EP1141449B1 - Verfahren zum abdunkeln einer oberflächenschicht eines materialstückes, die zink enthält - Google Patents

Verfahren zum abdunkeln einer oberflächenschicht eines materialstückes, die zink enthält Download PDF

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Publication number
EP1141449B1
EP1141449B1 EP99963569A EP99963569A EP1141449B1 EP 1141449 B1 EP1141449 B1 EP 1141449B1 EP 99963569 A EP99963569 A EP 99963569A EP 99963569 A EP99963569 A EP 99963569A EP 1141449 B1 EP1141449 B1 EP 1141449B1
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EP
European Patent Office
Prior art keywords
range
soaking
surface layer
carried out
piece
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.)
Expired - Lifetime
Application number
EP99963569A
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German (de)
English (en)
French (fr)
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EP1141449A2 (de
Inventor
Thomas Kruse
Peter Meisterjahn
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.)
Ewald Doerken AG
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Ewald Doerken AG
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Publication of EP1141449A2 publication Critical patent/EP1141449A2/de
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Publication of EP1141449B1 publication Critical patent/EP1141449B1/de
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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/60—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 using aqueous solutions using alkaline aqueous solutions with pH greater than 8

Definitions

  • the invention relates to a method for darkening a surface layer a piece of material containing zinc in which the piece of material oxidizes in an immersion bath , which contains an aqueous solution of a hydroxide and a nitrate, with Pieces of material treated with such a method and on electrolytes for implementation of the method and on methods for pretreating pieces of material.
  • EP 0 339 578 A1 describes a process for producing black-colored steel strips in which an electrolytic treatment is carried out, specifically in an immersion bath which contains 75 to 200 g / l of a compound selected from the group the hydroxides , Sulfates and chlorides of sodium, potassium or nickel.
  • the immersion bath preferably contains nitrate ions in an amount of 2 to 100 g / l.
  • current densities in the range from 30 to 200 A / cm 2 are used.
  • the method is preferably carried out using alternating current.
  • the immersion bath contains an inhibitor and a complex-forming substance.
  • FR 2758339 A1 describes a method for the anti-corrosion treatment of metallic Workpieces, especially workpieces containing iron. That for electrolysis immersion bath used contains between 300 to 700 g / l alkali hydroxides, between 20 and 50 g / l alkali nitrates and / or nitrites, between 40 and 100 g / l borax and between 10 up to 40 g / l surfactants, the immersion bath at a temperature in the range of 110 to 130 ° C. is held.
  • the invention is based on the object of methods for darkening to further develop a surface layer of a piece of material that contains zinc, that the treated surface layer has increased homogeneity, adhesion and Shows uniformity, as well as a piece of material having these properties and To provide electrolytes for performing the procedures.
  • the Solution of the immersion bath an alkali or ammonium salt in a concentration in the range from 10 to 60 g / l, the alkali or ammonium salt being selected from the group consisting of Phosphates, acetates, carbonates, sulfates, oxalates, citrates and borates of alkali metals or comprises ammonium.
  • the piece of material is placed in an immersion bath of a device at least two electrodes immersed for anodic oxidation, alternating or DC voltage to the electrodes before immersing the piece of material in the immersion bath is created and only then the piece of material in the immersion bath while maintaining the Voltage with an electrode spacing of 3 cm with AC voltage initially 8 volts and can initially be 20 V with DC voltage.
  • alternating or DC voltage to the electrodes before immersing the piece of material in the immersion bath is created and only then the piece of material in the immersion bath while maintaining the Voltage with an electrode spacing of 3 cm with AC voltage initially 8 volts and can initially be 20 V with DC voltage.
  • All suitable substrates come with a zinc layer are provided, the surface is treated, and pure zinc in question.
  • pure Zinc can also be used in a zinc alloy in which, based on the Dry layer, a high proportion of zinc, for example at least 50 wt .-%, zinc is present.
  • a pure zinc or zinc alloy layer can also be used in other processes applied to a substrate, such as by vapor deposition methods such as PVD and CVD, hot dip galvanizing and mechanical Application of such layers. Specifically, matt or bright galvanized can also be used Steel sheets are used. Possible zinc alloys come alongside others Zn / Fe, Zn / Ni, Zn / Fe / Co, Zn / Co, Zn / Al, Zn / Sn, Zn / Mn in question.
  • Titanium can be used as the counter electrode for the piece of material to be treated. However, it is also possible that electrodes made of a different material are used, whereby then the required current density has to be adjusted. Possible other materials for that Counter electrodes are precious metals, stainless steel, tantalum, graphite.
