い。The current density during deposition is preferably 2 to 10 A / dm 2 .
【００１５】[0015]
【作用】本発明の高耐食性めっき皮膜およびめっき液
は、硫酸ニッケル、モリブデン酸塩、タングステン酸塩
およびクエン酸から成るめっき液を用いて電解法により
めっきすることにより、容易に導電材料上にＮｉ−Ｍｏ
−Ｗの３元合金の非晶質めっき皮膜から成る高耐食性め
っき皮膜が得られる。The highly corrosion-resistant plating film and the plating solution of the present invention are easily electroplated by using a plating solution consisting of nickel sulfate, molybdate, tungstate and citric acid to form Ni on a conductive material. -Mo
A highly corrosion-resistant plating film composed of an amorphous plating film of a ternary alloy of -W is obtained.
【００１６】[0016]
【実施例】次に、本発明の高耐食性めっき皮膜およびめ
っき液の実施例を比較例と共に説明する。EXAMPLES Next, examples of the high corrosion resistant plating film and the plating solution of the present invention will be described together with comparative examples.
【００１７】（実施例１）Ｎｉ−Ｍｏ−Ｗの３元合金め
っき浴として、硫酸ニッケル；３４ｇ／Ｌ、モリブデン
酸ナトリウム；３２ｇ／Ｌ、タングステン酸ナトリウ
ム；４３ｇ／Ｌ、クエン酸；８０ｇ／Ｌから成る水溶液
を準備し、アンモニア水でｐＨ３に調整した。このめっ
き液を室温の状態のままで用い、清浄化した銅板上に電
流密度６Ａ／dm2 で２０分間電気めっきを行った。めっ
き後に断面観察からめっき厚を求めたところ、約７μｍ
であった。(Example 1) As a Ni-Mo-W ternary alloy plating bath, nickel sulfate; 34 g / L, sodium molybdate; 32 g / L, sodium tungstate; 43 g / L, citric acid; 80 g / L Was prepared and the pH was adjusted to 3 with aqueous ammonia. Using this plating solution at room temperature, electroplating was performed on a cleaned copper plate at a current density of 6 A / dm 2 for 20 minutes. Approximately 7 μm when the plating thickness was calculated from the cross-section observation after plating
Met.
【００１８】なお、Ｎｉ−Ｍｏ−Ｗの３元合金めっき浴
として、硫酸ニッケルを３４ｇ／Ｌと一定として、モリ
ブデン酸ナトリウムとタングステン酸ナトリウムの濃度
比を種々変化させて建浴し、電解を行い、析出しためっ
き皮膜の結晶性をＸ線回折装置で分析した。ここにおい
て錯化剤であるクエン酸は８０ｇ／Ｌとした。電析条件
として、めっき浴のｐＨはアンモニア水でｐＨ３．０に
調整し、浴温度は室温で、表面を清浄化した銅板上に電
流密度６Ａ／dm2 で２０分間電気めっきを行った。また
めっき厚は７μｍとなるようにした。As a Ni-Mo-W ternary alloy plating bath, nickel sulfate was kept constant at 34 g / L, and the bath was constructed by varying the concentration ratio of sodium molybdate and sodium tungstate and electrolyzing. The crystallinity of the deposited plating film was analyzed by an X-ray diffractometer. Here, the complexing agent, citric acid, was 80 g / L. As electrodeposition conditions, the pH of the plating bath was adjusted to 3.0 with ammonia water, the bath temperature was room temperature, and electroplating was performed on a copper plate whose surface was cleaned at a current density of 6 A / dm 2 for 20 minutes. The plating thickness was set to 7 μm.
【００１９】図２は浴中のモリブデン酸塩とタングステ
ン酸塩の濃度を種々変化させためっき液から電析させた
めっき皮膜の結晶性の有無に付いて調査した結果であ
る。FIG. 2 shows the results of an examination as to whether or not the plating film deposited from plating solutions having various concentrations of molybdate and tungstate in the bath has crystallinity.
【００２０】図２より、浴中のモリブデン酸塩とタング
ステン酸塩の濃度比が０．０６〜０．１５の場合は、Ｘ
線回折分析によりめっき皮膜が結晶質であることが分か
る。一方、建浴濃度比が０．２〜５．０の範囲では、Ｘ
線回折のピークはなだらかになり、めっき皮膜が非晶質
化していることが分かる。From FIG. 2, when the concentration ratio of molybdate and tungstate in the bath is 0.06 to 0.15, X
Line diffraction analysis reveals that the plating film is crystalline. On the other hand, when the bath concentration ratio is in the range of 0.2 to 5.0, X
It can be seen that the peak of the line diffraction becomes gentle and the plating film becomes amorphous.
