JPH04124293A - Nickel-molybdenum alloy plating bath and plating method - Google Patents
Nickel-molybdenum alloy plating bath and plating methodInfo
- Publication number
- JPH04124293A JPH04124293A JP24314790A JP24314790A JPH04124293A JP H04124293 A JPH04124293 A JP H04124293A JP 24314790 A JP24314790 A JP 24314790A JP 24314790 A JP24314790 A JP 24314790A JP H04124293 A JPH04124293 A JP H04124293A
- Authority
- JP
- Japan
- Prior art keywords
- amount
- plating
- nickel
- bath
- alloy plating
- 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.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 84
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001182 Mo alloy Inorganic materials 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 238000009713 electroplating Methods 0.000 claims abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000005078 molybdenum compound Substances 0.000 claims description 5
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 5
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 23
- 239000000956 alloy Substances 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 4
- 229910003296 Ni-Mo Inorganic materials 0.000 abstract 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- YXVFQADLFFNVDS-UHFFFAOYSA-N diammonium citrate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O YXVFQADLFFNVDS-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 101150091136 Mob4 gene Proteins 0.000 description 1
- 229910018062 Ni-M Inorganic materials 0.000 description 1
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、モリブデン量が２０％（重量％、以下同じ）
以上のニッケル−モリブデン合金めっき皮膜を高い陰極
電流効率で得ることができ、実用性の高いめっき浴及び
めっき方法に関する。[Detailed description of the invention] [Industrial application field] The present invention has a molybdenum content of 20% (weight%, the same hereinafter).
The present invention relates to a highly practical plating bath and plating method that can obtain the above nickel-molybdenum alloy plating film with high cathode current efficiency.
〔従来の技術及び発明が解決しようとする課題〕従来、
ニッケル−モリブデン（Ｎｉ−Ｍｏ）合金めっき皮膜を
形成するためのめっき浴として、硫酸ニッケル（ＮｉＳ
Ｏ４・６Ｈ２０）、モリブデン酸ナトリウム（Ｎａ２Ｍ
ｏＯ，・２Ｈ２０）に錯化剤としてクエン酸塩や酒石酸
塩を加えた浴が知られている。これらの浴は酸性浴と塩
基性浴とに大別され、酸性浴はｐＨ３〜５、塩基性浴は
通常ｐＨ１０〜１０．５であるが、酸性浴では陰極電流
効率が低く、良好なめっき皮膜が得難いという問題があ
る。一方、塩基性浴は上記ｐＨ１０〜１０．５に調整す
るため、アンモニア水（２８％）を７〜１７ｄ／ｌ（Ｎ
Ｈ３として０゜１〜０．２５モル／ｌ）添加するもので
あるが、従来のこの種の塩基性Ｎ ｉ −Ｍ ｏ合金め
っき浴も陰極電流効率が低く、２０％以上のＭｏ含有量
を有するＮ ｉ −Ｍｏ合金めっき皮膜を効率よく得る
ことが困難で、実用性が乏しい。[Problems to be solved by conventional techniques and inventions] Conventionally,
Nickel sulfate (NiS) is used as a plating bath to form a nickel-molybdenum (Ni-Mo) alloy plating film.
O4・6H20), sodium molybdate (Na2M
A bath containing citrate or tartrate as a complexing agent is known. These baths are roughly divided into acidic baths and basic baths, and acidic baths have a pH of 3 to 5, and basic baths usually have a pH of 10 to 10.5. However, acidic baths have low cathode current efficiency and are difficult to form a good plating film. The problem is that it is difficult to obtain. On the other hand, in order to adjust the pH of the basic bath to 10 to 10.5, aqueous ammonia (28%) was added at 7 to 17 d/l (N
However, conventional basic Ni-Mo alloy plating baths of this type also have low cathode current efficiency and require Mo content of 20% or more. It is difficult to efficiently obtain a Ni-Mo alloy plating film having the following properties, and its practicality is poor.
Ｍｏ含有量が２０％以上であるハステロイＮｉ−Ｍｏ合
金は非酸化性酸溶液中において優れた耐食性を示すこと
が知られており、このためかかるＭｏ含有量が２０％以
上のＮ ｉ −Ｍ ｏ合金をめっき法によって効率良く
得る方法が望まれている。It is known that Hastelloy Ni-Mo alloys with a Mo content of 20% or more exhibit excellent corrosion resistance in non-oxidizing acid solutions. A method for efficiently obtaining alloys by plating is desired.
また特に、耐食性の点からはＭｏ含有量が２７％以上、
とりわけ３０％以上の非晶質Ｎｉ−Ｍｏ合金めっき皮膜
が望まれるが、従来法ではかかる非晶質Ｎｉ−Ｍｏ合金
を効率よくしかも確実に得ることが困難である。In particular, from the viewpoint of corrosion resistance, the Mo content is 27% or more,
In particular, an amorphous Ni-Mo alloy plating film of 30% or more is desired, but it is difficult to efficiently and reliably obtain such an amorphous Ni-Mo alloy using conventional methods.
