JP6663335B2 - Palladium-nickel alloy coating and method for producing the same - Google Patents
Palladium-nickel alloy coating and method for producing the same Download PDFInfo
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Description
本発明は、電気・電子・機械部品等の構成材料としての、パラジウム−ニッケル合金皮膜及びその製造方法に関し、特に、膜厚を厚くしても、色調ムラが少なく、低応力でクラックや密着不良の発生が少なく、硬く耐久性・耐摩耗性に優れると共に、耐食性の高い、パラジウム−ニッケル合金皮膜及びその製造方法に関する。 The present invention relates to a palladium-nickel alloy film and a method for producing the same as constituent materials for electric / electronic / mechanical parts and the like. The present invention relates to a palladium-nickel alloy film which is hard, has excellent durability and wear resistance, and has high corrosion resistance, and a method for producing the same.
従来、電気・電子・機械部品等の製造を目的としためっき方法には、ニッケル、銅、金、銀などの金属を用いた電解めっきが用いられていた。しかし、ニッケルは卑な金属であり、その表面が酸化、腐食されやすいことから、耐食性が求められる部材には向いておらず、一方、金、銀などの貴な金属は、卑な金属に比べて、酸化、腐食され難いことから、耐食性には優れるものの、金属としては軟らかいため、機械的な耐久性、耐摩耗性に劣るということがあった。また、銀は、その表面が硫化されやすく、変色しやすいという欠点をもっていた。 Conventionally, electrolytic plating using metals such as nickel, copper, gold, and silver has been used as a plating method for manufacturing electric, electronic, and mechanical parts. However, nickel is a base metal and its surface is easily oxidized and corroded, so it is not suitable for members requiring corrosion resistance.On the other hand, noble metals such as gold and silver are compared with base metals. Thus, although it is difficult to be oxidized and corroded, it is excellent in corrosion resistance, but is soft as a metal, and thus has poor mechanical durability and abrasion resistance. Further, silver has a drawback that its surface is easily sulfided and easily discolored.
これに対して、貴金属の中でも、耐酸化性や耐食性に優れ、また、耐久性・耐摩耗性に優れた材料として、白金族元素のめっき皮膜が注目されており、白金族元素の中でも優れた耐食性、耐熱性、耐酸化性などの諸特性を持ち、比較的めっき処理が容易なパラジウム又はパラジウム合金が有望視されている。ここで、以下にパラジウムやパラジウム合金めっきに関する先行技術を示す。例えば、特許文献１には、クラックのない光沢性に優れたパラジウム−コバルト合金めっき液及び該めっき液を用いて形成した合金皮膜が開示されている。 On the other hand, among the noble metals, a plating film of a platinum group element is attracting attention as a material having excellent oxidation resistance and corrosion resistance, and also having excellent durability and abrasion resistance. Palladium or a palladium alloy, which has various properties such as corrosion resistance, heat resistance, and oxidation resistance, and is relatively easy to plating, is considered promising. Here, the prior art relating to palladium and palladium alloy plating will be described below. For example, Patent Literature 1 discloses a palladium-cobalt alloy plating solution excellent in gloss without cracks and an alloy film formed using the plating solution.
また、特許文献２には、パラジウム−リン合金めっき皮膜及びその製造方法が記載され、特許文献３には、電解用パラジウムめっき液及びそれを用いて形成されたリードフレームが開示されている。上記のようなパラジウムやパラジウム合金は、耐食性や耐摩耗性等を有する優れた材料であるが、めっき皮膜の膜厚が厚くなると、その硬さ故に、柔軟性が低いことに加えて、高い内部応力や水素吸蔵などの諸特性により、皮膜にクラックや剥がれが生じ、下地膜との密着不良が生じたり、素材を含めた部品全体に反りが生じたりする。 Patent Literature 2 describes a palladium-phosphorus alloy plating film and a method for manufacturing the same. Patent Literature 3 discloses a palladium plating solution for electrolysis and a lead frame formed using the same. Palladium and palladium alloys as described above are excellent materials having corrosion resistance, abrasion resistance, etc., but when the thickness of the plating film is large, due to its hardness, in addition to low flexibility, high internal Due to various characteristics such as stress and hydrogen absorption, cracks and peeling occur in the film, resulting in poor adhesion to the underlying film and warpage of the entire component including the material.
