JPS63266087A - Rhodium sulfate plating solution and method for maintaining function thereof - Google Patents
Rhodium sulfate plating solution and method for maintaining function thereofInfo
- Publication number
- JPS63266087A JPS63266087A JP9743387A JP9743387A JPS63266087A JP S63266087 A JPS63266087 A JP S63266087A JP 9743387 A JP9743387 A JP 9743387A JP 9743387 A JP9743387 A JP 9743387A JP S63266087 A JPS63266087 A JP S63266087A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- plating solution
- rhodium
- solution
- sulfuric acid
- 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 97
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims abstract description 5
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 14
- 230000007423 decrease Effects 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000010948 rhodium Substances 0.000 abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 238000009713 electroplating Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- 229910052703 rhodium Inorganic materials 0.000 description 24
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000218691 Cupressaceae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
開示技術は電気接点等の工業製品や装飾品等の工芸製品
の露呈表面の処理に用いられるところの高い耐摩耗性、
耐蝕性、及び、美麗な光沢を有するロジウムめっきのう
ち、反復するめつきの継続に伴いめっき液中の硫酸濃度
が増大して酸性が強くなる硫酸ロジウムめっき液の組成
を一定に保持し、長期間の安定した使用を可能ならしめ
ためつき液と、それを適切に使用して経済性を高めるよ
うにした方法についての技術分野に属する。[Detailed Description of the Invention] <Industrial Application Field> The disclosed technology is used to treat exposed surfaces of industrial products such as electrical contacts and craft products such as ornaments, which have high abrasion resistance.
Rhodium plating is corrosion resistant and has a beautiful luster.The concentration of sulfuric acid in the plating solution increases with repeated plating, making it more acidic. This field belongs to the technical field of tamping liquid that can be used stably and methods that can improve economic efficiency by using it appropriately.
〈要旨の概要〉
而して、この出願の発明は硫酸［］ジウムめっき液によ
り電気接点や装飾品等の工芸品の露呈表面にロジウムめ
っきを行うに際し、ロジウムか電着する経時的なプロセ
スにおいてｐ Ｈの、或は、硫酸濃度の低下を防止し、
めっき機能を確実に安定して維持することが出来るよう
にした硫酸ロジウムめっき液及びその機能維持方法に関
する発明であり、特に、ロジウムめっき液に水酸化カリ
ウム、又は、水酸化ナトリウム、或は、炭酸カリウムや
炭酸ナトリウム等を用いることにより硫酸ロジウム液の
Ｄ Ｉ−１を一定に保ち、更には、飽和濃度に達しため
つき液を室温に降下させて飽和濃度に達きしめ、Ｆａ酸
水素カリウム、又は、ｆ１酸水素ナトリウムの結晶を温
出させた後にめっき液から取り出し、めっき液の硫酸濃
度を一定に維持することが出来るようにした硫酸ロジウ
ムめっき液及びその機能維持方法に係る発明である。<Summary of the gist> The invention of this application, when plating exposed surfaces of crafts such as electrical contacts and ornaments with rhodium using a []dium sulfate plating solution, involves a process in which rhodium is electrodeposited over time. Preventing a decrease in pH or sulfuric acid concentration,
This invention relates to a rhodium sulfate plating solution that can reliably and stably maintain the plating function, and a method for maintaining the function. By using potassium, sodium carbonate, etc., the DI-1 of the rhodium sulfate solution is kept constant, and further, until the saturated concentration is reached, the prickling solution is lowered to room temperature to reach the saturated concentration. This invention relates to a rhodium sulfate plating solution in which the sulfuric acid concentration of the plating solution can be maintained constant by warming the crystals of sodium hydrogen oxide fl and then removing them from the plating solution, and a method for maintaining the function thereof.
〈従来技術〉
当業者にとり周知の如く、ロジウムめっきは電気接点の
製造の表面強度面上等の工業的用途に用いられたり、装
飾用等の工芸品の表面の審美性向上等の用途に用いられ
る態様かあり、製品のめつき面の滑らかさ、そのため、
結果的に光沢の良さを有する耐蝕性、耐摩耗性の被膜を
現出するのに大きく与っており、したがって、表面に対
する平滑化機能や光沢化機能がより強く求められるよう
になってきた。<Prior Art> As is well known to those skilled in the art, rhodium plating is used for industrial purposes such as improving the surface strength in the manufacture of electrical contacts, and for improving the aesthetic appearance of the surfaces of decorative and other crafts. The smoothness of the plating surface of the product, therefore,
As a result, it plays a major role in producing a corrosion-resistant and abrasion-resistant coating with good gloss, and therefore, there has been a strong demand for surface smoothing and glossing functions.
