EP0470878B1 - Beschichtung zum Schutz vor Verschleiss auf einem Substrat auf Titanbasis - Google Patents

Beschichtung zum Schutz vor Verschleiss auf einem Substrat auf Titanbasis Download PDF

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Publication number
EP0470878B1
EP0470878B1 EP91402065A EP91402065A EP0470878B1 EP 0470878 B1 EP0470878 B1 EP 0470878B1 EP 91402065 A EP91402065 A EP 91402065A EP 91402065 A EP91402065 A EP 91402065A EP 0470878 B1 EP0470878 B1 EP 0470878B1
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EP
European Patent Office
Prior art keywords
substrate
process according
deposition process
nickel
deposition
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
EP91402065A
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English (en)
French (fr)
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EP0470878A1 (de
Inventor
Robert Lucien Martinou
Michel Meyer Ruimi
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.)
Safran Aircraft Engines SAS
Original Assignee
Societe Nationale dEtude et de Construction de Moteurs dAviation SNECMA
SNECMA SAS
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Publication of EP0470878A1 publication Critical patent/EP0470878A1/de
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    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/027—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/917—Treatment of workpiece between coating steps

Definitions

  • the field of the present invention is that of methods of depositing anti-wear coatings on titanium or titanium alloy parts and the coatings thus obtained.
  • Zinc predepot from glycol-metal fluoride mixtures or aqueous mixtures based on fluoroboric acid, hydrofluoric acid and metal salts;
  • the invention therefore aims to overcome the aforementioned drawbacks, by eliminating the generation of hydrides by eliminating the prior chemical treatments of the substrate and by slowing the penetration of hydrogen into the substrate during the electrolytic process of depositing the anti-wear layer.
  • the invention also aims to allow an anti-wear deposit on titanium parts while reducing the fatigue drop compared to previous methods and thereby allowing the use of coated titanium substrates for parts subjected to a cyclic fatigue, where the parts obtained by the previous processes do not allow it.
  • the object of the invention is therefore to produce a range of deposition in which the techniques of deposition of nickel by magnetron sputtering are combined in order to ensure a underlay particularly adherent to the substrate with an electrolytic deposit allowing the deposition of a final anti-wear layer.
  • the object of the invention is more particularly to define parameters for the deposition of nickel by sputtering, compatible with subsequent electrolytic deposits.
  • step (b2) will be carried out by sputtering with a magnetron cathode, and preferably at a pressure between 0.4 and 0.8 Pa.
  • the curves give the admissible stresses in rotary bending according to the number of cycles carried out.
  • the parts are then placed in a vacuum enclosure in the range of high secondary vacuum, ie at a pressure between 3.10 ⁇ 4 and 3.10 ⁇ 1 Pa.
  • the substrate is then subjected to an ionic pickling which cleans the substrate by removing material.
  • the parts are placed in an inert gas atmosphere, for example argon injected into the enclosure under a pressure of between 1.10 ⁇ 1 and 50 Pa while applies a negative voltage to the substrate in order to attract the ions to the substrate during the luminescent discharge produced in the enclosure.
  • the operation can be carried out in a range of power densities between 0.05 and 0.4 W / cm2. The tests showed that the preferred range was 0.1 to 0.15 W / cm2 for a period of between 15 and 20 minutes.
  • this technique is a vacuum deposition process operating cold, in luminescent plasma, in a gas maintained at reduced pressure from 0.1 to 10 Pa.