特に、パラジウム−ニッケル合金めっきの光沢皮膜は、上記特許文献３にあるようなパラジウム単独の無光沢や半光沢の皮膜と比べて、内部応力が高いため、厚膜の作製は非常に困難とされている。なお、特許文献１は、パラジウム−コバルト合金めっき被膜に関する発明であり、また、特許文献２は、パラジウム−リン合金めっき被膜であって
パラジウム−ニッケル合金被膜について一切言及されていない。また、特許文献４は、パラジウム−ニッケル合金メッキ液に関する発明であるが、電着皮膜の膜厚は２μｍと膜厚の薄いものを対象としている。
In particular, since the glossy film of palladium-nickel alloy plating has a higher internal stress than a matte or semi-gloss film of palladium alone as described in Patent Document 3, it is extremely difficult to produce a thick film. ing. In addition, Patent Document 1 is an invention relating to a palladium-cobalt alloy plating film, and Patent Document 2 is a palladium-phosphorus alloy plating film, and does not mention a palladium-nickel alloy film at all. Patent Literature 4 is an invention relating to a palladium-nickel alloy plating solution, and is directed to a thin electrodeposited film having a thickness of 2 μm.
本発明は、上記問題を解決するものであって、膜厚の厚いパラジウム−ニッケル合金皮膜及びその製造方法を提供することを課題とし、特に、膜厚を厚くしても、低応力でクラックや密着不良の発生が少なく、また、耐久性・耐摩耗性、耐食性に優れ、さらに
色調ムラが少ない、パラジウム−ニッケル合金皮膜及びその製造方法を提供することを課題とする。
The present invention has been made to solve the above problems, and an object of the present invention is to provide a thick palladium-nickel alloy film and a method for producing the same. An object of the present invention is to provide a palladium-nickel alloy film and a method for producing the same, which are less likely to cause poor adhesion, have excellent durability, abrasion resistance, and corrosion resistance, and have less color tone unevenness.
上記の課題を解決するために、本発明者らは鋭意研究を行った結果、パラジウム−ニッケル合金めっきのめっき液成分の配合やめっき条件を工夫することで、めっき皮膜における内部応力を低い状態で維持することが可能となり、その結果、膜厚を厚くしてもクラックや密着不良が少ない、パラジウム−ニッケル合金皮膜を形成することができるとの知見が得られ、本発明を完成するに至った。前記課題は以下に示す本発明によって解決される。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research and as a result, by devising the composition of the plating solution components of the palladium-nickel alloy plating and the plating conditions, the internal stress in the plating film was reduced. As a result, it was found that even when the film thickness was increased, cracks and poor adhesion were small, and a knowledge that a palladium-nickel alloy film could be formed was obtained, and the present invention was completed. . The above object is achieved by the present invention described below.
１）膜厚が１０μｍ以上１２０μｍ以下であり、応力が５ＭＰａ以上１２０ＭＰａ以下であることを特徴とするパラジウム−ニッケル合金皮膜。
２）ビッカース硬さが２００Ｈｖ以上６００Ｈｖ以下であることを特徴とする上記１）記載のパラジウム−ニッケル合金皮膜。
３）ニッケル含有量が０．１質量％以上５０質量％以下であることを特徴とする上記１）又は２）記載のパラジウム−ニッケル合金皮膜。
４）皮膜外観が鏡面光沢又は全光沢であることを特徴とする上記１）〜３）のいずれか一に記載のパラジウム−ニッケル合金皮膜。
５）上記１）〜４）のいずれか一に記載のパラジウム−ニッケル合金皮膜の製造方法であって、電解めっき時の陽極を隔膜で覆うことを特徴とするパラジウム−ニッケル合金皮膜の製造方法。
６）上記１）〜４）のいずれか一に記載のパラジウム−ニッケル合金皮膜の製造方法であって、電解めっき時の陽極として、酸化イリジウム又は酸化イリジウムをコーティングしたもの使用することを特徴とするパラジウム−ニッケル合金皮膜の製造方法。
1) thickness Ri der than 120μm or less 10 [mu] m, palladium stress characterized der Rukoto below 120MPa or more 5 MPa - nickel alloy film.
