JPH0369995B2 - - Google Patents
Info
- Publication number
- JPH0369995B2 JPH0369995B2 JP58251999A JP25199983A JPH0369995B2 JP H0369995 B2 JPH0369995 B2 JP H0369995B2 JP 58251999 A JP58251999 A JP 58251999A JP 25199983 A JP25199983 A JP 25199983A JP H0369995 B2 JPH0369995 B2 JP H0369995B2
- Authority
- JP
- Japan
- Prior art keywords
- anode
- bath
- nickel
- tungsten
- electrolytic bath
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 60
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 30
- 238000007747 plating Methods 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 230000003287 optical effect Effects 0.000 claims description 11
- 229910001080 W alloy Inorganic materials 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 238000002835 absorbance Methods 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000003788 bath preparation Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000080590 Niso Species 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 229910019914 (NH4)10 W12 O41.5H2 O Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001156002 Anthonomus pomorum Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910004803 Na2 WO4.2H2 O Inorganic materials 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000711 polarimetry Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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】
本発明は、物品表面にNi−Ｗ合金めつきを連
続的に施す装置に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an apparatus for continuously applying Ni--W alloy plating to the surface of an article.
Ni−Ｗ合金は、表面光沢にすぐれ、かつその
耐久性に富み、耐酸、耐アルカリ等の耐薬品性、
機械的な硬度、強度も優秀であり、とくに高温ガ
ラスとの非粘着離型性にすぐれているところか
ら、被めつき物品たる金属製物品、たとえばテレ
ビブラウン管前面内壁成型用金型をはじめとする
各種金型、ローラ、時計のケース等に賞用せられ
ている。 Ni-W alloy has excellent surface gloss, high durability, and chemical resistance such as acid and alkali resistance.
It has excellent mechanical hardness and strength, and is particularly good in non-adhesive mold releasability with high-temperature glass, so it can be used to coat metal articles, such as molds for molding the front inner wall of television cathode ray tubes. It has been used in various molds, rollers, watch cases, etc.
このようなNi−Ｗ合金めつきにおいて電解浴
液（単に電解浴とも略す）として、ニツケル塩お
よびタングステン酸塩を含有し、くえん酸を有機
錯化剤としたポンプHolt法、同じく酒石酸を有
機錯化剤としたブレナーBrenner法などが知られ
ている。しかし、そのいずれもがバツチシステム
であるに止まり、工業的に好ましい連続めつき手
段の開発が望まれている。 In such Ni-W alloy plating, the electrolytic bath solution (also simply called electrolytic bath) contains nickel salt and tungstate, and the pump Holt method uses citric acid as an organic complexing agent, and the pump Holt method uses tartaric acid as an organic complexing agent. The Brenner method using a curing agent is known. However, all of these methods are still batch systems, and it is desired to develop an industrially preferable continuous plating means.
本発明は、このような要望に応えるべくなされ
たものであつて、ニツケル塩およびタングステン
酸を含有し、くえん酸を有機錯化剤とした電解浴
中で、ステンレスSUS材ならびにニツケル材を
陽極とし、タングステン酸含有液を補給しつつ電
解することを特徴とするNi−Ｗ合金めつき方法
およびその装置である。 The present invention was made in response to these demands, and uses stainless steel SUS material and nickel material as anodes in an electrolytic bath containing nickel salt and tungstic acid and using citric acid as an organic complexing agent. , a Ni-W alloy plating method and apparatus thereof, characterized in that electrolysis is performed while replenishing a tungstic acid-containing solution.
本発明に使用する電解浴が、Ni塩およびＷ酸
塩を含有し有機錯化剤としてくえん酸を選用する
点においては前述ホルト法に近似するが、ホルト
法は陽極がNiないしＷの単極である点において
不溶性陽極たるSUS材ならびに溶解性陽極とし
てNi材を用いる点において、また浴のPHが約9.0
の高値でない点において相違する。有機錯化剤と
してくえん酸を選用した理由は、得られるめつき
層中のＷ含量を、酒石酸系電解浴の場合の最高35
％にくらべ最高62％にも及ぼさしめることが可能
であるからである。 The electrolytic bath used in the present invention is similar to the aforementioned Holt method in that it contains a Ni salt and a W salt and citric acid is selected as an organic complexing agent, but in the Holt method, the anode is a single electrode of Ni or W. In certain respects, SUS material is used as an insoluble anode and Ni material is used as a soluble anode, and the pH of the bath is approximately 9.0.
