EP2857560A1 - Procédé plasma-chimique destiné à fabriquer des couches en céramique oxydée noires et objet revêtu correspondant - Google Patents

Procédé plasma-chimique destiné à fabriquer des couches en céramique oxydée noires et objet revêtu correspondant Download PDF

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Publication number
EP2857560A1
EP2857560A1 EP14184217.9A EP14184217A EP2857560A1 EP 2857560 A1 EP2857560 A1 EP 2857560A1 EP 14184217 A EP14184217 A EP 14184217A EP 2857560 A1 EP2857560 A1 EP 2857560A1
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Prior art keywords
mol
electrolyte
oxide ceramic
iron
vanadium
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EP14184217.9A
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German (de)
English (en)
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EP2857560B2 (fr
EP2857560B1 (fr
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Dr. Kyriaki Dascoulidou-Gritner
Tamara SCHWARZ
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Aalberts Surface Technologies GmbH Landsberg am Lech
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AHC Oberflaechenechnik GmbH
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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/14—Producing integrally coloured layers
    • 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
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • 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
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting

Definitions

  • the invention relates to a plasma-chemical process for producing black oxide ceramic layers on light metals, in particular aluminum, titanium, magnesium or their alloys after the process of anodic oxidation with spark discharge in aqueous electrolytes.
  • ANOF anodic oxidation under spark discharge
  • PCO plasma chemical oxidation
  • PEO plasma electrolytic oxidation
  • ASD anodic sparc deposition
  • MAO micro arc oxidation
  • this anodic oxidation in aqueous electrolytes is a gas-solid reaction under plasma conditions in which the high energy input at the base of the discharge column on the anode produces liquid metal which forms a short-time fused oxide with the activated oxygen.
  • the layer formation takes place via partial anodes.
  • the spark discharge is preceded by a forming area ( P. short; Dechema monographs Volume 121 - VCH Verlagsgesellschaft 1990, page 167-180 with further references).
  • the electrolytes have been combined to combine their positive properties to produce high quality anodic oxide ceramic layers on aluminum. By combining different salts, higher salt concentrations in the electrolyte bath and thus higher viscosities can be achieved.
  • Such high-viscosity electrolytes have a high heat capacity, stabilize the formed oxygen film on the anode and thus guarantee a uniform oxide layer formation (DD-WP 142 360).
  • the time is sufficient for the melt of the oxide ceramic to contract well, thus forming a sintered, low-porosity ceramic oxide layer.
  • the melt of the oxide ceramic is rapidly cooled by the electrolyte and the still migrating gases, in particular oxygen and water vapor leave an oxide ceramic layer with a marmaschig linked capillary system. From pore electron microscopic investigations, pore diameters of 0.1 ⁇ m to 30 ⁇ m were determined ( CERAMIC COATINGS BY ANODIC SPARK DEPOSITION GP Wirtz et al., MATERIALS & MANUFACTU-RING PROCESSES 6 (1), 87-115 (1991 ), in particular FIG. 12).
  • the DD 299 595 and DD 299 596 describe the preparation of black conversion coatings on light metals using electrolytes containing chromate.
  • DD 221 762 A1 and DD 257 275 A1 For example, it is known to add metal salts such as iron hexacyanoferrate, nickel, cobalt, or chromium salts to the electrolyte to produce dark colored oxide layers.
  • metal salts such as iron hexacyanoferrate, nickel, cobalt, or chromium salts
  • the known processes use substances of concern in the electrolytes, in particular carcinogenic chromium salts, or those metal salts which are on the ECHA list ( http://echa.europa.eu ), since they are classified as environmental and / or or hazardous to health.
  • electrolytes containing molybdenum, cobalt, chromium or nickel or cyanide ions or other substances of concern should no longer be used in the future because they can lead to work safety or environmental problems.
