EP2235236B1 - Galvanisches bad, verfahren zur galvanischen abscheidung und verwendung einer bipolaren membran zur separation in einem galvanischen bad - Google Patents

Galvanisches bad, verfahren zur galvanischen abscheidung und verwendung einer bipolaren membran zur separation in einem galvanischen bad Download PDF

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Publication number
EP2235236B1
EP2235236B1 EP08861431A EP08861431A EP2235236B1 EP 2235236 B1 EP2235236 B1 EP 2235236B1 EP 08861431 A EP08861431 A EP 08861431A EP 08861431 A EP08861431 A EP 08861431A EP 2235236 B1 EP2235236 B1 EP 2235236B1
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EP
European Patent Office
Prior art keywords
galvanic bath
membrane
galvanic
bath according
zinc
Prior art date
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Application number
EP08861431A
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German (de)
English (en)
French (fr)
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EP2235236A2 (de
Inventor
Hartmut Trenkner
Alexander Jimenez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coventya GmbH
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Coventya GmbH
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Priority to PL08861431T priority Critical patent/PL2235236T3/pl
Publication of EP2235236A2 publication Critical patent/EP2235236A2/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002—Cell separation, e.g. membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02—Tanks; Installations therefor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the invention relates to an alkaline, galvanic bath for applying zinc or zinc alloys on substrates, in which the anode space and the cathode space are separated by a bipolar membrane.
  • the electroplating bath is operated with zinc or zinc alloy baths, which may contain other additives.
  • the invention relates to a method for the galvanic deposition of zinc or zinc alloys on substrates, in which the substrate is introduced into the galvanic bath according to the invention.
  • the invention relates to the use of bipolar membranes for the separation of anode space and cathode space in electroplating baths and to avoid the anodic decomposition of organic components of the electrolyte in electroplating baths.
  • organic brighteners and wetting agents are added to the bath. Furthermore, the bath contains complexing to allow the deposition of other metals of the zinc alloy.
  • the complexing agent serves to regulate the potential and keep the metals in solution so that the desired alloy composition is achieved.
  • the use of the aforementioned organic components leads to operation of the baths to problems, as for example in the WO 00/06807 to be discribed.
  • these baths show a change in color from originally blue-violet to brown after a few hours of operation. The brown color comes from decomposition products, the amount of which increases during the operation of the bath. After several weeks or months, this staining intensifies. This causes considerable disruption of the coating of the workpieces, such as uneven layer thicknesses or blistering.
  • a continuous cleaning of the bath is therefore essential. This is time consuming and expensive.
  • US 2005/189231 discloses a method of depositing zinc alloys on substrates, in which the substrate is placed in an alkaline plating bath.
  • the bath receives a cathode compartment, each with associated cathode and catholyte, and an anode compartment, each with associated anode and analyte, wherein the cathode compartment is separated from the anode compartment by a bipolar membrane.
  • an alkaline galvanic bath for depositing zinc or zinc alloys on substrates which contains a cathode space with associated cathode and zinc ion-containing catholyte and an anode space with associated anode and anolyte, wherein the cathode space anode space are separated by a separator.
  • a bipolar membrane is used as the separator.
  • the galvanic bath has a further electrolyte space, which is separated by the bipolar membrane of Arodenraum and by an ion exchange membrane of cathode brown, and a second catholyte.
  • the bipolar membrane preferably has at least one cation exchange membrane, at least one anion exchange membrane and an intermediate layer arranged between these membranes and catalyzing the dissociation of water into protons and hydroxide ions.
  • the anode is preferably made of nickel, nickel-plated stainless steel, steel or stainless steel. This has the advantage over the known from the prior art electroplating baths, in which platinum-plated titanium anodes are generally used, that they are much cheaper.
  • the catholyte contains further metal salts. These include in particular salts of iron, nickel, manganese, cobalt and tin or mixtures thereof.
  • the catholyte complexing agent may in particular contain amines, polyalkyleneimines, dicarboxylic acids, tricarboxylic acids, hydroxycarboxylic acids, further chelating ligands, such as acetylacetone, urea, urea derivatives and further complexing ligands, in which the complexing functional group contains nitrogen, phosphorus and sulfur.
  • Further optional components of the catholyte are additives selected from the group consisting of brighteners, wetting agents and mixtures thereof. These include preferably benzylpyridinium carboxylate, nicotinic acid, N-methylpyridinium carboxylate and aldehydes.
  • the anolyte consists of 50 to 200 g / l NaOH and 950 to 800 g / l water.