The difference is that the price is not high. The reason for choosing citric acid as the organic complexing agent is that the W content in the resulting plating layer can be reduced to 35% in the case of a tartaric acid electrolytic bath.
This is because it is possible to achieve a maximum of 62% compared to %.
本発明に使用する電解浴液中のNi塩の形態と
しては、塩化ニツケル、硝酸ニツケルのような形
で使用不可能ではないが、電流効果が優れている
点で硫酸ニツケルないし硫酸ニツケル・アンモニ
ウム複塩Ni（SO4）・（NH4）2SO4・6H2Oが最良で
ある。同じく電解浴中のタングステン酸の塩とし
ては、そのアルカリ金属の塩、なかんずくナトリ
ウム塩の形態で使用するがよい。タングステン酸
塩をアンモニウム塩の形態ではなくNa2WO4・
2H2Oのようなアルカリ金属塩として使用した場
合には、浴中のNa濃度は連続めつき操作中、被
めつき体に付着して持ち出される以外には不変と
もいうことができるから、その建浴時における濃
度を基準として補給液の添加時期を定めることが
できる。 Although it is not impossible to use the Ni salt in the electrolytic bath solution used in the present invention in the form of nickel chloride or nickel nitrate, it is preferable to use nickel sulfate or nickel sulfate/ammonium complex because of its superior current effect. The salt Ni( SO4 ) . ( NH4 ) 2SO4.6H2O is the best. Similarly, the salt of tungstic acid in the electrolytic bath is preferably used in the form of its alkali metal salt, especially its sodium salt. Tungstate is not in the form of ammonium salt but Na2WO4 .
When used as an alkali metal salt such as 2H 2 O, the Na concentration in the bath can be said to remain unchanged during continuous plating operations, except when it adheres to the plated body and is taken out. The timing of adding the replenishing liquid can be determined based on the concentration at the time of bath preparation.
かくして、本発明方法に適した電解浴を例示す
れば次のとおりである。 Thus, examples of electrolytic baths suitable for the method of the present invention are as follows.
くえん酸…… 100±30ｇ／
Ni塩（NiSO4・6H2Oとして）…… 60±20ｇ／
Ｗ酸塩（Na2WO4・2H2Oとして）……
70±30ｇ／
PH（NH4OHによる調整）…… ６±２
アルカリ金属イオン（Na+）……
0.42±0.15mol／
なおPHが上記のとおり弱酸性であるから、従来
のアンモニアアルカリ性電解浴に比して電解槽付
近のアンモニア臭発生による循環衛生汚染の心配
は甚しく改善せられる。Citric acid... 100±30g/ Ni salt (as NiSO 4 6H 2 O)... 60±20g/ W salt (as Na 2 WO 4 2H 2 O)...
70±30g/PH (adjusted with NH 4 OH)...6±2 Alkali metal ion (Na + )...
0.42±0.15mol/ Since the PH is weakly acidic as mentioned above, concerns about circulation sanitation pollution due to ammonia odor generated near the electrolytic bath are greatly reduced compared to conventional ammonia-alkaline electrolytic baths.
次に本発明において、陽極としてSUS材とNi
材との２極を採る理由を述べる。 Next, in the present invention, SUS material and Ni are used as the anode.
I will explain the reason for choosing the two poles with wood.
それは基本的には、タングステン合金めつきに
おける金属析出の電流効率が100％ではなく、必
らず水素ガスの生成反応を伴うことによる。この
ようなタングステン合金めつき反応においても、
目的組成を有する合金めつき層を得るためには、
浴中の金属濃度を最適値に維持することが必要で
ある。そのためには、少なくとも陰極における水
素ガス生成電流に相当する電流だけは不溶性陽極
から供給し、同時にニツケルとタングステンの陰
極析出によるめつき浴中の濃度低下をなんらかの
形で補なわねばならない。ところで、金属タング
ステンは、現在の自由世界圏において可溶性陽極
として工業的に使用可能な形態では供給されな
い。また非常に高価でもある。かくて、陰極での
水素とＷ放電に相当する電流は、不溶性の陽極か
ら供給することが必要である。 This is basically because the current efficiency of metal deposition in tungsten alloy plating is not 100%, and a hydrogen gas production reaction is always involved. Even in such a tungsten alloy plating reaction,
In order to obtain an alloy plated layer with the desired composition,
It is necessary to maintain the metal concentration in the bath at an optimum value. To this end, at least a current corresponding to the hydrogen gas generation current at the cathode must be supplied from the insoluble anode, and at the same time, it is necessary to somehow compensate for the decrease in concentration in the plating bath due to cathodic deposition of nickel and tungsten. By the way, metallic tungsten is not currently available in a form that can be used industrially as a soluble anode in the free world. It is also very expensive. Thus, the current corresponding to the hydrogen and W discharges at the cathode needs to be supplied from the insoluble anode.