  • the object of the invention is therefore to provide a process for producing black oxide ceramic layers on aluminum, magnesium, titanium or their alloys and special materials containing these materials after the process of anodic oxidation under spark discharge (ANOF), are used in the electrolytes, the low pollution and easy to handle.
  • the electrolytes should not contain molybdenum, cobalt, chromium and nickel ions as well as cyanide ions and borates.
  • black and resistant oxide ceramic layers can be produced whose layer thickness can be varied over a wide range.
  • Deep black in the sense of the invention is understood as meaning all layers which have values of L * less than or equal to 30 according to the CIE L * a * b * system.
  • aluminum and its alloys come pure aluminum and alloys with the main component aluminum, such as the aluminum wrought alloys of the series EN-AW 1000, 2000, 3000, 4000, 5000, 6000, 7000, or the aluminum casting alloys EN-AC 21000, 21100, 42000, 43000, 43200, 43400, 44300, 46000, 46200, 47000, 47100, 48000, 51000, 51100 series.
  • Magnesium and its alloys include pure magnesium and the magnesium casting alloys of the ASTM designations AS41, AM60, AZ61, AZ63, AZ81, AZ91, AZ92, HK31, QE22, ZE41, ZH62, ZK51, ZK61, EZ33, HZ32 and the wrought alloys AZ31, AZ61, AZ 80, M1, ZK60, ZK40 in question.
  • pure titanium or titanium alloys such as TiAl6V4; TiAl5 Fe2.5 u.a. deploy.
  • the electrolyte has a pH of 5.4 to 10.0 in the case of anodic oxidation.
  • the electrolyte may also contain inorganic or organic anions. Preference is given to 0.2 to 0.9 mol / L of a phosphate of an alkali metal, preferably a dihydrogen phosphate or pyrophosphate, in particular potassium dihydrogen phosphate or potassium pyrophosphate, and / or 0.15 to 0.5 mol / L of citric acid or its salts. Citrates are particularly preferred because they support a controlled spark process. Phosphates allow better layer growth.
  • the electrolyte contains 0.8 to 2.9 mol / L, preferably 0.8 to 2.1 mol / L of a stabilizer, in particular hexamethylenetetramine.
  • iron and vanadium salts are added to the electrolyte to obtain the desired black color of the oxide ceramic layer.
  • deep black and thick layers are obtained by the combination of iron and vanadium according to the invention.
  • the presence of both metal salts is imperative.
  • no deep black layers within the meaning of the invention are obtained with just one of the two metal salts.
  • an iron (III) and a vanadium (V) salt are used for this purpose.
  • 0.04 to 0.09 mol / L of an iron (III) salt and 0.035 to 0.090 mol / L of a vanadium (V) salt are used.
  • ammonium iron (III) citrate and ammonium (mono) vanadate as the source of the metal ions.
  • 0.04 to 0.09 mol / L ammonium iron (III) citrate and 0.035 to 0.09 mol / L ammonium (mono) vanadate are therefore used.
  • An electrolyte temperature of 15 to 60, preferably up to 40 degrees Celsius has proven to be particularly suitable.
  • the current density used is between 0.02 and 0.10 Acm -2 , preferably 0.04 to 0.08 Acm -2 , without having to compromise on the quality and layer thickness of the oxide ceramic layers.
  • the current density is kept constant until a final voltage below 1000 V, preferably 300 to 650 V is reached.
  • the oxide ceramic layers obtainable by means of the invention can have a layer thickness of 5 ⁇ m to 100 ⁇ m and consist of oxides, in particular spinels, of aluminum, iron and vanadium.
  • the electrolyte combinations according to the invention deep black (of L * less than or equal to 30, see above) and also adhesive layer thicknesses greater than 50 ⁇ m can be produced for the first time.
  • the electrolyte combination according to the invention allows the production of thin or thick deep black and also adhesive layers of up to 100 microns.
  • the electrolyte is low in pollutants and easy to handle, ie contains no molybdenum, cobalt, chromium and nickel ions and cyanide ions and borate ions.
  • the electrolyte solutions were freshly prepared and placed in conventional anodic oxidation equipment. Prior to oxidation, all sample plates were degreased with a commercially available cleaner and then immersed in the electrolyte baths and contacted. The voltage was applied with a rectifier of the company RGB (30A / 380V). After about 10 min. the voltages were in the range of 230 to 290 volts.
  • the sample plates were removed, cleaned by conventional methods and examined.
  • the samples were subjected to characterization of the layer according to the CIE L * a * b * system according to DIN EN ISO 11664-4, layer thickness measurements and cross-hatch tests in accordance with DIN 2499.