〔課題を解決するための手段及び作用〕本発明者らは上
記要望に応えるため鋭意検討を進めた結果、水溶性ニッ
ケル化合物、水溶性モリブデン化合物に錯化剤としてク
エン酸を添加した浴に対し、アンモニア水を更に多量に
添加することにより、Ｍｏ含有量が２０％以上のＮ ｉ
−Ｍ 。[Means and effects for solving the problem] In order to meet the above-mentioned needs, the present inventors conducted intensive studies and found that a bath containing a water-soluble nickel compound, a water-soluble molybdenum compound, and citric acid as a complexing agent was developed. , by adding a larger amount of aqueous ammonia, Ni with a Mo content of 20% or more can be produced.
-M.
合金めっき皮膜を効率よく確実に形成し得、Ｍｏ含有量
が２７％以上、とりわけ３０％以上の非晶質Ｎｉ−Ｍｏ
合金めっき皮膜をも容易に得ることを知見した。Amorphous Ni-Mo that can efficiently and reliably form an alloy plating film and has a Mo content of 27% or more, especially 30% or more
It was discovered that alloy plating films can also be easily obtained.
即ち、上述したように、ＮｉＳＯ４・６Ｈ２０゜Ｎａ２
ＭｏＯ，・２Ｈ２０，Ｎａ、Ｃ，Ｈ２０，・２Ｈ２０を
含有するめっき浴にアンモニア水を添加することは知ら
れているが、アンモニア水の添加はめつき浴のｐＨを調
整するためのもので、その添加量は２８％アンモニア水
として７〜１７ｄ／ｌ（ＮＨ３として０．１〜０．２５
モル／ｌ）程度であり、ＮＨ，／Ｎｉモル比は０．９〜
１．４程度で、かかる添加量では陰極電流効率で２０％
以下と非常に低く、工業的な実用性が劣る。That is, as mentioned above, NiSO4.6H20°Na2
It is known that ammonia water is added to a plating bath containing MoO, .2H20, Na, C, H20, .2H20, but the purpose of adding ammonia water is to adjust the pH of the plating bath. The amount added is 7 to 17 d/l as 28% ammonia water (0.1 to 0.25 d/l as NH3).
mol/l), and the NH,/Ni molar ratio is from 0.9 to
1.4, and with this amount of addition, the cathode current efficiency is 20%.
It is very low and has poor industrial practicality.
ところが、アンモニア水を上記添加量を越えてより多く
、具体的には２８％アンモニア水を３０〜１００ｄｚｌ
（ＮＨ，として０．４〜１．５−１：／Ｌ／／１２
）添加すること、しかもこの場合Ｎ ｉ ／ Ｍ ｏモ
ル比を１〜４とし、Ｎ Ｈ３／ Ｎ １モル比を２〜５
とすることにより、Ｍｏ含有量が２０％以上のＮｉ−Ｍ
ｏ合金めっき皮膜が陰極電流効率５０％以上で確実に得
られることを見い出したものである。However, if the amount of ammonia water added exceeds the above amount, specifically, 30 to 100 dzl of 28% ammonia water.
(NH, 0.4~1.5-1:/L//12
), and in this case, the N i /Mo molar ratio is 1 to 4 and the N H3 / N 1 molar ratio is 2 to 5.
By doing so, Ni-M with a Mo content of 20% or more
It has been discovered that an o alloy plating film can be reliably obtained with a cathode current efficiency of 50% or more.
ここで、本発明において、アンモニア水を上記のように
多量に添加するのはＮｉ２“、Ｍｏｂ４”のクエン酸−
アンミン混合錯体を得ようとするもので、従来のめっき
浴におけるアンモニア水添加量ではかかるＮ ｉ ”、
Ｍ ｏ Ｏ，”−のクエン酸−アンミン混合錯体を形
成するには不十分であったものであるが、十分量のアン
モニア水を添加し、該錯体を形成した場合、高陰極電流
効率が達成される上、Ｍｏ含有量が２０％以上、とりわ
け２７〜３５％にも達する電着が可能になることを知見
したものである。なお、このようにＮｉ”、Ｍｏｂ４２
−のクエン酸−アンミン混合錯体を形成することにより
、上記のような効果を発揮する理由は、アンモニア水の
一部により、ニッケルクエン酸錯体に配位されている水
分子がアンミン基に置換されている放電反応性の高いニ
ッケルクエン酸アンミン混合錯体になり、残りのアンモ
ニア水がＭｏｂ、２−のクエン酸アンミン混合錯体にな
り、ＭＯの誘起共析に有利となるためと推測される。こ
のことは。Here, in the present invention, the reason why a large amount of ammonia water is added as described above is due to the citric acid-
This is intended to obtain an ammine mixed complex, and the amount of ammonia water added in a conventional plating bath is such that the amount of N i '',
Although it was insufficient to form a citric acid-ammine mixed complex of M o O,''-, high cathode current efficiency was achieved when a sufficient amount of ammonia water was added and the complex was formed. In addition, it was discovered that electrodeposition with a Mo content of 20% or more, especially 27 to 35%, is possible.