くえん酸のような有機錯化剤を含むめつき浴に
おける不溶性陽極の使用によつて生ずる問題は、
不溶性陽極における有機酸の分解、変質と、それ
によるめつき層の脆化であり、これが従来法をバ
ツチシステムに止めた理由に外ならない。 Problems caused by the use of insoluble anodes in plating baths containing organic complexing agents such as citric acid are
This is the decomposition and alteration of the organic acid in the insoluble anode and the resulting embrittlement of the plating layer, and this is the reason why the batch system was used as the conventional method.
ステンレス材を陽極として用いた理由は、本発
明者が、くえん酸の非分解触媒性にすぐれた不溶
性陽極として、ステンレス材を実験的に見出した
からである。不溶性陽極としてSUS材は、従来
のめつきに頻用せられる白金、ニツケル、グラフ
アイト、鉛などに比して、電解浴中のくえん酸
を、分解・変質せしめる速度が著しく小さく、グ
ラフアイト陽極の場合の約1/5のいう好成績を与
える。 The reason why a stainless steel material was used as an anode is that the present inventor experimentally discovered a stainless steel material as an insoluble anode with excellent non-decomposition catalytic properties of citric acid. Compared to platinum, nickel, graphite, lead, etc., which are frequently used in conventional plating, SUS materials have a significantly lower rate of decomposition and deterioration of citric acid in the electrolytic bath. It gives good results in about 1/5 of cases.
また、陽極としてNiを用いる理由は、Niの陰
極析出による浴中濃度の低下を補充するためであ
るが、この補充をNiSO4水溶液のような薬液の形
で行うと、長期連続電解に伴う薬液補充によつ
て、めつき浴中にSO4 2-が蓄積してめつきの品質
に問題を生じたからである。 Furthermore, the reason why Ni is used as an anode is to replenish the decrease in concentration in the bath due to cathodic precipitation of Ni, but if this replenishment is performed in the form of a chemical solution such as an aqueous NiSO 4 solution, the chemical solution associated with long-term continuous electrolysis This is because SO 4 2- accumulated in the plating bath due to replenishment, causing problems in the quality of plating.
上述したところにより、不溶性陽極に使用する
ステンレスSUS材とは、クロム10％以上を含有
する耐蝕性鉄−クロム合金を指称し、Ni、Si、
Mo、ＷないしNbを含むものが包含される。具体
的にはSUS304、同431、同316など広く供用でき
る。このうち、SUS316のようにMoを含有する
ものは、消耗率が低いすぐれた材料として注目さ
れる。 As mentioned above, the stainless steel SUS material used for the insoluble anode refers to a corrosion-resistant iron-chromium alloy containing 10% or more of chromium, including Ni, Si,
Those containing Mo, W or Nb are included. Specifically, it can be widely used such as SUS304, SUS431, and SUS316. Among these, materials containing Mo such as SUS316 are attracting attention as excellent materials with low wear rates.
また溶解性陽極としてのNi材としては、鉄Fe、
銅Cu、鉛Pbなどの不純物をほとんど含まないも
のが適当とされ、電気ニツケルアノード、SKニ
ツケルアノード、デボラライズドニツケールアノ
ードなどの名称のもとに市販されているニツケル
めつき用のものがそのまま使用できる。 In addition, Ni materials for soluble anodes include iron, Fe,
Anodes that contain almost no impurities such as copper Cu or lead Pb are considered suitable, and those for nickel plating that are commercially available under names such as electric nickel anodes, SK nickel anodes, and devolized nickel anodes are suitable. It can be used as is.
