EP0054743A1 - Process for the chemical removal of oxidic layers from titanium or titanium alloys - Google Patents

Process for the chemical removal of oxidic layers from titanium or titanium alloys Download PDF

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Publication number
EP0054743A1
EP0054743A1 EP81109537A EP81109537A EP0054743A1 EP 0054743 A1 EP0054743 A1 EP 0054743A1 EP 81109537 A EP81109537 A EP 81109537A EP 81109537 A EP81109537 A EP 81109537A EP 0054743 A1 EP0054743 A1 EP 0054743A1
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Prior art keywords
titanium
metals
nickel
alloys
fluoride
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German (de)
French (fr)
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EP0054743B1 (en
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Ludwig Fahrmbacher-Lutz
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FAHRMBACHER LUTZ LUDWIG
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FAHRMBACHER LUTZ LUDWIG
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Classifications

    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • 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
    • 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
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/08—Refractory metals

Definitions

  • the invention relates to a method for the chemical removal of oxide layers from objects made of metals, in particular titanium, titanium alloys, nickel, nickel alloys and chromium-nickel steels, for subsequent coating with metals, in particular in an organic electrolyte.
  • workpieces made of titanium, titanium alloys, nickel, nickel alloys and chrome-nickel steels always have an oxide layer on their surface, which spontaneously forms again after removal by chemical or mechanical means in air or in aqueous media.
  • the object of the invention is therefore to create a method by means of which it is possible to effectively remove the oxide films of workpieces made of metals, in particular the aforementioned metals or alloys, without impairing the dimensional accuracy of the workpieces and the material properties, remove screws, for example.
  • the organic media used are those in which both the hydrogen fluoride and alkali metal fluoride or ammonium fluoride can be dissolved.
  • the media preferably consist of alcohols, in particular methanol.
  • the treatment is preferably carried out with a medium containing 3 to 8% by weight of hydrogen fluoride, 5 to 8% by weight of ammonium fluoride and 5 to 10% by weight of an alkali fluoride, in particular sodium fluoride.
  • the treatment temperature is preferably between 10 ° C and 50 ° C.
  • the removal of the oxide layer can preferably be supported electrochemically by the process according to the invention, the procedure being in particular such that adding a conductive salt, e.g. Sodium sulfate, and using counter electrodes e.g. can consist of titanium or platinum, alternately switching the workpieces anodically and cathodically.
  • a conductive salt e.g. Sodium sulfate
  • counter electrodes e.g. can consist of titanium or platinum
  • the workpieces are preferably rinsed with an inert solvent under a water-vapor and oxygen-free atmosphere, in particular in an inert gas atmosphere, and they are fed to the device in which the metal coating, preferably by electrolytic means, is also carried out under oxygen-free and water-vapor-free conditions , takes place, in particular aluminum, copper, nickel and silver, but also germanium, beryllium, molybdenum, tungsten and zirconium.
  • electrolytic deposition known electrolyte systems can be used (US Pat. No. 2,763,605; Hurley FH, Wier TP "Electrodeposition of Al from nonaquous solutions", J. Elektrochem. Soc.
  • the workpiece Under inert gas, the workpiece is placed in a pickling solution consisting of a methanolic solution of 8% hydrogen fluoride, 5% ammonium fluoride and 10% sodium fluoride brings.
  • This solution contains platinum electrodes which, like the workpiece, are connected to a voltage source. These make it possible to change the potential from + 10 V to - 10 V within one second.
  • the electrolyte consists of an ethereal solution of 3 moles of aluminum chloride and about 1 mole of LiH or LiAlH and allows it to be reversed direct current at a current density of about 3 A. / Dm 2 smooth, dense aluminum layers of approx. 0.08 cm, whereby excellent adhesion to the base material is achieved.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Die Erfindung betrifft das Verfahren zur chemischen Entfernung von Oxidschichten von Gegenständen aus Metallen, insbesondere Titan, Titanlegierungen, Nickel, Nickellegierungen sowie Chrom-Nickel-Stählen, zur anschließenden Beschichtung mit Metallen mit einem wasserfreien organischen Medium mit einem Gemisch aus Fluorwasserstoff und einem oder mehreren Alkalifluoriden und/oder Ammoniumfluorid. Mit diesem Verfahren können von Werkstücken aus den genannten Metallen bzw. Metallegierungen unter exakter Beibehaltung der Maßhaltigkeit störende Oxidfilme vor einer anschließenden Beschichtung mit anderen Metallen, insbesondere Aluminium, Zink oder Silber, entfernt werden.The invention relates to the process for the chemical removal of oxide layers from objects made of metals, in particular titanium, titanium alloys, nickel, nickel alloys and chromium-nickel steels, for subsequent coating with metals with an anhydrous organic medium with a mixture of hydrogen fluoride and one or more alkali metal fluorides and / or ammonium fluoride. This method can be used to remove disruptive oxide films from workpieces made of the metals or metal alloys mentioned, while maintaining their dimensional accuracy, before subsequent coating with other metals, in particular aluminum, zinc or silver.