2) The palladium-nickel alloy coating as described in 1) above , wherein the Vickers hardness is 200 Hv or more and 600 Hv or less.
3) The palladium-nickel alloy coating as described in 1) or 2) above, wherein the nickel content is 0.1% by mass or more and 50% by mass or less.
4) The palladium-nickel alloy coating as described in any one of 1) to 3) above, wherein the coating has a specular gloss or a total gloss.
5) The method for producing a palladium-nickel alloy film according to any one of 1) to 4 ) above , wherein the anode during electrolytic plating is covered with a diaphragm.
6) The method for producing a palladium-nickel alloy film according to any one of 1) to 4 ) above , wherein an anode coated with iridium oxide or iridium oxide is used as an anode during electrolytic plating. A method for producing a palladium-nickel alloy film.
本発明によれば、クラックや下地との密着不良が少なく、膜厚の厚い、パラジウム−ニッケル合金皮膜を得ることができる。これにより、従来の技術では実現できなかった硬くて耐久性・耐摩耗性に優れ、耐食性の高い厚い膜厚のめっき皮膜を用いた電気部品・電子部品・機械部品、電鋳品等の製造が可能となる。さらに、めっき浴の配合成分の種類や濃度その他のめっき条件を適切に調整することで、上記めっき皮膜の光沢を、無光沢、半光沢、光沢（全光沢又は鏡面光沢）の少なくとも３段階に制御することができるので、外観上の品質要求も満たすことができる。 According to the present invention, a thick palladium-nickel alloy film having few cracks and poor adhesion to a base can be obtained. This makes it possible to manufacture electrical parts, electronic parts, machine parts, electroformed products, etc. using hard, durable, wear-resistant, and highly corrosion-resistant plating films with high film thickness that could not be achieved with conventional technologies. It becomes possible. Furthermore, by appropriately adjusting the type and concentration of the components of the plating bath and other plating conditions, the gloss of the plating film can be controlled to at least three levels of matte, semi-gloss, and gloss (total gloss or specular gloss). Therefore, appearance quality requirements can be satisfied.
本発明は、電解めっきにより形成したパラジウム−ニッケル合金膜であって、膜厚が１０μｍ以上１２０μｍ以下であることを特徴とするめっき膜である。先述のとおり、パラジウム−ニッケル合金めっき皮膜は、一般的に内部応力が高いため、厚膜のものを形成することが困難とされていたが、本発明は、めっき液やめっき条件等を適切に調整することで内部応力の上昇を抑制し、これにより、膜厚の厚いパラジウム−ニッケル合金膜の形成を可能としたものである。 The present invention is a palladium-nickel alloy film formed by electrolytic plating, wherein the thickness is 10 μm or more and 120 μm or less. As described above, the palladium-nickel alloy plating film is generally considered to be difficult to form a thick film because of high internal stress. The adjustment suppresses an increase in internal stress, thereby enabling a thick palladium-nickel alloy film to be formed.
パラジウム−ニッケル合金めっき皮膜は、パラジウムが高価であるにもかかわらず、皮膜の耐食性が高いことから、耐食性を有する部材等への応用が期待されている。しかし、耐食性を有する部材は、強酸性で金属腐食性の高い溶液に接触している場合が多く、耐食性の高いパラジウム−ニッケル合金皮膜であっても、数μｍ程度の厚さでは腐食による部材の物性低下は避けられない。したがって、めっき被膜の膜厚は１０μｍ以上、好ましくは３０μｍ以上、さらに好ましくは５０μｍ以上とする。 A palladium-nickel alloy plating film is expected to be applied to members having corrosion resistance because the film has high corrosion resistance despite the high price of palladium. However, a member having corrosion resistance is often in contact with a strongly acidic and highly corrosive metal solution, and even a palladium-nickel alloy film having high corrosion resistance has a thickness of about several μm, which causes corrosion of the member. Physical property deterioration is inevitable. Therefore, the thickness of the plating film is 10 μm or more, preferably 30 μm or more, and more preferably 50 μm or more.
