EP0341546A2 - Process for depositing an adherent metal layer on titanium or its alloys - Google Patents

Process for depositing an adherent metal layer on titanium or its alloys Download PDF

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Publication number
EP0341546A2
EP0341546A2 EP89107902A EP89107902A EP0341546A2 EP 0341546 A2 EP0341546 A2 EP 0341546A2 EP 89107902 A EP89107902 A EP 89107902A EP 89107902 A EP89107902 A EP 89107902A EP 0341546 A2 EP0341546 A2 EP 0341546A2
Authority
EP
European Patent Office
Prior art keywords
titanium
nickel
alloys
heat treatment
metal layer
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.)
Withdrawn
Application number
EP89107902A
Other languages
German (de)
French (fr)
Other versions
EP0341546A3 (en
Inventor
Gerd Dr. Linka
Michael Marquardt
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.)
Bayer Pharma AG
Original Assignee
Schering AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schering AG filed Critical Schering AG
Publication of EP0341546A2 publication Critical patent/EP0341546A2/en
Publication of EP0341546A3 publication Critical patent/EP0341546A3/en
Withdrawn legal-status Critical Current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
    • 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
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Definitions

  • the invention relates to a method for the adhesive metallization of titanium or titanium alloys by electroless deposition of a nickel-phosphorus alloy with subsequent heat treatment to form nickel-titanium diffusion layers.
  • the galvanizing of the materials mentioned is difficult because the surface is covered with a passivation layer.
  • the passivation layer In order to metallize titanium or titanium alloys firmly, the passivation layer must be removed. This is done in a known manner using aqueous solutions of hydrofluoric acid or fluoride-containing acids. If the passivation layer is removed from the surface, titanium or titanium alloys can be electroplated.
  • the object of the present invention is to provide a method of the type described in the introduction with which adherent nickel layers on titanium or titanium alloys can be produced without roughening the surface beforehand.
  • the roughening of the surface is avoided in the treatment step, which not only leads to a more homogeneous surface structure, but also ensures easier handling overall. Furthermore, it is independent of the method according to the invention whether the heat treatment takes place after the deposition of the nickel-phosphorus alloy without external current or only after the final decorative or functional coating.
  • the electroless plating of the nickel-phosphorus invention takes place in a manner known per se using conventional chemical nickel baths.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemically Coating (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention relates to a process for depositing an adherent metal layer on titanium or its alloys by electroless deposition of a nickel-phosphorus alloy followed by heat treatment to form nickel-titanium diffusion layers, characterised in that the nickel layer then still present is coated with an adherent metal layer.

Description

Die Erfindung betrifft ein Verfahren zur haftfesten Metallisierung von Titan oder Titanlegierungen durch außenstromlose Abscheidung einer Nickel-Phosphor-­Legierung mit anschließender Wärmebehandlung zur Ausbildung von Nickel-Titan-­Diffusionsschichten.The invention relates to a method for the adhesive metallization of titanium or titanium alloys by electroless deposition of a nickel-phosphorus alloy with subsequent heat treatment to form nickel-titanium diffusion layers.

Das Galvanisieren der genannten Werkstoffe ist schwierig, da die Oberfläche von einer Passivierungsschicht überzogen ist.The galvanizing of the materials mentioned is difficult because the surface is covered with a passivation layer.

Um Titan oder Titanlegierungen haftfest zu metallisieren, muß die Passivie­rungsschicht entfernt werden. Dies erfolgt in bekannter Weise mittels wäßriger Lösungen von Flußsäure oder fluoridhaltigen Säuren. Ist die Passivierungs­schicht von der Oberfläche entfernt, können Titan oder Titanlegierungen galva­nisch beschichtet werden.In order to metallize titanium or titanium alloys firmly, the passivation layer must be removed. This is done in a known manner using aqueous solutions of hydrofluoric acid or fluoride-containing acids. If the passivation layer is removed from the surface, titanium or titanium alloys can be electroplated.