  • the material to be deposited here nickel, called target and placed in cathode , is introduced into the vacuum enclosure in the form of a plate a few millimeters thick.
  • the substrate is arranged in an anode.
  • the electric field created between the 2 electrodes causes the ionization of the residual gas which creates a luminescent cloud between the electrodes.
  • the substrate is then covered with a layer of the same material as the target, due to the condensation of atoms coming from the target under the impact of positive ions contained in the luminescent gas and attracted to the target due to its negative bias.
  • the substrate to be coated placed in the anode position has been polarized at a voltage between -20 and -500V.
  • the target was pure nickel and it was bombarded with a power density between 70 and 700 W / dm2, the choice of the bombardment power density of the target being made as a function of the temperature admissible by the substrate to be covered.
  • the spraying was carried out under an inert atmosphere in a pressure range between 0.2 and 5 Pa, the best results being obtained between 0.4 and 0.8 Pa.
  • the part then undergoes an alkaline degreasing by soaking for 3 to 7 minutes (typically 5) in an aqueous bath containing 30 to 45 g / l of Turco 4215 NCLT or 40 to 60 g / l of Ardrox PST 39 (registered trademarks).
  • the part is then rinsed with cold water, checking the continuity of the water film.
  • An electrolytic activation of the part is then carried out by soaking it for one minute under a current density (ddc) of 1.5 to 3 A / dm2 in an aqueous bath comprising from 60 to 80 g / l of KCN and from 10 to 50 g / l of K2 CO3.
  • ddc current density
  • the part is then rinsed again with cold water and electrolytic nickel-plating operations are carried out.
  • the average thickness deposited is 15 ”m (microns).
  • the thickness of nickel deposited is between 3 and 5 »m (microns).
  • the part is then rinsed with cold water.
  • the part can then receive its anti-wear coating such as coatings in Cr, Ni-Co, Ni Co SiC or Ag-Ni.
  • the average thickness obtained is between 120 and 150 »m (microns).
  • Another example of an anti-wear coating is 29% Co-Ni.
  • Ni / Co mass ratio used is 20 and the Ni + Co sum in solution is 87.5 g / l.
  • the average thickness obtained is 120 to 140 ”m (microns).
  • the part is rinsed with cold water then dried with compressed air, then undergoes degassing at 200 ° + 5 ° C for 3 h.
  • Coated test pieces according to the invention were therefore compared to coated test pieces according to the state of the prior art represented by the teaching of document FR-A-1322970.
  • Table 1 shows the treatment ranges applied to 56 test pieces, some of which were left at various stages of the coating process before subjecting them to rotary bending fatigue tests.
  • Table 2 illustrates the precise operating conditions for electrolysis carried out during the operations indicated in table 1.
  • the curves of plates 1 and 2 illustrate these results by showing, during the rotational bending fatigue tests, the variation of the stresses as a function of the number of cycles according to the state of finish of the parts and according to whether they were obtained by the invention. or according to the state of the art.
  • Table 3 shows the results of vibration fatigue tests carried out, depending on the nature of the treatment carried out on each sample, the number of cycles and the maximum stresses applied.
  • the fatigue limit drop is 52% for parts according to the state of the art and only 15% for parts according to l 'invention.
  • the invention makes it possible to make coated titanium, parts which previously could not have been used in a restrictive environment.
  • titanium substrates which are much lighter than the materials usually used for parts subjected to lasting fatigue stresses, both in rotational bending and in vibration fatigue.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (11)