而して、これまで使用されているロジウムめっき液には
、大別すると、Ｆａ酸浴と燐醗浴、又、硫酸と燐酸の混
合浴があるが、使用の容易さやコスト等の面からｒｉａ
酸浴が広く用いられている。Rhodium plating solutions that have been used so far can be roughly divided into Fa acid baths, phosphorous baths, and mixed baths of sulfuric acid and phosphoric acid.
Acid baths are widely used.
〈発明が解決しようとする問題点〉
ＵＡＭロジウムめっきは普通、表面がＰｔから成る不溶
性アノードを用い、これに対しめっきすべきＲｈ Ｇ、
ｔ ｐＨが１以下の強酸性溶液である硫酸めっき液、即
ち、Ｒｈ２ （ＳＯ４）３水溶液で経時的に補充される
。<Problems to be Solved by the Invention> UAM rhodium plating usually uses an insoluble anode whose surface is made of Pt, and RhG, which is to be plated,
t It is replenished over time with a sulfuric acid plating solution, which is a strongly acidic solution with a pH of 1 or less, that is, an aqueous Rh2 (SO4)3 solution.
ところで、めっき中のＲｈの電着に伴う反応はＲｈ
（ＳＯＪ ）２ − ＋’ｌ トｌ”＋３ｅ＝Ｒ
ｈ＋２Ｈ３Ｏ４−
で表され、Ｒｈが経時的に電着するにつれて、上式のＨ
３Ｏ４−で表した硫酸水素イオン濃度（簡単に硫酸濃度
）は大きくなり、それに伴いめっき液のＩＩは低下し、
電着時の陰慎電位は卑になる。By the way, the reaction accompanying Rh electrodeposition during plating is Rh
(SOJ)2-+'l''+3e=R
h+2H3O4-, and as Rh is electrodeposited over time, H in the above formula
The hydrogen sulfate ion concentration (simply sulfuric acid concentration) expressed as 3O4- increases, and the II of the plating solution decreases accordingly.
The negative potential during electrodeposition becomes base.
換言すれば陰分極が大きくなる。In other words, the cathode polarization increases.
しかしながら、強酸性溶液では硫酸濃度が増してもｐＨ
の低下は僅かであるため、従来は特別のｐＨ調整はとら
れていないのが実状であった。However, in strongly acidic solutions, even if the sulfuric acid concentration increases, the pH
Since the decrease in pH is slight, no special pH adjustment has been done in the past.
したかつて、めっきに際しての電流効率が低下すると共
に、陰極に於ける電解還元作用も起こり易くなって還元
生成物の共析等でめっき面が黒色を帯びていく欠点があ
り、添加剤の還元生成物で液中のＲｈ （３０４）２−
イオンが還元され、ついにはめっき液そのものが分解す
るといったトラブルも生じる不具合があり、長時間主成
分のＲｈを補充しながらめっき液を使用することが難し
いという離点があり、したがって、いづれにしても、所
定時間後にはめつき液を廃棄して新たに建浴する必要が
あり、極めてリサイクルが煩瑣となる不都合さがあった
。In the past, the current efficiency during plating decreased, and the electrolytic reduction effect at the cathode became more likely to occur, resulting in the plating surface becoming black due to the eutectoid of reduction products, and the reduction formation of additives. Rh in liquid (304)2-
There is a problem in that the ions are reduced and eventually the plating solution itself decomposes, and it is difficult to use the plating solution while replenishing Rh, the main component, for a long period of time. However, it is necessary to discard the plating solution and prepare a new bath after a predetermined period of time, which is disadvantageous in that recycling becomes extremely troublesome.
而して、廃棄めっき液中のＲｈは回収して再利用するに
しても、回収廃液処理等のためのメンテナンスコストを
要し、不経済でおる不利点が必つた。Therefore, even if the Rh in the waste plating solution is recovered and reused, maintenance costs are required for processing the recovered waste solution, which is uneconomical.
