JPH0521992B2 - - Google Patents
Info
- Publication number
- JPH0521992B2 JPH0521992B2 JP19736988A JP19736988A JPH0521992B2 JP H0521992 B2 JPH0521992 B2 JP H0521992B2 JP 19736988 A JP19736988 A JP 19736988A JP 19736988 A JP19736988 A JP 19736988A JP H0521992 B2 JPH0521992 B2 JP H0521992B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- plating
- alloy
- bath
- chromium
- 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 - Lifetime
Links
- 238000007747 plating Methods 0.000 claims description 34
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000005260 corrosion Methods 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 17
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 9
- 150000001845 chromium compounds Chemical class 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- 239000005078 molybdenum compound Substances 0.000 claims description 6
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 description 22
- 239000000956 alloy Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、クロム−モリブデン（Cr−Mo）合
金皮膜の作製方法に関し、更に詳述すると、電気
めつき法によりクラツクフリーで耐食性に優れた
Cr−Mo合金皮膜を作製する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a chromium-molybdenum (Cr-Mo) alloy film.
This invention relates to a method for producing a Cr-Mo alloy film.
従来、Cr−Mo合金皮膜を電気めつき法により
作製する手段としては、例えばクロム酸等の水溶
性クロム化合物とモリブデン酸ナトリウム等の水
溶性モリブデン化合物とを含むめつき浴を用いて
電気めつきを行なう方法が知られている。
Conventionally, as a means of producing a Cr-Mo alloy film by electroplating, for example, electroplating is performed using a plating bath containing a water-soluble chromium compound such as chromic acid and a water-soluble molybdenum compound such as sodium molybdate. There are known ways to do this.
しかしながら、上述した手段で得られたCr−
Mo合金皮膜、特にMoを３〜10％含有する合金
皮膜は、クラツクが多く、大気中などで容易に腐
食し易く、耐食性に劣るという欠点を一般に有し
ており、実用化するにはその性能が不十分なもの
であつた。 However, the Cr-
Mo alloy coatings, especially alloy coatings containing 3 to 10% Mo, generally have the disadvantages of having many cracks, being easily corroded in the atmosphere, and having poor corrosion resistance. was insufficient.
この場合、かかるCr−Mo合金めつき皮膜の耐
食性を向上させるため、Cr−Mo合金めつき皮膜
上に更にポーラスクロムめつきを施す二重クロム
めつき方式が行なわれている。しかし、Cr−Mo
合金めつき後、更にポーラスクロムめつきを行な
うことは、２度手間となつて時間と費用を要する
上、Cr−Mo合金めつき皮膜上に別のめつき皮膜
を形成するので、Cr−Mo合金めつき皮膜の特性
が十分生かされないという問題がある。 In this case, in order to improve the corrosion resistance of such a Cr-Mo alloy plating film, a double chromium plating method is used in which porous chromium plating is further applied on the Cr-Mo alloy plating film. However, Cr−Mo
Performing porous chromium plating after alloy plating requires twice the effort, time and cost, and also forms another plating film on the Cr-Mo alloy plating film, so Cr-Mo There is a problem in that the characteristics of the alloy plating film are not fully utilized.
本発明は上記事情を改善するためになされたも
ので、従来のようにCr−Mo合金めつき皮膜上に
ポーラスクロムめつきを施すことにより該ポーラ
スクロムめつき皮膜の作用で間接的にCr−Mo合
金めつき皮膜の耐食性を向上するという方法とは
異なり、めつき法によりそれ自体クラツクフリー
で耐食性に優れたCr−Mo合金皮膜を作製するこ
とが可能なCr−Mo合金皮膜の作製方法を提供す
ることを目的とする。 The present invention has been made to improve the above-mentioned situation, and by applying porous chromium plating on a Cr-Mo alloy plating film as in the past, the Cr-Mo alloy plating film indirectly Provides a method for producing a Cr-Mo alloy film that is crack-free and has excellent corrosion resistance using a plating method, unlike methods that improve the corrosion resistance of Mo alloy plating films. The purpose is to
本発明者らは、上記目的を達成するため、高耐
食性Cr−Mo合金めつき皮膜を得ることができる
電析条件について種々検討を行なつた結果、めつ
き浴の温度を35℃以下又は65℃以上として電析を
行なつた場合、クラツクフリーであると共に、不
導態膜の保護性により耐食性が向上したCr−Mo
合金皮膜が得られることを見い出し、本発明をな
すに至つた。
In order to achieve the above object, the present inventors conducted various studies on the electrodeposition conditions under which a highly corrosion-resistant Cr-Mo alloy plating film could be obtained. When electrodeposited at temperatures above ℃, Cr-Mo is crack-free and has improved corrosion resistance due to the protective properties of the passive film
It was discovered that an alloy film can be obtained, and the present invention was completed.