The reason why the above effects are achieved by forming the citric acid-ammine mixed complex of - is that the water molecules coordinated to the nickel citric acid complex are replaced with ammine groups by a portion of the ammonia water. This is presumed to be because the remaining aqueous ammonia becomes a nickel ammine citrate mixed complex with high discharge reactivity, and the remaining ammonia water becomes a Mob, 2-ammine citrate mixed complex, which is advantageous for the induced eutectoid of MO. About this.
浴のカソード分極曲線からも説明することができる。即
ち、０．１３モル／ Ｑ Ｎ ｘ Ｓ Ｏ４・６Ｈ２０
＋０．０３モル／ Ｑ Ｎ ａ３Ｃ，Ｈ，Ｏ，・２ Ｈ
２０浴の電析電位は一７００ｍＶ （ｐＨ９，３０℃、
以下同じ）、０．１３モル／ｌＮａ、、Ｍｏｂ４’ ２
Ｈ２０＋０．１３モル／ｎＮａ、ＣＧＨｓ○７・２Ｈ２
０浴の電析電位は一１０００ｍＶ、０．１３モル／ｌＮ
ｉＳｏ４’ ６Ｈ２０＋０．１３モル／ Ｄ Ｎａ ２
Ｍ ｏ Ｏ４２Ｈ，Ｏ＋０．２６モル／ｌＮａ、Ｃ，
Ｈ，０７・２Ｈ２０浴のＮｉ−Ｍｏ共析電位は一８１０
ｍＶであるが、これに更に０．５４モル／ｌのアンモニ
ア水を添加するとＮｉ−Ｍｏ共析電位は責になり、−７
８０ｍＶとなってカソード分極も小さくなり、従ってア
ンモニア水の添加によってＮｉ−Ｍｏ合金の電析が容易
になることからも認めらる。This can also be explained from the cathode polarization curve of the bath. That is, 0.13 mol/Q N x SO4・6H20
+0.03 mol/Q N a3C,H,O,・2H
The electrodeposition potential of bath 20 was -700 mV (pH 9, 30°C,
Same below), 0.13 mol/lNa, , Mob4' 2
H20+0.13 mol/nNa, CGHs○7・2H2
The electrodeposition potential of bath 0 is -1000 mV, 0.13 mol/lN
iSo4' 6H20+0.13 mol/D Na2
M o O42H, O + 0.26 mol/l Na, C,
The Ni-Mo eutectoid potential of H,07・2H20 bath is -810
mV, but when 0.54 mol/l of aqueous ammonia is further added to this, the Ni-Mo eutectoid potential becomes negative, and -7
This can be seen from the fact that the cathode polarization becomes 80 mV and the cathode polarization becomes small, so that the addition of aqueous ammonia facilitates the electrodeposition of the Ni-Mo alloy.
以下、本発明につき更に詳述する。The present invention will be explained in more detail below.
本発明に係るＮ ｉ −Ｍ ｏ合金めっき浴は、水溶性
ニッケル化合物と、水溶性モリブデン化合物と、クエン
酸塩と、アンモニア水とを含有し、２８％アンモニア水
の添加量が３０〜１００ｍＱ／ｌ（ＮＨ，として０．４
〜１．５モル＃） であると共に、ニッケルとモリブデ
ンとのモル比が１＝１〜４：１、アンモニアとニッケル
とのモル比が２：１〜５：１であり、ｐＨが８以上のも
のである。The Ni-Mo alloy plating bath according to the present invention contains a water-soluble nickel compound, a water-soluble molybdenum compound, a citrate, and ammonia water, and the amount of 28% ammonia water added is 30 to 100 mQ/ l(NH, as 0.4
~1.5 mol #), the molar ratio of nickel and molybdenum is 1 = 1 to 4:1, the molar ratio of ammonia to nickel is 2:1 to 5:1, and the pH is 8 or more. It is something.
ここで、水溶性ニッケル化合物としては、ＮｉＳＯ４・
６Ｈ２ｏやＮｉＣｆ１２・６Ｈ２０等が挙げられ、水溶
性モリブデン化合物としてはＮａ２Ｍｏｂ４２Ｈ２０や
（ＮＨ４）２ＭｏＯ４・２Ｈ２０などのモリブデン酸塩
等が挙げられる。また、クエン酸塩としては、クエン酸
ナトリウム、クエン酸２アンモニウム、クエン酸アンモ
ニウム等が使用される。Here, the water-soluble nickel compound is NiSO4.