又、特公昭５６−６９４００号公報発明にみられるよう
に、イオン交換膜を用いた電気透析で［」３０４−イオ
ンを除去する手段も提案されてはいるが、過分な余剰施
設を要し、コス１へ高になる不利点があり、そのうえ、
制御管理も煩雑でおる不具合がある。Furthermore, as seen in the invention disclosed in Japanese Patent Publication No. 56-69400, a means for removing 304-ions by electrodialysis using an ion exchange membrane has been proposed, but this method requires excessive redundant facilities. There is a disadvantage that the cost is higher than 1, and in addition,
There is also a problem that control management is complicated.
〈発明の目的〉
この出願の発明の目的は上述従来技術に基づく硫酸ロジ
ウムめつき液の問題点を解決すべき技術的課題とし、該
硫酸ロジウムめっぎ液の本来的な平滑化機能、光沢付与
機能を損わず、通常のめっき条件の基ではめつぎ液が電
解還元を容易には受けず、経済的に安定したロジウムめ
っきを継続して行うことが出来るようにして機械製造産
業や工芸産業にあける仕上げ技術利用分野に益する優れ
た光沢ロジウムめっき液と、その機能維持方法を提供せ
んとするものである。<Object of the Invention> The object of the invention of this application is to solve the problems of the rhodium sulfate plating solution based on the above-mentioned prior art, and to improve the smoothing function and brightness of the rhodium sulfate plating solution. The plating solution does not easily undergo electrolytic reduction under normal plating conditions without impairing the imparting function, making it possible to continuously perform economically stable rhodium plating, which is useful in the machine manufacturing industry and crafts. The purpose of this invention is to provide an excellent bright rhodium plating solution that will benefit industrial finishing technology applications, and a method for maintaining its functionality.
〈問題点を解決するための手段・作用〉上述目的に沿い
先述特許請求の範囲を要旨とするこの出願の発明の構成
は前述問題点を解決するために、ロジウムめっきを継続
するにつれて、硫酸濃度、換言すれば、Ｈ８Ｏ＋−イオ
ンの濃度が増大し、ｐＨが低下することが通常の手段で
５Ａ酸ロジウムめっきを行う限り不可避的なものである
ことを前提としながらも、めっき液にカリウムイオン、
又は、ナトリウムイオンを予め加える他、めっき液のＤ
Ｈが一定になるようにＫ ＯＨ、又は、Ｎ ａ Ｏ＋」
でめっき液のｐ［−１を可及的に早期に調整し、めっき
液中に硫酸水素カリウム、又は、硫酸水素ナトリウムを
生成させて酸を中和するものである。<Means/effects for solving the problems> In order to solve the above-mentioned problems, the structure of the invention of this application, which is based on the above-mentioned claims, is to improve the concentration of sulfuric acid as rhodium plating continues. In other words, although it is assumed that the concentration of H8O+- ions increases and the pH decreases as long as 5A acid rhodium plating is carried out by normal means, potassium ions and
Alternatively, in addition to adding sodium ions in advance, D of the plating solution
K OH or N a O+ so that H is constant.
The p[-1 of the plating solution is adjusted as early as possible, and potassium hydrogen sulfate or sodium hydrogen sulfate is generated in the plating solution to neutralize the acid.
この場合、ＫＯＨ，ＮａＯＨに代えてに２ Ｃ０３、Ｎ
ａ２ ＣＯ３を用いることも作用効果上等価であり、而
して、めっき中に所定に空温等に徐冷して飽和に達さし
めて透明の針状結晶を析出させ水洗して純結品を取り出
し、これにより過剰の硫酸イオンを除去し、めっき液の
硫酸濃度をほぼ一定に維持し、半永久的にめっき液を使
用することが出来るようにした技術的手段を講じたもの
である。In this case, 2 C03, N instead of KOH, NaOH
Using a2 CO3 is equivalent in terms of function and effect, and during plating, it is gradually cooled to a specified air temperature, etc. to reach saturation, precipitates transparent needle-shaped crystals, and is washed with water to produce pure crystals. A technical measure was taken to remove excess sulfate ions, maintain the sulfuric acid concentration of the plating solution at a nearly constant level, and enable the plating solution to be used semi-permanently.
〈発明の背景〉
硫酸ロジウムめっき液は通常硫Ｍ瀧度が高く、強酸性で
ｐＨはＯ〜１．０程度であるが、それより硫酸濃度が高
くなりｐＨが低くなっても、前述のような副作用はある
が、めっきをすること自体は一応可能である。<Background of the Invention> Rhodium sulfate plating solutions usually have a high sulfur M content, are strongly acidic, and have a pH of about 0 to 1.0, but even if the sulfuric acid concentration is higher and the pH is lower, as mentioned above, Although there are some side effects, plating itself is possible.
