JP2008248318A - Electroless nickel plating method, and steel member - Google Patents

Electroless nickel plating method, and steel member Download PDF

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JP2008248318A
JP2008248318A JP2007090688A JP2007090688A JP2008248318A JP 2008248318 A JP2008248318 A JP 2008248318A JP 2007090688 A JP2007090688 A JP 2007090688A JP 2007090688 A JP2007090688 A JP 2007090688A JP 2008248318 A JP2008248318 A JP 2008248318A
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nickel plating
electroless nickel
complexing agent
complexing
steel member
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JP5158320B2 (en
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Masanori Tada
雅徳 多田
Hideyuki Takami
秀幸 高見
Kaname Yamada
山田　　要
Kenichi Kotani
賢一 小谷
Kengo Kawasumi
賢吾 河澄
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Kito KK
C Uyemura and Co Ltd
Kito Corp
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Kito KK
C Uyemura and Co Ltd
Kito Corp
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G13/00—Chains
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To form an electroless nickel plating film having satisfactory corrosion resistance, wear resistance and fatigue strength on the surface of a steel material, and to impart satisfactory corrosion resistance, wear resistance and fatigue strength to the surface of a steel member such as a link chain used for a chain block or the like. <P>SOLUTION: Disclosed is an electroless nickel plating method where electroless nickel plating is applied to the surface of a steel material by an electroless nickel plating bath comprising: a water soluble nickel salt; a reducing agent; and a complexing agent having a complex forming constant to Fe lower than the complex forming constant to Ni. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、鉄鋼材料表面に、耐食性、耐摩耗性及び疲労強度の良好な無電解ニッケルめっき皮膜を形成する無電解ニッケルめっき方法、及び表面に無電解ニッケルめっき皮膜を形成した鉄鋼部材に関する。   The present invention relates to an electroless nickel plating method for forming an electroless nickel plating film having good corrosion resistance, wear resistance and fatigue strength on the surface of a steel material, and a steel member having an electroless nickel plating film formed on the surface.

手動チェーンブロックや電動チェーンブロック等の揚重機、吊り具、コンベヤ等に使用されるリンクチェーンには耐食性向上のため亜鉛めっきが用いられることが多い。しかし、亜鉛めっき皮膜の場合、摺動部材（部分）においては、皮膜硬さが低く耐摩耗性が悪いという欠点を有している。   In order to improve corrosion resistance, galvanizing is often used for link chains used in lifting machines such as manual chain blocks and electric chain blocks, hoists, and conveyors. However, in the case of a galvanized film, the sliding member (part) has a defect that the film hardness is low and the wear resistance is poor.

一方、無電解ニッケルめっき皮膜の場合、耐食性及び皮膜硬さが硬いことによる耐摩耗性は良好であるが、疲労強度に関しては、元のリンクチェーンなどの鉄鋼材料よりも劣っている。無電解ニッケルめっき皮膜中のリンの含有率が低い方が、疲労強度の劣化が少ないことが知られている（（社）日本材料学会，「材料」，第２６巻，第２８１号，Ｐ１６４−１７１（非特許文献１）、（社）日本材料学会，「材料」，第２４巻，第２５９号，Ｐ３２０−３２５（非特許文献２）参照）が、一般的にリンの含有率が低い無電解ニッケルめっき皮膜の方が、高い皮膜よりも耐食性が悪く、かつめっき浴のニッケル濃度を高くする必要があるためコストも高くなる。   On the other hand, in the case of the electroless nickel plating film, the corrosion resistance and the wear resistance due to the hard film hardness are good, but the fatigue strength is inferior to the steel material such as the original link chain. It is known that the lower the phosphorus content in the electroless nickel plating film, the less the fatigue strength is deteriorated (Japan Society for Materials Science, "Materials", Vol. 26, No. 281, P164-). 171 (Non-patent Document 1), Japan Society for Materials Science, "Materials", Vol. 24, No. 259, P320-325 (Non-patent Document 2)) is generally low in phosphorus content. The electrolytic nickel plating film has poorer corrosion resistance than the higher film, and the nickel concentration of the plating bath needs to be increased, and the cost is also increased.