Examples of the water-soluble molybdenum compounds include molybdates such as Na2Mob42H20 and (NH4)2MoO4.2H20. Further, as the citrate, sodium citrate, diammonium citrate, ammonium citrate, etc. are used.
この場合、水溶性ニッケル化合物の使用量は０．１〜０
．３モル／ｌ、特に０．１３〜０．２モル／ｌとするこ
とが好ましく、水溶性モリブデン化合物の使用量は０．
０２〜０．１５モル／ｌ、特に０．０６〜０．１３モル
／ｌとすることが好ましいが、Ｎ ｉ ／ Ｍ ｏモル
比は上述したように１〜４、特に１．５〜２．３である
。Ｍｏ量が少なすぎるとめっき皮膜中のＭｏ量が少なく
なり、本発明の目的が達成し得ない。一方、Ｍｏ量が多
すぎると、陰極電流効率が低下し、めっき皮膜が剥離し
易く、微小クラックが生じやすくなる。また、クエン酸
塩の使用量は０．２〜０．４モル／ｌ、特に０．２６〜
ｏ、３２モル／ｌとすることが好ましいが、この場合、
クエン酸塩／（Ｎｉ＋Ｍｏ）モル比がｏ、７７〜１．５
４、特に１〜１．２であることが望ましい。In this case, the amount of water-soluble nickel compound used is 0.1 to 0.
．． It is preferably 3 mol/l, particularly 0.13 to 0.2 mol/l, and the amount of water-soluble molybdenum compound used is 0.1 mol/l.
02 to 0.15 mol/l, especially 0.06 to 0.13 mol/l, and the N i /Mo molar ratio is 1 to 4, especially 1.5 to 2. It is 3. If the amount of Mo is too small, the amount of Mo in the plating film will be too small, making it impossible to achieve the object of the present invention. On the other hand, if the amount of Mo is too large, the cathode current efficiency decreases, the plating film is likely to peel off, and microcracks are likely to occur. In addition, the amount of citrate used is 0.2 to 0.4 mol/l, especially 0.26 to 0.4 mol/l.
o, 32 mol/l, but in this case,
Citrate/(Ni+Mo) molar ratio is o, 77-1.5
4, particularly preferably 1 to 1.2.
本発明のめっき浴は、上記成分に加えて２８％アンモニ
ア水を３０〜１００ｄ＃ｌ （アンモニアとして０．４
〜１．５モル／ｌ）添加する。この場合、その添加量は
ＮＨ３／Ｎｉモル比が２〜５、特に２．５〜４となるよ
うに選定するもので、アンモニア量が少なすぎると陰極
電流効率が低く、またＭｏ含有量が２０％以上のＮ ｉ
−Ｍ ｏ合金めっき皮膜を得難くなる。一方、アンモ
ニア水が多すぎても陰極電流効率が低下するという不利
が生じる。In addition to the above components, the plating bath of the present invention contains 30 to 100 d#l of 28% ammonia water (0.4 d#l as ammonia).
~1.5 mol/l) is added. In this case, the amount added is selected so that the NH3/Ni molar ratio is 2 to 5, especially 2.5 to 4. If the amount of ammonia is too small, the cathode current efficiency will be low; Ni of % or more
-Mo It becomes difficult to obtain an alloy plating film. On the other hand, if there is too much ammonia water, there is a disadvantage that the cathode current efficiency decreases.
本発明のめっき浴のｐＨは８以上であり、好ましくは８
〜１０．５．特に９〜９．５である。この場合、ｐＨ調
整には硫酸等の酸や水酸化ナトリウム等のアルカリを使
用する。The pH of the plating bath of the present invention is 8 or more, preferably 8
~10.5. In particular, it is 9 to 9.5. In this case, an acid such as sulfuric acid or an alkali such as sodium hydroxide is used for pH adjustment.
なお、本発明のめっき浴には、必要に応じ炭酸ナトリウ
ム、ホウ酸、ホウ酸アンモニウム、炭酸アンモニウム、
その他の炭酸塩やホウ酸塩等の添加剤を添加しても差支
えない。In addition, the plating bath of the present invention may contain sodium carbonate, boric acid, ammonium borate, ammonium carbonate,
Other additives such as carbonates and borates may also be added.