パラジウム−ニッケル合金めっき皮膜の膜厚は、用途等に応じて、厚くしていくことが有効であるが、クラックや剥がれ、下地との密着性の観点から、膜厚１２０μｍ以下とするのが望ましい。一方、本発明は、１０μｍ未満の薄い膜を形成することも可能であり、下地との密着性や、応力による部材の反り等に敏感な薄いシート状の部材を形成する場合には、１０μｍ未満の膜厚の薄いパラジウム−ニッケル合金めっき皮膜は有効である。本発明において、めっき皮膜の厚みは、皮膜断面をＳＥＭで測定した。 It is effective to increase the film thickness of the palladium-nickel alloy plating film according to the application and the like. However, from the viewpoint of cracking and peeling and adhesion to the base, it is preferable that the film thickness be 120 μm or less. . On the other hand, the present invention can also form a thin film of less than 10 μm, and when forming a thin sheet-like member that is sensitive to adhesion to the base and warpage of the member due to stress, the thickness is less than 10 μm. A palladium-nickel alloy plating film having a small thickness is effective. In the present invention, the thickness of the plating film was measured by SEM on the cross section of the film.
また、本発明のパラジウム−ニッケル合金皮膜は、上記のような厚い膜厚であっても、応力が５ＭＰａ以上１２０ＭＰａ以下であることを特徴とする。低応力のめっき膜は、クラックや剥がれが生じ難く、また、下地との良好な密着性を維持することができる。本発明において、応力は、スペシャルティ テスティング アンド デベロップ社製 ストリップ電着応力測定器を用いて測定し、測定して得られたゲージ幅とめっき重量から得られた膜厚をもとに算出した。
Further, the palladium-nickel alloy film of the present invention is characterized in that the stress is not less than 5 MPa and not more than 120 MPa even with the above-mentioned thick film thickness. The low-stress plating film is less likely to crack or peel off, and can maintain good adhesion to the underlayer. In the present invention, the stress was measured using a strip electrodeposition stress meter manufactured by Specialty Testing and Development Co., Ltd., and was calculated based on the gauge width obtained by the measurement and the film thickness obtained from the plating weight.
また、本発明のパラジウム−ニッケル合金膜は、ビッカース硬度が２００Ｈｖ以上、６００Ｈｖ以下であることを特徴とする。このような硬度の高いめっき皮膜は、耐久性及び耐摩耗性に優れ、長期間使用しても、その機能を損なうことなく、安定した特性を維持することができる。硬度は、ニッケル含有量やめっき条件で変化し、ニッケル含有量が多くなると硬くなり、陰極電流密度が上がるとめっき皮膜は硬くなる。また、一般的に結晶粒径が小さくなると硬度が上がる。 Further, the palladium-nickel alloy film of the present invention has a Vickers hardness of 200 Hv or more and 600 Hv or less. Such a plating film having high hardness is excellent in durability and abrasion resistance, and can maintain stable characteristics even after long-term use without impairing its function. The hardness changes depending on the nickel content and plating conditions. The hardness increases as the nickel content increases, and the plating film increases as the cathode current density increases. In general, the hardness increases as the crystal grain size decreases.
本発明において、ビッカース硬度は、株式会社ミツトヨ製微小硬さ試験機ＨＭ−２２１を用いて測定した。具体的には、めっき皮膜を最低１０μｍ以上で成膜し、測定する皮膜は圧痕が見えやすいように平滑で光沢外観とした。試験力は２水準以上で同等の値がでるような試験力を求め、試験力が大きい値を採用した。また、硬度は２回測定の平均値を求めた。測定条件は、試験時間：負荷４秒、保持１０秒、除荷４秒とし、試験力は厚みにより任意に変更した。 In the present invention, the Vickers hardness was measured using a micro hardness tester HM-221 manufactured by Mitutoyo Corporation. Specifically, a plating film was formed with a thickness of at least 10 μm or more, and the film to be measured had a smooth and glossy appearance so that indentations were easily visible. As for the test force, a test force that gives an equivalent value at two or more levels was obtained, and a value with a large test force was adopted. The hardness was determined as an average of two measurements. The measurement conditions were as follows: test time: load 4 seconds, holding 10 seconds, unloading 4 seconds, and the test force was arbitrarily changed depending on the thickness.