Description

Die Erfindung betrifft ein Verfahren zur chemischen Entfernung von Oxidschichten von Gegenständen aus Metallen, insbesondere Titan, Titanlegierungen, Nickel, Nickellegierungen sowie Chrom-Nickel-Stählen, zur anschließenden Beschichtung mit Metallen, insbesondere in einem organischen Elektrolyten.The invention relates to a method for the chemical removal of oxide layers from objects made of metals, in particular titanium, titanium alloys, nickel, nickel alloys and chromium-nickel steels, for subsequent coating with metals, in particular in an organic electrolyte.

Insbesondere Werkstücke aus Titan, Titanlegierungen, Nickel, Nickellegierungen sowie Chrom-Nickel-Stählen besitzen an ihrer Oberfläche immer eine Oxidschicht, die sich nach einem Entfernen mit chemischen oder mechanischen Mitteln an der Luft oder in wäßrigen Medien spontan wieder neu ausbildet.In particular, workpieces made of titanium, titanium alloys, nickel, nickel alloys and chrome-nickel steels always have an oxide layer on their surface, which spontaneously forms again after removal by chemical or mechanical means in air or in aqueous media.

Eine haftfeste Beschichtung der Werkstoffe ist daher nur dann möglich, wenn diese Schichten vor dem Beschichten entfernt werden und die anschließende Beschichtung in einem organischen Elektrolyten erfolgt, wobei während und nach der Oxidschichtentfernung unter absolut sauerstoff- und wasserdampffreien Bedingungen in geschlossenen Apparaturen gearbeitet werden muß, die beispielsweise unter Argon oder Stickstoff stehen.An adherent coating of the materials is therefore only possible if these layers are removed before coating and the subsequent coating takes place in an organic electrolyte, during and after the oxide layer removal under absolutely oxygen and water vapor-free conditions in closed equipment that must be worked for example under argon or nitrogen.

Zur Entfernung von Oxidschichten von Werkstücken aus den genannten Metallen bzw. Legierungen sind Verfahren bekannt, die im Vakuum arbeiten, wobei eine Reinigung durch Sputtern erfolgt (DE-OS 28 09 444). Ferner ist eine Reinigung unter Einsatz von Metallschmelzen, die mit einem Flußmittel bedeckt sind,bekannt (US-PS 2 992 135). Bei diesem letzteren Verfahren kann es insbesondere dann, wenn aus Gründen einer verbesserten Haftung ein Diffusionsglühen durchgeführt wird, zu einer unerwünschten Bildung von intermetallischen Phasen kommen, die eine Versprödung des Werkstoffes verursachen (Faulkner G.E., Lewis W.J., "Recent development in Ti - brazing", DMIL Mem. (1960) Nr. 45, Battell Mem. Inst. Columbus, Ohio und Odgen H.R., Holden F.L. "Metallography of Ti alloys" TML Report 103, Battell Mem. Inst. Columbus, Ohio): Dieses Ver- 'fahren ist für hochwertige endbearbeitete Werkstücke mit hohen Anforderungen an die Maßhaltigkeit auch deshalb nicht geeignet, da die Maßhaltigkeiten bei den Temperaturen der Schmelzen leiden. Die erwähnten Vakuumverfahren sind nicht nur störanfällig, sondern auch mit dem Nachteil sehr hoher Investitionskosten behaftet.Methods are known for removing oxide layers from workpieces from the metals or alloys mentioned, which work in a vacuum, cleaning being carried out by sputtering (DE-OS 28 09 444). Furthermore, cleaning using molten metal covered with a flux is known (US Pat. No. 2,992,135). This latter method can lead to undesired formation of intermetallic phases, which cause embrittlement of the material, in particular if diffusion annealing is carried out for reasons of improved adhesion (Faulkner GE, Lewis WJ, "Recent development in Ti-brazing" , DMIL Mem. (1960) No. 45, Battell Mem. Inst. Columbus, Ohio and Odgen HR, Holden FL "Metallography of Ti alloys" TML Re port 103, Battell Mem. Inst. Columbus, Ohio): This method is also unsuitable for high-quality finished workpieces with high dimensional accuracy requirements because the dimensional stability suffers from the temperatures of the melts. The vacuum processes mentioned are not only prone to failure, but also have the disadvantage of very high investment costs.