しかしながら、副作用のなく本来的に望ましいｐｈ＋は
０．２〜０．９程度であり、したがって、めっき中はＤ
Ｈをこの間の適当な１直に保つようにすることが望まし
い。However, the inherently desirable pH+ without side effects is about 0.2 to 0.9, and therefore, during plating, D
It is desirable to keep H at an appropriate 1 shift during this time.
ところで、硫酸水素カリウムの溶解度はＫＨＳＯ３とし
てＯｏＣで約３６０９／Ｊ、１００’ＣＦ約１２００３
／Ｊ、一方、硫酸水素ナトリウムの溶解度はＮａＨ３Ｏ
４として２５℃で約２８０９／Ｊ、１００’Ｃで約１０
００ｇ／）である。By the way, the solubility of potassium hydrogen sulfate is about 3609/J in OoC as KHSO3, and about 12003 in 100'CF.
/J, while the solubility of sodium hydrogen sulfate is NaH3O
4, about 2809/J at 25℃, about 10 at 100'C
00g/).
そして、含水塩の溶解度もこれに近い１直であると推考
され、そこでロジウムめっき状態のめっき液の温度をめ
っき中の約４０〜６０’Ｃから常温の空温に冷却すると
、飽和している場合には透明の針状結晶が晶出すること
が分っている。The solubility of the hydrated salt is also thought to be close to this, so when the temperature of the plating solution in the rhodium plating state is cooled from about 40 to 60'C during plating to room temperature in the air, it becomes saturated. In some cases, transparent needle-like crystals have been found to crystallize.
この場合、周知の如く、徐冷によって晶出した核種針状
の結晶中には不純物がほとんど含まれないので、該結晶
中に含まれるＲｈの量は極めて少く、該結晶表面に付着
したＲｈを含んだ溶液を軽く洗うだけでほぼ純粋な結晶
を液から取り出すことが出来る。In this case, as is well known, the needle-shaped nuclide crystals crystallized by slow cooling contain almost no impurities, so the amount of Rh contained in the crystals is extremely small, and the amount of Rh attached to the surface of the crystals is very small. Almost pure crystals can be extracted from the solution by simply washing the solution.
そして、該結晶を取り出すことによりめっき液中の過剰
のＨ３Ｏ４−イオンも同様に除去することが出来ること
になり、めっき液の硫Ｍ１度をほぼ一定に保つことが可
能となる。By taking out the crystals, excess H3O4- ions in the plating solution can also be removed, making it possible to keep the sulfur M1 degree of the plating solution almost constant.
そして、ＫＨＳＯ３として３６０ｇ／Ｊの場合Ｓ０４と
しては２５／’４９．／１、ＮａＨ３Ｏ４として２８０
９／ノの場合ＳＯ４としては２２１Ｆ／Ｊでおる。When KHSO3 is 360g/J, S04 is 25/'49. /1, 280 as NaH3O4
In the case of 9/, the SO4 is 221F/J.
又、取り出した結晶は水に溶かした後、適宜の方法で微
開のＲｈを回収すれば、Ｒｈのロスは回避することが出
来、資材歩留を良好にすることが出来る。Further, if the extracted crystals are dissolved in water and then a small amount of Rh is recovered by an appropriate method, loss of Rh can be avoided and the material yield can be improved.
このようにして、硫酸濃度を一定に保持すれば、硫Ｗｍ
度の上昇に伴うめっき中の様々なトラブルを回避するこ
とが出来、ＷＩｔ酸ロジウムめっき液を半永久的に使用
することか可能となることが分る。In this way, if the sulfuric acid concentration is kept constant, sulfuric acid Wm
It can be seen that various troubles during plating caused by an increase in temperature can be avoided, and that the WIt acid rhodium plating solution can be used semi-permanently.
