EP2235236A2 - Bain galvanique, procédé de dépôt galvanique et utilisation d'une membrane bipolaire pour la séparation dans un bain galvanique - Google Patents

Bain galvanique, procédé de dépôt galvanique et utilisation d'une membrane bipolaire pour la séparation dans un bain galvanique

Info

Publication number
EP2235236A2
EP2235236A2 EP08861431A EP08861431A EP2235236A2 EP 2235236 A2 EP2235236 A2 EP 2235236A2 EP 08861431 A EP08861431 A EP 08861431A EP 08861431 A EP08861431 A EP 08861431A EP 2235236 A2 EP2235236 A2 EP 2235236A2
Authority
EP
European Patent Office
Prior art keywords
galvanic bath
galvanic
zinc
bath according
membrane
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
Application number
EP08861431A
Other languages
German (de)
English (en)
Other versions
EP2235236B1 (fr
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
Original Assignee
Coventya GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Coventya GmbH filed Critical Coventya GmbH
Priority to PL08861431T priority Critical patent/PL2235236T3/pl
Publication of EP2235236A2 publication Critical patent/EP2235236A2/fr
Application granted granted Critical
Publication of EP2235236B1 publication Critical patent/EP2235236B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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

  • Galvanic bath process for electrodeposition and use of a bipolar membrane for separation in a galvanic bath
  • 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 abovementioned organic constituents leads to problems during operation of the baths, as described, for example, in WO 00/06807.
  • 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, for example, uneven layer thicknesses or bubble formation.
  • a continuous cleaning of the bath is therefore essential. This is time consuming and expensive.
  • Bath dilution reduces the concentration of impurities in proportion to the degree of dilution.
  • a dilution is easy to carry out, but has the disadvantage that the amount of electrolyte removed from the bath has to be supplied to cost-intensive disposal.
  • a complete new approach of the bath can be considered in this context as a special case of Badver Mednung.
  • Alkaline zinc baths contain a factor of 5 to 10 lower organic content
  • EP 1 369 505 A2 discloses a method for cleaning a zinc / nickel electrolyte in a galvanic process in which a part of the process bath used in the process is evaporated until a phase separation into a lower phase Phase, at least one middle phase and an upper phase takes place and the lower and the upper phase are separated. This process requires several stages and is disadvantageous in terms of its energy requirements from a cost point of view.
  • WO 00/06807 and WO 01/96631 describe electroplating baths for applying zinc-nickel coatings. To the unwanted decomposition of
  • 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 service life of the bath is increased, b) saving of sodium hydroxide by the self-formation process in the anolyte after water splitting, c) prevention of excess volume in galvanic zinc electrolyte, d) prevention of oxidation reactions of the organic additives at the anode, e) preservation of a 90% efficiency, f) optimum use of the chemical constituents of the electrolyte, since there is no volume surplus, which must be treated or disposed of in addition to the wastewater, but a volume decrease due to the mass loss of metals and hydrogen in the electrolyte during the deposition process.
  • 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 usually platined titanium anodes are 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 chelate 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. re, N-methylpyridiniumcarboxylate and aldehydes.
  • g / l sodium or potassium hydroxide 4-20 g / l zinc in the form of a soluble zinc salt, 0.02-20 g / l nickel, iron, kobble, tin in the form of a soluble metal salt as alloying metal, 1-200 g / l complexing agent selected from the group consisting of polyalkenylamines, alkanolamines, polyhydroxycarboxylates and mixtures thereof and 0.1-5 g / l of aromatic and / or heteroaromatic brighteners.
  • 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., particularly preferably up to 60 ° C.
  • a further variant of the galvanic bath according to the invention provides that this has a further electrolyte space, which is arranged between the cathode space and the anode space.
  • This additional electrolyte space is separated from the anode space by an ion exchange membrane from the cathode space through the bipolar membrane.
  • a second catholyte is included in this electrolyte space.
  • the ion exchange membrane is 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 likewise possible for carboxylic acid and / or salts thereof, such as, for example, sodium formate or sodium acetate, to be present in the second catholyte.
  • the use of a second catholyte serves to protect the bipolar membrane.
  • hydrogen carbonate ions (HCO 3 -) on the catholyte side of the bipolar membrane with the protons (H +) formed from the water splitting form carbonic acid, which decomposes to carbon dioxide (CO 2 ) and water.
  • the carbon dioxide which forms can thereby force apart the cation and anion membrane of the bipolar membrane at the connection surface, as a result of which 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 it is above all hydroxide ions that arrive at the DC flow 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.
  • the invention likewise provides a process 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 0 C, more preferably at a temperature of 25 0 C.
  • the current density is in the deposition preferably in a range of 0.1 to 20 A / dm 2 , in particular from 0.5 to 3 A / dm second ,
  • the invention likewise provides the use of a bipolar membrane for separating the anode space and the cathode space in a galvanic bath.
  • the bipolar membrane makes it possible 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 prepared, 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 firmly bonded to the membrane by chloromethylation and reaction with tertiary amines be bound.
  • 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 a replacement 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, such as 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", which consists 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 from 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% by weight, but the preferred concentration is between about 3 and 15% by weight. 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 includes hydro lyse of aqueous polyvinylformamide with a re Salzkla- at a temperature between about 60 0 C and 100 0 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 wafer coating.
  • the solution is preferably applied at a temperature between about 1O 0 C and 50 0 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 is in the wet state is used, 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 anion-conducting membrane and the cation-conducting membrane during use. Bubbles and inclusions cause a reduction in 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 according to the invention 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 shows schematically the galvanic bath according to the invention.
  • 1 means the bath, 2 the anodes and 3 the cathode or the workpiece to be coated.
  • 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:
  • FIG. 2 shows the galvanic bath from FIG. 1, wherein it additionally has a further electrolyte space between the cathode space and the anode space, which contains a second catholyte 7, which in the present case contains sodium sulfate and sulfuric acid (in each case IM) , wherein the further electrolyte space is separated by an ion exchange membrane 6 from the cathode compartment.
  • a further electrolyte space between the cathode space and the anode space, which contains a second catholyte 7, which in the present case contains sodium sulfate and sulfuric acid (in each case IM) , wherein the further electrolyte space is separated by an ion exchange membrane 6 from the cathode compartment.
  • a galvanic bath was prepared for the deposition of zinc-nickel alloys with the following components:
  • Nickel 1.2 g / L (as nickel sulphate),
  • 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.
  • a galvanic bath was provided for the deposition of zinc with the following components:
  • This bath was operated with a bipolar membrane.
  • the bipolar membrane was placed in the bath between anode and cathode. Subsequently, iron sheets (7x10 cm) commonly used for hull cell tests were to be coated