  • the pH is preferably adjusted via a corresponding concentration of NaOH or KOH.
  • the pH is preferably greater than 13. This also applies to the methods according to the invention described later. In this case can anodize over a treatment time of 1 second to 10 minutes be carried out, so that subsequently a dark discolored surface layer is present.
  • the method can be carried out either with direct voltage or alternating voltage become.
  • the basic rule is that when working with DC voltage lower Current densities are required to achieve the darkening of the surface layer.
  • the bath temperature can be in the range from 15 to 45 ° C, while the current density is in the range from 0.0003 to 0.15 A / cm 2 .
  • Working with DC voltage has the advantage that good results regarding the darkening of the surface layer can also be seen at room temperature and very low current density.
  • the bath temperature can be 35 to 45 ° C., while the current density is in the range from 0.1 to 0.15 A / cm 2 .
  • the method described above can also be supplemented by pretreatment steps be in which structural inhomogeneities of the surface of the material pieces or high organic components in the surfaces of the material pieces are taken into account can.
  • the piece of material can undergo an anodization Submersible treatment (activating / decopying) in an acid.
  • At least 0.5 molar H 2 SO 4 can be used as the acid, the immersion treatment being carried out over a period of at least 10 seconds.
  • the treatment time depends on the visible impression that the surface layer conveys when viewed.
  • 2 molar H 2 SO 4 can be used as acid in a pretreatment step.
  • the piece of material can then be annealed at a temperature of approximately 200 ° C., the time period for this process being in the range of 1 hour.
  • the pretreatment steps described above are particularly suitable for Pieces of material whose surface layer consists of shiny zinc.
  • the one in the making of gloss zinc used for such a high organic content in ensure that the surface is not satisfactorily darkened Surface layer is reached.
  • the quality of the appearance of the surface layer can also vary according to the anodic Oxidation can still be improved by a post-treatment step in which the piece of material is also subjected to an immersion process in an acid.
  • This Post-treatment refers, for example, to the presence of iridescent films the darkened surface layer, which gives the visual impression of the surface layer tarnish.
  • the piece of material can be immersed in a 10% CH 3 COOH, the immersion treatment being carried out over a period of at least 30 seconds. Good results have been shown with a one minute dive time.
  • the surface layer has an average thickness of at least 8 ⁇ m. This particularly applies to pieces of material that are are frame parts. Such frame parts have edges, their surface treatment can be difficult. To preserve in particular the Corrosion resistance of the piece of material can be said average Support thickness are observed.
  • the invention also relates to a method described above manufactured, surface-treated piece of material.
  • the zinc-containing surface is characterized by the fact that its structure is due to the anodic oxidation is converted that it is very high, for example in the visible spectral range Absorbance shows, so that the surface appears colored black.
  • the thickness of the converted part of the surface layer of the piece of material is in the range of a few microns to a few 100 microns, but preferably about 5 to 500 microns. It can be especially for infrared radiation, set a very low degree of reflection.
  • the converted surface layer is also characterized in that it is in itself and adheres to the material adjacent to it and is therefore permanent.
  • the provision of the OH - groups can preferably be adjusted via an appropriate concentration of NaOH or KOH.
  • the electrolyte can also contain additives for defoaming, for improved substrate wetting or corrosion inhibitors in solid or liquid form in a concentration of 0.01-100 g / l.
  • Suitable organic solvent additives are glycols, glycol ethers, glycol ether esters and alcohols of all kinds depending on the intended use, which can be present individually or in a concentration with one another.
  • the proposed methods and the pieces of material produced thereafter have the following advantages: the use of harmful Cr 6 is avoided; there is compatibility with common galvanotechnical processes (eg anodizing processes of aluminum), so that the known plant technology (rack or drum process) and the associated know-how can be largely used here; In the event that the piece of material is to be overpainted with, for example, a colorless, dark, possibly black, paint system based on organic or inorganic binders, the difference in contrast of the paint layer to the converted surface of the piece of material is small, so that with little use of material a covering effect for the Material piece surface is reached.
  • a is used as the piece of material bright galvanized sheet steel used.
  • the steel sheet is, unless otherwise stated is placed in the respective immersion bath under voltage.