そして、硫酸濃度が変化すると、陰分極も変わり、それ
に伴ってロジウムめっき被膜の光沢、色調も微妙に変化
するので、早期に平衡状態のｌｉｉｌＹｍ濃度になるこ
とが望ましく、実験によれば、建浴時にそれぞれＫＨＳ
Ｏ３、又は、Ｎａｆ−ｌｓＯ４（これに代えＴＫ２ Ｃ
Ｏ３、Ｎａ２ ＣＯ３も可能でおる。）を０．０１モル
／ノ程度以上、望ましくは空温での飽和濃度まで加えて
おき、硫酸濃度の変動を小さく抑えることが望ましい。When the sulfuric acid concentration changes, the negative polarization also changes, and the gloss and color tone of the rhodium plating film also change subtly. Sometimes KHS
O3 or Naf-lsO4 (alternatively TK2 C
O3, Na2 CO3 are also possible. ) is preferably added to a saturation concentration of about 0.01 mol/no or more, preferably at air temperature, to keep fluctuations in the sulfuric acid concentration small.
〈実施例〉
次に、この出願の発明の詳細な説明すれば以上の通りで
ある。<Example> Next, the detailed description of the invention of this application is as above.
［第１実施例］
Ｒｈ ： ２９／ノＫＨ３Ｏ
ａ （初期）：５０び／Ｊ
硫酸（ＳＯ４として） ： １５０！７／Ｊρ
ト１
： ０．６光沢剤 ：
適 壜
から成るＦＡＷロジウムめっき液５Ｊて、０．０３μｍ
の厚さの光沢ロジウムめっきを延べ約１００７ｄのニッ
ケル素地上に施した。[First Example] Rh: 29/no KH3O
a (Initial): 50!7/J Sulfuric acid (as SO4): 150!7/Jρ
1
: 0.6 brightener :
FAW rhodium plating solution 5J consisting of a suitable bottle, 0.03μm
Bright rhodium plating with a thickness of approximately 1,007 d was applied to a nickel substrate.
この間、Ｒｈ１ＯＯ！７／ノの補充液でＲｈを補充する
と共に、めっき液のｐＨをＫＯＨで０．３になるように
調整した。During this time, Rh1OO! Rh was replenished with a 7/2 replenisher, and the pH of the plating solution was adjusted to 0.3 with KOH.
而して、夜間、めっき休止時に８０’Ｃから常温の室温
に温度が下った時に晶出した硫酸水素カリ１クム結晶を
めっき槽から取り出して除去した。Then, during the night, when the plating was stopped, the 1 cum potassium hydrogen sulfate crystals that had crystallized when the temperature dropped from 80'C to room temperature were taken out from the plating bath and removed.
当該態様におけるめっき液はめつき終了時も安定した状
態で、初期と同様のロジウムめっきを継続することが可
能であった。The plating solution in this embodiment remained stable even at the end of plating, and it was possible to continue rhodium plating in the same manner as in the initial stage.
［第２実施例］
Ｒｈ ： ２９／ノＮａＨ８
Ｏ４（初期）：５０９／Ｊ
硫酸（３０４として） ： １００９’／１ｐＨ
： ０．７
光沢剤 ： 適 量
から成る［２０ジウムめっき液で、上）ホ第１実施例と
同一操作、条件でめっきし、Ｎ ａ Ｏ＋−１でｐＨを
調節し、硫酸水素ナトリウム結晶を檜から取り出した。[Second Example] Rh: 29/No NaH8
O4 (initial): 509/J Sulfuric acid (as 304): 1009'/1pH
: 0.7 brightener : Appropriate amount of [20 dium plating solution] Plating was carried out under the same procedure and conditions as in the first example, the pH was adjusted with NaO+-1, and sodium hydrogen sulfate crystals were added. I took it out of the cypress.
結果は、上述第１実施例と同様であった。The results were similar to those of the first example described above.
［第３実施例］
第１実施例と同じ：
ただし、ＫＨＳＯ３（初期）を１．５ｇ／ノ（０，０１
１モル／））硫酸（ＳＯ，＋として）１０ｇ／Ｊとする
。[Third example] Same as the first example: However, KHSO3 (initial) was added at 1.5 g/no (0,01
1 mol/)) 10 g/J of sulfuric acid (SO, +).
［第４実施例］
第２実施例と同じ：
ただし、ＮａＨ３Ｏ４（初期）ヲ１．３９／１１（０，
０１１モル／））硫酸（ＳＯ，Ｌとして）１ＪＪ／ノと
する。[Fourth Example] Same as the second example: However, NaH3O4 (initial) was 1.39/11 (0,
011 mol/)) Sulfuric acid (SO, as L) 1 JJ/no.