In der DE-OS 36 22 032 wird dies mit einem Nickelsulfamatelektrolyten bei 5 A/dm² und 55o C für 10 min versucht. Es gelingt jedoch nicht, aus derartigen Elektrolyten Schichten mit ausreichender Haftung abzuscheiden, da die Eigen­spannungen der Schichten im Zugspannungsbereich liegen. In der DE 33 21 231 werden außemstromlos abgeschiedene Nickelschichten auf Oberflächen von Bautei­len aus Titan oder Titanbasislegierungen bei 400 - 600o C getempert, jedoch werden anschließend die Nickeldeckschicht und die Diffusionsschicht TiNi₃ che­misch entfernt. Dadurch wird die Oberfläche aufgerauht, was eine mechanische Verankerung der folgenden Beschichtung ermöglichen soll. Diese Aufrauhung der Oberfläche hat sich als nachteilig erwiesen.In DE-OS 36 22 032 this is attempted with a nickel sulfamate electrolyte at 5 A / dm² and 55 ° C. for 10 minutes. However, it is not possible to deposit layers with sufficient adhesion from such electrolytes, since the residual stresses of the layers lie in the tensile stress range. C 600 o annealed, but then the nickel layer and the diffusion layer TiNi₃ be chemically removed - in DE 33 21 231 are außemstromlos deposited nickel layers on surfaces of components made of titanium or titanium base alloys at 400th This will roughen the surface, which should allow the subsequent coating to be mechanically anchored. This roughening of the surface has proven to be disadvantageous.

Aufgabe der vorliegenden Erfindung ist die Schaffung eines Verfahrens der ein­gangs bezeichneten Art, mit dem sich haftfeste Nickelschichten auf Titan oder Titanlegierungen ohne vorherige Aufrauhung der Oberfläche herstellen lassen.The object of the present invention is to provide a method of the type described in the introduction with which adherent nickel layers on titanium or titanium alloys can be produced without roughening the surface beforehand.

Diese Aufgabe wir erfindungsgemäß gelöst durch ein Verfahren gemäß dem kenn­zeichnenden Teil des Patentanspruchs.This object is achieved according to the invention by a method according to the characterizing part of the patent claim.

Weitere Ausgestaltungen der Erfindung sind den Kennzeichnungsteilen der Unter­ansprüche zu entnehmen.Further refinements of the invention can be found in the characterizing parts of the subclaims.

In dem erfindungsgemäßen Verfahren wird auf den Behandlungsschritt der Aufrau­hung der Oberfläche vermieden, was nicht nur zu einer homogeneren Oberflächen­struktur führt, sondern auch insgesamt eine einfachere Handhabung gewährlei­stet. Weiterhin ist es bei dem erfindungsgemäßen Verfahren unabhängig, ob die Wärmebehandlung nach der außenstromlosen Abscheidung der Nickel-Phosphor-Le­gierung oder erst nach der endgültigen dekorativen oder funktionellen Beschich­tung erfolgt.In the method according to the invention, the roughening of the surface is avoided in the treatment step, which not only leads to a more homogeneous surface structure, but also ensures easier handling overall. Furthermore, it is independent of the method according to the invention whether the heat treatment takes place after the deposition of the nickel-phosphorus alloy without external current or only after the final decorative or functional coating.

Die außenstromlose Abscheidung der Nickel-Phosphor-Erfindung erfolgt in an sich bekannter Weise unter Verwendung üblicher chemischer Nicklebäder.The electroless plating of the nickel-phosphorus invention takes place in a manner known per se using conventional chemical nickel baths.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung mit den folgenden Verfahrensschritten:The following examples serve to illustrate the invention with the following process steps:

BEISPIEL 1EXAMPLE 1

- Es wird Titan beschichtet.
- Entfetten
- Spülen
- Tauchen in 5%iger HF-Lösung, 5 Sekunden, 40o C
- Spülen
- Vernickeln in einem außenstromlosen Nickelbad
- Spülen
- Vergolden in einem elektrolytischen Goldbad
- Wärmebehandlung bei 600o C für eine Stunde- Titanium is coated.
- degrease
- Do the washing up
- Diving in 5% HF solution, 5 seconds, 40 o C
- Do the washing up
- Nickel plating in an electroless nickel bath
- Do the washing up
- Gold plating in an electrolytic gold bath
- Heat treatment at 600 o C for one hour

