EP0333048B1 - Procédé pour l'obtention de revêtements sur le magnésium et les alliages de magnésium résistant la corrosion et à l'usure - Google Patents

Procédé pour l'obtention de revêtements sur le magnésium et les alliages de magnésium résistant la corrosion et à l'usure Download PDF

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Publication number
EP0333048B1
EP0333048B1 EP89104236A EP89104236A EP0333048B1 EP 0333048 B1 EP0333048 B1 EP 0333048B1 EP 89104236 A EP89104236 A EP 89104236A EP 89104236 A EP89104236 A EP 89104236A EP 0333048 B1 EP0333048 B1 EP 0333048B1
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EP
European Patent Office
Prior art keywords
magnesium
process according
protective layer
direct current
ions
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
EP89104236A
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German (de)
English (en)
Other versions
EP0333048A1 (fr
Inventor
Edith Luise Schmeling
Benno Prof.Dr.-Ing. Röschenbleck
Michael Hans Weidemann
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Electro Chemical Engineering GmbH
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Electro Chemical Engineering GmbH
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Publication date
Application filed by Electro Chemical Engineering GmbH filed Critical Electro Chemical Engineering GmbH
Priority to AT89104236T priority Critical patent/ATE89613T1/de
Publication of EP0333048A1 publication Critical patent/EP0333048A1/fr
Application granted granted Critical
Publication of EP0333048B1 publication Critical patent/EP0333048B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C25D11/30—Anodisation of magnesium or alloys based thereon

