EP2726650B1 - Elektrolytische vereisenung von zinkoberflächen - Google Patents
Elektrolytische vereisenung von zinkoberflächen Download PDFInfo
- Publication number
- EP2726650B1 EP2726650B1 EP20120725788 EP12725788A EP2726650B1 EP 2726650 B1 EP2726650 B1 EP 2726650B1 EP 20120725788 EP20120725788 EP 20120725788 EP 12725788 A EP12725788 A EP 12725788A EP 2726650 B1 EP2726650 B1 EP 2726650B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- galvanized
- acid
- iron
- alloy
- galvanized steel
- 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.)
- Not-in-force
Links
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
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Definitions
- the present invention relates to a process for the metallizing pretreatment of galvanized and / or alloy-galvanized steel surfaces or assembled metallic components, which at least partially have surfaces of zinc, in which from a water-containing electrolyte containing water-soluble compounds, which are a source of iron cations, a thin layer support is deposited on iron on the zinc surfaces.
- the method is carried out at least partially or permanently with the application of an electrolysis voltage, wherein the galvanized and / or alloy-galvanized steel surfaces are connected as a cathode.
- the aqueous electrolyte additionally contains an accelerator selected from oxo acids of the elements phosphorus, nitrogen and / or sulfur, wherein the elements phosphorus, nitrogen and / or sulfur are present in middle oxidation states.
- the prior art discloses methods for metallizing galvanized and / or alloy-galvanized steel surfaces. That's how it describes WO 2008/135478 a pretreatment process for the electroless deposition of metallic coatings, in particular of iron and tin, on galvanized and / or alloy-galvanized steel surfaces.
- the pretreatment provides moderately metallized zinc surfaces, which is advantageous for the application of subsequent anticorrosive coatings and provides excellent edge protection.
- the deposition of iron is preferably carried out from aqueous compositions which additionally contain accelerators based on oxo acids of the elements phosphorus and / or nitrogen in medium oxidation states.
- Alloy-galvanized steel surfaces are according to the invention, characterized in that their surface has more than 50 at .-% zinc based on all metallic elements, wherein the surface fraction of zinc by X-ray photoelectron spectroscopy using Al K-alpha radiation (1486.6 eV) is to be determined ,
- pretreatment is defined as the passivation by means of inorganic barrier layers (for example phosphating, chromating) or a process step preceding the lacquer coating for conditioning the cleaned metallic surface.
- inorganic barrier layers for example phosphating, chromating
- Such conditioning of the surface results in an improvement of the corrosion protection and the paint adhesion for the entire layer system resulting at the end of a process chain for the corrosion-protective surface treatment.
- the specifying designation of the pretreatment as "metallising” is to be understood as meaning a pretreatment process which directly effects a metallic deposition of iron or an iron alloy on the zinc surface, after metallizing Pretreatment the pretreated metal surface is at least 50 At .-% of iron based on all metallic elements, wherein the proportion of metallic iron is at least 50%, the determination of the surface layer coating and the metallic state by means of X-ray photoelectron spectroscopy (XPS) using Al K-alpha radiation (1486.6 eV).
- XPS X-ray photoelectron spectroscopy
- the contact time or pretreatment time with the aqueous electrolyte should preferably be at least 1 second but not longer than 60 seconds, preferably not longer than 20 seconds.
- the ratio of electrolysis time to contact time should preferably be at least 0.5, more preferably at least 0.8.
- the cathodic electrolysis current can be applied potentiostatically or galvanostatically and in each case by pulses, with galvanostatic methods being preferred.
- galvanostatic methods it is preferable that the galvanized or alloy-galvanized steel surface does not function as the anode during the contact time, so that no anodic electrolytic current is impressed.
- the metallization is particularly effective when the concentration of water-soluble compounds which are a source of iron cations, based on the element iron in the electrolyte, is preferably at least 0.01 mol / l, but preferably 0.4 mol / l, more preferably 0.1 mol / l does not exceed.
- the water-soluble compounds are preferably a source of iron (II) ions and thus preferably water-soluble salts selected from iron (II) sulfate, iron (II) nitrate, iron (II) lactate and / or iron (II) gluconate.
- the iron ions in the electrolyte represent at least 50% iron (II) ions.
- the accelerators with reduction action contained in the pretreatment process according to the invention for increasing the deposition rate of the iron cations, ie the metallization of the galvanized or alloy-galvanized surface are preferably selected from oxo acids of phosphorus.