  • the bipolar membrane is preferably thermally stable up to 50 ° C., more preferably up to 60 ° C.
  • the ion exchange membrane is preferably an anion exchange membrane. But it is also possible to use a cation exchange membrane.
  • the second catholyte preferably has a pH in the range of 1 to 7. Particularly preferably, the second catholyte contains sulfuric acid or sulfuric acid and sodium sulfate. It is also possible that carboxylic acid and / or its salts, e.g. Sodium formate or sodium acetate are contained in the second catholyte.
  • the use of a second catholyte serves to protect the bipolar membrane.
  • hydrogencarbonate ions (HCO 3 -) on the catholyte side of the bipolar membrane with the formed protons (H +) from the water splitting form carbonic acid, which decomposes to carbon dioxide (CO 2 ) and water.
  • the forming carbon dioxide can thereby push apart the cation and anion membrane of the bipolar membrane at the interface, whereby the function of water splitting in protons and hydroxide ions is gradually lost.
  • Due to the additional ion exchange membrane, in particular an anion exchange membrane, especially hydroxide ions arrive at the adjacent direct current in the second catholyte, with neutralization, bicarbonate decomposition and pH increase taking place. It can thus be achieved that the bipolar membrane on the cation exchanger side is no longer impaired by the hydrogencarbonate ions.
  • a method is likewise provided for the galvanic deposition of zinc or zinc alloys on substrates, in which the substrate is introduced into a galvanic bath, as described above, and zinc or zinc alloys are electrodeposited on the substrate.
  • the deposition is preferably carried out at a Temperature of 20 to 40 ° C, more preferably at a temperature of 25 ° C.
  • the current density during the deposition is preferably in a range of 0.1 to 20 A / dm 2 , in particular 0.5 to 3 A / dm 2 .
  • the use of a bipolar membrane for the separation of anode space and cathode space is also provided in a galvanic bath wherein the galvanic bath has a further electrolyte space which is separated by the bipolar membrane of anode space and by an ion exchange membrane from the cathode space, and a second catholyte, in particular to avoid the anodic decomposition of organic components of the electrolyte in a galvanic bath.
  • the bipolar membrane used according to the invention preferably has at least one cation exchange membrane, at least one anion exchange membrane and an intermediate layer arranged between the membranes and catalyzing the dissociation of water into protons and hydroxide ions.
  • the bipolar membranes of the present invention can be prepared using conventional ion exchange membranes.
  • Bipolar membranes can be produced, for example, by copolymerization of styrene and divinylbenzene or butadiene or by copolymerization of acrylonitrile and butadiene, the cations being firmly bonded to the membrane by, for example, sulfochlorination and the anions being firmly bound to the membrane by chloromethylation and reaction with tertiary amines ,
  • the thickness of the bipolar membranes is preferably between about 0.1 and 1 mm.
  • the bipolar membranes may optionally include a reinforcing material of various types and shapes, depending on the process by which cation exchange membranes are made.
  • the bipolar membranes of the present invention can be made with any conventional cation exchange membrane, including membranes having such an ion exchange group as a sulfonic acid group or a carboxylic acid group.
  • the most preferred cation exchange membranes include a sulfonic acid group which retains an exchange group even under an acidic condition.
  • the cation exchange membrane may include a small amount of an anion exchange group as long as it has cation transport numbers of not less than about 0.9.
  • the anion exchange layer may be prepared by any conventional anion exchange material having such ion exchange groups as positively charged organic ions, amino or quaternary ammonium groups.
  • the polymeric membrane structure would contain the anion exchange group included in the organic network.
  • the polymer may be a polymer of vinylpyridine, divinylbenzene with the monomers copolymerized in various amounts, styrene, ethylene, methacrylic acid or propylene.
  • the anion exchange membrane may comprise a reinforcing matrix which may include polyethylene, polypropylene, polyvinyl chloride and polyvinyl acetate.
  • the anion exchange membrane will preferably have a capacity of between about 1 and about 3 milliequivalents per gram (meq / g).
  • the anion exchange membrane may be a polymerizable type, a homogeneous type or a non-homogeneous type.
  • the ion exchange membranes are preferably bonded together using an adhesive such as an "ionic adhesive" consisting of positively and negatively charged ions
  • adhesives include, but are not limited to, epichlorohydrin, polyethylenimine, polyacrylic acid, polyvinylamine, poly (4-vinyl) pyridine, powdered commercial anion and cation exchange resin, and combinations thereof.
  • the cationic conductive material and the anionic conductive material are preferably hot-pressed around a plurality of removable members at sufficient temperature and pressure to bond the material to a bipolar membrane.
  • the removable elements can be removed by extraction or dissolution, leaving a passage for fluids.
  • a preferred adhesive is an aqueous solution containing a mixture of polyacrylic acid and polyethyleneimine, more preferably in a polyethyleneimine: polyacrylic acid ratio of about 6: 1.