本発明においては、上記めっき浴を用いて被めっき物に
めっきを施し、Ｍｏ含有量が２０％以上のＮｉ−Ｍｏ合
金めっき皮膜を得るものであるが、めっき条件としては
、陰極電流密度０．１〜２゜Ａ／ｄボ、特に２〜１８Ａ
／ｄボ、めっき温度１０〜７０℃、特に２０〜４０℃の
条件を採用することができる。また撹拌はエアー、カソ
ードロッカー、プロペラ等を用いて行なうことができる
が、無撹拌で実施することもできる。陽極としては、ニ
ッケル等の可溶性陽極、カーボン、白金。In the present invention, the object to be plated is plated using the above plating bath to obtain a Ni-Mo alloy plating film with a Mo content of 20% or more, and the plating conditions include a cathode current density of 0. 1~2°A/dbo, especially 2~18A
/dbo, plating temperature of 10 to 70°C, particularly 20 to 40°C can be adopted. Further, stirring can be performed using air, a cathode rocker, a propeller, etc., but it can also be performed without stirring. As an anode, a soluble anode such as nickel, carbon, or platinum can be used.
白金めっきチタン等の不溶性陽極を使用することができ
る。Insoluble anodes such as platinized titanium can be used.
ここで、上記めっき浴を用いて電気めっきを行なう場合
、調製直後のめっき浴は陰極電流効率も低く、めっき皮
膜中のＭｏ量も低い上、めっき皮膜の剥離が生じること
もあるので、めっき浴を調製した後に電解熟成してから
めっきすることが推奨される。この電解熟成としては、
２Ａ−ｈｒ／Ｕ以上、好ましくは３・”２０Ａ−ｈｒ／
ｌ程度電解することによりめっき浴を熟成する方法が好
ましく。Here, when performing electroplating using the above plating bath, the plating bath immediately after preparation has a low cathode current efficiency, a low amount of Mo in the plating film, and peeling of the plating film may occur. It is recommended that after preparation, electrolytic ripening is performed before plating. This electrolytic ripening is
2A-hr/U or more, preferably 3.”20A-hr/U
A preferred method is to age the plating bath by electrolyzing the plating bath.
これによって陰極電流効率を向上させ、まためっき皮膜
中のＭｏ含有量の増加を計ることができる。Thereby, it is possible to improve the cathode current efficiency and increase the Mo content in the plating film.
更に、めっき皮膜の剥離の問題も解消される。Furthermore, the problem of peeling of the plating film is also solved.
以上のようにして得られたＮｉ−Ｍｏ合金めっき皮膜は
、Ｍｏ量が２０％以上で、硫酸や塩酸等の非酸化性酸に
対する耐食性が高いものであるが、これらの酸に対する
耐食性をより高いものにするために、Ｎｉ−Ｍｏめっき
皮膜中のＭｏ量を２７％以上、とりわけ３０％以上の非
晶質とすることが好ましい。The Ni-Mo alloy plating film obtained as described above has a Mo content of 20% or more and has high corrosion resistance to non-oxidizing acids such as sulfuric acid and hydrochloric acid. In order to achieve this, it is preferable that the amount of Mo in the Ni-Mo plating film be 27% or more, particularly 30% or more, and be amorphous.
本発明によれば、Ｍｏ含有量が２０％以上の高耐食性の
Ｎｉ−Ｍｏ合金めっき皮膜を効率よく容易にかつ確実に
形成することができる。According to the present invention, a highly corrosion-resistant Ni-Mo alloy plating film having an Mo content of 20% or more can be formed efficiently, easily, and reliably.
以下、実施例により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〕
ムユ皇蚕
ＮｉＳＯ４・６Ｈ２００，１８２モル／ｌＮａ２Ｍｏ０
，１２Ｈ２００，０７８ｕＮａ、Ｃ６Ｈ５Ｏ，・２Ｈ２
０ｏ、３２ ｎ２８％アンモニア水 ０．５４
ｐＨ（硫酸で調整）９．Ｏ
査ユｉ条作
陰 極（被めっき物） 銅 板
陽 極 白金めっきチタン陰極電流密
度 ８Ａ／ｄボ
めっき温度 ３０℃
上記めっき浴を用い、上記めっき条件で所定通電量電解
した後の陰極電流効率及びＮｉ−Ｍｏ合金めっき皮膜中
のＭｏ量の結果を第１図に示す。[Example 1] Muyu imperial silkworm NiSO4.6H200,182 mol/lNa2Mo0
, 12H200,078uNa, C6H5O, 2H2
0o, 32n28% ammonia water 0.54 pH (adjusted with sulfuric acid)9. Cathode current density: 8 A/d Plating temperature: 30°C Cathode current after electrolysis using the above plating bath at a predetermined amount of current under the above plating conditions The results of the efficiency and the amount of Mo in the Ni-Mo alloy plating film are shown in FIG.