- Oxox acids of phosphorus are again preferably selected from hyposalpetriger acid, hypos nitric acid, nitrous acid, hypophosphoric acid, hypodiphosphonic acid, Diphosphorus (III, V) acid, phosphonic acid, diphosphonic acid and / or phosphinic acid and salts thereof, particularly preferably from phosphinic acid and salts thereof.
- the molar ratio of accelerator to the concentration of the water-soluble compounds, which are a source of iron cations, in the aqueous electrolyte is preferably not greater than 2: 1, more preferably not greater than 1: 1 and preferably not below 1: 5, the Concentration of the water-soluble compounds, which are a source of iron cations, referred to the element iron.
- the pH of the electrolyte should preferably not be less than 2, and preferably not greater than 6, in order, on the one hand, to minimize the acid corrosion of the zinc-containing substrate and, on the other hand, to ensure the stability of the iron (II) ions in the treatment solution.
- the electrolyte containing the water-soluble compounds of iron may further contain chelating complexing agents with oxygen and / or nitrogen ligands for stabilization, surprisingly a faster kinetics of iron deposition is observed, so that a shorter contact time can be achieved with optimum iron occupancy of the galvanized surface.
- Suitable chelating complexing agents are especially those which are selected from triethanolamine, diethanolamine, monoethanolamine, monoisopropanolamine, aminoethylethanolamine, 1-amino-2,3,4,5,6-pentahydroxyhexane, N- (hydroxyethyl) ethylenediaminetriacetic acid, Ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, 1,2-diamino-propanetetraacetic acid, 1,3-diaminopropane-tetraacetic acid, tartaric acid, ascorbic acid, lactic acid, mucic acid, gallic acid, gluconic acid and / or glucoheptonic acid and their salts and stereoisomers as well as sorbitol, glucose and Glucamine and their stereoisomers.
- a particularly effective formulation of the aqueous electrolyte is for the process according to the invention, when in this a molar ratio of chelating complexing agents to the concentration of water-soluble compounds which are a source of iron cations of not greater than 5: 1, preferably not greater 2: 1, but of at least 1: 5 is realized, wherein the concentration of the water-soluble compounds, which are a source of iron cations, based on the element iron.
- the electrolyte for the metallizing pretreatment may additionally contain surfactants which are able to liberate the metallic surface from impurities without itself inhibiting the surface by forming compact adsorbate layers for the metallization.
- Nonionic surfactants with average HLB values of at least 8 and at most 14 may be used for this purpose.
- the electrolyte is essentially free of electropositive metal cations selected from cations of the elements Ni, Co, Cu, and / or Sn, since these compete with the deposition of the iron cations.
- substantially free in this context, means that no water-soluble compounds that are a source of the electropositive metal cations are intentionally added to the electrolyte.
- the treatment according to the invention of alloy-zinc plated steel surfaces containing electropositive metals as an alloy constituent or composite metal surfaces may cause small amounts of these elements to enter the electrolyte.
- the electrolyte in the process according to the invention has a total of less than 2000 ppm of zinc ions, since zinc ions are able to displace the iron ions from their complexes in the presence of complexing agents according to a preferred embodiment of the invention.
- a dipping process which is common in strip steel production and strip steel refinement is practicable.
- layer deposits of preferably at least 1 mg / m 2 , but preferably not more than 100 mg / m 2 , and particularly preferably not more than 50 mg / m 2, based on the element iron result .
- the layer support is defined as the area-related mass fraction of iron on the galvanized or alloy-galvanized steel surface immediately after the pretreatment according to the invention.
- the pretreatment process according to the invention is based on the subsequent process steps of the surface treatment of galvanized and / or alloy-galvanized steel surfaces with regard to optimized corrosion protection and outstanding paint adhesion, especially tailored to cut edges, surface defects and bimetallic contacts. Consequently, the present invention encompasses various aftertreatment processes, ie conversion and lacquer coatings, which, in conjunction with the pretreatment described above, provide the desired results in terms of corrosion protection.
- the invention therefore relates in a further aspect to the production of a passivating conversion coating on the metallized pretreated galvanized and / or alloy-galvanized steel surface with or without intermediate rinsing and / or drying step.
- a chromium-containing or preferably chromium-free conversion solution can be used.
- Preferred conversion solutions with which the metal surfaces pretreated according to the present invention can be treated prior to the application of a permanent corrosion-protective organic coating can be used DE-A-199 23 084 and the literature cited herein.