本発明方法および装置においても、電解間電解
浴中のNiおよびＷ濃度は当然減少する。このNi
は前記のとおり溶解性陽極から供給されるが、Ｗ
は別途なんらかの形態で補給されなければならな
い。本発明にあつては、これをＷ含有補給液の形
で電解浴液中に補給して行くのである。補給に使
用する好ましいタングステンの形態は、典型的に
はパラタングステン酸アンモニウム
（NH4）10W12O41・5H2Oないし５（NH4）2O・
12WO3・5H2Oである。このものは、むろん常温
固体であるから、補給に当つては、溶液の形態、
とくに補給される電解浴を薄めないように濃厚な
溶液として補給されるべきである。 Also in the method and apparatus of the present invention, the Ni and W concentrations in the interelectrolytic bath are naturally reduced. This Ni
is supplied from the soluble anode as described above, but W
must be supplied separately in some form. In the present invention, this is replenished into the electrolyte bath solution in the form of a W-containing replenishment solution. The preferred form of tungsten used for replenishment is typically ammonium paratungstate ( NH4 ) 10W12O41.5H2O to 5 ( NH4 ) 2O .
12WO 3 5H 2 O. Of course, this substance is solid at room temperature, so when replenishing it, it must be in the form of a solution or
In particular, it should be replenished as a concentrated solution so as not to dilute the electrolyte bath being replenished.
パラタングステン酸アンモニウムは、常温で約
50ｇ／までは、容易に水に溶解する。ところ
が、これをくえん酸の水溶液として溶解させるな
らば、約100ｇ／の濃厚な水溶液とすることが
できる。その際使用するくえん酸の量は50〜200
ｇ／が適当とされる。というのは、補給液中の
くえん酸は、上記のとおり、沈澱防止剤として働
くばかりではなく、電解間に消耗されたくえん酸
の補充の役割を果たすものであるが、その消耗率
は、電流密度、ステンレス陽極の電流密度などの
操業条件に支配される。 Ammonium paratungstate is approximately
Up to 50g/g is readily soluble in water. However, if this is dissolved as an aqueous solution of citric acid, a concentrated aqueous solution of about 100 g/g can be obtained. The amount of citric acid used at that time is 50 to 200
g/ is considered appropriate. This is because, as mentioned above, the citric acid in the replenishment solution not only acts as an anti-settling agent, but also plays the role of replenishing the citric acid consumed during electrolysis, but its consumption rate is It is governed by operating conditions such as density and current density of the stainless steel anode.
したがつて、好ましい補給液は、パラタングス
テン酸アンモニウム100ｇ／に対し、くえん酸
量は50〜200ｇ／の幅をもつことになる。該補
給液のPHは、補給液としての性質上１〜６程度に
アンモニアによつて調整されるがよい。 Therefore, in a preferred replenishment solution, the amount of citric acid ranges from 50 to 200 g per 100 g of ammonium paratungstate. The pH of the replenishment liquid may be adjusted to about 1 to 6 with ammonia due to its properties as a replenishment liquid.
上述した補給液の補給時期は、電解浴中のＷ含
量が、建浴時のそれよりも減少した時点である。
むろん、電解浴中のＷ量測定手段にとくに限定は
ない。しかし、好ましい手段は、たとえば、常時
電解槽から電解液の一部を抜き取り、その旋光度
を測定することによつてＷを所定量たとえば
0.21mol／に維持するに足る量をポンピングす
ることによつて実施する。後述実施例に示したよ
うに、めつき層に移行することによつて減少した
浴中のＷは、前記補給液の補給によつて補充され
るのみならず、本発明者が実験的に見出した好ま
しいNa+浴濃度0.42mol／が保持できる。しか
しＷ酸塩をそのアンモニウム塩の形態でなく最も
ありふれたNa2WO4・2H2Oの形態で浴中のＷの
減少に見合う量だけ補給してやれば浴中のNa+は
最適濃度、前記0.42mol／よりも増加してしま
う。したがつて、この場合には抜き採つた電解液
からNa+を除去し、しかる後に除去後の電解液を
めつき槽へ循環することによつて解決でき、その
ようなNa+除去手段としてイオン交換樹脂の使用
も不可能ではない。しかしそれは装置的・経済的
負担をあまりに大ならしめることになるので、既
述したパラタングステン酸アンモニウム補給液使
用の有利さに及ばない。 The timing for replenishing the above-mentioned replenishment liquid is when the W content in the electrolytic bath is lower than that at the time of bath preparation.