【００２１】（比較例１）硫酸ニッケル；３２ｇ／Ｌ、
モリブデン酸ナトリウム；３２ｇ／Ｌ、クエン酸ナトリ
ウム；９４ｇ／Ｌから成るＮｉ−Ｍｏの２元合金めっき
液を建浴し、ｐＨ９、めっき浴温は室温のまま、電流密
度１０Ａ／dm2 で２０分間電気めっきを行った。めっき
厚は約８μｍであった。Comparative Example 1 Nickel sulfate; 32 g / L,
A Ni-Mo binary alloy plating solution consisting of sodium molybdate; 32 g / L, sodium citrate; 94 g / L was prepared in a bath, pH was 9 and the plating bath temperature was room temperature, and the current density was 10 A / dm 2 for 20 minutes. Electroplating was performed. The plating thickness was about 8 μm.
【００２２】（比較例２）硫酸ニッケル；３４ｇ／Ｌ、
モリブデン酸ナトリウム；８ｇ／Ｌ、タングステン酸ナ
トリウム；７３ｇ／Ｌ、クエン酸；８０ｇ／Ｌから成る
めっき液を準備し、ｐＨ６に調整した上、銅板上に６Ａ
／dm2 で２０分間、結晶質のＮｉ−Ｍｏ−Ｗの３元合金
めっき皮膜を設けた。(Comparative Example 2) Nickel sulfate; 34 g / L,
Prepare a plating solution consisting of sodium molybdate; 8 g / L, sodium tungstate; 73 g / L, citric acid; 80 g / L, adjust the pH to 6 and then add 6A on the copper plate.
A crystalline Ni-Mo-W ternary alloy plating film was provided for 20 minutes at / dm 2 .
【００２３】（比較例３）さらにオーステナイト系ステ
ンレス鋼のＳＵＳ３０４鋼板（０．５mmｔ）も準備し
た。Comparative Example 3 Further, an austenitic stainless steel SUS304 steel plate (0.5 mmt) was also prepared.
【００２４】次に、本発明の実施例１のめっき皮膜と比
較例１〜３のめっき皮膜およびＳＵＳ３０４金属板を用
いて、耐食性の評価を行った。耐食性試験は０．１Ｎ塩
酸水溶液中でアノード分極曲線を測定し、その結果によ
り耐食性の優劣を判断した。その際参照極は銀／塩化銀
電極を用い、また電位走査速度は１ｍＶ／ｓとした。ア
ノード分極曲線測定結果を図１に示す。Next, the corrosion resistance was evaluated using the plating film of Example 1 of the present invention, the plating films of Comparative Examples 1 to 3 and the SUS304 metal plate. In the corrosion resistance test, the anode polarization curve was measured in a 0.1N hydrochloric acid aqueous solution, and the superiority or inferiority of the corrosion resistance was judged from the result. At that time, a silver / silver chloride electrode was used as the reference electrode, and the potential scanning speed was 1 mV / s. The measurement result of the anodic polarization curve is shown in FIG.
【００２５】図１から分かるように本発明のＮｉ−Ｍｏ
−Ｗ非晶質めっき皮膜は、Ｎｉ−Ｍｏ−Ｗ結晶質めっき
皮膜、Ｎｉ−Ｍｏの２元合金めっき皮膜および耐食性の
比較的優れているＳＵＳ３０４よりも、自然浸漬状態、
すなわち浸漬電位近傍において、電位の変化に対する電
流値が小さく、優れた耐食性を発揮した。As can be seen from FIG. 1, the Ni-Mo of the present invention is used.
The -W amorphous plating film is in a natural immersion state as compared with the Ni-Mo-W crystalline plating film, the Ni-Mo binary alloy plating film, and SUS304 which has relatively excellent corrosion resistance.
That is, in the vicinity of the immersion potential, the current value was small with respect to the change in the potential, and excellent corrosion resistance was exhibited.