- a chromium-free aqueous conversion agent besides hexafluoro anions of Ti, Si and / or Zr may contain as further active ingredients: phosphoric acid, one or more compounds of Co, Ni, V, Fe, Mn, Mo or W, a water-soluble or water-dispersible film-forming organic polymer or copolymer and organophosphonic acids that have complexing properties.
- phosphoric acid one or more compounds of Co, Ni, V, Fe, Mn, Mo or W
- water-soluble and / or water-dispersible polymeric complexing agents with oxygen and / or nitrogen ligands based on Mannich addition products of polyvinylphenols with formaldehyde and aliphatic amino alcohols may be present.
- Such polymers are in the patent US 5,298,289 disclosed.
- the process parameters for a conversion treatment in the context of this invention are to be chosen such that a conversion layer is produced, the per m 2 surface at least 0.05, preferably at least 0.2, but not more than 3, Contains 5, preferably not more than 2.0 and more preferably not more than 1.0 mmol of the metal M, which is the essential component of the conversion solution.
- metals M are Cr (III), B, Si, Ti, Zr, Hf.
- the coverage of the zinc surface with the metal M can be determined, for example, by an X-ray fluorescence method.
- the chromium-free conversion medium additionally contains copper ions.
- the molar ratio of metal atoms M selected from zirconium and / or titanium to copper atoms in such a conversion agent is preferably selected such that it produces a conversion layer in which at least 0.1 mmol, preferably at least 0.3 mmol, but not more than 2 mmol of copper are additionally included.
- a method in which the metallizing pretreatment is followed by a conversion treatment to form a thin amorphous inorganic coating may also employ a method in which the metallization of the present invention comprises zinc phosphating to form a crystalline phosphate layer having a preferred coating weight of not less than 3 g / m 2 follows.
- the metallizing pretreatment and the subsequent conversion treatment usually follow further process steps for the application of additional layers, in particular organic paints or coating systems.
- the present invention relates to the galvanized and / or alloy-galvanized steel surface and the metallic component which consists at least partially of a zinc surface which has been metallized in the aqueous electrolyte according to the method of the invention or subsequently to this pretreatment with further passivating conversion layers and / or Lacquer is coated.
- Such a treated steel surface or treated component is used in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL12725788T PL2726650T3 (pl) | 2011-06-29 | 2012-06-06 | Elektrolityczne pokrywanie żelazem powierzchni cynkowych |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102011078258A DE102011078258A1 (de) | 2011-06-29 | 2011-06-29 | Elektrolytische Vereisenung von Zinkoberflächen |
PCT/EP2012/060642 WO2013000674A1 (de) | 2011-06-29 | 2012-06-06 | Elektrolytische vereisenung von zinkoberflächen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2726650A1 EP2726650A1 (de) | 2014-05-07 |
EP2726650B1 true EP2726650B1 (de) | 2015-04-29 |
Family
ID=46208558
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20120725788 Not-in-force EP2726650B1 (de) | 2011-06-29 | 2012-06-06 | Elektrolytische vereisenung von zinkoberflächen |
Country Status (10)
Country | Link |
---|---|
US (1) | US9309602B2 (ko) |
EP (1) | EP2726650B1 (ko) |
JP (1) | JP2014518332A (ko) |
KR (1) | KR101991141B1 (ko) |
CN (1) | CN103764878B (ko) |
AU (1) | AU2012278121B2 (ko) |
CA (1) | CA2840117C (ko) |
DE (1) | DE102011078258A1 (ko) |
PL (1) | PL2726650T3 (ko) |