Of course, there is no particular limitation on the means for measuring the amount of W in the electrolytic bath. However, a preferable means is to add a predetermined amount of W, for example, by constantly drawing out a part of the electrolyte from the electrolytic cell and measuring its optical rotation.
This is done by pumping enough to maintain it at 0.21 mol/. As shown in the Examples below, W in the bath, which has decreased due to transfer to the plating layer, is not only replenished by replenishing the replenishing liquid, but also A preferable Na + bath concentration of 0.42 mol/min can be maintained. However, if W salt is replenished not in its ammonium salt form but in the most common form of Na 2 WO 4 .2H 2 O in an amount commensurate with the decrease in W in the bath, the Na + in the bath reaches its optimum concentration, 0.42 It increases more than mol/. Therefore, this case can be solved by removing Na + from the extracted electrolyte and then circulating the removed electrolyte to the plating tank. It is not impossible to use exchangeable resins. However, this imposes an excessively large equipment and economical burden, and therefore cannot match the advantages of using the ammonium paratungstate replenishment liquid described above.
つぎにNi材陽極は、電解による浴のNi濃度の
減少を補償する意味で、ある一定速度で溶解し、
濃度が不足した場合には、溶解速度を増し、過剰
の場合には減速させてやる必要がある。これがた
め前記旋光度測定のために抜き取つた電解液を、
吸光度セルに導いて、その明るさを測光し、これ
を電圧に変換し、予め別途用意しておいた電解浴
の明るさと変調電圧との関係を基礎とするNi材
陽極ホイスター基礎本制御部に導き、サーボモー
タに連動させて、該陽極を上・下させ、浴への浸
漬度を調整することによつて、溶解速度を制御す
るがよい。このNi材陽極ホイスターの吸光度に
よる制御によつて、本発明方法が２陽極法である
にもかかわらず、陽極回路を２つ設ける必要をな
くしているという利点を伴うのである。 Next, the Ni material anode dissolves at a certain rate to compensate for the decrease in Ni concentration in the bath due to electrolysis.
When the concentration is insufficient, the dissolution rate must be increased, and when there is an excess, the dissolution rate must be slowed down. Therefore, the electrolyte extracted for the optical rotation measurement is
The Ni material anode is introduced into the absorbance cell, its brightness is photometered, and this is converted into voltage. The rate of dissolution may be controlled by guiding the anode and raising and lowering the anode in conjunction with a servo motor to adjust the degree of immersion in the bath. By controlling the absorbance of the Ni material anode hoister, although the method of the present invention is a two-anode method, it has the advantage of eliminating the need for two anode circuits.
さらにまた、Ni材陽極の不動態化を防止する
には、該陽極電位測定装置を付設し、予め定めた
しきい値を基準にして、該陽極表面に接触させる
Cl-の量を加減することによつて行うがよい。 Furthermore, in order to prevent passivation of the Ni material anode, an anode potential measuring device is attached and brought into contact with the anode surface based on a predetermined threshold value.
This can be done by adjusting the amount of Cl - .
上述した本発明方法を実施するに適した装置と
して、本発明者が創作した第１図装置を用いて行
つた実施例につき述べる。 An example will be described using the apparatus shown in FIG. 1 created by the present inventor as an apparatus suitable for carrying out the above-mentioned method of the present invention.
図中符１は電解槽であつて、この中に入れた電
解浴液２の組成は次のとおりである。 Reference numeral 1 in the figure is an electrolytic bath, and the composition of the electrolytic bath liquid 2 placed therein is as follows.
くえん酸…… 100ｇ／
NiSO4・6H2O…… 70ｇ／
Na2WO4・2H2O…… 70ｇ／
PH（NH4OHで調整）…… 6.0
Na+濃度…… 0.42mol／
該電解浴は70℃に保たれ、その中に陰極３とし
て100×50×0.3mmの鉄板を懸吊し、これと対向す
る位置に、SUS材陽極４ならびにNi材陽極５を
懸吊し、これら電極は電源７とリード線７ａ，７
ｂにより図示のとおりで結ばれている。Citric acid... 100g/ NiSO 4・6H 2 O... 70g/ Na 2 WO 4・2H 2 O... 70g/ PH (adjusted with NH 4 OH)... 6.0 Na + concentration... 0.42mol/ The electrolytic bath is maintained at 70°C, and a 100 x 50 x 0.3 mm iron plate is suspended therein as the cathode 3. A SUS material anode 4 and a Ni material anode 5 are suspended in the opposite position. Power supply 7 and lead wires 7a, 7
They are connected by b as shown.