  1. Verfahren zur Ablagerung eines verschleißfesten Überzugs aus Ag oder ausgewählt aus der aus Cr, Ni und Co gebildeten Gruppe, getrennt oder untereinander gemischt, mit oder ohne keramische Partikel, wie SiC, Cr₂C₃, Al₂O₃, Cr₂O₃, auf einem Trägermaterial auf Titanbasis,
    gekennzeichnet durch folgende Schritte:
    a) Aufrauhen des Trägermaterials durch Sandstrahlen,
    b) Ablagern einer Haftunterschicht aus Nickel durch Kathodenzerstäubung,
    c) Zwischenreinigungsschritt,
    d) Aktivierung durch Eintauchen des Teils in ein zyaniertes Bad,
    e) Ablagern einer elektrolytischen Nickelschicht,
    f) Ablagern der verschleißfesten Endschicht aus Ag oder ausgewählt aus der aus Cr, Ni und Co gebildeten Gruppe, allein oder untereinander gemischt, mit oder ohne keramische Partikel, wie SiC, Cr₂C₃, Al₂O₃, Cr₂O₃.
  2. Ablagerungsverfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Schritt b) aus zwei in einer Atmosphäre aus inertem Gas ausgeführten Teilschritten b₁) und b₂) besteht, und zwar
    - b₁) ionisches Beizen des Trägermaterials in einem Vakuumbehälter bei einem Druck zwischen 1.10⁻¹ und 5 Pa,
    - b₂) Vernickeln durch Kathodenzerstäubung in durch Einführen von Argon in den Behälter erzeugter inerter Atmosphäre bei einem Druck zwischen 2·10⁻¹ und 5 Pa.
  3. Ablagerungsverfahren nach Anspruch 2, dadurch gekennzeichnet, daß der Teilschritt b₂) bei einem Druck zwischen 0,4 und 0,8 Pa durchgeführt wird.
  4. Ablagerungsverfahren nach einem der Ansprüche 2 oder 3, dadurch gekennzeichnet, daß der Teilschritt b₂) durch Kathodenzerstäubung mit Magnetronkathode durchgeführt wird.
  5. Ablagerungsverfahren nach einem der Ansprüche 2 oder 3, dadurch gekennzeichnet, daß das in Anodenposition angeordnete mit dem Überzug zu versehende Trägermaterial auf eine Spannung zwischen -20V und -500V vorgespannt wird.
  6. Ablagerungsverfahren nach Anspruch 5, dadurch gekennzeichnet, daß das Trägermaterial auf eine Spannung zwischen -100V und -150V vorgespannt wird.
  7. Ablagerungsverfahren nach Anspruch 6, dadurch gekennzeichnet, daß das Target aus reinem Nickel besteht und daß es mit einer Leistungsdichte zwischen 70 W/dm² und 700 W/dm² beschossen wird, wobei die Wahl der Leistungsdichte für den Beschuß des Targets in Abhängigkeit von der zulässigen Temperatur für das mit dem Überzug zu versehende Trägermaterial erfolgt.
  8. Ablagerungsverfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Reinigungsschritt c) durch Eintauchen des Teils in ein alkalisches Bad für die Dauer von 3 bis 7 Minuten durchgeführt wird, gefolgt von einem Spülen in kaltem Wasser.
  9. Ablagerungsverfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Schritt e) aus den folgenden Teilschritten besteht:
    - e₁) Vorvernickeln in einem Säurebad bei 50°C ± 5K mit einer Stromdichte von 6 ± 1 A/dm² während einer Dauer von 3 Minuten, und dann mit einer Stromdichte von 4 ± 1 A/dm² während einer Dauer von 10 Minuten,
    - e₂) Vernickeln in einem Sulfamatbad mit Stromdichte zwischen 2 und 4 A/dm² während einer Dauer von 5 Minuten.
  10. Ablagerungsverfahren nach Anspruch 9, dadurch gekennzeichnet, daß zwischen jedem der Schritte d), e₁), e₂) und f) Spülungen in kaltem Wasser vorgesehen sind.
  11. Teil mit einem Trägermaterial Titanbasis, dadurch gekennzeichnet, daß es von dem Trägermaterial bis zur Oberfläche aufweist:
    - eine durch Magnetron-Kathodenzerstäubung abgelagerte Ni-Schicht mit einer Dicke zwischen 3 und 7 »m,
    - eine elektrolytische Nickelschicht, die durch Vorvernickeln in einem Säurebad, gefolgt von eine Vernickelung in einem Sulfamatbad erzeugt ist, wobei diese Schicht eine Dicke zwischen 18 und 20 »m besitzt,
    - eine verschleißfeste Endschicht aus Ag oder ausgewählt aus der aus Cr, Ni und Co gebildeten Gruppe, getrennt oder untereinander gemischt, mit oder ohne keramische Partikel, wie SiC, Cr₂C₃, Al₂O₃, Cr₂O₃, wobei die Dicke dieser Schicht größer ist als 80 »m.
EP91402065A 1990-07-26 1991-07-24 Beschichtung zum Schutz vor Verschleiss auf einem Substrat auf Titanbasis Expired - Lifetime EP0470878B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9009554 1990-07-26
FR9009554A FR2665185B1 (fr) 1990-07-26 1990-07-26 Revetement anti-usure sur un substrat a base titane.