［比較例（在来態様）］
Ｒｈ： ２ｇ／ノ硫酸（ＳＯ４と
して＞：５０ｇ／ｌ
ｐＨ： ０．７
光沢剤 ： 適 量
（第１実施例と同種のもの）
から成る硫酸ロジウムめっき液５１を用い、０．０３μ
ｍの厚さの光沢ロジウムめっきをニッケル素地上に施し
た。[Comparative example (conventional mode)] Rhodium sulfate plating solution 51 consisting of Rh: 2g/nosulfuric acid (as SO4 >: 50g/l pH: 0.7 Brightener: appropriate amount (same type as in the first example) using 0.03μ
Bright rhodium plating with a thickness of m was applied to the nickel base.
約１０７７ｊめっきした時には、液のｐＨＩ、ｔ Ｏ以
下になって、電流効率が低下し、めっき時間を約２倍に
しないと０．０３μｍのめっきは困難であった。When approximately 1077j was plated, the pH of the solution was below tO, the current efficiency decreased, and it was difficult to plate 0.03 μm unless the plating time was approximately doubled.
又、光沢剤が分解して液中に黒い沈澱を生じた仙、めっ
き面も黒味を帯びてきたために、めっき液のそれ以上の
使用は困難であった。In addition, the brightener decomposed and a black precipitate formed in the solution, and the plating surface also became blackish, making it difficult to use the plating solution any further.
尚、当該態様において、ＲｈをＲｈ２ （ＳＯ４）３水
溶液で補充し、光沢剤を適宜補充した以外には、液の調
節は行わなかった。In this embodiment, no adjustment of the liquid was performed except for replenishing Rh with an aqueous Rh2(SO4)3 solution and replenishing the brightener as appropriate.
〈発明の効果〉
以上、この出願の発明によれば、従来めっき液条件の調
整が充分性われていなかったために、長期間の使用に際
しめっき液の機能が降下し、継続してその使用が困難で
あった硫酸［］ジウムめっき液の寿命を特別の装置を要
−Ｕずに大幅に延長することが可能となり、省資源にか
ない、めっき作業の効率化に１ジ立ら、その工業的恩義
は大きいという優れた効果が奏される。<Effects of the Invention> As described above, according to the invention of this application, since the plating solution conditions were not sufficiently adjusted in the past, the function of the plating solution deteriorates when used for a long period of time, making it difficult to use it continuously. It has become possible to significantly extend the lifespan of the sulfuric acid []dium plating solution without the need for special equipment, which contributes to resource conservation and improves the efficiency of plating work. An excellent effect is achieved in that it is large.
而して、硫酸ロジウム液により電気接点等の工業製品や
装飾品等の工芸品の露呈する表面に対しロジウムめっき
をするに際し、不可避的に硫酸濃度が増大する潜在条件
を前提としながらも、水酸化カリウム、又は、水酸化ナ
トリウム、或は、炭酸カリウムや炭酸ナトリウム等のカ
リウムイオン、又は、ナトリウムイオン等を有する液を
添加してＤＨの調整を行い、該ｐＩを一定にするように
したことにより経時的に反復されるＷｔ酸ロジウム液に
よるロジウムめっきを経時的に反復して行っているプロ
セスにおいてもｐＨが常に一定であるように持続させる
ことが出来るという優れた効果が奏される。Therefore, when rhodium plating the exposed surfaces of industrial products such as electrical contacts and crafts such as ornaments with rhodium sulfate solution, it is necessary to use rhodium plating, even though it is assumed that the sulfuric acid concentration will inevitably increase. DH was adjusted by adding potassium oxide, sodium hydroxide, or a solution containing potassium ions, sodium ions, etc., such as potassium carbonate or sodium carbonate, and the pI was kept constant. Even in a process in which rhodium plating with a Wt acid rhodium solution is repeatedly performed over time, the excellent effect of maintaining a constant pH is achieved.