第１図の結果より、調製直後のめっき浴は陰極電流効率
が１７％と低く、まためっき皮膜中のＭｏ量も１２％と
低いものであったが、約３Ａ−ｈｒ／ｌの通電で陰極電
流効率は６０％を越え、めっき皮膜中のＭｏ量も２０％
を越えて、約１２Ａ−ｈｒ／ｌの通電では３０％になる
ことが認められた。更に、めっき皮膜も、調＃！直後の
浴では剥離が生じたが、２．４Ａ−ｈｒ／ｌ通電後は半
光沢の外観で密着性もよく、従って以上のことから電解
熟成の効果が認められた。From the results shown in Figure 1, the cathode current efficiency of the plating bath immediately after preparation was as low as 17%, and the amount of Mo in the plating film was also as low as 12%. The current efficiency is over 60%, and the amount of Mo in the plating film is 20%.
It was found that when the current flow exceeds 12 A-hr/l, the result is 30%. Furthermore, the plating film is also excellent! Peeling occurred in the bath immediately after, but after 2.4 A-hr/l current was applied, it had a semi-glossy appearance and good adhesion, and from the above, the effect of electrolytic ripening was recognized.
〔実施例２〕
めっき浴
Ｎａ５ＣＧＨ，Ｏ，・２Ｈ２００，３２ｎ２８％アンモ
ニア水 ０，５４ｎｐＨ（硫酸で調整）９．０
ＮｉＳＯ４・６Ｈ，○とＮ ａ 、 Ｍ ｏ○、・２Ｈ
，０との総量を０．２６モル／ｌとし、Ｎａ２Ｍｏｂ。[Example 2] Plating bath Na5CGH,O,・2H200,32n28% ammonia water 0.54npH (adjusted with sulfuric acid) 9.0 NiSO4・6H,○ and Na, Mo○,・2H
, 0 and the total amount of Na2Mob is 0.26 mol/l.
２Ｈ，Ｏの量を種々変化させた（０．０２Ｇ。The amounts of 2H and O were varied (0.02G.
０．０５２，０．０７８，０．１３モル／ｌ）。0.052, 0.078, 0.13 mol/l).
上記組成のめっき浴を用い、下記条件でめっきを行ない
、陰極電流効率と得られたＮ ｉ −Ｍ ｏ合金めっき
皮膜中のＭｏ量を測定した。その結果を第２図に示す。Plating was carried out under the following conditions using a plating bath having the above composition, and the cathode current efficiency and the amount of Mo in the obtained Ni-Mo alloy plating film were measured. The results are shown in FIG.
めっき条件
陰 極（被めっき物） 銅 板
陽 極 白金めっきチタン陰極電流密
度 ８Ａ／ｄｉ
めっき温度 ３０℃
第２図の結果より、浴中のモリブデン量を増加するにつ
れて皮膜中のモリブデン量が増加することが認められた
。Plating conditions Cathode (object to be plated) Copper plate anode Platinum plated titanium cathode Current density 8A/di Plating temperature 30℃ From the results shown in Figure 2, as the amount of molybdenum in the bath increases, the amount of molybdenum in the film increases. This was recognized.
〔実施例３〕
めっき浴
ＮｉＳＯ４・６Ｈ２００，１８２モル／ｌＮ ａ ｔ
Ｍ ｏ Ｏ４・２ Ｈｖ、 ＯＯ−０７２〃Ｎａ５Ｃ，
Ｈ，Ｏ，・２Ｈ２００，３２ｌＩ２８％アンモニア水
第３図に示す量上記めっき浴を使用し、実施例１と
同様にして電気めっきを行なった。陰極電流効率と得ら
れためっき皮膜中のモリブデン量の結果を第３図に示す
。[Example 3] Plating bath NiSO4.6H200, 182 mol/lN at
M o O4・2 Hv, OO-072〃Na5C,
H,O,・2H200,32lI28% ammonia water
Electroplating was carried out in the same manner as in Example 1 using the above plating bath in the amount shown in FIG. Figure 3 shows the results of the cathode current efficiency and the amount of molybdenum in the resulting plating film.
第３図の結果より、アンモニア添加量が少ないと、Ｍｏ
量が２０％を越えるＮｉ−Ｍｏ合金めっき皮膜を形成し
得る場合もあるが、陰極電流効率が非常に低いものであ
る。これに対し、アンモニア量が０．４モル／２以上に
なると電流効率も５゜％以上となり、Ｍｏ量も２０％以
上になることが認められる。From the results shown in Figure 3, when the amount of ammonia added is small, Mo
Although it is possible to form a Ni-Mo alloy plating film with an amount exceeding 20% in some cases, the cathode current efficiency is very low. On the other hand, it is recognized that when the amount of ammonia is 0.4 mol/2 or more, the current efficiency becomes 5% or more, and the amount of Mo also becomes 20% or more.
