JP6142198B2 - Method for regenerating anode for trivalent chromium plating - Google Patents
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- JP6142198B2 JP6142198B2 JP2013115113A JP2013115113A JP6142198B2 JP 6142198 B2 JP6142198 B2 JP 6142198B2 JP 2013115113 A JP2013115113 A JP 2013115113A JP 2013115113 A JP2013115113 A JP 2013115113A JP 6142198 B2 JP6142198 B2 JP 6142198B2
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- 238000007747 plating Methods 0.000 title claims description 102
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 86
- 229910052804 chromium Inorganic materials 0.000 title claims description 86
- 239000011651 chromium Substances 0.000 title claims description 86
- 238000000034 method Methods 0.000 title claims description 51
- 230000001172 regenerating effect Effects 0.000 title claims description 22
- 230000008929 regeneration Effects 0.000 claims description 34
- 238000011069 regeneration method Methods 0.000 claims description 34
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 11
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 150000007522 mineralic acids Chemical class 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001430 chromium ion Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229940074994 mercuric sulfate Drugs 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000370 mercury sulfate Inorganic materials 0.000 claims description 3
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000002411 adverse Effects 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
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Description
本発明は、３価クロムめっき用アノードの再生処理方法に関する。 The present invention relates to a method for regenerating a trivalent chromium plating anode.
クロムめっきは、装飾用、工業用等の各種の分野で広く利用されており、従来から、主に、クロム成分として６価クロムを多量に含有する６価クロムめっき浴を用いてめっき処理が行われている。 Chromium plating is widely used in various fields such as decoration and industrial use. Conventionally, plating treatment has been performed mainly using a hexavalent chromium plating bath containing a large amount of hexavalent chromium as a chromium component. It has been broken.
しかしながら、６価クロムめっき浴を用いる場合には、めっき時に発生する６価クロムを含有するミストの有害性が問題となっていることから、作業環境の改善や排水処理の効率などを考慮して、毒性の少ない３価クロム化合物を用いた３価クロムめっき浴が普及してきている（下記非特許文献１等参照）。 However, in the case of using a hexavalent chromium plating bath, since the harmfulness of mist containing hexavalent chromium generated during plating is a problem, the work environment is improved and the efficiency of wastewater treatment is taken into consideration. A trivalent chromium plating bath using a trivalent chromium compound with little toxicity has become widespread (see Non-Patent Document 1 below).
しかしながら、３価クロムめっき浴を用いた３価クロムめっきでは、めっき処理の経過に伴って、めっき浴中に６価クロムが蓄積し、これがめっき速度やめっき皮膜の外観等に悪影響を与えることが知られている。 However, in trivalent chromium plating using a trivalent chromium plating bath, hexavalent chromium accumulates in the plating bath as the plating process progresses, which may adversely affect the plating speed and the appearance of the plating film. Are known.
このような問題に対応すべく、めっき液の組成を改良することや、イオン交換膜等でアノードを区画し３価クロムとアノードを直接接触することを防止したアノードボックスを採用することなどによって、６価クロムの生成を抑制する試みがなされてきた。しかしながら、めっき液の組成の改良には限界があり、アノードボックスの使用はボックス内部液の更新等の管理が煩雑である。 In order to cope with such problems, by improving the composition of the plating solution, or by adopting an anode box that prevents the trivalent chromium and the anode from coming into direct contact by partitioning the anode with an ion exchange membrane or the like, Attempts have been made to suppress the production of hexavalent chromium. However, there is a limit in improving the composition of the plating solution, and the use of the anode box requires complicated management such as renewal of the solution inside the box.
そこで、近年では３価クロムめっき用のアノードとして、導電性の電極基体上に、酸化イリジウム、Ｉｒ−Ｔａ混合酸化物などの金属酸化物の被覆を施した不溶性電極等を用いることにより、３価クロムめっき浴中での６価クロムの生成を抑制する試みがなされている（下記特許文献１、２等参照）。 Therefore, in recent years, as an anode for trivalent chromium plating, an insoluble electrode or the like in which a conductive electrode substrate is coated with a metal oxide such as iridium oxide or an Ir-Ta mixed oxide is used. Attempts have been made to suppress the formation of hexavalent chromium in a chromium plating bath (see Patent Documents 1 and 2 below).