従つて、本発明は、水溶性クロム化合物と水溶
性モリブデン化合物とを含むめつき浴を用い、ク
ロム−モリブデン合金電気めつきをめつき浴温度
35℃以下又は65℃以上で行なつて、クラツクフリ
ーのクロム−モリブデン合金めつき皮膜を得るこ
とを特徴とする高耐食性クロム−モリブデン合金
皮膜の作製方法を提供するものである。 Therefore, the present invention uses a plating bath containing a water-soluble chromium compound and a water-soluble molybdenum compound to perform electroplating on a chromium-molybdenum alloy at a plating bath temperature.
The present invention provides a method for producing a highly corrosion-resistant chromium-molybdenum alloy film, which is characterized in that the process is carried out at 35°C or lower or 65°C or higher to obtain a crack-free chromium-molybdenum alloy plated film.
この場合、上記めつき浴からCr−Mo合金めつ
きを行なうことは従来行なわれているが、高耐食
性皮膜、特にMo含量が0.5〜４％の高耐食性Cr−
Mo合金めつき皮膜を得るための上記電析条件
は、本発明者らが新たに確立したものである。以
下、本発明につき更に詳しく説明する。 In this case, Cr-Mo alloy plating is conventionally performed from the above-mentioned plating bath.
The above electrodeposition conditions for obtaining a Mo alloy plating film were newly established by the present inventors. The present invention will be explained in more detail below.
本発明は、上述したように、水溶性クロム化合
物と水溶性モリブデン化合物とを含むめつき浴中
において、浴温を35℃以下又は65℃以上とした状
態でCr−Mo合金皮膜の電析を行なうようにした
ものである。 As described above, the present invention involves electrodeposition of a Cr-Mo alloy film in a plating bath containing a water-soluble chromium compound and a water-soluble molybdenum compound at a bath temperature of 35°C or lower or 65°C or higher. This is what I decided to do.
この場合、水溶性クロム化合物としてはクロム
酸等が用いられ、水溶性モリブデン化合物として
はモリブデン酸ナトリウム等を用いることができ
る。 In this case, chromic acid or the like can be used as the water-soluble chromium compound, and sodium molybdate or the like can be used as the water-soluble molybdenum compound.
また、これら化合物のめつき浴濃度としては、
クロム化合物をCrO3として100〜300ｇ／、よ
り好ましくは250〜300ｇ／、モリブデン化合物
をMoとして50〜300ｇ／、より好ましくは70
〜220ｇ／とすることができる。この場合、
Mo／CrO3は重量比として0.09〜0.25、特に0.09
〜0.15とすることが好ましく、これによりMo含
量が0.5〜４％のCr−Mo合金皮膜を得ることがで
きる。なお、浴中には必要に応じ硫酸等の他の適
宜な添加剤を加えることができる。 In addition, the plating bath concentration of these compounds is as follows:
100 to 300 g/, more preferably 250 to 300 g/, more preferably 250 to 300 g/ as CrO 3 of a chromium compound, 50 to 300 g/, more preferably 70 g/ of molybdenum compound as Mo
~220g/. in this case,
Mo/CrO 3 has a weight ratio of 0.09 to 0.25, especially 0.09
It is preferable to set the Mo content to 0.15 to 0.15, thereby making it possible to obtain a Cr-Mo alloy film with a Mo content of 0.5 to 4%. Note that other suitable additives such as sulfuric acid can be added to the bath as necessary.
本発明は、上記めつき浴の温度を35℃以下又は
65℃以上とするものであるが、浴温のより好まし
い範囲は25〜35℃、特に28〜32℃、或いは65〜75
℃、特に68〜72℃である。なお、浴温があまり低
くなつたり、高くなつたりすると、電流効率が悪
くなる場合がある。 In the present invention, the temperature of the plating bath is set to 35°C or lower or
The bath temperature should be 65°C or higher, but the more preferable range of bath temperature is 25 to 35°C, especially 28 to 32°C, or 65 to 75°C.
℃, especially 68-72℃. Note that if the bath temperature becomes too low or too high, the current efficiency may deteriorate.