SUS材陽極４の材質はSUS304で、その形状は
φ1mm針金を方形に編んだ65×50mmの寸法のもの
である。Ni材陽極５は市販電気ニツケルアノー
ドで、断面10×10mm、長さ70mmの角棒であつて、
後述するサーボモータ１４により、上下に浸漬高
さが調整される。Ni材陽極５には常法とおり陽
極バツク６がカバーされる。この場合バツク６の
材料としては東洋紙KK製＃No.２を用いた。 The material of the SUS material anode 4 is SUS304, and its shape is 65 x 50 mm in size, made by braiding φ1 mm wire into a rectangular shape. The Ni material anode 5 is a commercially available electric nickel anode, which is a square bar with a cross section of 10 x 10 mm and a length of 70 mm.
The immersion height is adjusted vertically by a servo motor 14, which will be described later. The Ni material anode 5 is covered with an anode back 6 as usual. In this case, #2 manufactured by Toyo Shi KK was used as the material for the bag 6.
電解浴液は、管路８ａを経てポンプ１０により
常時抜き取られ、冷却器９で常温にまで冷却され
管８ｂ、ポンプ１０、管路８ｃを経て650nｍの
吸光度セル１１、管路８ｄ、555nｍの旋光セル
１５で旋光度を測定したのち、管路８ｅを経て電
解槽１へ循環する。 The electrolytic bath liquid is constantly drawn out by a pump 10 through a pipe 8a, cooled to room temperature by a cooler 9, and passed through a pipe 8b, a pump 10, and a pipe 8c to an absorbance cell 11 at 650 nm, a pipe 8d, and an optical rotation at 555 nm. After the optical rotation is measured in the cell 15, it is circulated to the electrolytic cell 1 via the conduit 8e.
前述した吸光度セル１１で測定した吸光度と、
建浴時の吸光度との偏差は、変調電圧としてコン
トロール電圧発生回路１２から取り出され、Ni
陽極ホイスタ基本制御回路１３において、建浴時
の基準電圧に合致すべく、サーボモータ１４を駆
動させ、それによつてNi陽極５は、浴２への浸
漬度を変え、常に建浴時のNi濃度に等しいNi濃
度が保持できるよう溶解度が加減される。 The absorbance measured with the absorbance cell 11 described above,
The deviation from the absorbance at the time of bath preparation is taken out from the control voltage generation circuit 12 as a modulation voltage, and Ni
In the anode hoister basic control circuit 13, the servo motor 14 is driven in order to match the reference voltage at the time of bath preparation, thereby changing the degree of immersion of the Ni anode 5 into the bath 2, and always keeping the Ni concentration at the time of bath preparation. The solubility is adjusted to maintain a Ni concentration equal to .
他方、旋光セル１５では、旋光セルを通つた偏
向光が第２の偏向板を介して、光スイツチ機構１
６に導かれる。光スイツチ機構に入る光強度が、
建浴時の電解浴２についての基準値よりも強くな
つた場合、光スイツチ機構１６がポンプ１７を作
動させ、補給液槽１８中の補給液が、管路１９か
ら電解槽へ補給される。この補給によつて、光ス
イツチ機構１６へ入る光強度が基準値と等しくな
ると、ポンプ１７は停止する。 On the other hand, in the optical rotation cell 15, the polarized light that has passed through the optical rotation cell passes through the second polarization plate to the optical switch mechanism 1.
6. The light intensity entering the light switch mechanism is
When the strength of the electrolytic bath 2 becomes higher than the reference value at the time of bath preparation, the optical switch mechanism 16 activates the pump 17, and the replenishing liquid in the replenishing liquid tank 18 is replenished from the conduit 19 to the electrolytic bath. As a result of this replenishment, when the light intensity entering the optical switch mechanism 16 becomes equal to the reference value, the pump 17 is stopped.