Publications (2)

Publication Number Publication Date
EP0470878A1 EP0470878A1 (de) 1992-02-12
EP0470878B1 true EP0470878B1 (de) 1994-06-29

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EP91402065A Expired - Lifetime EP0470878B1 (de) 1990-07-26 1991-07-24 Beschichtung zum Schutz vor Verschleiss auf einem Substrat auf Titanbasis

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US (1) US5154816A (de)
EP (1) EP0470878B1 (de)
JP (1) JP2564218B2 (de)
CN (1) CN1029995C (de)
DE (1) DE69102687T2 (de)
FR (1) FR2665185B1 (de)
RU (1) RU2068032C1 (de)
WO (1) WO1992001823A1 (de)

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RU2175686C1 (ru) * 2000-05-03 2001-11-10 Институт надежности машин Национальной Академии Наук Беларуси Композиционное покрытие и способ его изготовления
US20040053197A1 (en) * 2002-09-16 2004-03-18 Zoran Minevski Biocompatible implants
RU2251589C1 (ru) * 2003-10-21 2005-05-10 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Способ нанесения двухслойного износостойкого покрытия на титан и его сплавы
DE102004006127A1 (de) * 2004-02-07 2005-08-25 Dr.Ing.H.C. F. Porsche Ag Verfahren zur Herstellung von korrosionsbeständigen und dekorativen Beschichtungen und Schichtsystemen für Substrate aus Metallen
US7063628B2 (en) * 2004-03-23 2006-06-20 Callaway Golf Company Plated magnesium golf club head
US7087268B2 (en) * 2004-03-30 2006-08-08 Callaway Golf Company Method of plating a golf club head
US7897265B2 (en) * 2006-01-26 2011-03-01 Hamilton Sundstrand Corporation Low cost, environmentally favorable, chromium plate replacement coating for improved wear performance
DE102008056741A1 (de) 2008-11-11 2010-05-12 Mtu Aero Engines Gmbh Verschleissschutzschicht für Tial
RU2398045C1 (ru) * 2008-12-25 2010-08-27 Борис Львович Горберг Способ модификации поверхности текстильного материала
RU2631573C1 (ru) * 2016-04-11 2017-09-25 Общество с ограниченной ответственностью "Научно-производственное предприятие "Уралавиаспецтехнология" Способ нанесения многослойного ионно-плазменного покрытия на поверхность гравюры штампа из жаропрочного никелевого сплава
CN106048534A (zh) * 2016-06-03 2016-10-26 南通市申海工业技术科技有限公司 航天互连片用钼箔的表面处理工艺
CN111424303B (zh) * 2020-05-19 2021-06-11 暨南大学 一种SiC纳米银复合电沉积涂层及其制备方法与应用
CN119144957A (zh) * 2024-11-20 2024-12-17 鑫鹏源(聊城)智能科技有限公司 一种高压输氢钛合金管道用阻氢涂层及其制备方法

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Also Published As

Publication number Publication date
US5154816A (en) 1992-10-13
JP2564218B2 (ja) 1996-12-18
CN1058429A (zh) 1992-02-05
FR2665185A1 (fr) 1992-01-31
EP0470878A1 (de) 1992-02-12
WO1992001823A1 (fr) 1992-02-06
RU2068032C1 (ru) 1996-10-20
JPH0693469A (ja) 1994-04-05
FR2665185B1 (fr) 1992-10-16
CN1029995C (zh) 1995-10-11
DE69102687T2 (de) 1994-11-17
DE69102687D1 (de) 1994-08-04

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