特開昭６３−２９３１７２号公報JP 63-293172 A 特開平９−３１７８３２号公報JP-A-9-317832 特公昭５５−３９６２１号公報Japanese Patent Publication No.55-39621 特公昭５１−２４９８５号公報Japanese Patent Publication No. 51-24985 （社）日本材料学会，「材料」，第２６巻，第２８１号，Ｐ１６４−１７１Japan Society of Materials Science, "Materials", Vol. 26, No. 281, P164-171 （社）日本材料学会，「材料」，第２４巻，第２５９号，Ｐ３２０−３２５Japan Society of Materials Science, “Materials”, Vol. 24, No. 259, P320-325

本発明は、上記事情に鑑みなされたものであり、鉄鋼材料表面に、耐食性、耐摩耗性及び疲労強度の良好な皮膜を形成する方法、及び表面に耐食性、耐摩耗性及び疲労強度の良好な皮膜を形成した鉄鋼部材を提供することを目的とする。   The present invention has been made in view of the above circumstances, and a method for forming a coating film with good corrosion resistance, wear resistance and fatigue strength on the surface of a steel material, and a good corrosion resistance, wear resistance and fatigue strength on the surface. It aims at providing the steel member in which the film was formed.

本発明者は、上記問題を解決するため鋭意検討を行なった結果、錯化剤としてＮｉに対する錯形成定数よりＦｅに対する錯形成定数が小さい錯化剤、特にグルタミン酸又はその化合物を含む無電解ニッケルめっき浴を用いることで、鉄鋼材料表面に、皮膜中のリンの含有率によらず耐食性及び耐摩耗性と共に、疲労強度も良好な無電解ニッケルめっき皮膜を形成でき、チェーンブロック等に用いられるリンクチェーンなどの耐食性、耐摩耗性及び疲労強度を要求される鉄鋼材料の表面処理として有効であることを見出し、本発明をなすに至った。   As a result of diligent studies to solve the above problems, the present inventor has found that as a complexing agent, a complexing agent having a smaller complexing constant for Fe than Ni, especially glutamic acid or a compound thereof containing glutamic acid or a compound thereof. By using a bath, it is possible to form an electroless nickel plating film with good fatigue strength as well as corrosion resistance and wear resistance on the surface of steel materials regardless of the phosphorus content in the film, and link chains used for chain blocks, etc. It has been found that the present invention is effective as a surface treatment for steel materials that require corrosion resistance, wear resistance, and fatigue strength such as the present invention.