しかしながら、このような電極を用いた場合であっても、めっき処理を開始してしばらくの間は６価クロムの生成を抑制することができるが、長期間めっき処理を行うことによって６価クロムの生成を避けられないという問題がある。 However, even when such an electrode is used, the formation of hexavalent chromium can be suppressed for a while after the plating process is started. There is a problem that generation cannot be avoided.
本発明は、上記した従来技術の問題点に鑑みてなされたものであり、その主な目的は、３価クロムめっき浴中での６価クロムの生成を抑制するための有効な手段を提供することである。 The present invention has been made in view of the above-described problems of the prior art, and its main object is to provide an effective means for suppressing the formation of hexavalent chromium in a trivalent chromium plating bath. That is.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、３価クロムめっき処理を行うに従って３価クロムめっき用アノードの酸素発生電位が上昇し、これがアノード上で３価クロムを酸化し６価クロムを生成させる一因となることを見出した。そして、特定の再生処理液中において、３価クロムめっき処理に用いたアノードを陰極として電解処理を行うことによって、電極の酸素発生電位を低下させることができ、その結果、電解処理後のアノードを用いて３価クロムめっき処理を行った場合に６価クロムの生成を抑制することが可能となることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, it was found that as the trivalent chromium plating treatment was performed, the oxygen generation potential of the anode for trivalent chromium plating increased, which contributed to the oxidation of trivalent chromium on the anode to produce hexavalent chromium. Then, by performing the electrolytic treatment using the anode used for the trivalent chromium plating treatment as a cathode in a specific regeneration treatment solution, the oxygen generation potential of the electrode can be lowered. It has been found that it is possible to suppress the formation of hexavalent chromium when the trivalent chromium plating treatment is performed, and the present invention has been completed here.
即ち、本発明は、下記の３価クロムめっき用アノードの再生処理方法を提供するものである。
項１． 導電性の電極基体上に金属酸化物を含む被覆を施した不溶性電極からなる３価クロムめっき用アノードの再生処理方法であって、無機酸及び／又は有機酸を含有するｐＨが３以下の酸性水溶液からなる再生処理液中において、３価クロムめっき処理に用いたアノードを陰極として、電解処理を行うことを特徴とする３価クロムめっき用アノードの再生処理方法。
項２． 再生処理液のｐＨが−１〜３である上記項１に記載の３価クロムめっき用アノードの再生処理方法。
項３． ３価クロムめっき用アノードが、導電性の金属基体上に酸化イリジウムを含む被覆を施した不溶性電極である上記項１又は２に記載の３価クロムめっき用アノードの再生処理方法。
項４． ３価クロムめっき用アノードが、チタン、タンタル、ジルコニウム、ニオブ又はこれらの合金からなる電極基体上に、電極触媒として酸化イリジウムとともに、チタン、タンタル、ニオブ、ジルコニウム、スズ、アンチモン、ルテニウム、白金、コバルト、モリブデン及びタングステンからなる群より選ばれる少なくとも１種の金属又はその酸化物の被覆を施した不溶性電極である上記項１〜３のいずれかに記載の３価クロムめっき用アノードの再生処理方法。
項５． ３価クロムめっき用アノードが、チタンからなる電極基体上に、電極触媒として酸化イリジウム及び酸化タンタルの混合酸化物の被覆を施した不溶性電極である上記項１〜４のいずれかに記載の３価クロムめっき用アノードの再生処理方法。
項６． ３価クロムめっき浴中の６価クロムイオン濃度が、１００ｐｐｍ以上となった場合の３価クロムめっき用アノードを処理対象とする上記項１〜５のいずれかに記載の３価クロムめっき用アノードの再生処理方法。
項７． 水銀／硫酸第一水銀電極を参照電極とし、９８％硫酸１５０ｇ／Ｌの水溶液を測定液として、電流密度５０Ａ／ｄｍ２で測定した場合の電位が、０．９６Ｖ以上となった場合の３価クロムめっき用アノードを処理対象とする上記項１〜５のいずれかに記載の３価クロムめっき用アノードの再生処理方法。
項８． 無機酸が硫酸である上記項１〜７のいずれかに記載の３価クロムめっき用アノードの再生処理方法。
項９． 陰極電流密度０．１〜４０Ａ／ｄｍ２で電解処理を行う上記項１〜８のいずれかに記載の３価クロムめっき用アノードの再生処理方法。
That is, the present invention provides the following method for regenerating an anode for trivalent chromium plating.
