JPS6344840B2 - - Google Patents
Info
- Publication number
- JPS6344840B2 JPS6344840B2 JP59261813A JP26181384A JPS6344840B2 JP S6344840 B2 JPS6344840 B2 JP S6344840B2 JP 59261813 A JP59261813 A JP 59261813A JP 26181384 A JP26181384 A JP 26181384A JP S6344840 B2 JPS6344840 B2 JP S6344840B2
- Authority
- JP
- Japan
- Prior art keywords
- eutectoid
- fluorine
- plating
- film
- current density
- 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
Links
- 238000007747 plating Methods 0.000 claims description 84
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 83
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 33
- 229910052731 fluorine Inorganic materials 0.000 claims description 33
- 239000011737 fluorine Substances 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 238000009713 electroplating Methods 0.000 claims description 11
- 230000001050 lubricating effect Effects 0.000 claims description 11
- 239000002861 polymer material Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- -1 Polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 239000000835 fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- UFINAXPUHDXMRL-UHFFFAOYSA-N C=CCl.F.F.F Chemical compound C=CCl.F.F.F UFINAXPUHDXMRL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明は耐摩耗性皮膜の形成方法に関し、特に
硬さと潤滑性を備えた耐摩耗性皮膜を得ることが
できる耐摩耗性皮膜の形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for forming a wear-resistant film, and more particularly to a method for forming a wear-resistant film that can provide a wear-resistant film with hardness and lubricity.
従来技術及びその問題点
従来より、表面処理によつて耐摩耗性皮膜を形
成することは広く行なわれている。この場合、耐
摩耗性皮膜は、主として硬度を大きくしたもの
と、潤滑性を付与したものとに大別され、従来は
その目的に応じて硬度を高めるための表面処理或
いは潤滑性を得るための表面処理がそれぞれ施さ
れていたが、同時に硬さと潤滑性とを兼備させた
耐摩耗皮膜を与えることは困難であつた。このた
め、本発明者は例えば電気めつき法により硬度の
大きいめつき皮膜を与えるめつき浴から第１層と
して硬度の大きい耐摩耗性皮膜を形成した後、そ
の上に上記めつき浴とは別個の潤滑性めつき皮膜
を与えるめつき浴から第２層として潤滑性を有す
る耐摩耗性皮膜を形成する（或いはこれとは逆に
第１層として潤滑性めつき皮膜を形成し、第２層
として高硬度めつき皮膜を形成する）など、別個
の表面処理により硬さと潤滑性とをそれぞれ有す
る複数層の耐摩耗性皮膜を形成する方法を検討し
たが、この方法は表面処理作業が複雑化し、面倒
となる上、硬さを与える層と潤滑性を与える層と
の間の密着性に問題が生じる場合が多い。Prior Art and its Problems Conventionally, forming a wear-resistant film by surface treatment has been widely practiced. In this case, wear-resistant coatings are mainly divided into those with increased hardness and those with lubricating properties. Conventionally, depending on the purpose, surface treatment to increase hardness or coating to obtain lubricity has been used. Although various surface treatments have been applied, it has been difficult to provide a wear-resistant coating that has both hardness and lubricity at the same time. For this reason, the present inventor has formed a hard and wear-resistant film as a first layer from a plating bath that provides a hard plating film by, for example, electroplating, and then uses the above-mentioned plating bath Forming a lubricating wear-resistant coating as a second layer from a plating bath that provides a separate lubricating plating coating (or conversely forming a lubricating plating coating as a first layer and forming a second layer) A method of forming a multi-layer wear-resistant film that has hardness and lubricity through separate surface treatments, such as forming a high-hardness plated film as a layer, has been investigated, but this method requires complicated surface treatment work. In addition, problems often occur in the adhesion between the hardness layer and the lubricity layer.
発明の概要
本発明者は、上記事情に鑑み、硬さと潤滑性の
両者を同時に満足し、しかも密着性に問題がない
耐摩耗性皮膜を簡単かつ確実に形成する方法につ
いて鋭意研究を行なつた結果、電気ニツケルめつ
き液中に水不溶性フツ素系高分子物質（複合材）
を分散させてなる複合電気ニツケルめつき浴を使
用し、この中に被処理物を浸漬して所定時間間隔
で陰極電流密度を変えてめつきを行なうことによ
り、ニツケルめつき皮膜中の複合材共析量が陰極
電流密度に依存して変動し、それ故複合材の共析
量の多少によつて硬さを主体としためつき皮膜、
潤滑性を主体としためつき皮膜が同一ニツケルめ
つき浴から連続して形成され、従つて上記目的を
達成した耐摩耗性皮膜が得られることを知見し
た。Summary of the Invention In view of the above circumstances, the present inventor has conducted extensive research into a method for easily and reliably forming a wear-resistant film that satisfies both hardness and lubricity at the same time and has no problems with adhesion. As a result, a water-insoluble fluorine-based polymer material (composite material) was added to the electric nickel plating solution.