即ち、本発明は、以下の無電解ニッケルめっき方法及び鉄鋼部材を提供する。
［１］ 鉄鋼材料表面への無電解ニッケルめっき方法であって、水溶性ニッケル塩と、還元剤と、錯化剤としてＮｉに対する錯形成定数よりＦｅに対する錯形成定数が小さい錯化剤とを含有する無電解ニッケルめっき浴にて無電解ニッケルめっき皮膜を形成することを特徴とする無電解ニッケルめっき方法。
［２］ 上記錯化剤がグルタミン酸又はその化合物であることを特徴とする［１］記載の無電解ニッケルめっき方法。
［３］ 無電解ニッケルめっき皮膜中の硫黄含有量が０．０１質量％以下であることを特徴とする［１］又は［２］記載の無電解ニッケルめっき方法。
［４］ リンクチェーン表面への無電解ニッケルめっきであることを特徴とする［１］乃至［３］のいずれかに記載の無電解ニッケルめっき方法。
［５］ 水溶性ニッケル塩と、還元剤と、錯化剤としてＮｉに対する錯形成定数よりＦｅに対する錯形成定数が小さい錯化剤とを含有する無電解ニッケルめっき浴にて無電解ニッケルめっきして、表面に無電解ニッケルめっき皮膜を形成したことを特徴とする鉄鋼部材。
［６］ 上記錯化剤がグルタミン酸又はその化合物であることを特徴とする［５］記載の鉄鋼部材。
［７］ 無電解ニッケルめっき皮膜中の硫黄含有量が０．０１質量％以下であることを特徴とする［５］又は［６］記載の鉄鋼部材。
［８］ リンクチェーンであることを特徴とする［５］乃至［７］のいずれかに記載の鉄鋼部材。 That is, the present invention provides the following electroless nickel plating method and steel member.
[1] A method for electroless nickel plating on a steel material surface, comprising a water-soluble nickel salt, a reducing agent, and a complexing agent having a complexing constant for Fe smaller than that for Ni as a complexing agent An electroless nickel plating method comprising forming an electroless nickel plating film in an electroless nickel plating bath.
[2] The electroless nickel plating method according to [1], wherein the complexing agent is glutamic acid or a compound thereof.
[3] The electroless nickel plating method according to [1] or [2], wherein the sulfur content in the electroless nickel plating film is 0.01% by mass or less.
[4] The electroless nickel plating method according to any one of [1] to [3], which is electroless nickel plating on the surface of the link chain.
[5] Electroless nickel plating in an electroless nickel plating bath containing a water-soluble nickel salt, a reducing agent, and a complexing agent having a complexing constant smaller than that of Ni as a complexing agent. A steel member characterized in that an electroless nickel plating film is formed on the surface.
[6] The steel member according to [5], wherein the complexing agent is glutamic acid or a compound thereof.
[7] The steel member according to [5] or [6], wherein the sulfur content in the electroless nickel plating film is 0.01% by mass or less.
[8] The steel member according to any one of [5] to [7], which is a link chain.

本発明によれば、鉄鋼材料表面に、耐食性、耐摩耗性及び疲労強度の良好な無電解ニッケルめっき皮膜を形成することができ、チェーンブロック等に用いられるリンクチェーンなどの鉄鋼部材の表面に良好な耐食性、耐摩耗性及び疲労強度を与えることができる。   According to the present invention, an electroless nickel plating film having good corrosion resistance, wear resistance and fatigue strength can be formed on the surface of a steel material, and the surface of a steel member such as a link chain used for a chain block or the like is good. Corrosion resistance, wear resistance and fatigue strength can be provided.

以下、本発明について更に詳しく説明する。
本発明においては、水溶性ニッケル塩と、還元剤と、錯化剤としてＮｉに対する錯形成定数よりＦｅに対する錯形成定数が小さい錯化剤とを含有する無電解ニッケルめっき浴を用いて、無電解ニッケルめっきすることにより、鉄鋼材料表面に無電解ニッケルめっき皮膜を形成する。 Hereinafter, the present invention will be described in more detail.
In the present invention, an electroless nickel plating bath containing a water-soluble nickel salt, a reducing agent, and a complexing agent having a complexing constant for Fe smaller than that for Ni as a complexing agent is used. By electroplating with nickel, an electroless nickel plating film is formed on the surface of the steel material.

本発明の無電解ニッケルめっき浴に含まれる水溶性ニッケル塩としては、塩化ニッケル、硫酸ニッケル、酢酸ニッケル等を用いることができ、めっき浴中の水溶性ニッケル塩の濃度は、ニッケル基準で２〜８ｇ／Ｌ、特に４〜６ｇ／Ｌであることが好ましい。   As the water-soluble nickel salt contained in the electroless nickel plating bath of the present invention, nickel chloride, nickel sulfate, nickel acetate and the like can be used, and the concentration of the water-soluble nickel salt in the plating bath is 2 to 2 on a nickel basis. It is preferably 8 g / L, particularly 4 to 6 g / L.

