EP0258283B1 - Verfahren zum beschichten eines substrates mit einem verschleissfesten, dekorativen überzug und ein gemäss diesem verfahren hergestellter artikel - Google Patents

Verfahren zum beschichten eines substrates mit einem verschleissfesten, dekorativen überzug und ein gemäss diesem verfahren hergestellter artikel Download PDF

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Publication number
EP0258283B1
EP0258283B1 EP87900794A EP87900794A EP0258283B1 EP 0258283 B1 EP0258283 B1 EP 0258283B1 EP 87900794 A EP87900794 A EP 87900794A EP 87900794 A EP87900794 A EP 87900794A EP 0258283 B1 EP0258283 B1 EP 0258283B1
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Prior art keywords
layer
gold
group
color
alloy
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Expired - Lifetime
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EP87900794A
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English (en)
French (fr)
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EP0258283A1 (de
Inventor
François Aubert
Bahman Miremad
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Preci-Coat SA
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Preci-Coat SA
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Priority to AT87900794T priority Critical patent/ATE65333T1/de
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    • 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
    • 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 present invention relates to a method for depositing on a substrate a wear-resistant decorative coating and having externally a predetermined desired color, this substrate constituting at least part of a decorative and / or utility object, in particular a piece of horology, in which, during a first step, at least one first wear-resistant layer having a color close to said desired color is deposited under vacuum on the surface of the substrate.
  • the surfaces of decorative objects have a golden color.
  • these objects are not solid gold, but made of a non-noble metal such as brass, stainless steel, zinc, etc.
  • this golden appearance can be obtained by applying a surface coating of gold or gold alloy, most often by a galvanic process. If this coating is to be resistant to wear and corrosion, its thickness must at least reach 10 micrometers.
  • a base layer consisting of a 14 or 18 carat precious metal alloy is generally galvanically deposited.
  • the corrosion resistance of these alloys is often insufficient, and their color does not correspond exactly to the colors of solid alloys, such as those defined for example by the standards of the Swiss watch industry NIHS 03-50 (alloy, 1N14, 2N18, 3N, 4N, 5N).
  • the corrosion resistance of gold plating, as well as their color, can be improved by galvanic application of a surface layer of gold alloy having a purity greater than or equal to 22 carats, and corresponding exactly to the desired color. .
  • titanium nitride coatings deposited by chemical reactions in the gas phase, by reactive evaporation, by ion spraying or by cathode sputtering, are commonly applied to decorative objects made of metal, carbides or sintered metal nitrides. , or ceramic. These coatings have the advantage of being very resistant to wear and having a golden appearance.
  • the British publication GB-A-1555467 describes a process intended to avoid certain drawbacks of the very conventional treatments for gaseous nitriding of steels, in particular the surface formation of a layer sensitive to corrosion, and which consists in remove this layer by ion stripping under vacuum and cover the surface with a metallic deposit obtained by introducing vapor of the material to be deposited in the deposition chamber, and with an electrolytic coating. This coating is not intended for a decorative function.
  • US Patent No. 3,857,682 proposes to deposit a thin layer of gold under vacuum over the titanium nitride. This idea was taken up in the American patent No. 4,252,862 and Swiss Patent No. 631,040, applied to the decorative field, with the aim of giving the surface of titanium nitride the exact color of gold, or of a gold alloy. During the use of a part thus coated, the wear of the gold coating only occurs on the sharp corners and reveals the coating of titanium nitride whose color can be distinguished from that of the rest of the coating. .
  • Japanese publication No. 58.153.776 and European publication No. 38.294 describe a process for the combined deposition of titanium nitride and gold, intended to form over all or part of the thickness of the coating, a titanium nitride / gold compound.
  • this procedure seems to pose corrosion problems, and the color obtained is also far from the standard colors of gold coatings.
  • the present invention proposes to overcome these various drawbacks and in particular makes it possible to considerably improve the resistance to wear, adhesion and appearance of a deposit based on titanium nitride with final gold coating.
  • said first layer comprises at least one metal chosen from the following: titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, aluminum, to which add at least one element chosen from the following: carbon, nitrogen, oxygen, boron, silicon, fluorine, chlorine, sulfur, phosphorus, so that the color of this first layer is close to said desired color, in that during from this first step, the proportion of the added element and the electrical polarization of the substrate are increased simultaneously from the inside to the outside of the layer, in that during a second step, this first layer by ion bombardment under vacuum, and a second thin layer of a metal and / or a metal alloy whose color is close to said desired color is deposited, in that during a first phase of the get In the second step, the first layer is ionically bombarded without depositing metal and / or decorative alloy, and in that during the second phase of the second phase of the
  • the method described consists in depositing under vacuum, for example by sputtering, by vacuum evaporation or by ion spraying, titanium in the presence of nitrogen on the surface of a metallic or non-metallic object. 10 schematically represented by FIG. 1.
  • the quantity of nitrogen introduced into the treatment enclosure continuously varies from zero to a value defined by the desired result, so that the composition of the coating 11 starting from the gross surface of the The object gradually varies from pure titanium to a titanium nitride having an approximately stoichiometric composition.
  • the electrical polarization of the treated object is varied simultaneously, in order to gradually vary the mechanical compression stresses from a minimum value at the start of the coating to a maximum value at the end of the coating.
  • a coating is obtained which, starting from the gross surface of the object, presents a determined gradient of nitrogen concentration, resistance and mechanical stress.
  • the coating obtained has minimal shear stresses on the contact surface of the object and the coating, as well as the desired optical, mechanical and anticorrosive surface properties.
  • the method After depositing the first layer of titanium nitride, the method consists in preparing the upper surface of this layer in order to make it suitable for receiving, thereafter a layer of gold or of gold alloy, deposited by galvanic process , having the desired final color, as close as possible to a standard color defined by the standards in use.