Es ist bekannt (White E.L. Miller, P.D. Peoples R.S. "Antigalling coatings and lubricants of Ti", TML Report 34, Titanium Metallurgical Laboratory Battell Institut), daß eine Beschichtung von Titan mit Aluminium zu einer Minderung des Werkzeugverschleißes bei Warmformvorgängen sowie zu einer Verhinderung einer starken Oxidation des Titans führt. Es ist ferner bekannt, daß metallische Schichten auf Titanoberflächen zu einer Verbesserung der Haftung von Schmiermitteln führen und damit einem starken Gleitverschleiß entgegenwirken (Factica N. "Lubrication of Ti" WDL Techn. Report 57-61 II ASTIA Doc. 155564 (1958); Laat de F.G.A., Adams T. "Inhibiting the Wear and Galling Characteristics of Ti", Metals Eng. Quarterly 8 (39-48) (1968); Padberg D.L., Crosby J.J., "Fretting Resistant Coatings for Ti alloys", 2. intern. Konferenz Ti 1972 MIT Cambridge/Mass und Kingsbary E.P. Rabinowicz E. "Friktion and Wear of Metals" Trans. ASME - Paper 58- Lub. 6 (1968). Eine Beschichtung von Titan mit Silber ermöglicht einen einfachen Hartlötprozeß (Odgen H.R., Holden F.L. "Metallography of Ti alloys" TML Report 103, Battell Mem. Inst. Columbus, Ohio). Ferner ist es bekannt, daß auf Titan aufgebrachte Zinkschichten als Schutz vor Kontaktkorrosion bei in Aluminium eingesetzten Titanverbindungselementen dienen (Metalworking Produktion, Zincplated Titanium 104 (Nr. 30 S. 9 1960).It is known (White EL Miller, PD Peoples RS "Antigalling coatings and lubricants of Ti", TML Report 34, Titanium Metallurgical Laboratory Battell Institute) that a coating of titanium with aluminum reduces tool wear during thermoforming processes and prevents strong oxidation of the titanium leads. It is also known that metallic layers on titanium surfaces lead to an improvement in the adhesion of lubricants and thus counteract severe sliding wear (Factica N. "Lubrication of Ti" WDL Technical Report 57-61 II ASTIA Doc. 155564 (1958); Laat de FGA, Adams T. "Inhibiting the Wear and Galling Characteristics of Ti", Metals Eng. Quarterly 8 (39-48) (1968); Padberg DL, Crosby JJ, "Fretting Resistant Coatings for Ti alloys", 2nd intern. Conference Ti 1972 with Cambridge / Mass and Kingsbary EP Rabinowicz E. "Friction and Wear of Metals" Trans. ASME - Paper 58- Lub. 6 (1968). A coating of titanium with silver enables a simple brazing process (Odgen HR, Holden FL "Metallography of Ti alloys" TML Report 103, Battell Mem. Inst. Columbus, Ohio) Furthermore, it is known that zinc layers deposited on titanium serve as protection against contact corrosion in titanium connecting elements used in aluminum (metalworking production, zinc plated titanium) nium 104 (no. 30 p. 9 1960).