還元剤としては、次亜リン酸及びその塩（ナトリウム塩、カリウム塩、アンモニウム塩など）が好適であり、その場合、無電解ニッケルリンめっき浴となる。めっき浴中の還元剤の濃度は１５〜４５ｇ／Ｌ、特に２０〜３０ｇ／Ｌであることが好ましい。   As the reducing agent, hypophosphorous acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) are suitable, and in that case, an electroless nickel phosphorus plating bath is obtained. The concentration of the reducing agent in the plating bath is preferably 15 to 45 g / L, particularly 20 to 30 g / L.

本発明の無電解ニッケルめっき浴には、錯化剤として、Ｎｉに対する錯形成定数よりＦｅに対する錯形成定数が小さい錯化剤が含まれる。このような錯化剤を配合することにより、形成される無電解ニッケルめっき皮膜の疲労強度を向上又は維持しつつ、無電解ニッケルめっき皮膜特有の耐食性及び耐摩耗性を鉄鋼材料表面に与えることができる。   The electroless nickel plating bath of the present invention includes a complexing agent having a complex formation constant for Fe smaller than that for Ni. By adding such a complexing agent, the corrosion resistance and wear resistance peculiar to the electroless nickel plating film can be imparted to the steel material surface while improving or maintaining the fatigue strength of the formed electroless nickel plating film. it can.

ニッケルに対する錯形成定数より鉄に対する錯形成定数が大きい錯化剤は、素材である鉄を溶解し易いためにめっきが付き難くなるが、ニッケルに対する錯形成定数より鉄に対する錯形成定数が小さい錯化剤は、素材である鉄を溶解し難くめっきが付き易い状態となっている（ニッケルが析出したところの鉄を掘らない）ため、密着性が良くなることで、疲労強度も良好となると考えられる。そのため、錯化剤として、ニッケルに対する錯形成定数より鉄に対する錯形成定数が小さい錯化剤が有効である。   Complexing agents with a complexing constant for iron that is larger than that for nickel are more difficult to plate because they easily dissolve iron, which is a raw material, but complexing that has a smaller complexing constant for iron than that for nickel The agent is in a state in which it is difficult to dissolve the iron material and is easy to be plated (does not dig the iron where nickel is deposited), so it is considered that the fatigue strength is also improved by improving the adhesion . Therefore, a complexing agent having a smaller complex formation constant for iron than that for nickel is effective as the complexing agent.

ニッケルに対する錯形成定数より鉄に対する錯形成定数が小さい錯化剤を無電解ニッケルめっき浴に使用すると、得られる皮膜の疲労強度が維持される又は疲労強度が向上する点において、特に有効であり、例えば、グルタミン酸、グリシン、マロン酸、アジピン酸、クエン酸、リンゴ酸又はそれらの化合物が好適であり、特にグルタミン酸又はその化合物が好適である。   Use of a complexing agent having a smaller complexing constant for iron than that for nickel in an electroless nickel plating bath is particularly effective in that the fatigue strength of the resulting film is maintained or the fatigue strength is improved, For example, glutamic acid, glycine, malonic acid, adipic acid, citric acid, malic acid or a compound thereof is preferable, and glutamic acid or a compound thereof is particularly preferable.

一方、ニッケルに対する錯形成定数より鉄に対する錯形成定数が大きい錯化剤（例えば、乳酸、アスパラギン酸、コハク酸、酢酸又はそれらの化合物）、特に、鉄に対する錯形成定数が比較的大きい（例えば２以上）の錯化剤（例えば、乳酸、アスパラギン酸、コハク酸又はそれらの化合物）を無電解ニッケルめっき浴に使用すると、得られる皮膜の疲労強度が低下する点において、これらの単独使用は好ましくない。しかしながら、本発明の目的を損なわない程度であれば、前者のニッケルに対する錯形成定数より鉄に対する錯形成定数が小さい錯化剤と、後者のニッケルに対する錯形成定数より鉄に対する錯形成定数が大きい錯化剤とを併用してもよい。   On the other hand, a complexing agent (for example, lactic acid, aspartic acid, succinic acid, acetic acid, or a compound thereof) having a complex formation constant for iron larger than that for nickel, in particular, a complex formation constant for iron is relatively large (for example, 2 Use of these complexing agents (for example, lactic acid, aspartic acid, succinic acid, or compounds thereof) in an electroless nickel plating bath is not preferable in that the fatigue strength of the resulting film is reduced. . However, as long as the object of the present invention is not impaired, a complexing agent having a smaller complexing constant for iron than the former complexing constant for nickel and a complex having a larger complexing constant for iron than the latter complexing constant for nickel. An agent may be used in combination.