The composite material in the nickel plating film is immersed in a composite electric nickel plating bath in which nickel is dispersed. The amount of eutectoid varies depending on the cathode current density, and therefore, depending on the amount of eutectoid in the composite material, a tight film mainly has hardness,
It has been found that tight coatings mainly having lubricity can be formed successively from the same nickel plating bath, and that a wear-resistant coating that achieves the above objective can be obtained.
即ち、電気ニツケルめつき液中にフツ素系高分
子物質を分散させた複合電気ニツケルめつき浴を
用いて被処理物を電気ニツケルめつきする場合、
図面に示したように陰極電流密度を1A／ｄm2よ
り小さい低電流密度にするとフツ素系高分子物質
の共析量が多くなり、陰極電流密度を１〜6A／
ｄm2の高電流密度にするとフツ素系高分子物質の
共析量が低くなり、それ故陰極電流密度を1A／
ｄm2より低くして電気ニツケルめつきを行なうこ
とにより、フツ素系高分子物質の共析量を多くし
て潤滑性を主体としたニツケルめつき皮膜を得る
と共に、陰極電流密度を１〜6A／ｄm2と高くし
て電気ニツケルめつきを行なうことにより、フツ
素系高分子物質の共析量を低くしてめつき皮膜母
相の硬さを機能させることで硬さを主体としたニ
ツケルめつき皮膜を得ることができ、しかもこれ
らのニツケルめつき皮膜がニツケルめつき中に電
流密度を変化させるだけで連続して完全一体に形
成、積層されるので、密着性に全く問題はなく、
上記方法によつて得られた皮膜が耐摩耗性皮膜と
して優れていることを知見し、本発明をなすに至
つたものでる。 That is, when electro-nickel plating a workpiece using a composite electric nickel plating bath in which a fluorine-based polymer substance is dispersed in an electric nickel plating solution,
As shown in the drawing, when the cathode current density is set to a low current density of less than 1A/ dm2 , the amount of eutectoid of the fluorine-based polymer increases.
A high current density of dm 2 results in a low eutectoid amount of fluorine-based polymers, therefore the cathode current density is reduced to 1A/dm2.
By performing electric nickel plating at a temperature lower than dm 2 , the amount of eutectoid fluorine-based polymer material is increased to obtain a nickel plating film mainly having lubricity, and the cathode current density is 1 to 6 A. By performing electric nickel plating at a high temperature of /dm 2 , the amount of fluorine-based polymer material eutectoid is lowered and the hardness of the plating film matrix is used to make the hardness of the plating film work. It is possible to obtain a plating film, and since these nickel plating films are formed and laminated continuously and completely in one piece simply by changing the current density during nickel plating, there is no problem with adhesion.
It was discovered that the film obtained by the above method is excellent as a wear-resistant film, and this led to the present invention.
以下、本発明につき更に詳しく説明する。 The present invention will be explained in more detail below.
発明の構成
本発明に係る耐摩耗性皮膜の形成方法は、電気
ニツケルめつき液中に水不溶性フツ素系高分子物
質を複合材として分散させた複合電気ニツケルめ
つき浴中に被処理物を浸漬し、1A／ｄm2より小
さい陰極電流密度で電気めつきを行なうことによ
りフツ素系高分子物質が共析した潤滑性めつき皮
膜を得る操作と、１〜6A／ｄm2の陰極電流密度
で電気めつきを行なうことによりフツ素系高分子
物質の共析量が前記潤滑性めつき皮膜中のフツ素
系高分子物質共析量よりも低い硬質めつき皮膜を
得る操作とを交互に連続して行なつて、前記陰極
電流密度に応じた互に異なるフツ素系高分子物質
の共析量を有するニツケルめつき皮膜を連続的に
順次一体形成するものである。Structure of the Invention The method for forming a wear-resistant film according to the present invention involves placing an object to be treated in a composite electric nickel plating bath in which a water-insoluble fluorine-based polymer substance is dispersed as a composite material in an electric nickel plating solution. immersion and electroplating at a cathode current density of less than 1 A/dm 2 to obtain a lubricating plating film in which a fluorine-based polymer substance is eutectoid; and a cathode current density of 1 to 6 A/dm 2 . and electroplating to obtain a hard plating film in which the amount of fluorine-based polymeric substance eutectoid is lower than the amount of fluorine-based polymeric substance eutectoided in the lubricating plating film. This is carried out continuously to integrally form nickel plating films having different eutectoid amounts of fluorine-based polymer substances depending on the cathode current density.