Es besteht daher der häufige Bedarf, Werkstücke aus Metallen, insbesondere Titan, Titanlegierungen, Nickel, Nickellegierungen sowie Chrom-Nickel-Stählen, mit einem Metall, insbesondere Aluminium, Zink oder Silber, insbesondere auf elektrolytischem Wege, zu beschichten, wobei im Falle der namentlich genannten Metalle bzw. Metallegierungen vorher der störende Oxidfilm unter exakter Beibehaltung der Maßhaltigkeit der Werkstücke entfernt werden muß.There is therefore a frequent need for workpieces made of metals, in particular titanium, titanium alloys, nickel, nickel alloys and chromium-nickel steels, with one metal, ins to coat special aluminum, zinc or silver, in particular by electrolytic means, whereby in the case of the metals or metal alloys mentioned by name, the disruptive oxide film must be removed beforehand while maintaining the dimensional accuracy of the workpieces.

Die Erfindung hat sich daher die Aufgabe gestellt, ein Verfahren zu schaffen, mit dessen Hilfe es möglich ist, die Oxidfilme von Werkstücken aus Metallen, insbesondere den vorstehend genannten Metallen bzw. Legierungen, in wirksamer Weise ohne Beeinträchtigung der Maßhaltigkeit der Werkstücke und der Werkstoffeigenschaften, beispielsweise von Schrauben, zu entfernen.The object of the invention is therefore to create a method by means of which it is possible to effectively remove the oxide films of workpieces made of metals, in particular the aforementioned metals or alloys, without impairing the dimensional accuracy of the workpieces and the material properties, remove screws, for example.

Diese Aufgabe wird durch die Erfindung gemäß dem Patentanspruch gelöst.This object is achieved by the invention according to the patent claim.

Als organische Medien werden solche verwendet, in denen sowohl der Fluorwasserstoff als auch Alkalifluoride bzw. Ammoniumfluoride lösbar sind. Vorzugsweise bestehen die Medien aus Alkoholen, insbesondere Methanol.The organic media used are those in which both the hydrogen fluoride and alkali metal fluoride or ammonium fluoride can be dissolved. The media preferably consist of alcohols, in particular methanol.

Die Behandlung erfolgt vorzugsweise mit einem Medium mit einem Gehalt von 3 bis 8 Gew.-% Fluorwasserstoff, 5 bis 8 Gew.-% Ammoniumfluorid und 5 bis 10 Gew.-% eines Alkalifluorids, insbesondere Natriumfluorid.The treatment is preferably carried out with a medium containing 3 to 8% by weight of hydrogen fluoride, 5 to 8% by weight of ammonium fluoride and 5 to 10% by weight of an alkali fluoride, in particular sodium fluoride.

Die Behandlungstemperatur liegt vorzugsweise zwischen 10°C und 50°C.The treatment temperature is preferably between 10 ° C and 50 ° C.

Die Entfernung der Oxidschicht kann vorzugsweise nach dem erfindungsgemäßen Verfahren elektrochemisch unterstützt werden, wobei man insbesondere in der Weise verfährt, daß man unter Zugabe eines Leitsalzes, z.B. Natriumsulfat, und unter Anwendung von Gegenelektroden, die z.B. aus Titan oder Platin bestehen können, die Werkstücke abwechselnd anodisch und kathodisch schaltet.The removal of the oxide layer can preferably be supported electrochemically by the process according to the invention, the procedure being in particular such that adding a conductive salt, e.g. Sodium sulfate, and using counter electrodes e.g. can consist of titanium or platinum, alternately switching the workpieces anodically and cathodically.