Definitions

  • Various methods are known for increasing the corrosion resistance and wear resistance of the surface of magnesium and magnesium alloys. These processes include chemical and electrochemical processes such as chromating and anodizing.
  • the degreased magnesium parts connected as anode are immersed in an electrolyte bath. If a current flows in this electrolyte, the negatively charged anions migrate to the anode and are discharged there. This creates atomic oxygen, which leads to the formation of magnesium oxide. This anodic coating is firmly anchored to the magnesium surface.
  • the oxidizing agents or peroxy compounds used in the known processes for the anodic oxidation of magnesium or magnesium alloys contain transition metals such as e.g. Chromium, vanadium or manganese. This has proven to be disadvantageous because some of these transition metal compounds are built into the protective layer produced on the magnesium surface, which can be seen from the color. The installation of these transition metal compounds leads to a reduction in the corrosion and wear resistance of the protective layer.
  • anodizing solution for anodic oxidation of magnesium or its alloys which is produced by dissolving silicate, carboxylate and alkali hydroxide in water and which can additionally contain borate, fluoride and phosphate (DE-A-37 15 663).
  • This anodizing solution is alkali-rich.
  • the object of the present invention is therefore to provide a method for producing a protective layer on magnesium or magnesium alloys by anodic oxidation, in which a protective layer with increased corrosion resistance and wear resistance.
  • a particularly corrosion-resistant and wear-resistant protective layer can be produced by anodic oxidation on magnesium or magnesium alloys if the conditions specified in the main claim are met at the same time.
  • borate or sulfate anions are used according to the invention which form peroxides, which decompose easily, but which easily replicate due to the high current density in the pores of the protective layer formed.
  • Borate and Sulfate anions have proven to be particularly suitable here, since they only reach the cathode to a small extent as a result of the transfer and are reduced there.
  • the electrolyte must contain such anions that form poorly soluble compounds with the magnesium to be oxidized.
  • phosphate ions in combination with fluoride ions are suitable here. If, according to the invention, a magnesium-aluminum alloy is anodically oxidized, the aluminum illuminations formed result which, with magnesium ions, result in a poorly soluble magnesium aluminate.
  • the protective layer that forms must also have pores or conductive points so that a sufficient current flow is ensured. This is achieved by the fluoride ions added to the electrolyte bath according to the invention.
  • the bath is therefore adjusted to a pH of 5 to 12, preferably between 8 and 9, in particular by adding buffering substances.
  • the desired concentration of anions to be incorporated into the protective layer in the vicinity of the surface to be coated can be achieved by supplying a briefly interrupted direct current instead of a constant direct current or by reversing the polarity for a short time, in order to prevent the formation of magnesium phosphate and magnesium fluoride and - If a magnesium alloy containing aluminum is oxidized - to enable the formation of magnesium aluminate.
  • the current density is in particular 1 to 2 A / dm2. It is preferable to work with a constant direct current with superimposed alternating current with a frequency of two 10 and 100 Hz.
  • the superimposition is carried out by connecting the direct current source and the sine current source in series, the alternating voltage component of which is 15-30% of the direct voltage component.
  • Frequency adjustable frequency can be generated to superimpose the direct current with the help of frequency converters.
  • These are, for example, motor-generator units with adjustable speed, in which a change in the speed leads to a proportional change in frequency.
  • the AC voltage is adjusted to the desired percentage of the DC voltage by means of a regulating transformer in accordance with the DC voltage.
  • the frequency with which the alternating current is available from the network is preferably selected, for example in the Federal Republic of Germany at 50 Hz or in the USA at 60 Hz.
  • the anodic oxidation according to the invention can also be carried out with rectified alternating current, the frequency of which is 50 Hz or 60 Hz, with a ripple of 15 to 35%.
  • the rectification can take place both through one-way circuit M1, preferably through center circuit M2 (according to DIN draft 41 761).
  • the current generated in this way is smoothed by suitable inductances, which reduce the ripple to 15 - 35% (literature e.g.: R. Jäger, Power Electronics Fundamentals and Applications, Berlin 1977), page 75).
  • a direct current pulsed at 30 to 70 Hz the switch-off time between two voltage pulses being equal to or twice as long as the duration of the voltage pulses.
  • the pulsing of the direct current can take place both by electronic and mechanical switches which are controlled by a frequency generator. Suitable electronic switches are e.g. Switching thyristors.
  • a similar current profile can also be generated by one-way rectification M1 (according to DIN Draft 41 761) of an alternating current from 30 to 70 Hz with leading edge.
  • the length of the voltage pulses can be controlled by changing the phase gating angle (literature e.g.: O. Limann, Electronics without Ballast, Kunststoff 1973, page 347).
  • Amines which react weakly alkaline and generally have dissociation constants between 10 ⁇ 2 and 10 ⁇ 7 are particularly suitable for buffering the electrolyte bath.
  • Cyclic amines such as pyridine, ⁇ -picoline, piperidine and piperazine are particularly suitable as such amines. These amines are usually readily water soluble.
  • Other readily water-soluble amines that can be used are, for example, sodium sulfanilate, dimethylamine, ethylamine, diethylamine or triethylamine. Hexamethylenetetramine is used in a particularly preferred manner.
  • the voltage rises to 400 volts.