本実施例に用いた補給液の組成は下記のとおり
であつた。 The composition of the replenishment liquid used in this example was as follows.
（NH4）10W12O41・5H2O…… 100ｇ／
くえん酸…… 110ｇ／
PH（NH4OHで調整）…… ５
なお、Ni材陽極５には、その表面不動態防止
のため、Cl-イオンの必要最小量が補給せられる。
図中、符２０は、その先端がNi材陽極５に接触
したNi材陽極の電位測定用電解液導管であつて、
その他端は、電位測定部２１に液絡している。測
定された電位が30秒以上1.1Vを示した場合、し
きいスイツチ２２がポンプ２４を作動させ、
NH4Cl水溶液が、その貯槽２３からテフロン製
管路２５を経てNi陽極に供給され、電位が1.0V
に下ればポンプ２４は停止する。(NH 4 ) 10 W 12 O 41・5H 2 O...100g/Citric acid...110g/PH (adjusted with NH4OH )...5 The Ni material anode 5 has a , the required minimum amount of Cl - ions is replenished.
In the figure, reference numeral 20 is an electrolyte conduit for measuring the potential of the Ni material anode, the tip of which is in contact with the Ni material anode 5.
The other end is in liquid junction with the potential measuring section 21. If the measured potential shows 1.1V for more than 30 seconds, the threshold switch 22 activates the pump 24;
The NH 4 Cl aqueous solution is supplied from the storage tank 23 to the Ni anode through the Teflon pipe 25, and the potential is 1.0V.
The pump 24 will stop if the temperature drops to below.
本例では180AH／までの浴寿命テストを行
つたが。タングステン補給液中になんらのNa+が
含有されておらず、Cl-イオンの供給も必要最小
限であり、浴液の基本組成が乱されることなく、
Ｗ含量44％の合金組成・外観のほぼ一定しためつ
き槽が連続して得られた。 In this example, we conducted a bath life test up to 180AH/. The tungsten replenishment solution does not contain any Na + and the supply of Cl - ions is minimal, so the basic composition of the bath solution is not disturbed.
Tightening tanks with an almost constant alloy composition and appearance with a W content of 44% were obtained continuously.
本発明は以上のように構成されるから、未だ試
みられたことのないNi−Ｗ合金めつきの少なく
とも確認された180AH／の連続化が可能とな
つたのである。しかも本発明方法および装置によ
ればめつき層中のＷ含量は最高62％にも及ぶ低温
かつ弱酸性電解浴に起因して、NH3揮発に伴う
環境汚染問題は消滅したのである。なお電流効率
は60％の好成績である。 Since the present invention is constructed as described above, it has become possible to achieve continuous Ni--W alloy plating of at least 180AH/, which has never been attempted. Moreover, according to the method and apparatus of the present invention, the W content in the plating layer is as high as 62% due to the low temperature and weakly acidic electrolytic bath, which eliminates the environmental pollution problem caused by NH 3 volatilization. The current efficiency was a good 60%.
第１図は本発明の一実施例の装置の説明図であ
る。
１……電解槽、２……電解浴、３……陰極、４
……ステンレス材陽極、５……Ni材陽極、６…
…陽極バツグ、７……めつき電源、８（ａ，ｂ，
ｃ，ｃ，ｄ，ｅ）……電解液循環管路、９……冷
却器、１０……ポンプ、１１……吸光度セル、１
２……コントロール電圧発生回路、１３……ニツ
ケルホイスタ基本制御回路、１４……サーボモー
タ、１５……旋光度セル、１６……光スイツチ機
構、１７……ポンプ、１８……補給液槽、１９…
…管路、２０……センサーチユーブ、２１……電
位測定部、２２……しきいスイツチ、２３……
NH4Cl水溶液貯槽。
FIG. 1 is an explanatory diagram of an apparatus according to an embodiment of the present invention. 1... Electrolytic cell, 2... Electrolytic bath, 3... Cathode, 4
...Stainless steel anode, 5...Ni material anode, 6...
... Anode bag, 7... Plating power supply, 8 (a, b,
c, c, d, e)... Electrolyte circulation pipe, 9... Cooler, 10... Pump, 11... Absorbance cell, 1
2... Control voltage generation circuit, 13... Nickel Heuster basic control circuit, 14... Servo motor, 15... Optical rotation cell, 16... Optical switch mechanism, 17... Pump, 18... Replenishment liquid tank, 19...