【００２６】このように本発明のＮｉ−Ｍｏ−Ｗの３元
合金めっき皮膜は、非晶質化することで結晶質めっき皮
膜より優れた耐食性を有するようになり、また、わずか
数μｍのめっき厚で腐食環境の厳しい塩酸水溶液中で
も、ＳＵＳ３０４鋼板よりも極めて良好な耐食性を示す
ものである。As described above, the Ni-Mo-W ternary alloy plating film of the present invention becomes superior in corrosion resistance to the crystalline plating film by being made amorphous, and the plating film having a thickness of only a few μm. Even in a hydrochloric acid solution that is thick and has a severe corrosive environment, it exhibits significantly better corrosion resistance than the SUS304 steel plate.
【００２７】このようにＮｉ−Ｍｏ−Ｗの３元合金めっ
き皮膜は、めっき液浴中のニッケル塩濃度に対して、モ
リブデン酸塩およびタングステン酸塩の濃度比を特定範
囲とすることにより、非晶質めっき皮膜を得ることがで
きる。As described above, the Ni-Mo-W ternary alloy plating film has a non-specific content of the molybdate and tungstate concentration ratios with respect to the nickel salt concentration in the plating solution bath. A crystalline plating film can be obtained.
【００２８】そしてＮｉ−Ｍｏ−Ｗの３元合金めっき皮
膜を非晶質化することにより、結晶質めっき皮膜よりも
一段と優れた耐食性を有するようになる。しかも銅合金
材等の上に数μｍのめっきを施すことにより、高耐食性
材料の代表であるＳＵＳ３０４鋼板よりも優れた耐食性
を発揮する。このことは被めっき材を予め特定の形状に
加工してからめっきすることにより、優れた耐食性を付
与できることを意味する。例えば微細加工や複雑な形状
の加工を行った導電性材料を後からめっきすることによ
り高耐食化できる。By amorphizing the Ni-Mo-W ternary alloy plating film, the Ni-Mo-W ternary alloy plating film has more excellent corrosion resistance than the crystalline plating film. Moreover, by plating a copper alloy material or the like with a thickness of several μm, it exhibits better corrosion resistance than the SUS304 steel plate, which is a representative of high corrosion resistance materials. This means that excellent corrosion resistance can be imparted by processing the material to be plated into a specific shape in advance and then plating. For example, it is possible to enhance corrosion resistance by later plating a conductive material that has been subjected to fine processing or processing of a complicated shape.
【００２９】また本発明では電気めっき法でめっき皮膜
を作製することができるので、蒸着法やスパッタリング
法はもとより、無電解めっき法に比べても析出速度が速
く、しかも安価である。Further, in the present invention, since the plating film can be formed by the electroplating method, the deposition rate is higher and the cost is lower than the electroless plating method as well as the vapor deposition method and the sputtering method.
【００３０】[0030]
【発明の効果】本発明の高耐食性めっき皮膜およびめっ
き液によればＳＵＳ３０４より優れた耐食性を発揮する
めっき皮膜が得られるものであり、工業上有用である。EFFECTS OF THE INVENTION According to the highly corrosion resistant plating film and the plating solution of the present invention, a plating film exhibiting corrosion resistance superior to that of SUS304 can be obtained and is industrially useful.
【図１】本発明の実施例１の高耐食性めっき皮膜、従来
の比較例１〜２のめっき皮膜およびＳＵＳ３０４金属板
の耐食性試験結果を示したグラフである。FIG. 1 is a graph showing the corrosion resistance test results of a highly corrosion resistant plating film of Example 1 of the present invention, conventional plating films of Comparative Examples 1 and 2 and a SUS304 metal plate.
【図２】本発明のめっき液の組成と非晶質めっき皮膜形
成性との関係を示したグラフである。FIG. 2 is a graph showing the relationship between the composition of the plating solution of the present invention and the amorphous plating film forming property.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 関根 功 東京都新宿区神楽坂１丁目３番地 学校法 人東京理科大学内 (72)発明者 湯浅 真 東京都新宿区神楽坂１丁目３番地 学校法 人東京理科大学内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Isao Sekine 1-3 Kagurazaka, Shinjuku-ku, Tokyo School Hojin Tokyo University of Science (72) Inventor Makoto Yuasa 1-3-3 Kagurazaka, Shinjuku-ku, Tokyo Hokkojin Tokyo Inside the University of Science
Claims (5)
皮膜から成ることを特徴とする高耐食性めっき皮膜。1. A high corrosion resistant plating film comprising an amorphous plating film of a ternary alloy of Ni-Mo-W.