Item 1. A method for regenerating a trivalent chromium plating anode comprising an insoluble electrode in which a coating containing a metal oxide is coated on a conductive electrode substrate, wherein the acid containing an inorganic acid and / or an organic acid has a pH of 3 or less. A method for regenerating an anode for trivalent chromium plating, comprising performing an electrolytic treatment in a regeneration treatment solution comprising an aqueous solution, using the anode used for the trivalent chromium plating as a cathode.
Item 2. Item 2. The method for regenerating an anode for trivalent chromium plating according to Item 1, wherein the pH of the regenerating solution is -1 to -3.
Item 3. Item 3. The method for regenerating a trivalent chromium plating anode according to Item 1 or 2, wherein the trivalent chromium plating anode is an insoluble electrode in which a conductive metal substrate is coated with iridium oxide.
Item 4. An anode for trivalent chromium plating is formed on an electrode substrate made of titanium, tantalum, zirconium, niobium or an alloy thereof, and with iridium oxide as an electrode catalyst, titanium, tantalum, niobium, zirconium, tin, antimony, ruthenium, platinum, cobalt Item 4. The method for regenerating a trivalent chromium plating anode according to any one of Items 1 to 3, which is an insoluble electrode coated with at least one metal selected from the group consisting of molybdenum and tungsten, or an oxide thereof.
Item 5. Item 3. The trivalent element according to any one of Items 1 to 4, wherein the trivalent chromium plating anode is an insoluble electrode in which an electrode base made of titanium is coated with a mixed oxide of iridium oxide and tantalum oxide as an electrode catalyst. A method for regenerating the anode for chromium plating.
Item 6. The anode for trivalent chromium plating according to any one of the above items 1 to 5, wherein the anode for trivalent chromium plating when the concentration of hexavalent chromium ions in the trivalent chromium plating bath is 100 ppm or more is treated. Playback processing method.
Item 7. Trivalent when the potential when measured at a current density of 50 A / dm 2 using a mercury / mercuric sulfate electrode as a reference electrode and an aqueous solution of 150 g / L of 98% sulfuric acid at a current density of 0.96 V or more. Item 6. The method for regenerating a trivalent chromium plating anode according to any one of Items 1 to 5, wherein the anode for chromium plating is a treatment target.
Item 8. Item 8. The method for regenerating a trivalent chromium plating anode according to any one of Items 1 to 7, wherein the inorganic acid is sulfuric acid.
Item 9. Cathode current density 0.1 to 40 A / dm 2 at either trivalent chromium plating anode regeneration processing method according to the claim 1 to 8 for performing electrolytic treatment.
以下、本発明について、詳細に説明する。 Hereinafter, the present invention will be described in detail.
３価クロムめっき用アノード
本発明の再生処理方法において処理対象となる３価クロムめっき用アノードは、３価クロムめっき処理において用いられる、導電性の電極基体上に金属酸化物を含む被覆を施した不溶性電極である。特に、このような不溶性電極としては、導電性の電極基体上に電極触媒として酸化イリジウム等を含む被覆を施した不溶性電極は酸素発生電位が低いことから、３価クロムめっき用アノードとして好ましく用いられている。本発明では、これらの不溶性電極をいずれも処理対象とすることができる。
Anode for trivalent chromium plating The anode for trivalent chromium plating to be treated in the regeneration treatment method of the present invention has a coating containing a metal oxide on a conductive electrode substrate used in the trivalent chromium plating treatment. It is an insoluble electrode. In particular, as such an insoluble electrode, an insoluble electrode obtained by coating a conductive electrode substrate containing iridium oxide or the like as an electrode catalyst is preferably used as an anode for trivalent chromium plating because of its low oxygen generation potential. ing. In the present invention, any of these insoluble electrodes can be treated.