〔実施例４〕
佐ユ棗庵
Ｎ１５Ｏ＋・６Ｈ２０
６Ｈ２０Ｎａ２・２Ｈ２０
Ｎａ３Ｃ，Ｈ，０７・２Ｈ２０
２８％アンモニア水
ｐＨ（硫酸で調整）
支ユｉ条丘
陰極
陽極
陰極電流密度
めっき温度
５５ ｇ ／ Ｑ
１３ 〃
９４ 〃
３６ｍＱ／１２
９．０
銅板
白金めっきチタン
４Ａ／ｄボ
３０”Ｃ
上記めっき浴を用いて上記めっき条件で１００分間電解
し、めっき浴を熟成した後、めっきを行なった。[Example 4] Sayu Natsumean N15O+・6H20 6H20Na2・2H20 Na3C,H,07・2H20 28% ammonia water pH (adjusted with sulfuric acid) Support i ray cathode anode cathode current density plating temperature 55 g / Q 13 94 〃 36mQ/12 9.0 Copper plate platinum plated titanium 4A/dbo 30''C Using the above plating bath, electrolysis was carried out under the above plating conditions for 100 minutes, and after the plating bath was aged, plating was performed.
その結果、銀灰色のＮｉ−Ｍｏ合金めっき皮膜を得た。As a result, a silver-gray Ni-Mo alloy plating film was obtained.
ＩＣＰによる定量分析を行った結果はＭｏ量は２０％で
あった。また、この皮膜をＩＮＨ２３０４，ＩＮＨＣＱ
溶液に３０℃で浸漬した場合の腐食速度はそれぞれＱ、
１５ｇ／ｍ・ｈｒ。As a result of quantitative analysis by ICP, the amount of Mo was 20%. In addition, this film can be used as INH2304, INHCQ.
The corrosion rate when immersed in a solution at 30°C is Q, respectively.
15g/m・hr.
０、４７５ ｇ／ｒｄ ・ｈｒであった。It was 0.475 g/rd・hr.
〔実施例５〕
ムユｌ権
ＮｉＳＯ４・６Ｈ２０４８ｇ ／ Ｑ
Ｎａ２ＭｏＯ，・２Ｈ２０１９ｎ
Ｎａ５ＣｓＨｓ○、・２Ｈ２０９４１１２８％アンモニ
ア水 ３６ｄ／ｌｐＨ（硫酸で調整）９．０
ムユ棗条芥
陰極 銅板
陽 極 白金めつきチタン陰極電流密
度 ５Ａ／ｄボめっき温度
３０℃
上記めっき浴を用い、上記めっき条件で１００分間電解
を行なってめっき浴を熟成した後、めっきを行なってＭ
ｏ量が３０％の銀灰色のＮｌＭｏ非晶質合金めっき皮膜
を得た。また、この皮膜を実施例４と同様にＩＮＨ２Ｓ
ｏ、、ＩＮＨＣＱ溶液に３０℃で浸漬した時の腐食速度
はそれぞれ０．０３７ｇ／ｒｒＬｈｒ、ｏ、１．６９ｇ
／ｒｒｒ・ｈｒであった。[Example 5] Muyu l right NiSO4・6H2048g/Q Na2MoO,・2H2019n Na5CsHs○,・2H20941128% ammonia water 36d/lpH (adjusted with sulfuric acid) 9.0 Muyu jujube strip cathode Copper plate anode Platinized titanium cathode current Density 5A/d plating temperature
30°C Using the above plating bath, perform electrolysis for 100 minutes under the above plating conditions to age the plating bath, and then perform plating to obtain M
A silver-gray NlMo amorphous alloy plating film with an o content of 30% was obtained. In addition, this film was coated with INH2S in the same manner as in Example 4.
o,,corrosion rate when immersed in INHCQ solution at 30℃ is 0.037g/rrLhr, o, 1.69g, respectively.
/rrr・hr.