...Pipeline, 20...Sensor tube, 21...Potential measuring section, 22...Threshold switch, 23...
NH 4 Cl aqueous solution storage tank.
Claims (1)
えん酸を有機錯化剤とした電解浴中で、ステンレ
ス材ならびにニツケル材を陽極とし、タングステ
ン含有液を補給しつつ電解することを特徴とする
Ni−Ｗ合金の連続めつき方法。 ２ 不溶性ステンレス材陽極４と、溶解性ニツケ
ル陽極５とを有し、ニツケル濃度測定手段ならび
にタングステン濃度測定手段を有する電解浴循環
路８を備えた電解槽１と、タングステン補給液槽
１８とより成り、ニツケル材陽極の浸漬度を測定
した浴中のニツケル濃度に連動させ、タングステ
ン補給液の補給量を測定した浴中のタングステン
濃度に連動させたことを特徴とするNi−Ｗ合金
連続めつき装置。 ３ ニツケル濃度測定手段は、電解浴液の吸光度
測定である特許請求の範囲１記載のNi−Ｗ合金
連続めつき装置。 ４ タングステン濃度測定手段は電解浴液の旋光
度測定である特許請求の範囲１記載の装置。[Claims] 1. Electrolyzing in an electrolytic bath containing nickel salts and tungstates and using citric acid as an organic complexing agent, using stainless steel material and nickel material as anodes and replenishing a tungsten-containing solution. characterized by
Continuous plating method for Ni-W alloy. 2. Consists of an electrolytic cell 1 having an insoluble stainless steel anode 4 and a soluble nickel anode 5, an electrolytic bath circulation path 8 having a nickel concentration measuring means and a tungsten concentration measuring means, and a tungsten replenishment liquid tank 18. , a Ni-W alloy continuous plating apparatus characterized in that the degree of immersion of the nickel material anode is linked to the measured nickel concentration in the bath, and the replenishment amount of the tungsten replenishment liquid is linked to the measured tungsten concentration in the bath. . 3. The Ni-W alloy continuous plating apparatus according to claim 1, wherein the nickel concentration measuring means is a measurement of absorbance of an electrolytic bath solution. 4. The device according to claim 1, wherein the tungsten concentration measuring means is measuring the optical rotation of the electrolytic bath liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25199983A JPS60135593A (en) | 1983-12-23 | 1983-12-23 | Continuous ni-w alloy plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25199983A JPS60135593A (en) | 1983-12-23 | 1983-12-23 | Continuous ni-w alloy plating |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3030482A Division JPH0674520B2 (en) | 1991-02-25 | 1991-02-25 | Ni-W alloy continuous plating electrolytic bath replenisher |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60135593A JPS60135593A (en) | 1985-07-18 |
| JPH0369995B2 true JPH0369995B2 (en) | 1991-11-06 |
Family
ID=17231141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25199983A Granted JPS60135593A (en) | 1983-12-23 | 1983-12-23 | Continuous ni-w alloy plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60135593A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02217497A (en) * | 1989-02-18 | 1990-08-30 | Takada Kenkyusho:Kk | Nickel-tungsten-silicon carbide composite plating method |
| JPH0674520B2 (en) * | 1991-02-25 | 1994-09-21 | 株式会社シミズ | Ni-W alloy continuous plating electrolytic bath replenisher |
| JP2611626B2 (en) * | 1993-06-30 | 1997-05-21 | 山口県 | Heat-resistant nickel-tungsten alloy plating film and method of forming the same |
| JP5513938B2 (en) * | 2010-03-11 | 2014-06-04 | 奥野製薬工業株式会社 | Tungsten replenisher for electric nickel-tungsten plating bath |
| JP5649249B2 (en) * | 2012-01-30 | 2015-01-07 | 新日鐵住金株式会社 | Hot working tool and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5357138A (en) * | 1976-11-04 | 1978-05-24 | Hitachi Chemical Co Ltd | Electrolyte for tungsten type alloy plating |
-
1983
- 1983-12-23 JP JP25199983A patent/JPS60135593A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5357138A (en) * | 1976-11-04 | 1978-05-24 | Hitachi Chemical Co Ltd | Electrolyte for tungsten type alloy plating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60135593A (en) | 1985-07-18 |
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