Landscapes

  • 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)

Abstract

L'invention concerne un bain galvanique alcalin destiné à l'application de zinc ou d'alliages de zinc sur des substrats, dans lequel l'espace anodique et l'espace cathodique sont séparés l'un de l'autre par une membrane bipolaire. Le bain galvanique fonctionne avec des bains de zinc ou d'alliages de zinc pouvant contenir d'autres additifs. L'invention concerne également un procédé de dépôt galvanique de zinc ou d'alliages de zinc sur des substrats, consistant à introduire le substrat dans le bain galvanique selon l'invention. L'invention concerne également l'utilisation de membranes bipolaires pour la séparation de l'espace anodique et de l'espace cathodique et pour l'élimination de la décomposition anodique de composants organiques de l'électrolyte dans des bains galvaniques.
EP08861431A 2007-12-14 2008-12-15 Bain galvanique, procédé de dépôt galvanique et utilisation d'une membrane bipolaire pour la séparation dans un bain galvanique Active EP2235236B1 (fr)

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 (fr) 2007-12-14 2008-12-15 Bain galvanique, procédé de dépôt galvanique et utilisation d'une membrane bipolaire pour la séparation dans un bain galvanique

Publications (2)

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

Family

ID=40394014

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08861431A Active EP2235236B1 (fr) 2007-12-14 2008-12-15 Bain galvanique, procédé de dépôt galvanique et utilisation d'une membrane bipolaire pour la séparation dans un bain galvanique

Country Status (6)

Country Link
EP (1) EP2235236B1 (fr)
BR (1) BRPI0820988B1 (fr)
DE (1) DE102007060200A1 (fr)
ES (1) ES2396801T3 (fr)
PL (1) PL2235236T3 (fr)
WO (1) WO2009077146A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3042985A4 (fr) * 2015-07-22 2016-08-17 Dipsol Chem Procédé de placage d'un alliage de zinc
EP3042984A4 (fr) * 2015-07-22 2016-11-23 Dipsol Chem Procédé de placage d'un alliage de zinc

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EP2489763A1 (fr) * 2011-02-15 2012-08-22 Atotech Deutschland GmbH Matériau de couche d'alliage de zinc et de fer
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
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 (fr) * 2019-02-15 2020-08-19 Coventya GmbH Procédé de production d'un moulage en alliage d'aluminium-silicium résistant à la corrosion, moulage en alliage d'aluminium-silicium résistant à la corrosion et son utilisation
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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Cited By (6)

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Publication number Priority date Publication date Assignee Title
EP3042985A4 (fr) * 2015-07-22 2016-08-17 Dipsol Chem Procédé de placage d'un alliage de zinc
EP3042984A4 (fr) * 2015-07-22 2016-11-23 Dipsol Chem Procédé de placage d'un alliage de zinc
CN106550607A (zh) * 2015-07-22 2017-03-29 迪普索股份公司 锌合金镀敷方法
US9903038B2 (en) 2015-07-22 2018-02-27 Dipsol Chemicals Co., Ltd. Zinc alloy plating method
CN106550607B (zh) * 2015-07-22 2018-09-18 迪普索股份公司 锌合金镀敷方法
US10156020B2 (en) 2015-07-22 2018-12-18 Dipsol Chemicals Co., Ltd. Zinc alloy plating method

Also Published As

Publication number Publication date
ES2396801T3 (es) 2013-02-27
BRPI0820988A2 (pt) 2015-08-04
BRPI0820988B1 (pt) 2018-12-04
WO2009077146A2 (fr) 2009-06-25
EP2235236B1 (fr) 2012-10-03
WO2009077146A3 (fr) 2010-01-14
DE102007060200A1 (de) 2009-06-18
PL2235236T3 (pl) 2013-03-29

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