ここで、電気ニツケルめつき液としては公知の
めつき液が使用できる。 Here, a known plating solution can be used as the electric nickel plating solution.
また、電気めつき液に分散させるフツ素系高分
子物質（複合材）としては、水不溶性粒子又は繊
維であればいずれのものでもよく、特に制限され
ないが、例示すると４フツ化エチレン樹脂、４フ
ツ化エチレン―６フツ化プロピレン共重合樹脂、
３フツ化塩化エチレン樹脂、フツ化ビニリデン樹
脂、フツ化ビニル樹脂、フツ化黒鉛等のフツ素系
高分子物質が潤滑性を付与するのに好適に使用で
きる。なお、本発明においては、必要によつて上
記のフツ素系高分子物質以外の複合材を添加する
こともできる。 Further, the fluorine-based polymer substance (composite material) to be dispersed in the electroplating solution may be any water-insoluble particles or fibers, and is not particularly limited, but examples include tetrafluoroethylene resin, Fluorinated ethylene-hexafluorinated propylene copolymer resin,
Fluorine-based polymeric substances such as chloroethylene trifluoride resin, vinylidene fluoride resin, vinyl fluoride resin, and graphite fluoride can be suitably used to impart lubricity. In the present invention, a composite material other than the above-mentioned fluorine-based polymer substance may be added if necessary.
なお、複合材として水不溶性粒子を用いる場
合、その粒径は0.01〜100μm、特に0.5〜20μmと
することが好ましく、また繊維を用いる場合、そ
の長さは0.1〜500μm、特に0.5〜10μmとすること
が好ましい。 In addition, when using water-insoluble particles as a composite material, the particle size is preferably 0.01 to 100 μm, especially 0.5 to 20 μm, and when using fibers, the length is 0.1 to 500 μm, especially 0.5 to 10 μm. It is preferable.
また、複合材のめつき液に対する添加量は種々
変更し得るが、0.1〜500ｇ／、特に１〜100
ｇ／とすることが好ましい。この場合、複合材
の分散剤としてめつき液中にアニオン系、ノニオ
ン系、カチオン系、両性イオン系といつた界面活
性剤の１種又は２種以上を添加することができ
る。 The amount of composite material added to the plating solution can be varied, but it is 0.1 to 500 g/, especially 1 to 100 g/
It is preferable to set it as g/. In this case, one or more types of surfactants such as anionic, nonionic, cationic, and amphoteric surfactants can be added to the plating solution as a dispersant for the composite material.
本発明は上述した複合材（フツ素系高分子物
質）を電気ニツケルめつき液に分散させてなる複
合ニツケルめつき浴により被処理物を電気ニツケ
ルめつきするものであるが、この場合陰極電流密
度を所定時間間隔で変化させ、これにより複合材
の共析量を所定時間間隔で変化させながら電気ニ
ツケルめつきを行なうものである。 In the present invention, a workpiece is electrically plated with nickel using a composite nickel plating bath formed by dispersing the above-mentioned composite material (fluorine-based polymer material) in an electrolytic nickel plating solution. Electric nickel plating is performed while changing the density at predetermined time intervals, thereby changing the eutectoid amount of the composite material at predetermined time intervals.