  • a low-alkali aqueous electrolyte bath according to the invention is preferably to be understood as one which contains less than 100 mg / l alkali ions.
  • the ions to be avoided are those of the alkali metals lithium, sodium, potassium etc.
  • the ammonium ion is not considered an alkali ion here.
  • the content of the borate or sulfate ions in the aqueous electrolyte bath is preferably 10 to 80 g / l.
  • the content of phosphate ions calculated as H3PO4 is preferably between 10 and 70 g / l.
  • the amount of the fluoride ions to be used in combination with the phosphate ions is calculated as HF 5 to 35 g / l.
  • the workpieces made of magnesium or magnesium alloys are subjected to the usual chemical pretreatments for degreasing, in particular an alkaline cleaning with a strongly alkaline bath. This is usually followed by acid pickling, for example with dilute aqueous solutions of phosphoric acid and sulfuric acid and, if necessary, also activation with hydrofluoric acid.
  • the protective layers produced according to the invention on the surface of the magnesium alloys or the pure magnesium are preferably also painted or subjected to an aftertreatment.
  • the protective layers produced according to the invention form a very good primer for lacquers, as are common for workpieces made of magnesium, aluminum or zinc.
  • These include Two-component paints based on polyurethane, acrylic resin, epoxy resin and phenolic resin paints.
  • Products 3, 4, 5 and 6 showed a clearly recognizable increase in the corrosion resistance of the layers.
  • the layer treated in product 6 also resulted in a significant reduction in the coefficient of friction.
  • an aftertreatment can also be carried out with a solid lubricant which can anchor itself in the existing pores.
  • lubricants are, for example, fluorinated and / or chlorinated aliphatic and aromatic hydrocarbon compounds as well as molybdenum disulfide and graphite.
  • a preferred aftertreatment of the protective layers according to the invention is carried out with the aqueous solution of an alkali silicate.
  • the Mg (OH) 2 present in the protective layer reacts with the alkali silicate to form sparingly soluble magnesium silicate and alkali hydroxide.
  • the workpiece with the protective layer removed from the alkali silicate bath is preferably exposed to an atmosphere rich in carbon dioxide.
  • the remaining "water glass” forms from the silicate treatment with the CO2 of the atmosphere SiO2 and alkali carbonate, since the stronger carbonic acid displaces the weaker silica from its compound.
  • the pores of the protective layer are closed by the SiO2, this process being accelerated by the gassing with CO2. Since with the use of stronger acids in the outer region of the pores, SiO2 precipitates rapidly, the alkali silicate located in the interior of the pores can then no longer react. The continuous precipitation of SiO2 in the pores by the weak carbonic acid, however, results in a much better protection against corrosion.
  • the present invention further relates to magnesium alloys coated with a protective layer containing magnesium phosphate and magnesium fluoride with a thickness of 15 to 30 ⁇ m and a wear resistance, measured with the Taber abraser (CS 10, 10 N), of less than 20 mg mass loss after 10,000 revolutions are.
  • a protective layer containing magnesium phosphate and magnesium fluoride with a thickness of 15 to 30 ⁇ m and a wear resistance, measured with the Taber abraser (CS 10, 10 N), of less than 20 mg mass loss after 10,000 revolutions are.
  • a protective layer which meets these conditions can be applied, for example, using the method according to the invention described above.
  • the corrosion resistance of the magnesium alloys according to the invention is preferably less than 10 corrosion points / dm 2 after a sample of the alloy has been exposed to an exposure time of 240 h in a salt spray test in accordance with DIN 50021 SS.
  • the magnesium casting alloys of the ASTM designations AS41, AM 60, AZ61, AZ63, AZ81, AZ91, AZ92, HK31, QE22, ZE41, ZH62, ZK51, ZK61, are particularly suitable for the process according to the invention for producing corrosion-resistant and wear-resistant protective layers.
  • the protective layer preferably additionally contains hydroxide, borate, aluminate, phenolate or silicate ions.
  • the protective layer preferably contains, in particular in the pores, silicon dioxide, which can be obtained by the after-treatment of the protective layer described above with an aqueous solution of an alkali silicate.
  • the color of the protective layer applied to the magnesium alloys according to the invention is preferably white to whitish-gray or beige.
  • the surfaces of magnesium or magnesium alloys to be treated were first pretreated in an alkaline cleaning bath.
  • This cleaning bath had the following composition: Sodium hydroxide 50 g / l Trisodium phosphate 10 g / l Wetting agent / synthetic soap 1 g / l
  • the pickling was carried out at a temperature of 20 ° C., the treatment time being about 30 seconds. After pickling, the surface sample was activated in hydrofluoric acid.
  • the anodic oxidation was then carried out to produce the protective layer according to the invention.
  • An electrolyte bath with the following composition was used: HF 30 g / l H3PO4 60 g / l H3BO3 70 g / l
  • the anodic oxidation was carried out with a direct current superimposed with an alternating current of 50 Hz. A voltage rising to 240 V was used. The duration of the anodic oxidation was approximately 15 minutes. The layer thickness of the protective layer produced on the treated surfaces was approximately 20 ⁇ m.
  • the magnesium alloy AZ 91 was anodized in an electrolyte of the following composition and under the specified conditions: Hydrofluoric acid (H2F2) (40%) 28 g / l Phosphoric acid (H3PO4) (98%) 58 g / l Boric acid (H3BO3) 35 g / l Hexamethylenetetramine 360 g / l pH value: 7.0 - 7.3 adjusted with NH4OH (25%) Current density: 1.4 A / dm2 (rectified alternating current, ripple approx. 28%) Final voltage: 325 V Electrolyte temperature: 15 ° C Exposure time: 15 minutes
  • the layer thickness obtained was 21 ⁇ m.
  • the wear resistance in the Taber Abraser test was 30 mg mass loss after 104 revolutions.
  • the corrosion and wear resistance of the layer obtained was analogous to that described in Example 2.