  • the adhesive may include a polyvinylamine in which the amino group is substituted with an alkyl group having 1 to 4 carbon atoms and the polyvinylamine has a molecular weight between about 10 4 and 10 6 .
  • the concentration of the aqueous polyvinylamine solution may be between about 0.5 and 70 weight percent, but the preferred concentration is between about 3 and 15 weight percent. Solutions of the aqueous polyvinylamine can be obtained, for example, by a conventional method of acidic or alkaline hydrolysis of polyvinylformamide or polyvinylacetamide with sodium hydroxide solution or hydrochloric acid.
  • a preferred method for preparing an aqueous polyvinylamine solution involves hydrolyzing aqueous polyvinylformamide with hydrochloric acid at a temperature between about 60 ° C and 100 ° C.
  • the polyvinylformamide concentration in water is preferably between about 1 and 50% by weight, more preferably between about 5 and 20% by weight.
  • the resulting polyvinylamine solutions are still liquid and can be easily applied to the membranes.
  • the adhesive solutions may be applied to one or both of the ion exchange membranes using any conventional technique, including brushing or roller coating.
  • the solution is preferably applied at a temperature between about 10 ° C and 50 ° C. It is also possible to impregnate the membranes on both sides with the solution. However, the outer membrane surface is preferably washed free of adhesive during the completion of the bipolar membrane.
  • the thickness of the adhesive layer is preferably between about 0.001 and about 0.05 mm.
  • the cation exchange membrane can be bound to the anion exchange membrane by any method.
  • the cation exchange membrane and the anion exchange membrane are closely adhered to each other with a peel strength of not less than 0.2 kg ⁇ f / 25 mm in a wet state to prevent separation of the two membranes when the bipolar membrane used in the wet state, such as in water splitting.
  • a bipolar membrane with a low peel strength will allow bubbles or inclusions to form at the interface between the anionic conductive membrane and the cationic conductive membrane during use. Bubbles and inclusions cause a reduction in the current efficiency per membrane surface unit and a gradual increase over longer periods of use of the membrane potential.
  • Such Diaphragms must be replaced periodically.
  • Fig. 1 shows a schematic representation of the structure of a galvanic bath and the chemical reaction taking place therein.
  • Fig. 2 shows a schematic representation of the structure of a further galvanic bath according to the invention with the chemical reactions taking place therein.
  • Fig. 1 schematically shows a galvanic bath.
  • 1 means the bath, 2 the anodes and 3 the cathode or the workpiece to be coated. Also shown are the anolyte 4 surrounding the anode and the catholyte 5 surrounding the cathode. Anolyte and catholyte are separated from one another by a bipolar membrane 6.
  • the anode space is preferably made smaller than the cathode space, since the essential processes take place there.
  • the electrochemical processes shown in Table 2 take place: ⁇ b> Table 2 ⁇ / b> (1) Zn ++ + 2 e - ⁇ Zn (metal deposition at the cathode) (2) Ni ++ + 2e - ⁇ Ni (metal deposition at the cathode) (3) Na + + e - ⁇ Na (corresponding reaction charge carrier transport at the cathode) (4) Na + + OH - ⁇ NaOH (dissociation reaction NaOH in the anolyte) (5) 4 H 2 O ⁇ 4 H + + 4 OH - (water splitting reaction in the intermediate layer of the membrane) (6) 4 OH - ⁇ 2H 2 O + O 2 ⁇ (anode reaction) (7) OH - + H + ⁇ H 2 O (reaction with protons from water splitting in the catholyte) (8) OH
  • Fig. 2 is the galvanic bath off Fig. 1 shown, wherein this additionally between the cathode compartment and the anode compartment has a further electrolyte space containing a second catholyte 7, which in this case contains sodium sulfate and sulfuric acid (each 1M), wherein the further electrolyte space is separated by an ion exchange membrane 6 from the cathode compartment.
  • a second catholyte 7 which in this case contains sodium sulfate and sulfuric acid (each 1M)
  • each 1M sodium sulfate and sulfuric acid
  • This bath was operated with a bipolar membrane.
  • the bipolar membrane was placed in the bath between anode and cathode.
  • iron sheets (7 ⁇ 10 cm), which are usually used for Hull cell tests, were used as workpieces to be coated and coated at a current density of 1 to 2 A / dm 2 .
  • the movement of the iron sheets was carried out mechanically at a speed of 1.4 m / min.
  • This bath was operated with a bipolar membrane.
  • the bipolar membrane was placed in the bath between anode and cathode.
  • iron sheets (7 ⁇ 10 cm), which are usually used for Hull cell tests, were used as workpieces to be coated and coated at a current density of 1 to 2 A / dm 2 .
  • the movement of the iron sheets was carried out mechanically at a speed of 1.4 m / min.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Cosmetics (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
EP08861431A 2007-12-14 2008-12-15 Galvanisches bad, verfahren zur galvanischen abscheidung und verwendung einer bipolaren membran zur separation in einem galvanischen bad Active EP2235236B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08861431T PL2235236T3 (pl) 2007-12-14 2008-12-15 Kąpiel galwaniczna, sposób galwanicznego osadzania i zastosowanie bipolarnej membrany do separacji w kąpieli galwanicznej

