EP0545230B1 - Procédé de préparation d'une couche d'oxyde céramique modifiée sur des métaux formant couche barrière et produits obtenus - Google Patents

Procédé de préparation d'une couche d'oxyde céramique modifiée sur des métaux formant couche barrière et produits obtenus Download PDF

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Publication number
EP0545230B1
EP0545230B1 EP92120006A EP92120006A EP0545230B1 EP 0545230 B1 EP0545230 B1 EP 0545230B1 EP 92120006 A EP92120006 A EP 92120006A EP 92120006 A EP92120006 A EP 92120006A EP 0545230 B1 EP0545230 B1 EP 0545230B1
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EP
European Patent Office
Prior art keywords
accordance
bath
plasma
oxide
alloys
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
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EP92120006A
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German (de)
English (en)
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EP0545230B2 (fr
EP0545230A1 (fr
Inventor
Peter Prof. Dr. Kurze
Hans-Jürgen Kletke
Dora Banerjee
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Electro Chemical Engineering GmbH
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Electro Chemical Engineering GmbH
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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
    • C25D11/026—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
    • 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

Definitions

  • the invention relates to a method for producing oxide ceramic layers on barrier layer-forming metals or their alloys by plasma-chemical anodic oxidation in aqueous organic electrolytes, wherein the oxide ceramic layer can also be modified for special applications.
  • this anodic oxidation is a gas-solid reaction under plasma conditions, in which the high energy input at the base of the discharge column produces liquid metal on the anode, which forms a briefly melted oxide with the activated oxygen.
  • the layer formation takes place via partial anodes.
  • the spark discharge is preceded by a formation area (P. Kurz; Dechema-Monographien Volume 121 - VCH Verlagsgesellschaft 1990, pages 167-180 with further references).
  • the electrolytes have been combined in such a way that their positive properties are combined and high-quality anodic oxide ceramic layers are created on aluminum. By combining different salts, higher salt concentrations in the electrolyte bath and thus higher viscosities can be achieved.
  • Such highly viscous electrolytes have a high heat capacity, stabilize the oxygen film formed on the anode and thus guarantee a uniform oxide layer formation (DD-WP 142 360).
  • the barrier layer grows by increasing the voltage of the anodically polarized metal.
  • An oxygen plasma then partially forms at the metal / gas / electrolyte phase boundary, through which the oxide ceramic layer is formed.
  • the metal ion in the oxide ceramic layer comes from the metal, the oxygen from the anodic reaction in the aqueous electrolyte used.
  • the oxide ceramic is liquid at the determined plasma temperatures of around 7,000 Kelvin. There is enough time on the side of the metal so that the melt of the oxide ceramic can contract well and thus form a sintered, low-pore oxide ceramic layer.
  • the melt of the oxide ceramic is quickly cooled by the electrolyte and the gases that migrate, in particular oxygen and water vapor, leave an oxide ceramic layer with a wide-meshed capillary system.
  • Pore diameters from 0.1 .mu.m to 30 .mu.m were determined from scanning electron microscopic examinations (CERAMIC COATINGS BY ANODIC SPARK DEPOSITION G.P. Wirtz et al, MATERIALS & MANUFACTURING PROCESSES 6 (1), 87-115 (1991), in particular FIG. 12).
  • DE-A-2 902 162 describes a method in which, by using spark discharges during the anodization, porous layers on aluminum are produced which are intended for use in chromatography.
  • EP-A-280 886 describes the use of anodic oxidation under spark discharges on Al, Ti, Ta, Nb, Zr and their alloys for the production of decorative layers on these metals.
  • oxide ceramic layers on the aforementioned metals which have a substantially higher layer thickness up to 150 ⁇ m, are abrasion-resistant and corrosion-resistant and have a high flexural fatigue strength.
  • pure aluminum and, inter alia, aluminum and its alloys are AIMn alloys; AIMnCu; AIMgI; Almgl, 5; E-AIMgSi; AIMgSi0.5; AIZnMgCu0.5; AIZnMgCu1.5; G-AISi-12; G-AISi5Mg; G-AISi8Cu3; G-AICu4Ti; G-AICu4TiMg understood.
  • magnesium casting alloys of the ASTM designations AS41, AM60, AZ61, AZ63, AZ81, AZ91, AZ92, HK31, QE22 are particularly suitable for the purposes of the invention.
  • TiA16V4 Pure titanium or titanium alloys such as TiA16V4; TiA15Fe2.5 and others deploy.
  • the chloride-free electrolyte bath can contain the inorganic anions customary in processes for plasma chemical anodic oxidation, namely phosphate, borate, silicate, aluminate, fluoride or anions of inorganic acids such as citrate, oxalate and acetate.
  • the electrolyte bath preferably contains phosphate, borate and fluoride ions in combination and in an amount of at least 0.1 mol / l of each of these anions up to a total of 2 mol / l.
  • the cations of the electrolyte bath are chosen so that they form salts which are as soluble as possible with the respective anions in order to enable high salt concentrations and viscosities. This is usually the case with alkali, ammonium, alkaline earth and aluminum ions up to 1 mol / I.