また、ニッケルに対する錯形成定数より鉄に対する錯形成定数が小さい錯化剤は、めっき皮膜中のＰ（りん）共析量を下げる傾向があることから、必要に応じて、Ｐ共析量を上げる傾向のある錯化剤を併用することも有効である。本発明においては、各用途に適したＰ含有量を有するＮｉ−Ｐ合金めっき皮膜を形成することが可能である。   In addition, a complexing agent having a complex formation constant for iron smaller than that for nickel tends to lower the amount of P (phosphorus) eutectoid in the plating film. Therefore, if necessary, the amount of P eutectoid is increased. It is also effective to use a complexing agent having a tendency. In this invention, it is possible to form the Ni-P alloy plating film which has P content suitable for each use.

ニッケルに対する錯形成定数より鉄に対する錯形成定数が小さい錯化剤と、ニッケルに対する錯形成定数より鉄に対する錯形成定数が大きい錯化剤とを併用する場合、全錯化剤中、ニッケルに対する錯形成定数より鉄に対する錯形成定数が小さい錯化剤を５０質量％以上、特に７０質量％以上、とりわけ７５質量％以上とすることが好ましい。   When a complexing agent having a smaller complexing constant for iron than that for nickel and a complexing agent having a larger complexing constant for iron than that for nickel are used in combination, complexation for nickel in all complexing agents The complexing agent having a smaller complex-forming constant for iron than the constant is preferably 50% by mass or more, particularly 70% by mass or more, and particularly preferably 75% by mass or more.

上述した錯化剤の化合物としては、ナトリウム塩、カリウム塩、アンモニウム塩などの塩を挙げることができる。なおニッケルに対する錯形成定数より鉄に対する錯形成定数が小さい錯化剤のめっき浴中の濃度は１０〜５０ｇ／Ｌ、特に１５〜３０ｇ／Ｌであることが好ましい。   Examples of the complexing agent compound described above include salts such as sodium salt, potassium salt and ammonium salt. In addition, it is preferable that the density | concentration in the plating bath of the complexing agent whose complex formation constant with respect to iron is smaller than the complex formation constant with respect to nickel is 10-50 g / L, especially 15-30 g / L.

本発明の無電解ニッケルめっき浴には、無電解ニッケルめっき浴の添加剤として公知の酢酸鉛等のＰｂ化合物、酢酸ビスマス等のＢｉ化合物などの無機化合物安定剤、ブチンジオール等の有機化合物安定剤、ｐＨ調整剤、ｐＨ緩衝剤、ピット防止剤、界面活性剤などの添加剤を、本発明の効果を損なわない程度に添加することができるが、有機硫黄化合物（炭素と硫黄を含む化合物）の濃度は０．００１ｐｐｍ（ｍｇ／Ｌ）以下であることが好ましく、有機硫黄化合物を含んでいないことが特に好ましい。有機硫黄化合物が無電解ニッケルめっき浴に含まれていると疲労強度が低下する傾向にある。この有機硫黄化合物以外の添加物の濃度は、通常０．０００１〜３０ｇ／Ｌ、特に０．０００２〜２０ｇ／Ｌである。   The electroless nickel plating bath of the present invention includes known inorganic compound stabilizers such as Pb compounds such as lead acetate, Bi compounds such as bismuth acetate, and organic compound stabilizers such as butynediol as additives for the electroless nickel plating bath. Additives such as pH adjusters, pH buffers, pit inhibitors and surfactants can be added to the extent that the effects of the present invention are not impaired, but organic sulfur compounds (compounds containing carbon and sulfur) The concentration is preferably 0.001 ppm (mg / L) or less, and particularly preferably contains no organic sulfur compound. When the organic sulfur compound is contained in the electroless nickel plating bath, the fatigue strength tends to decrease. The concentration of additives other than the organic sulfur compound is usually 0.0001 to 30 g / L, particularly 0.0002 to 20 g / L.