即ち、上述したように電気ニツケルめつき浴に
分散したフツ素系高分子物質（複合材）の共析量
は陰極電流密度を1A／ｄm2より低くすることに
より増大し、陰極電流密度を１〜6A／ｄm2と高
くすることにより減少するので、耐摩耗性皮膜の
目的に応じてフツ素系高分子物質の共析量を変化
させ、目的とする耐摩耗特性を得るものである。
即ち、電気ニツケルめつき液にフツ素系高分子物
質を分散させた複合めつき浴を用いてめつきする
場合、最初陰極電流密度を１〜6A／ｄm2にして
めつきを行ない、所定のニツケルめつき皮膜の厚
みのうち半分の厚みはフツ素系高分子物質の共析
量を少なくし、次に陰極電流密度を1A／ｄm2よ
り低くしてめつきを行ない、残りの半分の厚みに
対するフツ素系高分子物質の共析量を多くする。
これにより、ニツケルめつき皮膜の下層はフツ素
系高分子物質の共析量が低く、硬さを主体とした
皮膜となるのに対し、めつき皮膜の上層はフツ素
系高分子物質の共析量が多く、潤滑性を主体とし
た皮膜となるので、この耐摩耗性皮膜は最初に摺
動部の相手材とのなじみ作用を発揮すると共に、
ニツケルめつき皮膜の潤滑性を主体とする上層が
摩耗してきた場合にはニツケルめつき皮膜の下層
においてマトリツクスの硬さで耐摩耗性効果を与
えることができるものである。また、これとは逆
に、最初に1A／ｄm2より低い電流密度でめつき
し、次に１〜6A／ｄm2の高電流密度でめつきす
る場合は、ニツケルめつき皮膜の下層がフツ素系
高分子物質の共析量が多く、潤滑性を主体とした
皮膜となり、ニツケルめつき皮膜の上層がフツ素
系高分子物質の共析量が少なく、硬さを主体とし
た皮膜となるが、この耐摩耗性皮膜も種々の用途
に有効に使用されるものである。 That is, as mentioned above, the eutectoid amount of the fluorine-based polymer material (composite material) dispersed in the electric nickel plating bath increases by lowering the cathode current density to below 1 A/dm2; Since it decreases by increasing the wear resistance to 6 A/dm 2 , the amount of eutectoid of the fluorine-based polymer substance is varied depending on the purpose of the wear-resistant coating to obtain the desired wear-resistant properties.
That is, when plating is performed using a composite plating bath in which a fluorine-based polymer substance is dispersed in an electric nickel plating solution, plating is first performed at a cathode current density of 1 to 6 A/ dm2 , and a predetermined For half of the thickness of the nickel plating film, reduce the amount of fluorine-based polymer substance eutectoid, then perform plating at a cathode current density lower than 1A/ dm2 , and then for the remaining half thickness. Increase the amount of eutectoid of fluorine-based polymer material.
As a result, the lower layer of the nickel plating film has a low eutectoid amount of fluorine-based polymer material, resulting in a film that is mainly hard, whereas the upper layer of the plating film has a low eutectoid amount of fluorine-based polymer material, whereas the upper layer of the plating film has a low eutectoid amount of fluorine-based polymer material. Since the coating has a large amount of lubricity, this wear-resistant coating initially exerts a conforming effect with the mating material of the sliding part, and
When the upper layer of the nickel plating film, which mainly has lubricating properties, wears out, the hardness of the matrix in the lower layer of the nickel plating film can provide a wear-resistant effect. Conversely, if you first plate at a current density lower than 1 A/dm 2 and then plate at a higher current density of 1 to 6 A/dm 2 , the lower layer of the nickel plating film will become exposed. There is a large amount of eutectoid polymeric substances, resulting in a film mainly for lubricity, and the upper layer of the nickel plating film has a small amount of eutectoid polymeric substances, resulting in a film mainly for hardness. However, this wear-resistant coating can also be effectively used for various purposes.
なお、電流密度の変化、即ち複合材共析量の変
化は必要に応じ複数回行なうことができ、これに
よつて３層以上の複合材共析量の異なるめつき皮
膜を形成することもできる。 Note that the change in current density, that is, the change in the amount of composite material eutectoid, can be performed multiple times as necessary, and thereby it is also possible to form a plated film with three or more layers with different amounts of composite material eutectoid. .
ここで、所定時間間隔で陰極電流密度を変化さ
せる方法としては、タイマーを用いたり、パルス
法を採用するなどのことによつて行なうことがで
き、まためつき時間の長短によつてめつき皮膜の
厚みを調節することができる。この場合、電流密
度を変化させる時期は必ずしも制限されないが、
１〜500μmの析出量において電流密度を変化させ
ることが好ましい。なお、めつき皮膜の総厚みは
使用目的等によつて選定されるが、特に10〜
50μmとすることが好ましい。 Here, as a method of changing the cathode current density at predetermined time intervals, it can be done by using a timer or by adopting a pulse method. The thickness can be adjusted. In this case, the timing of changing the current density is not necessarily limited, but
It is preferable to change the current density at a deposition amount of 1 to 500 μm. The total thickness of the plating film is selected depending on the purpose of use, etc., but in particular,
The thickness is preferably 50 μm.