BEISPIEL 2EXAMPLE 2

- Tauchen in 5 %iger HF-Lösung, 5 Sekunden, 40o C
- Spülen
- Vernickeln in einem außenstromlosen Nickelbad
- Wärmebehandlung bei 650o C für 30 Minuten
- Entfetten
- Spülen
- Vergolden in einem elektrolytischen Goldbad- Diving in 5% HF solution, 5 seconds, 40 o C
- Do the washing up
- Nickel plating in an electroless nickel bath
- Heat treatment at 650 o C for 30 minutes
- degrease
- Do the washing up
- Gold plating in an electrolytic gold bath

Claims (5)

1. Verfahren zur haftfesten Metallisierung von Titan oder Titanlegierungen durch außenstromlose Abscheidung einer Nickel-Phosphor-Legierung mit an­schließender Wärmebehandlung zur Ausbildung von Nickel-Titan-Diffusions­schicht, dadurch gekennzeichnet, daß die danach noch vorhandene Nickel­schicht haftfest metallisiert wird.1. A process for the adhesive metallization of titanium or titanium alloys by electroless deposition of a nickel-phosphorus alloy with subsequent heat treatment to form a nickel-titanium diffusion layer, characterized in that the nickel layer which is still present thereafter is metallized in a adherent manner. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Titan oder die Titanlegierungen vor der außenstromlosen Abscheidung einer Nickel-Phosphor-­Legierung in einer fluoridhaltigen Lösung gereinigt werden.2. The method according to claim 1, characterized in that the titanium or the titanium alloys are cleaned in a fluoride-containing solution prior to the external currentless deposition of a nickel-phosphorus alloy. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die fluoridhaltige Lösung Flußsäure oder Alkalifluorid in Konzentrationen von 0,01 % bis zur Löslichkeitsgrenze enthält.3. The method according to claim 2, characterized in that the fluoride-containing solution contains hydrofluoric acid or alkali fluoride in concentrations of 0.01% to the solubility limit. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß nach dem Beschichten eine Wärmebehandlung bei Temperaturen über 200o C durchgeführt wird.4. The method according to claim 1, characterized in that after coating a heat treatment is carried out at temperatures above 200 o C. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Wärmebehandlung unter Schutzgas oder im Vakuum durchgeführt wird.5. The method according to claim 4, characterized in that the heat treatment is carried out under a protective gas or in a vacuum.
EP89107902A 1988-05-10 1989-05-02 Process for depositing an adherent metal layer on titanium or its alloys Withdrawn EP0341546A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19883816495 DE3816495A1 (en) 1988-05-10 1988-05-10 METHOD FOR ADHESIVE METALIZATION OF TITANIUM OR TITANIUM ALLOYS
DE3816495 1988-05-10

Publications (2)

Publication Number Publication Date
EP0341546A2 true EP0341546A2 (en) 1989-11-15
EP0341546A3 EP0341546A3 (en) 1990-05-16

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EP89107902A Withdrawn EP0341546A3 (en) 1988-05-10 1989-05-02 Process for depositing an adherent metal layer on titanium or its alloys

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EP (1) EP0341546A3 (en)
JP (1) JPH0270073A (en)
DE (1) DE3816495A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999053119A1 (en) * 1998-04-13 1999-10-21 Acm Research, Inc Method and apparatus for enhancing adhesion between barrier layer and metal layer formed by plating

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62124290A (en) * 1985-11-22 1987-06-05 Citizen Watch Co Ltd Plate method to titanium surface

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62124290A (en) * 1985-11-22 1987-06-05 Citizen Watch Co Ltd Plate method to titanium surface

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 61, 1964, Zusammenfassung Nr. 6313h, Columbus, Ohio, US; S.F. YUR'EV et al.: "Chemical coating of titanium with an antifriction nickel-phosphorus alloy", & METALLOVED. I. TERM. OBRABOTKA METAL. No. 6, 28-33(1964) *
METAL FINISHING, Band 77, Nr. 11, 1979, Seite 24; RAJAGOPAL et al.: "Plating of reactive metals" *
PATENT ABSTRACTS OF JAPAN, Band 11, Nr. 353 (C-457)[2800], 18. November 1987; & JP-A³62 124 290 (CITIZEN WATCH) 05-06-1987 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999053119A1 (en) * 1998-04-13 1999-10-21 Acm Research, Inc Method and apparatus for enhancing adhesion between barrier layer and metal layer formed by plating

Also Published As

Publication number Publication date
EP0341546A3 (en) 1990-05-16
DE3816495A1 (en) 1989-11-23
JPH0270073A (en) 1990-03-08

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