本発明の処理対象とすることができる不溶性電極についてより具体的に説明すると、例えば、チタン、タンタル、ジルコニウム、ニオブ又はこれらの合金からなる電極基体上に、電極触媒として酸化イリジウムとともに、チタン、タンタル、ニオブ、ジルコニウム、スズ、アンチモン、ルテニウム、白金、コバルト、モリブデン及びタングステンからなる群より選ばれる少なくとも１種の金属又はその酸化物の被覆を施した不溶性電極等を挙げることができる。 More specifically, the insoluble electrode that can be treated according to the present invention will be described. For example, on an electrode substrate made of titanium, tantalum, zirconium, niobium, or an alloy thereof, together with iridium oxide as an electrode catalyst, titanium, tantalum. And an insoluble electrode coated with at least one metal selected from the group consisting of niobium, zirconium, tin, antimony, ruthenium, platinum, cobalt, molybdenum and tungsten, or an oxide thereof.
中でも、チタンからなる電極基体上に、電極触媒として酸化イリジウム及び酸化タンタルの混合酸化物の被覆を施した不溶性電極が３価クロムめっき用アノードとして広く用いられている。本発明の再生処理方法をこの不溶性電極に適用する場合には、該不溶性電極を再生して繰り返し使用することが可能となり、該不溶性電極の優れた性能を長期間維持することができる。 In particular, an insoluble electrode obtained by coating an electrode base made of titanium with a mixed oxide of iridium oxide and tantalum oxide as an electrode catalyst is widely used as an anode for trivalent chromium plating. When the regeneration treatment method of the present invention is applied to this insoluble electrode, the insoluble electrode can be regenerated and used repeatedly, and the excellent performance of the insoluble electrode can be maintained for a long time.
再生処理液
本発明の再生処理方法において用いる再生処理液は、無機酸及び／又は有機酸を含有するｐＨ３以下の水溶液であればよい。ｐＨが低いほど再生処理液の電気伝導度が高くなり再生処理効果が向上することから、−１〜３程度の範囲内にあることが好ましく、−１〜１程度の範囲内にあることがより好ましい。なお、ｐＨは２５℃で測定した値である。
Regeneration Treatment Solution The regeneration treatment solution used in the regeneration treatment method of the present invention may be an aqueous solution containing an inorganic acid and / or an organic acid having a pH of 3 or less. The lower the pH is, the higher the electrical conductivity of the regeneration treatment liquid is and the regeneration treatment effect is improved. preferable. The pH is a value measured at 25 ° C.
無機酸及び有機酸の種類については特に限定的ではなく、無機酸としては、硫酸、塩酸、硝酸などを例示することができ、有機酸としては、クエン酸、リンゴ酸、乳酸などを例示することができる。これらの無機酸及び有機酸の中でも再生処理液の取扱いが容易であることから硫酸が好ましい。無機酸及び有機酸は上記したｐＨの範囲内となるように添加すればよい。例えば、無機酸として９８％硫酸を用いる場合には、０．１〜２００ｍＬ／Ｌ程度添加することによって、上記したｐＨの範囲に調整することができる。 The types of inorganic acid and organic acid are not particularly limited, and examples of the inorganic acid include sulfuric acid, hydrochloric acid, and nitric acid, and examples of the organic acid include citric acid, malic acid, and lactic acid. Can do. Of these inorganic acids and organic acids, sulfuric acid is preferred because the reprocessing solution is easy to handle. What is necessary is just to add an inorganic acid and an organic acid so that it may become in the above-mentioned pH range. For example, when 98% sulfuric acid is used as the inorganic acid, it can be adjusted to the above pH range by adding about 0.1 to 200 mL / L.