  • An aluminum-degreased aluminum plate made of the wrought alloy EN-AW 6082 / AlSi1MgMn is dissolved in an aqueous electrolyte containing 0.4 mol / L citric acid; 1.5 mol / L hexamethylenetetramine; 0.7 mol / L potassium dihydrogen phosphate; 0.05 mol / L ammonium iron (III) citrate; 0.075 mol / L ammonium (mono) vanadate with a pH of 6.1 immersed and contacted as an anode and coated at a current density of 0.035 Acm -2 , at 25 ° C for 15 min running time by means of spark discharge.
  • a deep black adherent coating was obtained with a layer thickness of 20 ⁇ m and a color characteristic L * 28.68; a * -0.01; b * -0.33.
  • An aluminum-degreased aluminum plate made of the wrought alloy EN-AW 6082 / AlSi1MgMn is dissolved in an aqueous electrolyte comprising 0.4 mol / L of citric acid; 1.5 mol / L hexamethylenetetramine; 0.7 mol / L potassium dihydrogen phosphate; 0.05 mol / L ammonium iron (III) citrate; 0.075 mol / L ammonium (mono) vanadate with a pH of 6.1 contacted as an anode and coated at a current density of 0.035 Acm -2 , at 25 ° C for 60 min run time by spark discharge.
  • a deep black adherent coating was obtained with a layer thickness of 80 ⁇ m and a color characteristic L * 26.38; a * -0.15; b * -0.76.
  • An aluminum-degreased aluminum plate made of the casting alloy EN-AC 46000 / GD-AISi9Cu3 (Fe) is dissolved in an aqueous electrolyte comprising 0.4 mol / L of citric acid; 1.5 mol / L hexamethylenetetramine; 0.7 mol / L potassium dihydrogen phosphate; 0.05 mol / L ammonium iron (III) citrate; 0.075 mol / L ammonium (mono) vanadate with a pH of 6.1 contacted as an anode and coated at a current density of 0.05 Acm -2 , at 30 ° C for 40 min run time by spark discharge.
  • a deep black adherent coating was obtained with a layer thickness of 22 ⁇ m and a color characteristic L * 25.97; a * 0.40; b * 0.20.
  • An aluminum-degreased aluminum plate made of the wrought alloy EN-AW 6082 / AlSi1MgMn is dissolved in an aqueous electrolyte comprising 1.3 mol / L hexamethylenetetramine; 0.35 mol / L potassium pyrophosphate; 0.05 mol / L ammonium iron (III) citrate; 0.075 mol / L ammonium (mono) vanadate with a pH of 9.6 contacted as an anode and at a current density of 0.032 Acm -2 , at 40 ° C for 30 min run time coated by spark discharge.
  • a deep black adherent coating was obtained with a layer thickness of 22 ⁇ m and a color characteristic L * 26.60; a * 0.00; b * -0.60.
  • An alkaline degreased and acidified pure titanium plate (grade 2) is dissolved in an aqueous electrolyte having the composition 0.4 mol / l citric acid; 1.5 mol / l hexamethylenetetramine; 0.7 mol / l potassium dihydrogen phosphate; 0.05 ammonium iron (III) citrate; 0.075 mol / l ammonium (mono) vanadate immersed with a pH of 6.1 and contacted as an anode and coated at a current density of 0.03 Acm -2 , at 20 ° C for 15 min running time by spark discharge.
  • a deep black adherent coating was obtained with a layer thickness of 26.5 ⁇ m and a color characteristic L * 29.67; a * 3.91; b * 4.01.
  • An aluminum-degreased aluminum plate of the wrought alloy EN-AW 6082 / AlSi1MgMn is dissolved in an aqueous electrolyte comprising 0.35 mol / L citric acid, 2.85 mol / L hexamethylenetetramine, 0.5 mol / L potassium dihydrogen phosphate, 0.05 mol / L Immersed ammonium iron (III) citrate and 0.07 mol / L ammonium (mono) vanadate with a pH of 6.6 and contacted as the anode and at a current density of 0.035 Acm -2 , at 25 ° C for 15 min running time Spark discharge coated.
  • a deep black adherent coating was obtained with a layer thickness of 12.3 ⁇ m and a color characteristic L * 27.91; a * 0.34; b * -0.16.
  • the layer thickness measurements were carried out with the specified measuring device from Helmut Fischer GmbH & Co. KG (see above). For each sample plate, 10 measurements of layer thickness were made and the mean reported.
  • Querschliffuntersuchungen show that in the comparison variant according to DD 221 762 A1 to EN-AW 6082 AlSi1MgMn there are large variations in layer thickness, in some cases the oxide layer is not closed ( Fig.1 and 2 ).
  • the layer thickness according to embodiment 1 ( Fig. 3 and 4 ) is significantly higher and more homogeneous than that of the comparison variant.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
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EP14184217.9A 2013-09-26 2014-09-10 Procédé plasma-chimique destiné à fabriquer des couches en céramique oxydée noires et objet revêtu correspondant Active EP2857560B2 (fr)