なお、その他のめつき条件、例えばめつき温度
や撹拌などはめつきの種類等に応じ、通常採用さ
れる条件を選定することができる。更にめつき
後、必要により熱処理その他の後処理を施すこと
ができる。 Note that other plating conditions such as plating temperature and stirring can be selected from commonly used conditions depending on the type of plating. Furthermore, after plating, heat treatment and other post-treatments can be performed if necessary.
また、被処理物の材質に特に制限はなく、複合
電気めつき可能なものであればいずれのものをも
用いることができる。例示すると、スチール、ス
テンレススチール、銅、銅合金、亜鉛、アルミニ
ウム、マグネシウム等の金属素材、無電解めつき
法などの適宜な方法で導電化処理したプラスチツ
ク等が挙げられ、これらの素材は適宜な前処理を
行ない、更に必要に応じて下地めつき皮膜を形成
した後、本発明の耐摩耗性皮膜が形成される。 Further, there is no particular restriction on the material of the object to be treated, and any material that can be used for composite electroplating can be used. Examples include metal materials such as steel, stainless steel, copper, copper alloys, zinc, aluminum, and magnesium, and plastics that have been made conductive by an appropriate method such as electroless plating. After pretreatment and, if necessary, formation of a base plating film, the wear-resistant film of the present invention is formed.
発明の効果
本発明の耐摩耗性皮膜の形成方法によれば、電
気ニツケルめつき液中に水不溶性フツ素系高分子
物質を複合材として分散させた複合電気ニツケル
めつき浴中に被処理物を浸漬し、1A／ｄm2より
小さい陰極電流密度で電気めつきを行なうことに
よりフツ素系高分子物質が共析した潤滑性めつき
皮膜を得る操作と、１〜6A／ｄm2の陰極電流密
度で電気めつきを行なうことによりフツ素系高分
子物質の共析量が前記潤滑性めつき皮膜中のフツ
素系高分子物質共析量よりも低い硬質めつき皮膜
を得る操作とを交互に連続して行なつて、前記陰
極電流密度に応じた互に異なるフツ素系高分子物
質の共析量を有するニツケルめつき皮膜を連続的
に順次一体形成するようにしたので、潤滑性を主
体としたニツケルめつき皮膜と硬さを主体とした
ニツケルめつき皮膜とを同一ニツケルめつき浴か
ら連続して一体に形成でき、このため両皮膜の密
着性に全く問題は生ぜず、目的とする耐摩耗特性
に応じた複合ニツケル皮膜を簡単かつ確実に形成
し得る。Effects of the Invention According to the method for forming a wear-resistant film of the present invention, the object to be treated is placed in a composite electric nickel plating bath in which a water-insoluble fluorine-based polymer substance is dispersed as a composite material in an electric nickel plating solution. and electroplating at a cathode current density of less than 1 A/dm 2 to obtain a lubricating plating film in which a fluorine-based polymer substance is eutectoid, and a cathode current of 1 to 6 A/dm 2. Alternating with the operation of performing electroplating at high density to obtain a hard plating film in which the amount of the fluorine-based polymer substance is lower than the amount of the fluorine-based polymer substance eutectoid in the lubricating plating film. The nickel plating film having different eutectoid amounts of fluorine-based polymer substances depending on the cathode current density is formed in succession, thereby improving the lubricity. A nickel plating film mainly composed of nickel and a nickel plating film mainly composed of hardness can be formed continuously and integrally from the same nickel plating bath, so there is no problem with the adhesion between the two films, and the objective is achieved. It is possible to easily and reliably form a composite nickel film according to the wear resistance properties.
以下、実施例を示し、本発明を具体的に説明す
るが、本発明は下記の実施例に制限されるもので
はない。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.
実施例 １ 下記組成の複合電気めつき浴を製造した。Example 1 A composite electroplating bath having the following composition was manufactured.
硫酸ニツケル 280ｇ／
塩化ニツケル 45 〃
ホウ酸 40 〃
ポリテトラフルオロエチレン粒子
100 〃
分散剤 0.1 〃
次に、このめつき浴を用い、常法により前処理
した鋼板上に下記条件で複合めつきを施した。 Nickel sulfate 280g/Nickel chloride 45 Boric acid 40 Polytetrafluoroethylene particles
100 〃 Dispersant 0.1 〃 Next, using this plating bath, composite plating was performed under the following conditions on a steel plate pretreated by a conventional method.