また、再生処理液は、電気伝導度が低いと浴電圧が上昇して電解中に浴温が上昇することがあるため、必要に応じて電導性塩を添加してもよい。電導性塩としては、硫酸ナトリウム、硫酸カリウム、塩化ナトリウム、塩化カリウム、硝酸カリウムなどのアルカリ金属塩；塩化アンモニウム、硫酸アンモニウムなどのアンモニウム塩等が挙げられる。これらの電導性塩は、一種単独又は二種以上混合して使用することができる。これらの電導性塩の中でも、電解処理時に電極表面の金属酸化物皮膜の剥離が生じにくい点においてアンモニウム塩を用いることが好ましい。電導性塩の添加量は要求される電気伝導度の範囲に応じて適宜決定すればよく、特に限定的ではないが、通常５０〜４００ｇ／Ｌ程度とすればよい。 Moreover, since the bath voltage may increase when the electrical conductivity of the regenerating liquid is low and the bath temperature may increase during electrolysis, a conductive salt may be added as necessary. Examples of the conductive salt include alkali metal salts such as sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, and potassium nitrate; ammonium salts such as ammonium chloride and ammonium sulfate. These conductive salts can be used singly or in combination of two or more. Among these conductive salts, it is preferable to use an ammonium salt in that the metal oxide film on the electrode surface is less likely to be peeled off during the electrolytic treatment. What is necessary is just to determine suitably the addition amount of electroconductive salt according to the range of the electrical conductivity requested | required, Although it does not specifically limit, What is necessary is just about 50-400 g / L normally.
３価クロムめっき用アノードの再生処理方法
前述した通り、本発明者の研究によって、３価クロムめっき浴中で６価クロムが生成する原因として、めっき処理を長期間行うことによって３価クロムめっき用アノードの酸素発生電位が上昇することによるものであることが見出された。
As described above, as a cause of the formation of hexavalent chromium in the trivalent chromium plating bath, the anode treatment for trivalent chromium plating can be performed for a trivalent chromium plating by performing plating for a long period of time. It has been found that this is due to an increase in the oxygen evolution potential of the anode.
本発明の再生処理方法によれば、上記した再生処理液中において、３価クロムめっき処理に用いたアノードを陰極として、後述する条件で電解処理を行うことによって酸素発生電位を低下させることができ、その結果、３価クロムめっき用アノードの性能を回復させ、６価クロムの生成を抑制することができる。 According to the regeneration treatment method of the present invention, the oxygen generation potential can be lowered by performing electrolytic treatment under the conditions described later, using the anode used for the trivalent chromium plating treatment as a cathode in the above-described regeneration treatment solution. As a result, the performance of the trivalent chromium plating anode can be recovered and the production of hexavalent chromium can be suppressed.
再生処理を行う時期については特に限定的ではなく、例えば、３価クロムめっき浴中に６価クロムの蓄積が生じた場合、３価クロムめっき用アノードの酸素発生電位が上昇した場合等に適宜、再生処理を行えばよい。 The timing for performing the regeneration treatment is not particularly limited. For example, when accumulation of hexavalent chromium occurs in the trivalent chromium plating bath, the oxygen generation potential of the anode for trivalent chromium plating increases, etc. A reproduction process may be performed.
３価クロムめっき浴中に６価クロムの蓄積が生じた場合を本発明の再生処理を行う時期の目安とする場合、基準となる６価クロムイオンの濃度は、目的とするめっき液の性能に応じて適宜決めればよい。 When the accumulation of hexavalent chromium in the trivalent chromium plating bath is used as a guideline for the timing of the regeneration treatment of the present invention, the standard concentration of hexavalent chromium ions depends on the performance of the intended plating solution. What is necessary is just to decide suitably according to.