WO (1) | WO2013000674A1 (ko) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA3034712C (en) | 2016-08-24 | 2021-10-12 | Ppg Industries Ohio, Inc. | Alkaline composition for treating metal substartes |
US11155928B2 (en) | 2019-12-19 | 2021-10-26 | The United States Of America As Represented By The Secretary Of The Navy | Electrolytic process for deposition of chemical conversion coatings |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3974044A (en) * | 1975-03-31 | 1976-08-10 | Oxy Metal Industries Corporation | Bath and method for the electrodeposition of bright nickel-iron deposits |
US4089754A (en) * | 1977-07-18 | 1978-05-16 | Oxy Metal Industries Corporation | Electrodeposition of nickel-iron alloys |
JPS5573888A (en) * | 1978-11-22 | 1980-06-03 | Nippon Kokan Kk <Nkk> | High corrosion resistant zinc-electroplated steel sheet with coating and non-coating |
DE3217145A1 (de) * | 1982-05-07 | 1983-11-10 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zum reinigen, entfetten sowie aktivieren von metalloberflaechen |
JPH0654986B2 (ja) * | 1985-07-08 | 1994-07-20 | ソニー株式会社 | 垂直センタ−位置調整回路 |
JPH0657871B2 (ja) * | 1986-10-15 | 1994-08-03 | 大洋製鋼 株式会社 | 耐食性と導電性を兼ね備えた鋼板 |
JPS63195296A (ja) * | 1987-02-09 | 1988-08-12 | Nippon Steel Corp | 着色表面処理鋼板の製造方法 |
JPS63243299A (ja) * | 1987-03-30 | 1988-10-11 | Nippon Steel Corp | 複合メッキ鋼板の製造方法 |
US5298289A (en) | 1987-12-04 | 1994-03-29 | Henkel Corporation | Polyphenol compounds and treatment and after-treatment of metal, plastic and painted surfaces therewith |
JPH0637711B2 (ja) * | 1989-06-22 | 1994-05-18 | 新日本製鐵株式会社 | 黒色表面処理鋼板の製造方法 |
JP2978208B2 (ja) * | 1990-05-18 | 1999-11-15 | シチズン時計株式会社 | キャラクタージェネレータにおけるフォントデータ圧縮方式 |
JPH0790610A (ja) * | 1993-09-20 | 1995-04-04 | Kobe Steel Ltd | 耐黒変性、塗膜密着性および耐蝕性に優れた亜鉛系溶融 めっき鋼板の製造方法 |
CA2176332C (en) * | 1993-11-16 | 2005-05-03 | David Peter Buxton | Anticorrosion treatment of metal coated steel having coatings of aluminium, zinc or alloys thereof |
US5849423A (en) * | 1995-11-21 | 1998-12-15 | Nkk Corporation | Zinciferous plated steel sheet and method for manufacturing same |
JP3211686B2 (ja) * | 1996-11-13 | 2001-09-25 | トヨタ自動車株式会社 | 鉄・リン電気めっき浴 |
DE19923084A1 (de) * | 1999-05-20 | 2000-11-23 | Henkel Kgaa | Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren |
CN100497733C (zh) * | 2003-01-31 | 2009-06-10 | 杰富意钢铁株式会社 | 黑色镀锌系钢板 |
DE102007021364A1 (de) * | 2007-05-04 | 2008-11-06 | Henkel Ag & Co. Kgaa | Metallisierende Vorbehandlung von Zinkoberflächen |
-
2011
- 2011-06-29 DE DE102011078258A patent/DE102011078258A1/de not_active Ceased
-
2012
- 2012-06-06 KR KR1020137034840A patent/KR101991141B1/ko active IP Right Grant
- 2012-06-06 CN CN201280031855.XA patent/CN103764878B/zh not_active Expired - Fee Related
- 2012-06-06 PL PL12725788T patent/PL2726650T3/pl unknown
- 2012-06-06 JP JP2014517557A patent/JP2014518332A/ja active Pending
- 2012-06-06 AU AU2012278121A patent/AU2012278121B2/en not_active Ceased
- 2012-06-06 WO PCT/EP2012/060642 patent/WO2013000674A1/de active Application Filing
- 2012-06-06 CA CA2840117A patent/CA2840117C/en not_active Expired - Fee Related
- 2012-06-06 EP EP20120725788 patent/EP2726650B1/de not_active Not-in-force
-
2013
- 2013-03-12 US US13/795,528 patent/US9309602B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
AU2012278121A1 (en) | 2014-01-16 |
DE102011078258A1 (de) | 2013-01-03 |
JP2014518332A (ja) | 2014-07-28 |
WO2013000674A1 (de) | 2013-01-03 |
CN103764878A (zh) | 2014-04-30 |
PL2726650T3 (pl) | 2015-10-30 |
KR101991141B1 (ko) | 2019-06-19 |
AU2012278121B2 (en) | 2016-07-21 |
CA2840117A1 (en) | 2013-01-03 |
CA2840117C (en) | 2019-07-02 |
CN103764878B (zh) | 2016-06-15 |
US20130206603A1 (en) | 2013-08-15 |
KR20140037149A (ko) | 2014-03-26 |
US9309602B2 (en) | 2016-04-12 |
EP2726650A1 (de) | 2014-05-07 |
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