  • the electrolyte bath contains urea, hexamethylenediamine, hexamethylenetetramine, glycol or glycerin in an amount up to a total of 1.5 mol / l as a stabilizer.
  • very dilute electrolyte baths of the types described above can also be used Use a composition in which the concentration of the anions is only 0.01 to 0.1 mol / l.
  • the pH value is between 10 and 12, preferably 11. Due to the low conductivity of this electrolyte bath, the final voltage value can reach up to 2,000 V. The energy input caused by the plasma chemical reaction is accordingly very high.
  • the oxide ceramic layer that forms on the aluminum materials consists of corundum, as shown by X-ray diffraction studies. The oxide ceramic layer is hardened up to 2,000 HV. These oxide ceramic layers can be used in particular where extremely high abrasive wear protection is required.
  • the choice of the voltage and current form such as direct, alternating, three-phase, pulse and / or multiphase alternating current in frequencies up to 500 Hz, surprisingly has no influence on the layer formation process for producing the ceramic layer on the metals.
  • the power supply for plasma chemical anodizing to form the ceramic layer takes place in such a way that the required current density of at least 1 A / dm 2 is kept constant and that the voltage is brought to a final value which is established.
  • the final voltage value is between 50 and 400 volts and is determined by the metal used or by its alloy components, by the composition of the electrolyte bath and by its bath management.
  • the invention also relates to the objects made of barrier layer-forming metals or their alloys produced with the method according to the invention with plasma-chemically produced oxide ceramic layers with a thickness of 40 to 150 ⁇ m, preferably 50 to 120 ⁇ m.
  • a sample plate made of AIMgSi1 with a surface area of 2 dm 2 is degreased and then rinsed with distilled water.
  • the sample thus treated is in an aqueous / organic chloride-free electrolyte bath of the composition at a current density of 4 A / dm 2 and an electrolyte temperature of 12 ° C ⁇ 2 ° C plasma-anodized. After a coating time of 60 minutes, the final voltage value of 250 V is reached.
  • the ceramicized sample plate is rinsed and dried.
  • the layer thickness of the ceramic layer is 100 ⁇ m.
  • the hardness of the ceramic layer was determined to be 750 (HV 0.015).
  • a die-cast housing made of GD-AISi12 with a surface area of 1 dm 2 is treated in a stain, half of which consists of 40% HF and 65% HN0 3 , for 1 minute at room temperature and then rinsed with distilled water.
  • the die-cast housing thus pickled is oxidized in the aqueous / organic chloride-free electrolyte bath from Example 1 at a current density of 8 A / dm2 and an electrolyte temperature of 10 ° C. ⁇ 2 ° C. in a plasma-chemical-anodic manner. After a coating time of 30 minutes, a final voltage value of 216 volts is registered.
  • the ceramic die-cast housing is rinsed and dried.
  • the layer thickness of the ceramic layer is 40 ⁇ m.
  • a sample plate made of a magnesium alloy of type AZ 91 with a surface area of 1 dm 2 is pickled in 40% hydrofluoric acid at room temperature for 1 minute.
  • the sample treated in this way is oxidized in an aqueous / organic chloride-free electrolyte bath according to Example 1 at a current density of 4 A / dm 2 and an electrolyte temperature of 12 ° C. ⁇ 2 ° C. in a plasma-chemical-anodic manner.
  • the ceramic layer has a layer thickness of 50 ⁇ m.
  • a rod made of pure titanium (length: 30 mm, diameter: 5 mm) is pickled in a pickle as in Example 2 and then rinsed with distilled water.
  • the sample treated in this way is in an aqueous chloride-free electrolyte bath of the composition: at a current density of 18 A / dm2 and an electrolyte temperature of 10 ° C ⁇ 2 ° C plasma-chemical-anodized.
  • the ceramicized rod is rinsed with distilled water and dried.
  • the layer thickness is 40 ⁇ m.
  • a gear wheel made of AIMgSi1 with a surface area of 6 dm 2 is degreased and rinsed with distilled water.
  • An aqueous / organic chloride-free electrolyte bath is an electrolyte bath from Example 1 diluted 100 times with water, which additionally contains 0.1 mol / l sodium aluminate and sodium silicate.
  • the gearwheel is oxidized at a current density of 10 A / dm 2 by plasma chemical anodizing. After a coating time of 120 minutes, a final voltage value of 800 volts is reached.
  • the ceramized gear is rinsed and dried.
  • the layer thickness of the oxide ceramic layer is 130 ⁇ m.
  • the hardness of the ceramic layer was determined to be 1900 HV (0.1).
  • the service life of the gear coated in this way increases fourfold compared to the conventional anodized gear of the same size.
  • An ultrasonic sonotrode made of AlZnMgCu1.5 with a surface area of 6.4 dm 2 is degreased and then rinsed with distilled water.
  • the ultrasound sonotrode treated in this way is oxidized in an aqueous / organic chloride-free electrolyte bath, as described in Example 1, at a current density of 3.5 A / dm 2 and an electrolyte temperature of 15 ° C. in a plasma-chemical-anodic manner. After a coating time of 25 minutes, the chip rated value of 250 volts reached.