通常、３価クロムめっき浴中の６価クロムイオン濃度が２００ｐｐｍ程度以上となると、３価クロムめっき処理のめっき速度やめっき皮膜の外観等に悪影響を及ぼすことがある。このため、３価クロムめっき浴中の６価クロムイオン濃度が２００ｐｐｍ程度以上となった場合に再生処理を行えばよいが、より高いめっき品質を望む場合には、１００ｐｐｍ程度以上となった時期を本発明の再生処理を行う時期の目安とすることが好ましい。３価クロムめっき浴中の６価クロム濃度は、ジフェニルカルバジドを用いた吸光度分析法等により測定することができる。 Usually, when the hexavalent chromium ion concentration in the trivalent chromium plating bath is about 200 ppm or more, the plating rate of the trivalent chromium plating treatment, the appearance of the plating film, and the like may be adversely affected. For this reason, regeneration treatment may be performed when the hexavalent chromium ion concentration in the trivalent chromium plating bath is about 200 ppm or more. However, when higher plating quality is desired, the time when the concentration becomes about 100 ppm or more is set. It is preferable to use it as a guideline for performing the regeneration process of the present invention. The hexavalent chromium concentration in the trivalent chromium plating bath can be measured by an absorbance analysis method using diphenylcarbazide or the like.
また、上記した３価クロムめっき浴中の６価クロムイオン濃度を測定する方法だけでなく、３価クロムめっき用アノードの酸素発生電位を測定することによっても本発明の再生処理を行う時期を決定することができる。電極の酸素発生電位を測定する方法は特に限定されないが、例えば、簡易的な方法として、図１に示すような電位測定装置を用いて測定した電位を酸素発生電位の目安とすることができる。 Further, not only the method for measuring the hexavalent chromium ion concentration in the trivalent chromium plating bath described above but also the time for performing the regeneration treatment of the present invention is determined by measuring the oxygen generation potential of the anode for trivalent chromium plating. can do. The method for measuring the oxygen generation potential of the electrode is not particularly limited. For example, as a simple method, a potential measured using a potential measuring device as shown in FIG. 1 can be used as a measure of the oxygen generation potential.
具体的には図１に示すように、対極としてチタンを用い、水銀／硫酸第一水銀電極を参照電極として、２５℃の９８％硫酸中で、測定対象物を陽極として、電流密度が５０Ａ／ｄｍ２となるように一定電流を流した場合の３価クロムめっき用アノードの電位を測定すればよい。 Specifically, as shown in FIG. 1, using titanium as a counter electrode, using a mercury / mercuric sulfate electrode as a reference electrode, in 98% sulfuric acid at 25 ° C., using a measurement object as an anode, a current density of 50 A / the anode potential for trivalent chromium plating in passing a constant current so that the dm 2 may be measured.
上記した方法で測定した場合の未使用の３価クロムめっき用アノードの電位は、通常０．９５Ｖ程度である。本発明者の研究によれば、上記した方法で測定した電位が０．９７Ｖ程度以上の３価クロムめっき用アノードを用いると、３価クロムめっき浴中で６価クロムの生成が確認された。このため、例えば、上記した方法で測定した場合の電位が０．９７Ｖ程度以上となった場合に再生処理を行えばよい。なお、より高いめっき品質を望む場合には、０．９６Ｖ程度以上となった時期を本発明の再生処理を行う時期の目安とすればよい。 The potential of the unused trivalent chromium plating anode when measured by the above method is usually about 0.95V. According to the study of the present inventor, it was confirmed that hexavalent chromium was produced in a trivalent chromium plating bath when an anode for trivalent chromium plating having a potential measured by the above-described method of about 0.97 V or more was used. For this reason, for example, the reproduction process may be performed when the potential measured by the above method becomes about 0.97 V or more. In addition, when higher plating quality is desired, the time when it becomes about 0.96 V or more may be used as a guideline for the time when the regeneration process of the present invention is performed.
