WO1986000649A1 - Procede pour ameliorer l'effet de couleur de couches de nitrure de titane - Google Patents

Procede pour ameliorer l'effet de couleur de couches de nitrure de titane Download PDF

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Publication number
WO1986000649A1
WO1986000649A1 PCT/EP1985/000324 EP8500324W WO8600649A1 WO 1986000649 A1 WO1986000649 A1 WO 1986000649A1 EP 8500324 W EP8500324 W EP 8500324W WO 8600649 A1 WO8600649 A1 WO 8600649A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
titanium nitride
nitride layers
improving
hydrocarbon
Prior art date
Application number
PCT/EP1985/000324
Other languages
German (de)
English (en)
Inventor
Helmut Steininger
Heinz-Werner Etzkorn
Original Assignee
Battelle-Institut E.V.
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 Battelle-Institut E.V. filed Critical Battelle-Institut E.V.
Publication of WO1986000649A1 publication Critical patent/WO1986000649A1/fr

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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
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases

Definitions

  • the invention relates to a method for improving the color impression of titanium nitride layers by means of plasma-supported coating methods, in particular by means of
  • Magnetron nuts using a process gas consisting of an inert gas and nitrogen.
  • Decorative hard material coatings made of titanium nitride on substrates made of any material such as plastic, ceramic, metal or metal alloy can be deposited using physical coating methods such as magnetron sputtering or ion plating.
  • the color scale of such layers ranges from white to yellow to rose gold. Compared to pure gold layers, however, gold-colored titanium nitride layers are generally perceived as cold. This fact is very disruptive when using titanium nitride for decorative applications, especially as a gold substitute.
  • the color impression of the titanium nitride layers can be influenced by varying the process conditions such as bias voltage and temperature.
  • the morphology of the layer is also changed.
  • the temperature is higher, so the layers show an undesirably stalky appearance.
  • Titanium nitride layers are desired that have the outstanding physical and chemical properties of titanium nitride such as great hardness and thus high scratch resistance and corrosion resistance and also show a warm gold color.
  • the subjective impression of a warm gold color is created e.g. B. by increasing the red value or by reducing the proportion of green, ie the black haze of the layer. This is not achieved by simply increasing the nitrogen content in the titanium nitride layer, since the associated increase in the red value always goes hand in hand with a decrease in the yellow content. Therefore, reddish-brown layers are increasingly obtained.
  • the object of the invention is to increase the red value of titanium nitride layers by a simple variation of the coating conditions, or to reduce the proportion of green without influencing the yellow value of the layer. Furthermore, the process should not cause any change in the physical and chemical properties, in particular the corrosion resistance and the scratch resistance of the titanium nitride.
  • This object is achieved in that carbon is introduced into the reaction space between a target and a substrate to be coated and. that the coating is carried out at substrate temperatures of less than 250 ° C, and that the properties of the layer depend on the substrate temperature and
  • Bias voltage and the color impression can be adjusted via the carbon content. Preferred embodiments of the method according to the invention are described in subclaims 2 to 11.
  • the titanium nitride layers are deposited in a manner known per se by plasma-assisted deposition methods in a vacuum coating apparatus, preferably by magnetron sputtering.
  • a hydrocarbon is admitted to the process gases argon and nitrogen which are usually used. All saturated and unsaturated substituted or unsubstituted hydrocarbons with 1 to 6, preferably 1 to 3, carbon atoms are suitable.
  • the reaction conditions, in particular the bias voltage and the temperature of the substrate, are set to values favorable for advantageous properties of use of the layer, such as adhesion, homogeneity and unity.
  • the red value of the deposited titanium nitride layers depends sensitively on the flow rate of the hydrocarbon introduced into the apparatus.
  • low substrate temperatures of less than 250 ° C, preferably 20 to 200 ° C, are used.
  • the flow rates of the hydrocarbons added to influence the color impression are between about 0.05 and 1 cm 3 / min.
  • carbon is supplied by using a titanium carbide target instead of a pure titanium target.
  • a titanium carbide target instead of a pure titanium target.
  • noble gases preferably argon
  • nitrogen are used as process gases.
  • the flow rate of the nitrogen can also be continuously reduced or increased from about the middle of the total coating time or towards the end of the coating, as a result of which the layer only has the desired color on the surface.
  • the coating is typically carried out at a residual gas pressure of less than 2.10 -6 torr.
  • Deposition rates are between 1 0 and 20 ⁇ / sec. , preferably 1 5 ⁇ / sec.
  • the argon flow rate is e.g. B. 1 0, 5 to 1 3, 5 cm 3 / min. who have favourited Sticks toff flow rate e.g. B. 2 to 1 0 cm 3 / min.
  • the flow rate of the hydrocarbon can be between 0.05 and 1 cm 3 / min. vary.
  • a gold-colored titanium nitride layer is obtained by reactive magnetron sputtering of a pure titanium target on a stainless steel workpiece.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Pour améliorer l'effet de couleur de couches de nitrure de titane préparées selon des procédés d'enduction à l'aide d'un plasma avec l'utilisation d'un gaz de procédé formé d'un gaz rare et d'azote, on introduit du carbone dans la chambre de réaction entre une cible et un substrat à enduire. Selon une variante, des hydrocarbures sont dirigés à cet effet dans la chambre de réaction. Dans un autre mode de réalisation, on utilise une cible à base de carbure de titane.
PCT/EP1985/000324 1984-07-11 1985-07-04 Procede pour ameliorer l'effet de couleur de couches de nitrure de titane WO1986000649A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3425467.6 1984-07-11
DE19843425467 DE3425467A1 (de) 1984-07-11 1984-07-11 Verfahren zur verbesserung des farbeindrucks von titannitrid-schichten