本発明のパラジウム−ニッケル合金膜は、ニッケルの含有量が０．１質量％以上５０質量％以下であることが好ましい。ニッケルの含有量は、めっき皮膜の外観や、皮膜の内部応力、硬度に影響を与える。パラジウム−ニッケル合金膜中の合金比率は、めっき液中のニッケル塩の濃度、及び、パラジウムの濃度とニッケルの濃度の比によって調整することができる。例えば、パラジウムの濃度１０ｇ／Ｌに固定した場合、ニッケルの濃度を１〜１０ｇ／Ｌと変化させることで、ニッケルの含有量を０．１〜５０質量％に変化させることができる。０．１質量％を未満であると、めっき皮膜の光沢が失われると共に皮膜の応力が上昇し、一方、５０質量％を超えると、耐食性が低下する。 The palladium-nickel alloy film of the present invention preferably has a nickel content of 0.1% by mass or more and 50% by mass or less. The nickel content affects the appearance of the plating film and the internal stress and hardness of the film. The alloy ratio in the palladium-nickel alloy film can be adjusted by the concentration of the nickel salt in the plating solution and the ratio of the concentration of palladium to the concentration of nickel. For example, when the concentration of palladium is fixed at 10 g / L, the content of nickel can be changed to 0.1 to 50% by mass by changing the concentration of nickel to 1 to 10 g / L. If the amount is less than 0.1% by mass, the gloss of the plating film is lost and the stress of the film increases, while if it exceeds 50% by mass, the corrosion resistance decreases.
本発明は、パラジウム−ニッケル合金皮膜の外観が光沢（鏡面光沢、全光沢）であることを特徴とする。めっき皮膜には、無光沢、半光沢又は光沢（鏡面光沢又は全光沢）の少なくとも３段階の光沢具体があり、用途等に適しためっき外観とする必要がある。光沢は、ニッケルの含有量やめっき条件の影響を受け、また一般的に、結晶の大きさが小さくなると、表面の凹凸も小さくなるため光沢度は強くなる。鏡面光沢又は全光沢は外観に艶があり見た目が良いものの、クラックや剥がれ、色ムラを生じ易いが、本発明によれば、鏡面光沢又は全光沢で外観不良（クラック等）のないめっき皮膜を形成することができる。 The present invention is characterized in that the appearance of the palladium-nickel alloy film is glossy (specular gloss, total gloss). The plating film has at least three levels of glossiness, that is, matte, semi-gloss or gloss (specular gloss or total gloss), and it is necessary to have a plating appearance suitable for the application and the like. The gloss is affected by the nickel content and the plating conditions. In general, as the size of the crystal becomes smaller, the surface roughness becomes smaller, so that the gloss becomes stronger. Although specular gloss or total gloss is glossy in appearance and good in appearance, cracks, peeling, and color unevenness are likely to occur. Can be formed.
以下に、本発明のパラジウム−ニッケル合金皮膜の製造方法について具体的に示す。まず、一例として、次の成分からなるパラジウム−ニッケルめっき浴を建浴する。
テトラアンミンパラジウム（II）塩化物
硫酸ニッケル（II）六水和物
硫酸アンモニウム
サッカリンナトリウム二水和物
ベンゼンスルホン酸ナトリウム
安息香酸
Hereinafter, the method for producing a palladium-nickel alloy film of the present invention will be specifically described. First, as an example, a palladium-nickel plating bath composed of the following components is built.