Nach der Entfernung der Oxidschicht werden die Werkstücke vorzugsweise mit einem inerten Lösungsmittel unter einer wasserdampf- und sauerstofffreien Atmosphäre gespült, insbesondere in einer Inertgasatmosphäre, wobei sie unter ebenfalls sauerstoff- und wasserdampffreien Bedingungen der Vorrichtung zugeführt werden, in welcher die Metallbeschichtung, vorzugsweise auf elektrolytischem Wege, erfolgt, wobei insbesondere als aufzuschichtende Metalle Aluminium, Kupfer, Nickel und Silber, jedoch auch-Germanium, Beryllium, Molybdän, Wolfram und Zirkonium, in Frage kommen. Im Falle einer elektrolytischen Abscheidung kann man auf bekannte Elektrolytsysteme zurückgreifen (US-PS 2 763 605; Hurley F.H., Wier T.P. "Elektrodeposition of Al from nonaquous solutions", J. Elektrochem. Soc. 96, 48-56 (1949), US-PSen 2 446 331, 2 446 349 und 2 446 350; Elze Lange Meyer "Zur elektrolytischen Abscheidung von Al", Metall 13, 541-549 (1959); Ziegler, Lehmkul, "Zeitschrift anorg. chem." 283, 414 (1956); Heritage R.J. "The Electrodeposition of Al", Trans. Inst. Met. Finishing 32, 61-71 (1955) undConnor J.H., Reid E.E., Wood "Elektrodeposition of Magnesium and Mg. alloys", J. electrochem. Soc. 104, 38/41 (1957)).After the oxide layer has been removed, the workpieces are preferably rinsed with an inert solvent under a water-vapor and oxygen-free atmosphere, in particular in an inert gas atmosphere, and they are fed to the device in which the metal coating, preferably by electrolytic means, is also carried out under oxygen-free and water-vapor-free conditions , takes place, in particular aluminum, copper, nickel and silver, but also germanium, beryllium, molybdenum, tungsten and zirconium. In the case of electrolytic deposition, known electrolyte systems can be used (US Pat. No. 2,763,605; Hurley FH, Wier TP "Electrodeposition of Al from nonaquous solutions", J. Elektrochem. Soc. 96, 48-56 (1949), US Pat. PSen 2 446 331, 2 446 349 and 2 446 350; Elze Lange Meyer "For the electrolytic deposition of Al", Metall 13, 541-549 (1959); Ziegler, Lehmkul, "Zeitschrift anorg. Chem." 283, 414 (1956 ); Heritage RJ "The Electrodeposition of Al", Trans. Inst. Met. Finishing 32, 61-71 (1955) and Connor JH, Reid EE, Wood "Electrodeposition of Magnesium and Mg. Alloys", J. electrochem. Soc. 104 , 38/41 (1957)).

Das folgende Beispiel erläutert die Erfindung:

  • Ein aus Titan bestehendes Werkstück wird an einer geeigneten Vorrichtung, welche eine sichere Handhabung sowie einen sicheren Stromkontakt gewährleistet, befestigt. Das Teil wird danach in Methanol, das ebenso mit z.B. sauerstoff-und wasserstofffreiem Argon gesättigt ist, von Fettrückständen und allenfalls anhaftenden sonstigen Partikeln befreit.
The following example explains the invention:
  • A workpiece made of titanium is attached to a suitable device, which ensures safe handling and a safe current contact. The part is then freed of fat residues and any other adhering particles in methanol, which is also saturated with, for example, oxygen-free and hydrogen-free argon.

Unter Inertgas wird das Werkstück in eine Beizlösung, die aus einer methanolischen Lösung von 8 % Fluorwasserstoff, 5 % Ammoniumfluorid und 10 % Natriumfluorid besteht, eingebracht. In dieser Lösung befinden sich Platinelektroden, die ebenso wie das Werkstück mit einer Spannungsquelle verbunden sind. Diese ermöglichen es, das Potential von + 10 V auf - 10 v innerhalb einer Sekunde zu wechseln. Während dieses Beizprozesses wird bei einer Temperatur von 15°C ein Spannungsverhältnis von Anode/Kathode = 2-1 aufrechterhalten, wobei die Stromrichtung alle 10 Sekunden wechselt. Der beschriebene Prozeß ist nach etwa 3 Minuten beendet.Under inert gas, the workpiece is placed in a pickling solution consisting of a methanolic solution of 8% hydrogen fluoride, 5% ammonium fluoride and 10% sodium fluoride brings. This solution contains platinum electrodes which, like the workpiece, are connected to a voltage source. These make it possible to change the potential from + 10 V to - 10 V within one second. During this pickling process, a voltage ratio of anode / cathode = 2-1 is maintained at a temperature of 15 ° C, with the current direction changing every 10 seconds. The process described is complete after about 3 minutes.