第１図は電解熟成の通電量と陰極電流効率及びめっき皮
膜中のＭｏ量との関係を示すグラフ、第２図はめっき浴
中のＭｏ量と陰極電流密度及びめっき皮膜中のＭｏ量と
の関係を示すグラフ、第３図はめっき浴へのアンモニア
添加量と陰極電流効率及びめっき皮膜中のＭｏ量との関
係を示すグラフである。
出願人 上 村 工 業 株式会社
代理人 弁理士 小 島 隆 同
第１図
１１鮎鰺屹・１１
（Ａし／ｌ ）
第２図
］Ｏ
７゜
ハ。ｂかＸｆ９Ｍ。／田十８０
（す４−’ｌンFigure 1 is a graph showing the relationship between the amount of electricity applied during electrolytic ripening, cathode current efficiency, and the amount of Mo in the plating film, and Figure 2 is a graph showing the relationship between the amount of Mo in the plating bath, the cathode current density, and the amount of Mo in the plating film. FIG. 3 is a graph showing the relationship between the amount of ammonia added to the plating bath, the cathode current efficiency, and the amount of Mo in the plating film. Applicant Uemura Kogyo Co., Ltd. Agent Patent Attorney Takashi Kojima Figure 1 11 (Ashi/l) Figure 2] O 7゜ha. b or Xf9M. / 田JU80 (Su4-'ln
Claims (1)
と、クエン酸塩と、アンモニア水とを含有し、アンモニ
ア水の添加量がアンモニアとして０．４〜１．５モル／
ｌであると共に、ニッケルとモリブデンとのモル比が１
：１〜４：１、アンモニアとニッケルとのモル比が２：
１〜５：１であり、ｐＨが８以上であることを特徴とす
るニッケル−モリブデン合金めっき浴。 ２、被めっき物に請求項１に記載のめっき浴を用いて陰
極電流密度０．１〜２０Ａ／ｄｍ＾２において電気めっ
きを施して、モリブデン量が２０重量％以上のニッケル
−モリブデン合金めっき皮膜を析出させることを特徴と
するニッケル−モリブデン合金めっき方法。[Claims] 1. Contains a water-soluble nickel compound, a water-soluble molybdenum compound, a citrate, and ammonia water, and the amount of ammonia water added is 0.4 to 1.5 mol/ammonia.
l, and the molar ratio of nickel and molybdenum is 1.
:1 to 4:1, molar ratio of ammonia and nickel is 2:
A nickel-molybdenum alloy plating bath characterized by having a ratio of 1 to 5:1 and a pH of 8 or more. 2. Electroplating the object to be plated using the plating bath according to claim 1 at a cathode current density of 0.1 to 20 A/dm^2 to produce a nickel-molybdenum alloy plating film having a molybdenum content of 20% by weight or more. A nickel-molybdenum alloy plating method characterized by depositing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2243147A JP2522101B2 (en) | 1990-09-13 | 1990-09-13 | Nickel-molybdenum alloy plating bath and plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2243147A JP2522101B2 (en) | 1990-09-13 | 1990-09-13 | Nickel-molybdenum alloy plating bath and plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04124293A true JPH04124293A (en) | 1992-04-24 |
| JP2522101B2 JP2522101B2 (en) | 1996-08-07 |
Family
ID=17099491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2243147A Expired - Lifetime JP2522101B2 (en) | 1990-09-13 | 1990-09-13 | Nickel-molybdenum alloy plating bath and plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2522101B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005082856A (en) * | 2003-09-08 | 2005-03-31 | Osaka Prefecture | Nickel-molybdenum alloy plating liquid, plating film thereof, and plated article |
| US7696428B2 (en) | 2007-05-28 | 2010-04-13 | Kabushiki Kaisha Kawai Gakki Seisakusho | Electronic keyboard musical instrument |
| DE102013110263A1 (en) * | 2013-09-18 | 2015-03-19 | Harting Kgaa | Galvanic bath |
| CN110331423A (en) * | 2019-07-12 | 2019-10-15 | 中国原子能科学研究院 | A kind of electric depositing solution formula preparing foam nickel-molybdenum alloy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5711397A (en) * | 1980-06-24 | 1982-01-21 | Nippon Musical Instruments Mfg | Electronic musical instrument |
-
1990
- 1990-09-13 JP JP2243147A patent/JP2522101B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5711397A (en) * | 1980-06-24 | 1982-01-21 | Nippon Musical Instruments Mfg | Electronic musical instrument |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005082856A (en) * | 2003-09-08 | 2005-03-31 | Osaka Prefecture | Nickel-molybdenum alloy plating liquid, plating film thereof, and plated article |
| US7696428B2 (en) | 2007-05-28 | 2010-04-13 | Kabushiki Kaisha Kawai Gakki Seisakusho | Electronic keyboard musical instrument |
| DE102013110263A1 (en) * | 2013-09-18 | 2015-03-19 | Harting Kgaa | Galvanic bath |
| WO2015039647A1 (en) | 2013-09-18 | 2015-03-26 | Harting Kgaa | Galvanic bath |
| CN105579620A (en) * | 2013-09-18 | 2016-05-11 | 哈廷股份两合公司 | Galvanic bath |
| JP2016532004A (en) * | 2013-09-18 | 2016-10-13 | ハルティング アクチエンゲゼルシャフト ウント コンパニー コマンディートゲゼルシャフトＨＡＲＴＩＮＧ ＡＧ＆Ｃｏ．ＫＧ | Electroplating bath |
| CN110331423A (en) * | 2019-07-12 | 2019-10-15 | 中国原子能科学研究院 | A kind of electric depositing solution formula preparing foam nickel-molybdenum alloy |
| CN110331423B (en) * | 2019-07-12 | 2023-08-18 | 中国原子能科学研究院 | Formula of electrodeposition solution for preparing foam nickel-molybdenum alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2522101B2 (en) | 1996-08-07 |
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