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007060200A DE102007060200A1 (de) 2007-12-14 2007-12-14 Galvanisches Bad, Verfahren zur galvanischen Abscheidung und Verwendung einer bipolaren Membran zur Separation in einem galvanischen Bad
PCT/EP2008/010635 WO2009077146A2 (de) 2007-12-14 2008-12-15 Galvanisches bad, verfahren zur galvanischen abscheidung und verwendung einer bipolaren membran zur separation in einem galvanischen bad

Publications (2)

Publication Number Publication Date
EP2235236A2 EP2235236A2 (de) 2010-10-06
EP2235236B1 true EP2235236B1 (de) 2012-10-03

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Country Status (6)

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EP (1) EP2235236B1 (pl)
BR (1) BRPI0820988B1 (pl)
DE (1) DE102007060200A1 (pl)
ES (1) ES2396801T3 (pl)
PL (1) PL2235236T3 (pl)
WO (1) WO2009077146A2 (pl)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2489763A1 (en) * 2011-02-15 2012-08-22 Atotech Deutschland GmbH Zinc-iron alloy layer material
JP5805055B2 (ja) * 2012-11-24 2015-11-04 丸仲工業株式会社 水平搬送式電解メッキ装置
JP5995906B2 (ja) 2014-05-19 2016-09-21 株式会社豊田中央研究所 隔膜の製造方法、及び金属被膜の製造方法
CN106550606B (zh) 2015-07-22 2019-04-26 迪普索股份公司 锌合金镀敷方法
RU2613826C1 (ru) * 2015-07-22 2017-03-21 Дипсол Кемикалз Ко., Лтд. Способ гальваностегии цинковым сплавом
CN106987879A (zh) * 2016-11-23 2017-07-28 瑞尔太阳能投资有限公司 电沉积装置及其电沉积方法
EP3696299A1 (en) 2019-02-15 2020-08-19 Coventya GmbH Method for producing a corrosion-resistant aluminum-silicon alloy casting, corresponding corrosion-resistant aluminum-silicon alloy casting and its use
CN111663167A (zh) * 2020-06-16 2020-09-15 合肥工业大学 一种基于bpe技术的金属线制备方法
CN113025829B (zh) * 2021-04-26 2022-12-06 福建师范大学 一种应用双极膜电渗析处理铜矿石冶炼废渣的方法

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DE4122543A1 (de) * 1991-03-18 1992-10-08 Hans Josef May Verfahren zur elektrochemischen beschichtung von metallbaendern
DE29615084U1 (de) * 1996-08-29 1996-10-24 Ko, Chien-Hsin, Taipeh/T`ai-pei Vorrichtung zum kontinuierlichen Galvanisieren von Platten
DE19834353C2 (de) 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkalisches Zink-Nickelbad
US6827832B2 (en) * 1999-12-22 2004-12-07 National Research Council Of Canada Electrochemical cell and process for reducing the amount of organic contaminants in metal plating baths
DE60023190T3 (de) 2000-06-15 2016-03-10 Coventya, Inc. Zink-nickel-elektroplattierung
US6528185B2 (en) * 2001-02-28 2003-03-04 Hong Kong Polytechnic University Cobalt-tungsten-phosphorus alloy diffusion barrier coatings, methods for their preparation, and their use in plated articles
GB2383337A (en) * 2001-12-21 2003-06-25 Accentus Plc Electroplating plant and method
DE10225203A1 (de) 2002-06-06 2003-12-18 Goema Ag Verfahren und Vorrichtung zur Spülwasserrückführung und Reinigung eines Prozessbades
US7442286B2 (en) * 2004-02-26 2008-10-28 Atotech Deutschland Gmbh Articles with electroplated zinc-nickel ternary and higher alloys, electroplating baths, processes and systems for electroplating such alloys
US20050274620A1 (en) * 2004-06-15 2005-12-15 Kovarsky Nicolay Y Copper replenishment system for interconnect applications
WO2006004662A1 (en) * 2004-06-25 2006-01-12 Ge Ionics, Inc. Bipolar membrane and method of making same

Also Published As

Publication number Publication date
BRPI0820988B1 (pt) 2018-12-04
PL2235236T3 (pl) 2013-03-29
BRPI0820988A2 (pt) 2015-08-04
EP2235236A2 (de) 2010-10-06
WO2009077146A3 (de) 2010-01-14
WO2009077146A2 (de) 2009-06-25
ES2396801T3 (es) 2013-02-27
DE102007060200A1 (de) 2009-06-18

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