Publications (1)

Publication Number Publication Date
WO1986000649A1 true WO1986000649A1 (fr) 1986-01-30

Family

ID=6240323

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1985/000324 WO1986000649A1 (fr) 1984-07-11 1985-07-04 Procede pour ameliorer l'effet de couleur de couches de nitrure de titane

Country Status (3)

Country Link
EP (1) EP0190179A1 (fr)
DE (1) DE3425467A1 (fr)
WO (1) WO1986000649A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0413853A1 (fr) * 1989-08-21 1991-02-27 Balzers Aktiengesellschaft Pièce pourvue d'une couche cristalline mixte, procédé et dispositif pour sa production
DE4020595A1 (de) * 1990-06-28 1992-01-09 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Elektrische lampe mit lichtreflektierender schicht
CN108505004A (zh) * 2018-05-04 2018-09-07 武汉理工大学 带有彩色TiN涂层的不锈钢刀具制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4962612A (en) * 1987-04-23 1990-10-16 Nisshin Steel Co., Ltd. Decorative panel as construction material
CA1296289C (fr) * 1987-06-30 1992-02-25 Inco Limited Procede de fabrication de pieces de couleur or
DE3726731A1 (de) * 1987-08-11 1989-02-23 Hartec Ges Fuer Hartstoffe Und Verfahren zum aufbringen von ueberzuegen auf gegenstaende mittels magnetfeldunterstuetzter kathodenzerstaeubung im vakuum
DE4205017A1 (de) * 1992-02-19 1993-08-26 Leybold Ag Verfahren zur erzeugung einer dekorativen goldlegierungsschicht

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1951362A1 (de) * 1969-10-11 1971-06-16 Heraeus Gmbh W C Schreibfeder

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE787599A (fr) * 1971-08-16 1973-02-16 Battelle Memorial Institute Vitrage filtrant antisolaire et isolant thermique
CH624817B (de) * 1979-09-04 Balzers Hochvakuum Verfahren zur herstellung goldfarbener ueberzuege.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1951362A1 (de) * 1969-10-11 1971-06-16 Heraeus Gmbh W C Schreibfeder

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 102, No. 8, 25 February 1985, Columbus, Ohio (US) J. GOEBEL: "Some Examples for the Application of Surface Analysis in Thin Film Technology", see page 561, Abstract 70473e, & Fresenius Zeitschrift fur Analytische Chemie, 1984, 319(6,7) 771-6 *
CHEMICAL ABSTRACTS, Volume 91, No. 6, 06 August 1979, Columbus, Ohio (US) J.J. CUOMO et al.: "Reactive Sputtering of Carbon and Carbide Targets in Nitrogen", see page 576, Abstract 47995x, & J. Vac. Sci. Technol. 1979, 16(2) 299-302 (Eng) *
CHEMICAL ABSTRACTS, Volume 96, No. 22, 31 May 1982, Columbus, Ohio (US) A. MUMTAZ et al.: "Color of Titanium Nitride Prepared by Reactived d.c. Magnetron Sputtering", see page 683, Abstract 190846h, & J. Vac. Sci. Tchnol. 1982, 20(3) 345-8 (Eng.) *
Metal Science & Heat Treatment, Volume 22, No 3/4, March/April 1980, New York (US), G.F. PROSTASEVICH et al.: "Decorative Diffusion Coating", pages 179-184, see pages 183, 184: "Deposition of Titanium Carbonitride" *
Thin Solid Films, Volume 105, published by Elsevier 1983, (NL) J.E. SUNDGREN et al.: "Mechanism of Reactive Sputtering of Titanium Nitride and Titanium Carbide II: Morphology and Structure", pages 367-384, see page 368 "Experimental Details", page 376; page 377; figure 10 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0413853A1 (fr) * 1989-08-21 1991-02-27 Balzers Aktiengesellschaft Pièce pourvue d'une couche cristalline mixte, procédé et dispositif pour sa production
AU645758B2 (en) * 1989-08-21 1994-01-27 Balzers Aktiengesellschaft Workpiece coated with a solid solution layer, method for its production, use of the workpiece, and apparatus for carrying out the method
DE4020595A1 (de) * 1990-06-28 1992-01-09 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Elektrische lampe mit lichtreflektierender schicht
CN108505004A (zh) * 2018-05-04 2018-09-07 武汉理工大学 带有彩色TiN涂层的不锈钢刀具制备方法

Also Published As

Publication number Publication date
DE3425467A1 (de) 1986-01-23
EP0190179A1 (fr) 1986-08-13
DE3425467C2 (fr) 1988-06-30

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