Das gereinigte und vor allem von jeglicher Oxidschicht befreite Werkstück wird danach gespült, wiederum mit einem inertgasgesättigten Methanol, und unter ununterbrochener Inertatmosphäre (Argon) in den Elektrolyt eingebracht. Entsprechend den US-PSen 2 446 331, 2 446 349 und 2 446 350 besteht der Elektrolyt aus einer ätherischen Lösung von 3 Mol Aluminiumchlorid und ca. 1 Mol LiH bzw. LiAlH und erlaubt es bei reversierendem Gleichstrom bei einer Stromdichte von ca. 3 A/Dm2 glatte, dichte Aluminiumschichten von ca. 0,08 cm abzuscheiden, wobei eine ausgezeichnete Haftung zum Grundwerkstoff erzielt wird.The cleaned and, above all, any oxide layer is then rinsed, again with methanol saturated with inert gas, and introduced into the electrolyte under an uninterrupted inert atmosphere (argon). According to US Pat. Nos. 2,446,331, 2,446,349 and 2,446,350, the electrolyte consists of an ethereal solution of 3 moles of aluminum chloride and about 1 mole of LiH or LiAlH and allows it to be reversed direct current at a current density of about 3 A. / Dm 2 smooth, dense aluminum layers of approx. 0.08 cm, whereby excellent adhesion to the base material is achieved.

Claims (6)

1. Verfahren zur chemischen Entfernung von Oxidschichten von Gegenständen aus Metallen, insbesondere Titan, Titanlegierungen, Nickel, Nickellegierungen sowie Chrom-Nickel-Stählen, zur anschließenden Beschichtung mit Metallen, dadurch gekennzeichnet, daß die Behandlung in einem wasserfreien organischen Medium mit einem Gemisch aus Fluorwasserstoff und einem oder mehreren Alkalifluoriden und/oder Ammoniumfluorid durchgeführt wird.1. A process for the chemical removal of oxide layers from objects made of metals, in particular titanium, titanium alloys, nickel, nickel alloys and chromium-nickel steels, for subsequent coating with metals, characterized in that the treatment in an anhydrous organic medium with a mixture of hydrogen fluoride and one or more alkali fluorides and / or ammonium fluoride is carried out. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das verwendete Medium, insbesondere im Falle von Titan, aus einem wasserfreien Alkohol, insbesondere Methanol, mit einem Gehalt von 3 bis 8 Gew.-% Fluorwasserstoff, 5 bis 8 Gew.-% Ammoniumfluorid und 5 bis 10 Gew.-% eines Alkalifluorids, insbesondere Natriumfluorid, besteht.2. The method according to claim 1, characterized in that the medium used, in particular in the case of titanium, from an anhydrous alcohol, in particular methanol, with a Content of 3 to 8 wt .-% hydrogen fluoride, 5 to 8 wt .-% ammonium fluoride and 5 to 10 wt .-% of an alkali fluoride, in particular sodium fluoride. 3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die Behandlung bei einer Temperatur von 10 °C bis 50°C durchgeführt wird.3. Process according to claims 1 and 2, characterized in that the treatment is carried out at a temperature of 10 ° C to 50 ° C. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Entfernung der Oxidschicht auf elektrochemischem Wege unterstützt wird.4. The method according to claims 1 to 3, characterized in that the removal of the oxide layer is supported electrochemically. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die elektrochemische Unterstützung der Abtragung der Oxidschicht durch Zusatz von Alkalisalzen zur Erhöhung der Leitfähigkeit der Lösung und durch Gegenelektroden durchgeführt wird.5. The method according to claim 4, characterized in that the electrochemical support for the removal of the oxide layer is carried out by adding alkali salts to increase the conductivity of the solution and by counter electrodes. 6. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die von der Oxidschicht befreiten Werkstücke vor der Beschichtung mit einem Metall in einer wasserdampf- und sauerstofffreien Atmosphäre mit einem inerten Lösungsmittel gespült werden.6. The method according to claims 1 to 5, characterized in that the workpieces freed from the oxide layer are rinsed with an inert solvent before coating with a metal in a water vapor and oxygen-free atmosphere.
EP81109537A 1980-12-19 1981-11-05 Process for the chemical removal of oxidic layers from titanium or titanium alloys Expired EP0054743B1 (en)

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DE3048083C2 (en) 1983-09-29
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EP0054743B1 (en) 1985-01-23

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