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DE102013110660.9A DE102013110660A1 (de) 2013-09-26 2013-09-26 Plasmachemisches Verfahren zur Herstellung schwarzer Oxidkeramikschichten und entsprechend beschichteter Gegenstand

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
EP2857560B1 (fr) 2013-09-26 2017-03-22 AHC-Oberflächentechnik GmbH Procédé plasma-chimique destiné à fabriquer des couches en céramique oxydée noires et objet revêtu correspondant
DE102018110905A1 (de) * 2018-05-07 2019-11-07 Lucas Automotive Gmbh Elektrode für ein Eloxal-Verfahren
WO2021005031A1 (fr) * 2019-07-09 2021-01-14 BSH Hausgeräte GmbH Procédé de fabrication d'un composant, composant et table de cuisson au gaz

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WO2019098378A1 (fr) * 2017-11-17 2019-05-23 株式会社東亜電化 Élément métallique en magnésium ou en aluminium doté d'un revêtement d'oxyde noir, et son procédé de fabrication
US11032930B2 (en) * 2019-05-28 2021-06-08 Apple Inc. Titanium surfaces with improved color consistency and resistance to color change
CN111058077B (zh) * 2020-01-19 2022-03-22 常州大学 一种用于微弧氧化黑色陶瓷膜的电解液及其制备方法和微弧氧化方法
CN112663112B (zh) * 2020-12-02 2022-10-04 斯特凯新材料(上海)有限公司 一种电解液及镁合金复合氧化黑色陶瓷膜的制备方法
CN114016108B (zh) * 2021-12-20 2022-11-25 哈尔滨三泳金属表面技术有限公司 一种高硅高铜压铸铝合金的表面氧化膜及其制备工艺
DE102022206126A1 (de) 2022-06-20 2023-03-09 Carl Zeiss Smt Gmbh Bauteil zum Einsatz in einer Projektionsbelichtungsanlage

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I. J. HWANG ET AL: "Formation of Black Ceramic Layer on Aluminum Alloy by Plasma Electrolytic Oxidation in Electrolyte Containing Na2WO4", MATERIALS TRANSACTIONS, vol. 53, no. 3, 1 January 2012 (2012-01-01), pages 559 - 564, XP055170972, ISSN: 1345-9678, DOI: 10.2320/matertrans.M2011263 *
P. KURZE: "Dechema-Monographien", vol. 121, 1990, VCH VERLAGSGESELLSCHAFT, pages: 167 - 180
WIRTZ G P ET AL: "CERAMIC COATINGS BY ANODIC SPARK DEPOSITION", MATERIALS AND MANUFACTURING PROCESSES, vol. 6, no. 1, 1 January 1991 (1991-01-01), MARCEL DEKKER, NEW YORK, NY, US, pages 87 - 119, XP000934359, ISSN: 1042-6914 *

Cited By (4)

* Cited by examiner, † Cited by third party
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EP2857560B1 (fr) 2013-09-26 2017-03-22 AHC-Oberflächentechnik GmbH Procédé plasma-chimique destiné à fabriquer des couches en céramique oxydée noires et objet revêtu correspondant
DE102018110905A1 (de) * 2018-05-07 2019-11-07 Lucas Automotive Gmbh Elektrode für ein Eloxal-Verfahren
WO2019214879A1 (fr) 2018-05-07 2019-11-14 Zf Active Safety Gmbh Électrode pour procédé d'anodisation
WO2021005031A1 (fr) * 2019-07-09 2021-01-14 BSH Hausgeräte GmbH Procédé de fabrication d'un composant, composant et table de cuisson au gaz

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