Claims (15)

  1. Procédé d'obtention de revêtements protecteurs résistant à la corrosion et à l'usure sur du magnésium ou sur des alliages de magnésium par oxydation anodique, caractérisé en ce qu'on utilise un bain aqueux d'électrolytes qui contient
    a) 10 à 80 g/l d'ions borate ou sulfate,
    b) 10 à 70 g/l d'ions phosphate, et
    c) 5 à 35 g/l d'ions fluorure
    et moins de 100 mg/l d'ions alcalins et dont le pH peut être ajusté à une valeur de 5 à 11, de préférence de 7 à 9,
    et en ce qu'on opère avec un courant continu en faisant croître la tension jusqu'à 400 volts et en interrompant brièvement le courant continu et en inversant sa polarité.
  2. Procédé suivant la revendication 1, caractérisé en ce qu'on opère avec un courant continu constant auquel on superpose un courant alternatif de 10 à 100 Hz dont la densité de courant s'élève à 15-35 % du courant continu.
  3. Procédé suivant la revendication 1, caractérisé en ce qu'on opère avec du courant alternatif redressé ayant une ondulation de 15 à 35 %.
  4. Procédé suivant la revendication 1, caractérisé en ce qu'on opère avec un courant continu pulsé de 30-70 Hz, le temps de coupure entre deux impulsions de tension étant aussi long et jusqu'à deux fois plus long que la durée des impulsions de tension.
  5. Procédé suivant l'une des revendications 1 à 4, caractérisé en ce que le bain est tamponné avec une amine.
  6. Procédé suivant l'une des revendications 1 à 5, caractérisé en ce que le bain est tamponné par l'hexaméthylènetétramine.
  7. Procédé suivant l'une des revendications 1 à 6, caractérisé en ce qu'on opère avec une densité de courant de 1 à 2 A/dm².
  8. Procédé suivant l'une des revendications 1 à 7, caractérisé en ce que le revêtement est post-traité avec la solution aqueuse d'un silicate alcalin.
  9. Procédé suivant la revendication 8, caractérisé en ce que la pièce usinée portant le revêtement protecteur, retirée du bain de silicate alcalin, est exposée à une atmosphère riche en anhydride carbonique.
  10. Procédé suivant l'une des revendications 1 à 9, caractérisé en ce que la couche protectrice est recouverte de laque.
  11. Alliage de magnésium portant un revêtement d'oxyde protecteur contenant du phosphate de magnésium et du fluorure de magnésium, en une couche de 15 à 30 µm d'épaisseur et ayant une résistance à l'usure, mesurée avec l'appareil d'abrasion de Taber (CS 10, 10N) représentant une perte de masse de moins de 20 mg après 10 000 tours, pouvant être obtenu par le procédé suivant les revendications 1 à 10.
  12. Alliage de magnésium suivant la revendication 11, caractérisé par une résistance à la corrosion de moins de 10 points de corrosion au dm² après un temps d'exposition de 240 h dans l'essai de pulvérisation de sel selon la norme DIN 50 021 SS.
  13. Alliage de magnésium suivant la revendication 11 ou 12, caractérisé en ce que le revêtement protecteur contient en outre de l'hydroxyde, du borate, de l'aluminate, du phénate ou du silicate de magnésium.
  14. Alliage de magnésium suivant l'une des revendications 11 à 13, caractérisé en ce que le revêtement protecteur contient du dioxyde de silicium, en particulier dans les pores.
  15. Alliage de magnésium suivant l'une des revendications 11 à 14, caractérisé en ce que le revêtement protecteur produit a une couleur allant du blanc au gris blanchâtre ou au beige.
EP89104236A 1988-03-15 1989-03-10 Procédé pour l'obtention de revêtements sur le magnésium et les alliages de magnésium résistant la corrosion et à l'usure Expired - Lifetime EP0333048B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89104236T ATE89613T1 (de) 1988-03-15 1989-03-10 Verfahren zur erzeugung von korrosions- und verschleissbestaendigen schutzschichten auf magnesium und magnesiumlegierungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3808609 1988-03-15
DE3808609A DE3808609A1 (de) 1988-03-15 1988-03-15 Verfahren zur erzeugung von korrosions- und verschleissbestaendigen schutzschichten auf magnesium und magnesiumlegierungen

Publications (2)

Publication Number Publication Date
EP0333048A1 EP0333048A1 (fr) 1989-09-20
EP0333048B1 true EP0333048B1 (fr) 1993-05-19

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US (1) US4978432A (fr)
EP (1) EP0333048B1 (fr)
JP (1) JPH01301888A (fr)
AT (1) ATE89613T1 (fr)
DE (2) DE3808609A1 (fr)

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Also Published As

Publication number Publication date
US4978432A (en) 1990-12-18
EP0333048A1 (fr) 1989-09-20
JPH01301888A (ja) 1989-12-06
DE58904381D1 (de) 1993-06-24
JPH0551679B2 (fr) 1993-08-03
ATE89613T1 (de) 1993-06-15
DE3808609A1 (de) 1989-09-28

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