Tetraamminepalladium (II) chloride Nickel (II) sulfate hexahydrate Ammonium sulfate Sodium saccharin dihydrate Sodium benzenesulfonate Benzoic acid
めっき浴は、パラジウム塩及びニッケル塩を主成分とし、さらに応力緩和剤、及び、電導塩を添加する。パラジウム塩として、上記テトラアンミンパラジウム（II）塩化物の他、ジブロモテトラアンミンパラジウム（[Ｐｄ（ＮＨ３）４]Ｂｒ２）、ジイオドテトラアンミンパラジウム（［Ｐｄ（ＮＨ３）４］Ｉ２）、サルフェイトテトラアンミンパラジウム（［Ｐｄ（ＮＨ３］４）（ＳＯ４））、のようなテトラアンミンパラジウム化合物；ジクロロジアミンパラジウム（［Ｐｄ（ＮＨ３）２Ｃｌ２］）、ジブロモジアンミンパラジウム（［Ｐｄ（ＮＨ３）２Ｂｒ２］）、ジイオドジアンミンパラジウム（［Ｐｄ（ＮＨ３）２Ｉ２］）、サルフェイトジアンミンパラジウム（［Ｐｄ（ＮＨ３）２（ＳＯ４）］）のようなジアンミンパラジウム化合物などを用いることができる。
また、ニッケル塩としては、硫酸ニッケル（II）水和物の他、酢酸ニッケル、アミド硫酸ニッケル、塩化ニッケルなどを用いることができ、ニッケル塩の酸根は限定されない。皮膜中の合金比率は、めっき浴中のパラジウムとニッケルの濃度で変化させることができるが、ニッケル塩の役割は合金比率のコントロールだけでなく、外観及び皮膜の内部応力にも影響を与えるので、この点を考慮してそれぞれの濃度を決める必要がある。
The plating bath contains a palladium salt and a nickel salt as main components, and further includes a stress relaxation agent and a conductive salt. As the palladium salt, dibromotetraamminepalladium ([Pd (NH 3 ) 4 ] Br 2 ), diiodotetraamminepalladium ([Pd (NH 3 ) 4 ] I 2 ), sulfate, in addition to the above tetraamminepalladium (II) chloride tetraamminepalladium ([Pd (NH 3] 4 ) (sO 4)), tetraammine palladium compound such as; dichlorodiamine palladium ([Pd (NH 3) 2 Cl 2]), dibromo diammine palladium ([Pd (NH 3) 2 Br 2]), diisopropyl odo diammine palladium ([Pd (NH 3) 2 I 2]), Sulfate diammine palladium ([Pd (NH 3) 2 (sO 4)]) using such a diammine palladium compound as be able to.
As the nickel salt, nickel acetate, nickel amide sulfate, nickel chloride and the like can be used other than nickel sulfate (II) hydrate, and the acid radical of the nickel salt is not limited. The alloy ratio in the coating can be changed by the concentration of palladium and nickel in the plating bath, but the role of the nickel salt not only controls the alloy ratio but also affects the appearance and the internal stress of the coating, It is necessary to determine each density in consideration of this point.
応力緩和剤としては、ナフタレンスルフォン酸類、芳香族スルファミド及び芳香族カルボン酸などを添加する。例えば、サッカリン、ベンゼンスルホン酸ナトリウム、クロモトロープ酸ナトリウム、安息香酸などが挙げられる。特に、ベンゼンスルホン酸ナトリウム、クロモトロープ酸ナトリウム、安息香酸を用いることが好ましい。なお、これらの応力緩和剤は、電鋳に使用されているが、その効果の発現機構はほとんど知られておらず、また、本発明のような、パラジウム−ニッケル合金厚付めっきに応用された例は確認できない。 As the stress relieving agent, naphthalene sulfonic acid, aromatic sulfamide, aromatic carboxylic acid and the like are added. For example, saccharin, sodium benzenesulfonate, sodium chromotropic acid, benzoic acid and the like can be mentioned. In particular, it is preferable to use sodium benzenesulfonate, sodium chromotropic acid, and benzoic acid. In addition, although these stress relaxation agents are used in electroforming, little is known about the manifestation mechanism of the effect, and also applied to palladium-nickel alloy thick plating as in the present invention. No examples can be found.