めつき温度 45℃
撹 拌 ポンプによる液撹拌
アノード 電気ニツケル
この場合、最初の９分間は陰極電流密度6A／
ｄm2でめつきを行ない、ポリテトラフルオロエチ
レン粒子共析量７容量％の硬さを主体とする皮膜
を約10μm形成し、次にめつきしつつある状態の
まま陰極電流密度を0.3A／ｄm2に変えて約250分
間めつきを行ない、上記の硬さを主体とする皮膜
上に共析量14容量％の潤滑性を主体とする皮膜を
15μm形成した。 Plating temperature 45℃ Stirring Liquid stirring by pump Anode Electric nickel In this case, the cathode current density is 6A/1 for the first 9 minutes.
Plating is carried out at dm 2 to form a film with a hardness of approximately 10 μm with a eutectoid content of polytetrafluoroethylene particles of 7% by volume, and then the cathode current density is increased to 0.3 A/dm while the plating is in progress. dm 2 and plating for about 250 minutes to form a film mainly having lubricity with a eutectoid content of 14% by volume on top of the film mainly having the above-mentioned hardness.
A thickness of 15 μm was formed.
この耐摩耗性皮膜は、特に摺動部品等の用途に
有効である。 This wear-resistant film is particularly effective for applications such as sliding parts.
実施例 ２ 下記組成の複合電気めつき浴を製造した。Example 2 A composite electroplating bath having the following composition was manufactured.
スルフアミン酸ニツケル 500ｇ／
塩化ニツケル 20 〃
ホウ酸 35 〃
ポリテトラフルオロエチレン粒子
80 〃
分散剤 0.05 〃
次に、このめつき浴を用い、常法により前処理
した鋼板上に下記条件で複合めつきを施した。 Nickel sulfamate 500g/Nickel chloride 20 Boric acid 35 Polytetrafluoroethylene particles
80 〃 Dispersant 0.05 〃 Next, using this plating bath, composite plating was performed under the following conditions on a steel plate pretreated by a conventional method.
めつき温度 45℃
撹 拌 ポンプによる液撹拌
アノード 電気ニツケル
この場合、最初の約70分間は陰極電流密度
0.5A／ｄm2でめつきを行ない、ポリテトラフル
オロエチレン粒子共析量42容量％の潤滑性を主体
とする皮膜を7μm形成し、次にめつきしつつある
状態のまま陰極電流密度を2A／ｄm2に変えて約
12分間めつきを行ない、上記の潤滑性を主体とす
る皮膜上に共析量25容量％の硬さを主体とする皮
膜を5μm形成した。 Plating temperature 45℃ Stirring Liquid stirring by pump Anode Electric nickel In this case, the cathode current density is
Plating was carried out at 0.5 A/dm 2 to form a 7 μm film mainly having lubricity with a polytetrafluoroethylene particle eutectoid content of 42% by volume, and then a cathode current density of 2 A was applied while the plating was in progress. /dm 2 to approx.
Plating was carried out for 12 minutes to form a 5 μm thick film mainly having hardness with a eutectoid content of 25% by volume on the above film mainly having lubricity.
この耐摩耗性皮膜は、特にシヨツト数の多い金
型等の用途に有効である。 This wear-resistant coating is particularly effective for applications such as molds with a large number of shots.
次に、参考例として陰極電流密度と共析量との
関係を示す。 Next, as a reference example, the relationship between the cathode current density and the amount of eutectoid is shown.
参考例
下記組成の複合電気めつき浴を製造し、常法に
より前処理した鋼板上に下記めつき条件でめつき
を行ない、得られた複合めつき皮膜中のポリテト
ラフルオロエチレン粒子の共析量を測定して、陰
極電流密度との関係を調べた。結果を図面に示
す。Reference example: A composite electroplating bath with the following composition was manufactured, and plating was performed under the following plating conditions on a steel plate pretreated by a conventional method, and the polytetrafluoroethylene particles in the resulting composite plating film were eutectoid. The amount was measured and its relationship with cathode current density was investigated. The results are shown in the drawing.