本発明において、浴温以外の電析条件に特に制
限はないが、陰極電流密度は20〜50A／ｄとす
ることが好ましい。また攪拌を行なうことが好ま
しい。 In the present invention, there are no particular limitations on the electrodeposition conditions other than the bath temperature, but the cathode current density is preferably 20 to 50 A/d. It is also preferable to stir.
以上説明したように、本発明方法によれば、ク
ラツクフリーで、耐食性に優れたCr−Mo合金皮
膜を得ることができる。従つて、鉄、ニツケル等
の素地上に本発明方法でCr−Mo合金めつきを施
すことにより、素地が侵食されるのを防止し、素
地の寿命を延長することが可能である。また、本
発明によるめつき皮膜は、大気中において腐食し
難いため、広い実用的用途に用いることができ
る。更に、本発明による皮膜は、高硬度であるた
め、耐食性、耐摩耗性の両特性を同時に要求され
る用途に使用可能である。
As explained above, according to the method of the present invention, a crack-free Cr-Mo alloy film having excellent corrosion resistance can be obtained. Therefore, by applying Cr-Mo alloy plating to a substrate made of iron, nickel, etc. by the method of the present invention, it is possible to prevent the substrate from being eroded and extend the life of the substrate. Furthermore, the plating film according to the present invention is difficult to corrode in the atmosphere, so it can be used in a wide range of practical applications. Furthermore, since the coating according to the present invention has high hardness, it can be used in applications that require both corrosion resistance and wear resistance at the same time.
以下、実施例により本発明を具体的に示すが、
本発明は下記実施例に限定されるものではない。 Hereinafter, the present invention will be specifically illustrated by examples.
The present invention is not limited to the following examples.
モリブデン酸（Na2MoO4・2H2O）を75ｇ／
（浴No.１）、125ｇ／（浴No.２）又は170ｇ／
（浴No.３）とクロム酸とを含むめつき浴を用
い、種々の浴温、電流密度にて銅板上にCr−Mo
合金電気めつきを行なつた。なお、クロム酸重量
に対するモリブデン重量の割合（Mo／CrO3）
は、浴No.１は0.09、No.２は0.15、No.３は0.20とし
た。また、その他の添加剤としては、浴中Cr3+濃
度を一定に保つためにしゆう酸5.2ｇ／を添加
した。めつき条件は浴温度30〜70℃、電流密度20
〜100A／ｄとした。
75g of molybdic acid (Na 2 MoO 4・2H 2 O)/
(Bath No.1), 125g/(Bath No.2) or 170g/
Using a plating bath containing (bath No. 3) and chromic acid, Cr-Mo was deposited on a copper plate at various bath temperatures and current densities.
Alloy electroplating was performed. Furthermore, the ratio of molybdenum weight to chromic acid weight (Mo/CrO 3 )
The values were 0.09 for Bath No. 1, 0.15 for No. 2, and 0.20 for No. 3. Further, as other additives, 5.2 g of oxalic acid was added in order to keep the Cr 3+ concentration in the bath constant. Plating conditions are bath temperature 30~70℃, current density 20
~100A/d.
結果を第１図（浴No.１）、第２図（浴No.２）、第
３図（浴No.３）にそれぞれ示す。なお、図中○は
クラツクフリーで高耐食性の皮膜が得られた場
合、×はクラツクを有し耐食性が劣る皮膜が得ら
れた場合、△は〇と×との中間的な性質の皮膜が
得られた場合を示す。また、これらのめつきによ
り得られたCr−Mo合金皮膜中のMo含量は0.5〜
４％であつた。 The results are shown in Fig. 1 (bath No. 1), Fig. 2 (bath No. 2), and Fig. 3 (bath No. 3), respectively. In the figure, ○ indicates that a crack-free film with high corrosion resistance was obtained, × indicates that a film with cracks and poor corrosion resistance was obtained, and △ indicates that a film with properties intermediate between ○ and × was obtained. This shows the case where In addition, the Mo content in the Cr-Mo alloy film obtained by these plating is 0.5~
It was 4%.
第１〜３図の結果より、浴温を30℃以下、70℃
以上とすることにより、高耐食性皮膜が得られる
ことが知見される。 Based on the results shown in Figures 1 to 3, the bath temperature should be 30℃ or below and 70℃.
It has been found that a highly corrosion resistant film can be obtained by doing the above.