また、めっき液の電導塩は、一般的に使用するｐＨ付近に緩衝作用があるものを選択することができるが、電導塩の種類によっては、皮膜外観及び内部応力に影響を与えることから、所望の特性を考慮しながら決める必要がある。電導塩としては上記で挙げた硫酸アンモニウムの他、塩化アンモニウム、アミド硫酸アンモニウム、クエン酸アンモニウムなどを用いることができる。また、電導塩は、１５〜５０ｇ／Ｌ添加することが好ましい。 In addition, the conductive salt of the plating solution can be selected from those having a buffering action near the generally used pH. However, depending on the type of the conductive salt, it affects the film appearance and internal stress. Must be determined in consideration of the characteristics of As the conductive salt, in addition to the above-described ammonium sulfate, ammonium chloride, ammonium amidosulfate, ammonium citrate, and the like can be used. Further, it is preferable to add 15 to 50 g / L of the conductive salt.
次に、上記めっき浴を用いて、例えば、以下の条件で電解めっきを行い、めっき皮膜を形成する。なお、下記の条件は、一例であって、本発明はこの条件に限定されるものでない。
電流： ０．６Ａ
電解時間： １２０分
電流密度： ２Ａ／ｄｍ２
浴量： ３Ｌ
ｐＨ： ７
温度： ４０℃
撹拌速度： ３００ｒｐｍ
カソード： 銅（下地めっきなし）
アノード： 酸化イリジウムコーティングチタン
陽極隔膜： 有り
上記の通り、めっき時の不溶性陽極として、白金の代わりに酸化イリジウムを用いることでめっき液成分の酸化反応による副生成物の蓄積を低減し、応力上昇を抑えることができる。また、パラジウムめっき皮膜に水素が吸蔵されて内部応力が上昇することが知られていることから、めっき条件を調整し電析する結晶サイズを小さくすることで、結晶格子内への水素吸蔵等による格子ひずみを抑制して、皮膜全体の応力を低下させることが好ましい。
Next, using the plating bath, for example, electrolytic plating is performed under the following conditions to form a plating film. The following conditions are merely examples, and the present invention is not limited to these conditions.
Current: 0.6A
Electrolysis time: 120 minutes Current density: 2 A / dm 2
Bath volume: 3L
pH: 7
Temperature: 40 ° C
Stirring speed: 300 rpm
Cathode: Copper (no plating)
Anode: Iridium oxide coated titanium Anode diaphragm: Yes As described above, by using iridium oxide instead of platinum as the insoluble anode during plating, the accumulation of by-products due to the oxidation reaction of the plating solution components is reduced, and the rise in stress is reduced. Can be suppressed. In addition, since it is known that hydrogen is occluded in the palladium plating film and the internal stress increases, by adjusting the plating conditions to reduce the size of the crystal to be deposited, it is possible to occlude hydrogen in the crystal lattice and the like. It is preferable to suppress the lattice strain and reduce the stress of the entire coating.
ところで、パラジウム−ニッケルめっきにおいて、長時間電解を行うと内部応力が上昇するという問題がある。これについて研究を進めったところ、めっき液中の内部応力上昇は、アノード酸化反応により生成する無機塩及び有機物の酸化体とめっき成分の相互作用により引き起こされることが分かった。このような知見から、本発明では、隔膜を使用することにより、陽極上で発生する亜硝酸イオンが陰極へ拡散するのを抑制して、内部応力の上昇を抑えることを特徴としている。なお、上述した隔膜において、隔膜内の液成分は必ずしもめっき液成分と同じである必要はなく、むしろ金属塩や添加剤を含まない液を用いた方が好ましく、また、隔膜内の液を適宜、交換するのが好ましい。 By the way, in palladium-nickel plating, there is a problem that the internal stress increases when electrolysis is performed for a long time. Investigation into this matter revealed that the increase in internal stress in the plating solution was caused by the interaction between the plating components and the oxidized inorganic salts and organic substances generated by the anodic oxidation reaction. From such findings, the present invention is characterized in that the use of a diaphragm suppresses the diffusion of nitrite ions generated on the anode to the cathode, thereby suppressing an increase in internal stress. In the above-described diaphragm, the liquid component in the diaphragm does not necessarily have to be the same as the plating solution component, but rather it is preferable to use a solution that does not contain a metal salt or an additive. , It is preferable to replace.