  • the first process step for treating the surface of the piece of material consists of a dipping process in 0.5 MH 2 SO 4 for about one minute. This process step serves to improve the homogeneity of the surface to be treated in a later process step by means of anodic oxidation and is only required if the material surface to be treated has above-average inhomogeneities.
  • an anodic oxidation of the material piece is carried out (electrode spacing: 3 cm; a few volts AC voltage), a titanium sheet being used as the counter electrode.
  • an immersion bath is used which has an aqueous solution of NaOH and NaNO 3 as the electrolyte, the following concentrations being selected: 30 g / l NaOH and 40 g / l NaNO 3 .
  • the bath temperature T is 40 ° C., while the current density i is chosen to be 0.1 A / cm 2 .
  • the treatment time t is in the range of 2-10 minutes.
  • the piece of material forms the Working electrode of an alternating current circuit, which is operated with 50 Hz alternating current, while the titanium sheet acts as a counter electrode.
  • the piece of material is removed from the immersion bath for the anodic Oxidation removed, then in a possibly multi-stage rinsing process washed and finally dried.
  • the anodic oxidation makes the surface layer of the piece of material so converted that there is a homogeneous structure and an even dark discoloration of the surface layer gives the thickness of the converted part of the surface layer depends primarily on the treatment time t and is in the range of some 10 to some 100 nm.
  • the converted surface layer is inherently adhesive and solid with the Surface of the unconverted zinc bonded.
  • the second process step can also be carried out with the following parameters while maintaining the mentioned treatment time t, the titanium sheet counterelectrode and the bath temperature T: electrolyte composition 13 g / l NaOH and 50 g / l NaNO 3 in water; Current density i 0.05 A / cm 2 .
  • electrolyte composition 13 g / l NaOH and 50 g / l NaNO 3 in water electrolyte composition 13 g / l NaOH and 50 g / l NaNO 3 in water
  • Current density i 0.05 A / cm 2 This again results in pieces of material with a converted surface, the properties of which correspond to those which were explained in Example 1 using the second method step.
  • the two exemplary embodiments described for the second process step each lie in an end range for the process parameters NaOH concentration, NaNO 3 concentration and current density. These parameters can be varied within the limits described above, essentially maintaining the surface layer quality.
  • the bath temperature T and the treatment time t can also be application-specific be changed.
  • the first process step consists of a dipping process in 2 M H 2 SO 4 for more than 10 seconds, for example up to 2 minutes.
  • the first process step also includes annealing the piece of material at about 200 ° C. The annealing step takes about 1 hour.
  • This example takes into account the fact that especially with bright zinc-coated Steel sheets in spite of carrying out the aforementioned and using Examples 1 to 3 explained process steps after the anodic oxidation iridescent films on the Can show material surface.
  • the piece of material is subjected to a dip treatment in 10% CH 3 COOH over a period of at least 3 seconds.
  • Example 2 in contrast to Example 1, the method with DC voltage carried out. In turn, a bright galvanized steel sheet is used as the material.
  • Electrolyte NaOH 30 g / l, NaNO 3 40 g / l in water.
  • the DC current density is 0.017 A / cm 2 , while the treatment time is 5 minutes.
  • the bath temperature corresponds to the room temperature.
  • This example has the particular advantages that compared to AC voltage lower current density can be worked.
  • the formation of hydrogen, at AC voltage is formed in the cathodic half-wave, completely avoided.
  • the Hydrogen can lead to embrittlement of the surface layer of the piece of material.
  • an in its structure is essentially the same as the piece of material Piece of material used so that work is bipolar.
  • both pieces of material are treated simultaneously, with each other again darkened surface layers of the material pieces result.
  • an alternating current in the range from 0.1 to 0.15 A / cm 2 is used to anodize zinc layers. Darkening of the surfaces with good homogeneity was observed for the following sodium salts: sodium phosphate (10-40 g / l), sodium acetate (10-40 g / l), sodium carbonate (10 g / l), sodium sulfate (10-40 g / l l), sodium oxalate (10-40 g / l), sodium citrate (10-40 g / l) and sodium borate (10-40 g / l).
  • Salt concentrations of at least up to 60 g / l are also easily conceivable.
  • the immersion bath can also contain several salts without worsening the darkening, for example a mixture of sodium nitrate and sodium borate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)
  • Coating With Molten Metal (AREA)
  • Laminated Bodies (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP99963569A 1998-12-18 1999-12-17 Verfahren zum abdunkeln einer oberflächenschicht eines materialstückes, die zink enthält Expired - Lifetime EP1141449B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19858795A DE19858795C2 (de) 1998-12-18 1998-12-18 Verfahren zum Abdunkeln einer Oberflächenschicht eines Materialstücks, die Zink enthält
DE19858795 1998-12-18
PCT/EP1999/010036 WO2000037717A2 (de) 1998-12-18 1999-12-17 Verfahren zum abdunkeln einer oberflächenschicht eines materialstückes, die zink enthält