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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)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Laminated Bodies (AREA)

Claims (10)

1. Procédé de production de couches céramiques d'oxydes sur AI, Mg, Ti, Ta, Zr, Nb, Hf, Sb, W, Mo, V, Bi ou leurs alliages par oxydation anodique plasma-chimique, caractérisé en ce qu'une densité de courant au moins égale à 1 A/dm2 est maintenue constante dans un bain électrolytique dépourvu de chlorure ayant une valeur de pH de 2 à 8 à une température constante du bain de -30 à + 15 ° C, jusqu'à ce que la tension s'établisse à une valeur finale.
2. Procédé suivant la revendication 1, caractérisé en ce que la température du bain s'élève à une valeur de -10 à + 15 ° C.
3. Procédé suivant la revendication 1 ou la revendication 2, caractérisé en ce que la température du bain est maintenue constante dans les limites de ± 2 ° C.
4. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce que le bain contient moins de 5 x 10-3 mole/I d'ions chlorure.
5. Procédé suivant l'une des revendications 1 à 4, caractérisé en ce que le bain électrolytique contient des ions phosphate, borate et fluorure jusqu'à un total de 2 moles/I.
6. Procédé suivant l'une des revendications 1 à 5, caractérisé en ce que le bain électrolytique contient jusqu'à 1,5 mole/I d'un agent stabilisant du groupe de l'urée, de l'hexaméthylènediamine et de l'hexaméthylènetétramine, du glycol et du glycérol.
7. Procédé de production de couches céramiques d'oxydes particulièrement résistantes à l'usure sur de l'aluminium ou ses alliages par oxydation anodique plasmachimique à une densité de courant d'au moins 5 A/dm2 qui est maintenue constante jusqu'à ce que la tension s'établisse à une valeur finale, avec utilisation de l'électrolyte suivant l'une des revendications 1 à 6 après dilution à une concentration de 0,01 à 0,1 mole/I et élévation de la valeur du pH à 10-12, de préférence à 11.
8. Procédé suivant l'une des revendications 1 à 7, caractérisé en ce que la tension a des fréquences allant jusqu'à 500 Hz.
9. Objet en aluminium, magnésium, titane ou leurs alliages portant une couche céramique d'oxyde produite par voie plasma-chimique, caractérisé en ce que la couche céramique d'oxyde a une épaisseur de 40 à 150 um, de préférence de 50 à 120 um.
10. Objet en aluminium ou en alliages d'aluminium suivant la revendication 9, caractérisé en ce que la couche céramique d'oxyde produite pae voie plasma-chimique est constituée de corindon.
EP92120006A 1991-11-27 1992-11-25 Procédé de préparation d'une couche d'oxyde céramique modifiée sur des métaux formant couche barrière. Expired - Lifetime EP0545230B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4139006 1991-11-27
DE4139006A DE4139006C3 (de) 1991-11-27 1991-11-27 Verfahren zur Erzeugung von Oxidkeramikschichten auf sperrschichtbildenden Metallen und auf diese Weise erzeugte Gegenstände aus Aluminium, Magnesium, Titan oder deren Legierungen mit einer Oxidkeramikschicht

Publications (3)

Publication Number Publication Date
EP0545230A1 EP0545230A1 (fr) 1993-06-09
EP0545230B1 true EP0545230B1 (fr) 1995-06-28
EP0545230B2 EP0545230B2 (fr) 2003-03-12

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EP92120006A Expired - Lifetime EP0545230B2 (fr) 1991-11-27 1992-11-25 Procédé de préparation d'une couche d'oxyde céramique modifiée sur des métaux formant couche barrière.

Country Status (5)

Country Link
US (2) US5385662A (fr)
EP (1) EP0545230B2 (fr)
JP (1) JP2912101B2 (fr)
AT (1) ATE124472T1 (fr)
DE (2) DE4139006C3 (fr)

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DE202008010896U1 (de) 2008-08-05 2008-10-23 AHC Oberflächentechnik GmbH Werkstoff, insbesondere Bauteile, mit verbesserten Verschleißschutzschichten
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DE4139006C3 (de) 2003-07-10
DE4139006A1 (de) 1993-06-03
ATE124472T1 (de) 1995-07-15
EP0545230B2 (fr) 2003-03-12
JPH05239692A (ja) 1993-09-17
US5385662A (en) 1995-01-31
DE4139006C2 (de) 1996-10-24
EP0545230A1 (fr) 1993-06-09
JP2912101B2 (ja) 1999-06-28
US5811194A (en) 1998-09-22
DE59202722D1 (de) 1995-08-03

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