本発明の無電解ニッケルめっき浴のｐＨは、通常４〜７、特に４．５〜６である。また、めっき処理の温度及び時間は、めっき速度及び形成するめっき皮膜の厚さによっても異なるが、めっき温度は、通常７０〜９５℃であり、めっき時間は、通常１０〜３０分程度である。   The pH of the electroless nickel plating bath of the present invention is usually 4 to 7, particularly 4.5 to 6. Moreover, although the temperature and time of a plating process change also with the plating rate and the thickness of the plating film to form, plating temperature is 70-95 degreeC normally, and plating time is about 10-30 minutes normally.

本発明において形成する無電解めっき皮膜中の硫黄含有量は、０．０１質量％以下、好ましくは０．００５質量％以下であることが好ましい。   The sulfur content in the electroless plating film formed in the present invention is 0.01% by mass or less, preferably 0.005% by mass or less.

本発明において、対象とする鉄鋼材料は、例えば純鉄、電解鉄、炭素鋼（低炭素鋼、高炭素鋼など）、合金鋼（低炭素ニッケルクロム合金鋼など）、超合金、リムド鋼、キャップド鋼、セミキルド鋼、キルド鋼などであるが、チェーンブロック等に用いられるリンクチェーンなどのように、使用中に表面に摺動による摩擦を受けるような鉄鋼部材の表面に良好な耐食性、耐摩耗性及び疲労強度を与えるから、本発明の無電解ニッケルめっき方法は、このような摺動部材、特にリンクチェーンの表面処理として好適である。   In the present invention, target steel materials include, for example, pure iron, electrolytic iron, carbon steel (low carbon steel, high carbon steel, etc.), alloy steel (low carbon nickel chromium alloy steel, etc.), superalloy, rimmed steel, cap Steel, semi-killed steel, killed steel, etc., but good corrosion resistance and wear resistance on the surface of steel members that receive friction due to sliding on the surface during use, such as link chains used in chain blocks, etc. Therefore, the electroless nickel plating method of the present invention is suitable as a surface treatment for such a sliding member, particularly a link chain.

鉄鋼材料の表面に形成する無電解ニッケルめっき皮膜中のリン含有量は、特に限定されず、本発明の無電解ニッケルめっき皮膜は、リンの含有率によらず耐食性及び耐摩耗性と共に、疲労強度が良好であるが、通常１．５〜１３質量％、特に３〜１０質量％程度の範囲である。また、無電解ニッケルめっき皮膜の膜厚は３〜３０μｍ、特に５〜１０μｍが好適である。   The phosphorus content in the electroless nickel plating film formed on the surface of the steel material is not particularly limited, and the electroless nickel plating film of the present invention has fatigue strength as well as corrosion resistance and wear resistance regardless of the phosphorus content. Is usually in the range of about 1.5 to 13% by mass, particularly about 3 to 10% by mass. Further, the film thickness of the electroless nickel plating film is preferably 3 to 30 μm, particularly 5 to 10 μm.

以下、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the following Example.