Publications (2)

Publication Number Publication Date
EP1141449A2 EP1141449A2 (de) 2001-10-10
EP1141449B1 true EP1141449B1 (de) 2003-05-02

Family

ID=7891788

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99963569A Expired - Lifetime EP1141449B1 (de) 1998-12-18 1999-12-17 Verfahren zum abdunkeln einer oberflächenschicht eines materialstückes, die zink enthält

Country Status (9)

Country Link
US (2) US6758956B1 (ja)
EP (1) EP1141449B1 (ja)
JP (1) JP2002533573A (ja)
AT (1) ATE239109T1 (ja)
DE (2) DE19858795C2 (ja)
DK (1) DK1141449T3 (ja)
ES (1) ES2197702T3 (ja)
PT (1) PT1141449E (ja)
WO (1) WO2000037717A2 (ja)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080169200A1 (en) * 2007-01-17 2008-07-17 Thomas David Burleigh Method of Anodizing Steel
CN111448342B (zh) * 2017-09-15 2023-01-03 欧瑞康表面处理解决方案股份公司普费菲孔 制造具有彩色表面的涂层的方法
JP7517355B2 (ja) 2022-02-18 2024-07-17 Ｊｆｅスチール株式会社 亜鉛めっき鋼板の製造方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1953997A (en) * 1932-11-14 1934-04-10 New Jersey Zinc Co Anodic coating of zinc base metals
US3647650A (en) * 1969-07-16 1972-03-07 Nippon Kokan Kk Method of treating tin plate or galvanized sheet
US3642586A (en) * 1970-05-12 1972-02-15 Republic Steel Corp Anodic treatment for stainless steel
US3723102A (en) * 1970-06-15 1973-03-27 Airco Inc High strength iron-chromium-nickel alloy
JPS5993900A (ja) * 1982-11-20 1984-05-30 Nippon Steel Corp 溶接性に優れた亜鉛メツキ鋼板
IL69507A (en) * 1983-08-16 1986-11-30 Chromagen Metal Works Selective surfaces for collectors of solar and other radiation
JPS61113794A (ja) * 1984-11-08 1986-05-31 Sumitomo Metal Ind Ltd 黒色化処理鋼板の製造方法
JPH0230795A (ja) * 1988-04-28 1990-02-01 Kawasaki Steel Corp 黒色鋼板の製造方法
JPH03277798A (ja) * 1990-03-28 1991-12-09 Kawasaki Steel Corp 黒色化処理鋼板の製造方法
JPH04131396A (ja) * 1990-09-21 1992-05-06 Kawasaki Steel Corp 黒色鋼板の製造方法
FR2758339B1 (fr) * 1997-01-14 1999-06-04 Cirdep Procede de traitement anticorrosion de pieces metalliques et en particulier de pieces en metaux ferreux

Also Published As

Publication number Publication date
DE19858795C2 (de) 2001-03-15
DE59905366D1 (de) 2003-06-05
DK1141449T3 (da) 2003-08-25
US7311787B2 (en) 2007-12-25
EP1141449A2 (de) 2001-10-10
ATE239109T1 (de) 2003-05-15
ES2197702T3 (es) 2004-01-01
JP2002533573A (ja) 2002-10-08
WO2000037717A3 (de) 2000-10-19
WO2000037717A2 (de) 2000-06-29
US6758956B1 (en) 2004-07-06
DE19858795A1 (de) 2000-06-21
PT1141449E (pt) 2003-09-30
US20050126921A1 (en) 2005-06-16

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