なお、３価クロムめっき浴中に６価クロムの蓄積が生じた場合を、再生処理を行う時期の目安とする場合には、蓄積した６価クロムがめっき速度やめっき皮膜の外観等に悪影響を与えることがあり、さらには蓄積した６価クロムを３価クロムめっき浴から除去する手間等が生じることから、電極の酸素発生電位を測定することによって本発明の再生処理を行う時期を決定することが好ましい。 In addition, when the accumulation of hexavalent chromium in the trivalent chromium plating bath is used as a guideline for the timing of the regeneration treatment, the accumulated hexavalent chromium will adversely affect the plating speed and the appearance of the plating film. In addition, since it takes time to remove accumulated hexavalent chromium from the trivalent chromium plating bath, the timing for performing the regeneration treatment of the present invention is determined by measuring the oxygen generation potential of the electrode. Is preferred.
再生処理を行う場合の陰極電流密度については特に限定的ではないが、電流密度が極端に低い場合には良好な再生処理効果が得られず、再生処理後に短時間で酸素発生電位が上昇することがあるため好ましくない。このため、通常は０．１〜４０Ａ／ｄｍ２程度とすればよく、０．５〜２５Ａ／ｄｍ２程度とすることが好ましく、１０〜１５Ａ／ｄｍ２程度とすることがより好ましい。 The cathode current density when performing the regeneration process is not particularly limited, but if the current density is extremely low, a good regeneration process effect cannot be obtained, and the oxygen generation potential increases in a short time after the regeneration process. This is not preferable. Therefore, usually it is sufficient with 0.1 to 40 A / dm 2, preferably about be 0.5~25A / dm 2 about, and more preferably a 10~15A / dm 2 about.
再生処理を行う時間については特に限定的ではないが、処理時間が極端に短い場合には十分な再生処理効果が得られないことがあるため好ましくない。このため、通常は１〜３０分程度の電解処理時間とすればよく、５〜２０分程度の電解処理時間とすることが好ましい。 The time for performing the reproduction process is not particularly limited. However, when the processing time is extremely short, a sufficient reproduction process effect may not be obtained, which is not preferable. For this reason, what is necessary is just to set it as the electrolytic treatment time of about 1 to 30 minutes normally, and it is preferable to set it as the electrolytic treatment time of about 5 to 20 minutes.
再生処理液の液温については特に限定的ではないが、１０〜７０℃程度とすることが好ましく、２５〜６０℃程度とすることがより好ましい。 The temperature of the regenerating solution is not particularly limited, but is preferably about 10 to 70 ° C, and more preferably about 25 to 60 ° C.
再生処理に用いるアノードとしては、電気伝導性の不溶性電極であればよく、特に限定的ではないが、例えば、カーボン、チタン−白金電極などを使用できる。また、これらの不溶性電極を用いることなく、処理対象の３価クロムめっき用アノードを２本利用して、交互に陽極と陰極を入れ替えることによって効率よくアノードの再生処理を行うことができる。 The anode used for the regeneration treatment is not particularly limited as long as it is an electrically conductive insoluble electrode, and for example, a carbon, titanium-platinum electrode, or the like can be used. Also, without using these insoluble electrodes, the anode can be efficiently regenerated by alternately using the two trivalent chromium plating anodes to be treated and alternately switching the anode and the cathode.
本発明の３価クロムめっき用アノードの再生処理方法によれば、電解法という簡単な方法によって、上昇した３価クロムめっき用アノードの酸素発生電位を低下させることができる。その結果、３価クロムめっき用アノードの性能を回復させて再利用することが可能となり、高価な３価クロムめっき用アノードを長期間継続して使用することができる。 According to the regeneration treatment method for an anode for trivalent chromium plating of the present invention, the oxygen generation potential of the increased anode for trivalent chromium plating can be lowered by a simple method called electrolysis. As a result, the performance of the trivalent chromium plating anode can be recovered and reused, and the expensive trivalent chromium plating anode can be used continuously for a long period of time.