［実施例１〜４、比較例１〜４］
表１に示される組成の無電解ニッケルリンめっき浴を用い、浸炭処理を施して表面硬化層を形成した低炭素ニッケルクロム合金鋼のリンクチェーンの表面に、膜厚８μｍの無電解ニッケルリンめっき皮膜を形成し、疲労強度を評価した。評価は、ＪＩＳ Ｂ ８８１２：２００４（チェーンブロック用リンクチェーン）の疲れ強さ試験に準拠して行った。結果を表１に示す。また、めっき皮膜中のリン含有量及びめっきの析出速度を表１に併記した。なお、めっきしていないチェーンの疲労強度は２９０Ｎ／ｍｍ2である。 [Examples 1-4, Comparative Examples 1-4]
An electroless nickel phosphorus plating film having a thickness of 8 μm is formed on the surface of a link chain of a low carbon nickel chromium alloy steel formed by carburizing and forming a hardened surface layer using an electroless nickel phosphorus plating bath having the composition shown in Table 1. The fatigue strength was evaluated. Evaluation was performed based on the fatigue strength test of JIS B 8812: 2004 (link chain for chain block). The results are shown in Table 1. Table 1 also shows the phosphorus content in the plating film and the deposition rate of plating. The fatigue strength of the unplated chain is 290 N / mm 2 .

Figure 2008248318
Figure 2008248318

Claims (8)

鉄鋼材料表面への無電解ニッケルめっき方法であって、水溶性ニッケル塩と、還元剤と、錯化剤としてＮｉに対する錯形成定数よりＦｅに対する錯形成定数が小さい錯化剤とを含有する無電解ニッケルめっき浴にて無電解ニッケルめっき皮膜を形成することを特徴とする無電解ニッケルめっき方法。   An electroless nickel plating method on the surface of a steel material, comprising a water-soluble nickel salt, a reducing agent, and a complexing agent having a complexing constant for Fe smaller than that for Ni as a complexing agent An electroless nickel plating method comprising forming an electroless nickel plating film in a nickel plating bath. 上記錯化剤がグルタミン酸又はその化合物であることを特徴とする請求項１記載の無電解ニッケルめっき方法。   2. The electroless nickel plating method according to claim 1, wherein the complexing agent is glutamic acid or a compound thereof. 無電解ニッケルめっき皮膜中の硫黄含有量が０．０１質量％以下であることを特徴とする請求項１又は２記載の無電解ニッケルめっき方法。   The electroless nickel plating method according to claim 1 or 2, wherein the sulfur content in the electroless nickel plating film is 0.01 mass% or less. リンクチェーン表面への無電解ニッケルめっきであることを特徴とする請求項１乃至３のいずれか１項記載の無電解ニッケルめっき方法。   4. The electroless nickel plating method according to claim 1, wherein the electroless nickel plating is performed on the surface of the link chain. 水溶性ニッケル塩と、還元剤と、錯化剤としてＮｉに対する錯形成定数よりＦｅに対する錯形成定数が小さい錯化剤とを含有する無電解ニッケルめっき浴にて無電解ニッケルめっきして、表面に無電解ニッケルめっき皮膜を形成したことを特徴とする鉄鋼部材。   Electroless nickel plating in an electroless nickel plating bath containing a water-soluble nickel salt, a reducing agent, and a complexing agent having a complexing constant smaller than that of Ni as a complexing agent. An iron and steel member formed with an electroless nickel plating film. 上記錯化剤がグルタミン酸又はその化合物であることを特徴とする請求項５記載の鉄鋼部材。   The steel member according to claim 5, wherein the complexing agent is glutamic acid or a compound thereof. 無電解ニッケルめっき皮膜中の硫黄含有量が０．０１質量％以下であることを特徴とする請求項５又は６記載の鉄鋼部材。   The steel member according to claim 5 or 6, wherein the sulfur content in the electroless nickel plating film is 0.01 mass% or less. リンクチェーンであることを特徴とする請求項５乃至７のいずれか１項記載の鉄鋼部材。   The steel member according to any one of claims 5 to 7, wherein the steel member is a link chain.
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