次に、本願発明の実施例及び比較例について説明する。なお、以下の実施例は、あくまで代表的な例を示しているもので、本願発明はこれらの実施例に制限される必要はなく、明細書の記載される技術思想の範囲で解釈されるべきものである。 Next, examples and comparative examples of the present invention will be described. The following embodiments are merely representative examples, and the present invention is not limited to these embodiments, and should be interpreted within the scope of the technical idea described in the specification. Things.
（実施例１−４）
下記の表１に記載される成分からなるパラジウム−ニッケルめっき浴を建浴し、それぞれのめっき浴を用いて、同表に掲載される条件にて電解めっきを行い、めっき皮膜を形成した。その結果、実施例１−４のいずれも、めっき外観が良好な（クラック、剥がれ、色ムラ等がなく、鏡面光沢）、膜厚１００μｍのパラジウム−ニッケル合金皮膜が得られた。また、いずれのめっきにおいても、応力の上昇は抑えられ、また硬度も所定の範囲内であった。なお、実施例１−４のめっき皮膜の膜厚は、いずれも１００μｍであるが、それよりも薄いものは当然、外観不良のなく形成することができることから、表への掲載は、省略した。
(Example 1-4)
A palladium-nickel plating bath composed of the components shown in Table 1 below was established, and electrolytic plating was performed using each plating bath under the conditions listed in the table to form a plating film. As a result, in each of Examples 1-4 , a palladium-nickel alloy film having a good plating appearance (no cracks, peeling, uneven color, etc., and a specular gloss) and a film thickness of 100 μm was obtained. Further, in each of the platings, an increase in stress was suppressed, and the hardness was within a predetermined range. The thickness of each of the plating films of Examples 1-4 was 100 μm. However, since the thickness of a thinner film can be formed without any poor appearance, it is omitted from the table.
（比較例１−６）
下記の表１に記載される成分からなるパラジウム−ニッケルめっき浴を建浴し、それぞれのめっき浴を用いて、同表に掲載される条件にて電解めっきを行い、めっき皮膜を形成した。その結果、比較例１−４において、膜厚が１０μｍになる前にめっき不良（色無あら）が発生し、１００μｍのものは得られなかった。なお、比較例５、６は、膜厚が１０μｍ未満のパラジウム−ニッケル合金皮膜であるが、このような膜厚の薄いものについては隔膜を使用せずとも、めっき外観が良好な（クラック、剥がれ、色ムラ等がなく、鏡面光沢）ものが得られた。
(Comparative Example 1-6)
A palladium-nickel plating bath composed of the components shown in Table 1 below was established, and electrolytic plating was performed using each plating bath under the conditions listed in the table to form a plating film. As a result, in Comparative Example 1-4, plating failure (colorlessness) occurred before the film thickness became 10 μm, and a film having a thickness of 100 μm was not obtained. Comparative Examples 5 and 6 are palladium-nickel alloy films having a film thickness of less than 10 μm, but those having such a small film thickness have good plating appearance (cracks and peeling) without using a diaphragm. With no unevenness in color and mirror gloss).
本発明のパラジウム−ニッケル合金皮膜は膜厚が厚く、クラックや下地との密着不良が少ないことから、従来の技術では実現できなかった、耐久性や耐摩耗性、耐食性に優れた厚膜めっき皮膜を用いた電気部品・電子部品・機械部品、電鋳品等に有用である。また、本発明は、前記用途以外にも、眼鏡、時計、楽器、アクセサリー等の装飾品にも用いることができる。
The palladium-nickel alloy film of the present invention has a large thickness, and has a small number of cracks and poor adhesion to an underlayer. Therefore, a thick film plating film excellent in durability, abrasion resistance, and corrosion resistance, which cannot be realized by conventional techniques. It is useful for electric parts, electronic parts, machine parts, electroformed products, etc. using the same. Further, the present invention can be used for decorative articles such as glasses, watches, musical instruments, accessories, and the like, in addition to the above uses.
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