テン酸塩およびクエン酸から成ることを特徴とするめっ
き液。2. A plating solution comprising nickel sulfate, molybdate, tungstate and citric acid.
またはモリブデン酸カリウムであることを特徴とする請
求項２記載のめっき液。3. The plating solution according to claim 2, wherein the molybdate is sodium molybdate or potassium molybdate.
ウムまたはタングステン酸カリウムであることを特徴と
する請求項２記載のめっき液。4. The plating solution according to claim 2, wherein the tungstate is sodium tungstate or potassium tungstate.
あるモリブデン酸塩／タングステン酸塩＝０．２〜５．
０であることを特徴とする請求項２記載のめっき液。5. A molybdate / tungstate ratio which is molybdate / tungstate = 0.2-5.
It is 0, The plating liquid of Claim 2 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8333894A JPH07292491A (en) | 1994-04-21 | 1994-04-21 | High corrosion resistant plating film and plating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8333894A JPH07292491A (en) | 1994-04-21 | 1994-04-21 | High corrosion resistant plating film and plating liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07292491A true JPH07292491A (en) | 1995-11-07 |
Family
ID=13799656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8333894A Pending JPH07292491A (en) | 1994-04-21 | 1994-04-21 | High corrosion resistant plating film and plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07292491A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014890A1 (en) * | 2003-07-23 | 2005-02-17 | Seamless Plating (Uk) Limited | An electrolyte solution |
| KR100579411B1 (en) * | 2001-08-21 | 2006-05-12 | 주식회사 포스코 | Zn-Ni-W alloy electrodeposited steel sheets for good adhesion and corrosion resistance |
| CN105420775A (en) * | 2015-12-31 | 2016-03-23 | 上海应用技术学院 | Method for preparing La-Ni-Mo-W/GO composite deposit layer on carbon steel substrate |
| JP2018115371A (en) * | 2017-01-18 | 2018-07-26 | 株式会社Ｊｃｕ | Plating solution for coloring, and coloring method |
| WO2020173574A1 (en) * | 2019-02-28 | 2020-09-03 | Circuit Foil Luxembourg | Composite copper foil and method of fabricating the same |
| CN115354371A (en) * | 2022-08-03 | 2022-11-18 | 国网福建省电力有限公司电力科学研究院 | Method for improving mechanical property of multi-element Ni-based alloy coating by element doping and heat treatment |
-
1994
- 1994-04-21 JP JP8333894A patent/JPH07292491A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100579411B1 (en) * | 2001-08-21 | 2006-05-12 | 주식회사 포스코 | Zn-Ni-W alloy electrodeposited steel sheets for good adhesion and corrosion resistance |
| WO2005014890A1 (en) * | 2003-07-23 | 2005-02-17 | Seamless Plating (Uk) Limited | An electrolyte solution |
| CN105420775A (en) * | 2015-12-31 | 2016-03-23 | 上海应用技术学院 | Method for preparing La-Ni-Mo-W/GO composite deposit layer on carbon steel substrate |
| JP2018115371A (en) * | 2017-01-18 | 2018-07-26 | 株式会社Ｊｃｕ | Plating solution for coloring, and coloring method |
| WO2018135197A1 (en) * | 2017-01-18 | 2018-07-26 | 株式会社Ｊｃｕ | Plating solution for coloring, and coloring method |
| CN110191977A (en) * | 2017-01-18 | 2019-08-30 | 株式会社杰希优 | Coloring plating solution and color method |
| US11214883B2 (en) | 2017-01-18 | 2022-01-04 | Jcu Corporation | Plating solution for coloring, and coloring method |
| CN110191977B (en) * | 2017-01-18 | 2022-04-26 | 株式会社杰希优 | Plating solution for coloring and coloring method |
| WO2020173574A1 (en) * | 2019-02-28 | 2020-09-03 | Circuit Foil Luxembourg | Composite copper foil and method of fabricating the same |
| JP2020180366A (en) * | 2019-02-28 | 2020-11-05 | サーキット フォイル ルクセンブルグ | Composite copper foil, printed-circuit board, electronic device, and production method of composite copper foil |
| US11639557B2 (en) | 2019-02-28 | 2023-05-02 | Circuit Foil Luxembourg | Composite copper foil and method of fabricating the same |
| CN115354371A (en) * | 2022-08-03 | 2022-11-18 | 国网福建省电力有限公司电力科学研究院 | Method for improving mechanical property of multi-element Ni-based alloy coating by element doping and heat treatment |
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