組 成
スルフアミン酸ニツケル 500ｇ／
塩化ニツケル 30 〃
ホウ酸 35 〃
ポリテトラフルオロエチレン粒子
80 〃
分散剤 0.05 〃
図面の結果より、陰極電流密度を変化させるこ
とによつて複合材（ポリテトラフルオロエチレ
ン）の共析量を効果的に変えることができること
が知見される。Composition Nickel sulfamate 500g/Nickel chloride 30 Boric acid 35 Polytetrafluoroethylene particles
80 〃 Dispersant 0.05 〃 From the results in the drawings, it is found that the amount of eutectoid in the composite material (polytetrafluoroethylene) can be effectively changed by changing the cathode current density.
図面は陰極電流密度と共析材共析量との関係を
示すグラフである。
The drawing is a graph showing the relationship between the cathode current density and the amount of eutectoid material.
Claims (1)
高分子物質を複合材として分散させた複合電気ニ
ツケルめつき浴中に被処理物を浸漬し、1A／ｄ
m2より小さい陰極電流密度で電気めつきを行なう
ことによりフツ素系高分子物質が共析した潤滑性
めつき皮膜を得る操作と、１〜6A／ｄm2の陰極
電流密度で電気めつきを行なうことによりフツ素
系高分子物質の共析量が前記潤滑性めつき皮膜中
のフツ素系高分子物質共析量よりも低い硬質めつ
き皮膜を得る操作とを交互に連続して行なつて、
前記陰極電流密度に応じた互に異なるフツ素系高
分子物質の共析量を有するニツケルめつき皮膜を
連続的に順次一体形成することを特徴とする耐摩
耗性皮膜の形成方法。1. The object to be treated is immersed in a composite electric nickel plating bath in which a water-insoluble fluorine-based polymer substance is dispersed as a composite material in an electric nickel plating solution.
Electroplating is performed at a cathode current density smaller than m 2 to obtain a lubricating plating film in which a fluorine-based polymer material is eutectoid. Alternating and consecutively performing the operations to obtain a hard plating film in which the amount of the fluorine-based polymeric substance eutectoid is lower than the amount of the fluorine-based polymeric substance eutectoid in the lubricating plating film. hand,
A method for forming a wear-resistant film, which comprises continuously and sequentially integrally forming nickel plating films having eutectoid amounts of different fluorine-based polymer substances depending on the cathode current density.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26181384A JPS61143596A (en) | 1984-12-13 | 1984-12-13 | Formation of wear resistant film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26181384A JPS61143596A (en) | 1984-12-13 | 1984-12-13 | Formation of wear resistant film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61143596A JPS61143596A (en) | 1986-07-01 |
| JPS6344840B2 true JPS6344840B2 (en) | 1988-09-07 |
Family
ID=17367070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26181384A Granted JPS61143596A (en) | 1984-12-13 | 1984-12-13 | Formation of wear resistant film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61143596A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0530983Y2 (en) * | 1988-09-02 | 1993-08-09 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0277593A (en) * | 1988-09-13 | 1990-03-16 | Asahi Daiyamondo Kogyo Kk | Production of sharp-edged blade |
| JP2713848B2 (en) * | 1993-01-25 | 1998-02-16 | 住友大阪セメント株式会社 | Composite plating method and composite plating film |
| US5520791A (en) * | 1994-02-21 | 1996-05-28 | Yamaha Hatsudoki Kabushiki Kaisha | Non-homogenous composite plating coating |
| JPH11217699A (en) * | 1998-01-30 | 1999-08-10 | Noge Denki Kogyo:Kk | Plated formed body |
| JP6346778B2 (en) * | 2013-04-16 | 2018-06-20 | 株式会社ベスト | Electroplating solution for forming fluororesin particle-dispersed nickel plating film and method for forming plating film using the electroplating solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52109439A (en) * | 1976-03-10 | 1977-09-13 | Suzuki Motor Co | Composite plating method |
| JPS5437641A (en) * | 1977-08-31 | 1979-03-20 | Toshiba Corp | Optical system character reader |
-
1984
- 1984-12-13 JP JP26181384A patent/JPS61143596A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52109439A (en) * | 1976-03-10 | 1977-09-13 | Suzuki Motor Co | Composite plating method |
| JPS5437641A (en) * | 1977-08-31 | 1979-03-20 | Toshiba Corp | Optical system character reader |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0530983Y2 (en) * | 1988-09-02 | 1993-08-09 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61143596A (en) | 1986-07-01 |
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