また、３価クロムめっき用アノードの性能を回復させることによって、３価クロムめっき浴中で６価クロムが生成することを抑制することができるため、３価クロムめっき浴を長期間使用することができ、安定した３価クロムめっき処理を行うことが可能となる。 In addition, by restoring the performance of the anode for trivalent chromium plating, it is possible to suppress the formation of hexavalent chromium in the trivalent chromium plating bath. This makes it possible to perform a stable trivalent chromium plating process.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１〜５
処理対象として、３価クロムめっき処理に使用して酸素発生電位が上昇したアノードを用いて、以下の方法で再生処理を行った。処理対象のアノードは、チタンからなる電極基体上に、酸化イリジウムを含む被覆を施した電極（TCPアノード、ペルメレック電極（株）製）である。
Examples 1-5
A regeneration treatment was performed by the following method using an anode having an increased oxygen generation potential used for a trivalent chromium plating treatment as a treatment target. The anode to be treated is an electrode (TCP anode, manufactured by Permerek Electrode Co., Ltd.) on which an electrode substrate made of titanium is coated with iridium oxide.
再生処理方法としては、下記表１に記載した実施例１〜５の再生処理液を用い、各再生処理液中に、上記したアノードをそれぞれ２本浸漬し、一方を陽極とし、他方を陰極として、表１に記載した処理条件で電解処理を行った。 As a regeneration treatment method, the regeneration treatment liquids of Examples 1 to 5 described in Table 1 below were used. In each regeneration treatment liquid, two of the above-described anodes were immersed, one as an anode and the other as a cathode. The electrolytic treatment was performed under the treatment conditions described in Table 1.
処理対象アノードの電位の測定方法
処理対象アノードの電位の測定は、図１に示す電位測定装置を用いて、下記表２に示す条件で一定電流を流したときの電位をテスターにより測定し、得られた電位を酸素発生電位の目安とした。なお、この電位が低いほど、６価クロムの生成が起こりにくい電極であることを示す。
Method for Measuring the Potential of the Processed Anode The measurement of the potential of the treated anode was performed by measuring the potential when a constant current was passed under the conditions shown in Table 2 below with a tester using the potential measuring device shown in FIG. The obtained potential was used as a measure of the oxygen generation potential. In addition, it shows that it is an electrode with which the production | generation of hexavalent chromium hardly occurs, so that this electric potential is low.
上記した方法で測定した再生処理前及び再生処理後の電位を下記表３に示す。 Table 3 below shows the potentials measured by the above method before and after the regeneration process.
表３から明らかなように、実施例１〜５の再生処理液を用いて電解処理を行った場合には、上記方法で測定した酸素発生電位の目安となる電位の低下が確認できた。上記した方法で測定した場合の未使用の３価クロムめっき用アノードの電位は０．９５Ｖ程度であることから、本発明の再生処理方法によって３価クロムめっき用アノードの酸素発生電位を新品と同程度にまで再生できたことが分かる。 As is apparent from Table 3, when electrolytic treatment was performed using the regeneration treatment liquids of Examples 1 to 5, it was possible to confirm a decrease in potential that was a measure of the oxygen generation potential measured by the above method. Since the potential of the unused trivalent chromium plating anode when measured by the above-described method is about 0.95 V, the oxygen generation potential of the trivalent chromium plating anode is the same as that of a new one by the regeneration treatment method of the present invention. It turns out that it was able to reproduce to the extent.
Claims (8)
無機酸及び／又は有機酸を含有するｐＨが３以下の酸性水溶液からなる再生処理液中において、３価クロムめっき処理に用いたアノードを陰極として、電解処理を行うことを特徴とする３価クロムめっき用アノードの再生処理方法。 A method for regenerating an anode for trivalent chromium plating comprising an insoluble electrode having a coating containing iridium oxide on a conductive electrode substrate,
A trivalent chromium characterized in that an electrolytic treatment is carried out using a cathode used for a trivalent chromium plating treatment as a cathode in a regeneration treatment solution comprising an acidic aqueous solution containing an inorganic acid and / or an organic acid and having a pH of 3 or less. A method for regenerating the anode for plating.
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