一方、上記めつき皮膜を用い、５％H2SO4、
60℃溶液中における浸漬試験を行なつた。結果を
第４図に示すが、浴温30℃、70℃において電析し
た膜は優れた耐食性を示すのに対し、上記両温度
の中間温度で電析した膜は耐食性が悪く、実用的
でないことが認められる。 On the other hand, using the above plating film, 5% H 2 SO 4 ,
An immersion test was conducted in a 60°C solution. The results are shown in Figure 4. Films deposited at bath temperatures of 30°C and 70°C show excellent corrosion resistance, whereas films deposited at a temperature intermediate between the above two temperatures have poor corrosion resistance and are not practical. It is recognized that
また、上記めつき皮膜を用い、３％NaCl、30
℃溶液中における孔食電位を測定した。結果を第
５図に示すが、30℃、70℃にて電析した膜は極め
て高い電位を示すことが認められる。 In addition, using the above plating film, 3% NaCl, 30
The pitting potential in a solution at ℃ was measured. The results are shown in Figure 5, and it can be seen that the films deposited at 30°C and 70°C exhibit extremely high potentials.
更に、上記めつき皮膜を用い、塩水墳霧試験を
行なつた。結果を参考図の写真に示すが、30℃、
70℃にて電析した皮膜は発錆が認められず、耐食
性に優れていることが知見される。 Furthermore, a salt water fog test was conducted using the above plated film. The results are shown in the photo of the reference figure.
The coating deposited at 70°C showed no rust and was found to have excellent corrosion resistance.
第１図乃至第３図はそれぞれ種々の電析条件で
Cr−Mo合金電気めつきを行なつたときの皮膜の
状態を示すグラフ、第４図は同皮膜の硫酸溶液へ
の浸漬試験結果を示すグラフ、第５図は同皮膜の
塩化ナトリウム溶液中における孔食電位を示すグ
ラフである。
Figures 1 to 3 are for various electrodeposition conditions.
A graph showing the state of the film when Cr-Mo alloy electroplating was performed. Figure 4 is a graph showing the results of an immersion test of the same film in a sulfuric acid solution. Figure 5 is a graph showing the state of the film in a sodium chloride solution. It is a graph showing pitting corrosion potential.
Claims (1)
物とを含むめつき浴を用い、クロム−モリブデン
合金電気めつきをめつき浴温度35℃以下又は65℃
以上で行なつて、クラツクフリーのクロム−モリ
ブデン合金めつき皮膜を得ることを特徴とする高
耐食性クロム−モリブデン合金皮膜の作製方法。1. Chromium-molybdenum alloy electroplating using a plating bath containing a water-soluble chromium compound and a water-soluble molybdenum compound at a plating bath temperature of 35°C or lower or 65°C.
A method for producing a highly corrosion-resistant chromium-molybdenum alloy film, which is characterized in that a crack-free chromium-molybdenum alloy plating film is obtained by carrying out the above steps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19736988A JPH0247285A (en) | 1988-08-08 | 1988-08-08 | Method for producing highly corrosion-resistant chromium-molybdenum alloy film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19736988A JPH0247285A (en) | 1988-08-08 | 1988-08-08 | Method for producing highly corrosion-resistant chromium-molybdenum alloy film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0247285A JPH0247285A (en) | 1990-02-16 |
| JPH0521992B2 true JPH0521992B2 (en) | 1993-03-26 |
Family
ID=16373351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19736988A Granted JPH0247285A (en) | 1988-08-08 | 1988-08-08 | Method for producing highly corrosion-resistant chromium-molybdenum alloy film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0247285A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196108A (en) * | 1991-04-24 | 1993-03-23 | Scot Industries, Inc. | Sucker rod oil well pump |
| JP3299680B2 (en) * | 1996-12-12 | 2002-07-08 | 帝国ピストンリング株式会社 | Cr-Mo-I alloy plating film and member having said film |
| DE10354760A1 (en) * | 2003-11-21 | 2005-06-23 | Enthone Inc., West Haven | Process for depositing nickel and chromium (VI) free metallic matte layers |
| DE102015105761A1 (en) | 2015-04-15 | 2016-10-20 | HDO Druckguss- und Oberflächentechnik GmbH | Component with applied chromium layer with tungsten content and molybdenum content and method for producing such a component by means of ternary deposition |
-
1988
- 1988-08-08 JP JP19736988A patent/JPH0247285A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0247285A (en) | 1990-02-16 |
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