又、経時的に反復するロジウムめっき液によるめっきプ
ロセスにおいて、めっき液に飽和濃度に達した際に降温
して室温の常温に達せしめる等により過飽和の硫酸水素
カリウム、又は、ｖｊＩ酸水素ナトリウムの結晶を析出
させるために、硫酸ロジウム液の硫酸濃度をほぼ一定に
、維持することが出来、めっき液が電解還元を容易には
受けず、安定したロジウムめっきを継続して行うことが
出来る優れた効果が秦される。In addition, in the plating process using a rhodium plating solution that is repeated over time, crystals of supersaturated potassium hydrogen sulfate or sodium hydrogen oxide may be formed by lowering the temperature of the plating solution when it reaches a saturated concentration and allowing it to reach room temperature. The sulfuric acid concentration of the rhodium sulfate solution can be maintained almost constant in order to precipitate the rhodium sulfate solution, and the plating solution is not easily subjected to electrolytic reduction, making it possible to continuously perform stable rhodium plating. is conquered by Qin.
出願人 石福金属興業株式会社 ＼−エ、′Applicant: Ishifuku Metal Kogyo Co., Ltd. ＼－E、′
Claims (3)
リウムイオンを０．０１モル／ｌ以上、飽和濃度以下に
含有させることを特徴とする硫酸ロジウムめっき液。(1) A rhodium sulfate plating solution, characterized in that the plating solution or replenisher contains potassium ions or sodium ions at a concentration of 0.01 mol/l or more and below the saturation concentration.
してそのめっき機能を維持するようにする方法において
、めっき中に電着するにつれて低下する硫酸ロジウムめ
っき液のｐＨを水酸化カリウム又は水酸化ナトリウムで
一定に保つことから成る硫酸ロジウムめっき液の機能維
持方法。(2) In a method of maintaining the plating function by keeping the pH of the rhodium sulfate plating solution constant during plating, the pH of the rhodium sulfate plating solution, which decreases as electrodeposition occurs during plating, is reduced by potassium hydroxide or hydroxide. A method for maintaining the function of rhodium sulfate plating solution, which consists of maintaining a constant level of sodium.
定にしてそのめっき機能を維持するようにした方法にお
いて、飽和濃度に達しためっき液から晶出した硫酸水素
カリウム又は硫酸水素ナトリウムの結晶をめっき液から
取り出して除去しめっき液の硫酸濃度を一定に維持する
ようにしたことを特徴とする硫酸ロジウムめっき液の機
能維持方法。(3) In a method that maintains the plating function by keeping the sulfuric acid concentration in the plating solution of rhodium sulfate plating solution constant, the crystals of potassium hydrogen sulfate or sodium hydrogen sulfate that crystallize from the plating solution that has reached the saturation concentration are removed. A method for maintaining the function of a rhodium sulfate plating solution, characterized in that the concentration of sulfuric acid in the plating solution is maintained constant by removing it from the plating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9743387A JPS63266087A (en) | 1987-04-22 | 1987-04-22 | Rhodium sulfate plating solution and method for maintaining function thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9743387A JPS63266087A (en) | 1987-04-22 | 1987-04-22 | Rhodium sulfate plating solution and method for maintaining function thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63266087A true JPS63266087A (en) | 1988-11-02 |
| JPH0583640B2 JPH0583640B2 (en) | 1993-11-26 |
Family
ID=14192247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9743387A Granted JPS63266087A (en) | 1987-04-22 | 1987-04-22 | Rhodium sulfate plating solution and method for maintaining function thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63266087A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779920A (en) * | 2016-08-26 | 2018-03-09 | 赵占平 | A kind of preparation method of rhodium liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5214538A (en) * | 1975-07-25 | 1977-02-03 | Tanaka Precious Metal Ind | Rhodium plating bath |
| JPS5517119A (en) * | 1978-07-21 | 1980-02-06 | Ricoh Co Ltd | Variable magnifying power copying apparatus |
| JPS6160898A (en) * | 1984-08-31 | 1986-03-28 | Nisshin Steel Co Ltd | Production of copper plated steel sheet for multi-wound pipe |
-
1987
- 1987-04-22 JP JP9743387A patent/JPS63266087A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5214538A (en) * | 1975-07-25 | 1977-02-03 | Tanaka Precious Metal Ind | Rhodium plating bath |
| JPS5517119A (en) * | 1978-07-21 | 1980-02-06 | Ricoh Co Ltd | Variable magnifying power copying apparatus |
| JPS6160898A (en) * | 1984-08-31 | 1986-03-28 | Nisshin Steel Co Ltd | Production of copper plated steel sheet for multi-wound pipe |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779920A (en) * | 2016-08-26 | 2018-03-09 | 赵占平 | A kind of preparation method of rhodium liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0583640B2 (en) | 1993-11-26 |
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