  • an activation of the titanium nitride surface is carried out during a first step of the second treatment phase by intense ion bombardment. After this first treatment step, gold atoms are deposited, forming an intermediate layer 12, during a second step of this second treatment phase.
  • This deposition of gold atoms is carried out under vacuum by evaporation, by ion projection or by sputtering, while continuing to carry out an ion bombardment of the titanium nitride surface. During this second step, the power of this ion bombardment is gradually reduced.
  • the activated titanium nitride surface is ready to receive a layer 13 of pure gold or of a gold alloy of high purity, deposited by a galvanic process, making it possible to give it the desired color.
  • This color can be modified at will by changing the composition of the galvanic bath or by modifying the parameters defining the conditions of the galvanic deposition process.
  • different objects of the same batch previously coated with a base layer of titanium nitride, then with a thin layer of gold, by a vacuum process can be coated with a final layer having shades of different colors depending on whether they have been treated in a particular galvanic bath or according to whether the treatment conditions have been modified.
  • the embodiment described above consisting in applying an object a base layer of titanium nitride, then depositing by a vacuum process a thin layer of gold, then performing a galvanic deposition of the same metal, can easily be generalized and applied to various other metals.
  • the base layer which can have a thickness of between 0.1 and 20 micrometers, can be produced by vacuum deposition of at least one of the following metals: Titanium, Zirconium, Hafnium, Vanadium, Niobium, Tantalum , Chromium, Molybdenum, Tungsten and Aluminum.
  • This deposit can be made in the presence of one of the following elements: Carbon, Nitrogen, Oxygen, Boron, Silicon, Fluorine, Chlorine, Sulfur and Phospore.
  • the level of these elements is gradually increased during the vacuum deposition phase of the metal or metals mentioned above.
  • the objects to be treated are increasingly polarized. This makes it possible to obtain a coating having an increasing concentration of non-metallic elements and having states of increasing mechanical stresses.
  • a thin metallic layer is deposited, partly simultaneously, which may be made of gold or of a gold alloy, but also of one or more precious metals such as for example Platinum, Palladium, Rhodium, Silver, Irridium, Osmium, Rhenium and Ruthenium.
  • This second layer preferably has a thickness of between 0.01 and 1 ⁇ m (100 and 10′000 ⁇ ).
  • This galvanic deposit is generally gold or a high-carat gold alloy, for example a gold alloy at least 22 carats comprising, as an alloying element, Indium, Nickel, Cobalt , Cadmium, Copper, Silver, Palladium, Zinc or Antimony.
  • this deposit can also consist of one or more precious metals such as Platinum, Palladium, Rhodium, Silver, Irridium, Osmium, Rhenium or Ruthenium, an alloy of one of these metals with one or more other metals, or possibly a non-precious metal or alloy.
  • the thickness of the surface layer is preferably between 0.1 and 30 micrometers.
  • the method makes it possible to treat the surface of an object so as to dress it with a hard adherent and corrosion-resistant layer having approximately the desired color, then to carry out on this base layer a final coating having exactly the color desired and adhering perfectly to this base coat.
  • a stainless steel watch case previously degreased and dried, is placed in a cathode sputtering chamber under vacuum. During a first stage, it undergoes an ion bombardment with argon ions, so as to remove the last superficial traces of contaminant. The object is then negatively polarized at a few tens of volts, and we begin to deposit titanium by sputtering. As the thickness of the coating increases, the electric polarization of this object is gradually increased, and an increasing flow of nitrogen is introduced into the enclosure, so as to deposit an increasingly titanium nitride compound. richer in nitrogen.
  • the polarization of the object can rise to a value between 150 and 250 volts, and the proportion of nitrogen atoms in the titanium nitride will be approximately 50%.
  • the surface color of the coating is then close to that of gold.
  • the next step is to bombard the titanium nitride layer with argon ions. As the power of this bombardment is reduced, a thin layer of gold is deposited by sputtering, with an increasing flow of gold atoms, until that this layer reaches a thickness of 0.1 micrometer. The watch case is then removed from the enclosure. It is given its final surface color by electrolytically applying a coating of 0.3 microns of 22-carat gold alloy, containing traces of indium and nickel, the color of which corresponds to the 2 N 18 standard.
  • a thin layer of rhodium having good wear resistance on the exterior surface of a brass ball-point pen tube.
  • the object is introduced into the sputtering enclosure where it undergoes the same treatment as in the previous example.
  • the nitrogen is replaced by a hydrocarbon, such as for example methane, so as to deposit a titanium carbide with an increasing proportion of carbon.
  • a thin layer of silver is deposited by sputtering.
  • a final layer of rhodium is then galvanically deposited over the silver until this layer reaches a thickness of 0.3 micrometers.
  • Figure 2 illustrates the principle of measuring the color of the light reflected by the surface of an object according to the CIE 1976 standard of the International Commission on Lighting. Three quantities are measured and correspond to three axes defining a three-dimensional orthogonal coordinate system.
  • the L axis defines the brightness, the - a, + a axis corresponds to the two complementary colors respectively green and red.
  • the axis - b, + b corresponds to the two complementary colors respectively blue and yellow.
  • FIG. 3 represents a comparative graph between the brightness of titanium nitride and of various standard gold alloys.
  • the brightness is represented in arbitrary units and on the abscissa the rate of nitrogen entering into the composition of titanium nitride, according to an arbitrary unit.
  • the shine of the surface of a coating of titanium nitride is represented by a curve 20.
  • the brilliance of different gold alloys is represented by a succession of dots. It can be seen that the gloss of all the standard alloys represented is greater than all of the titanium nitride compounds.
  • FIG. 4 represents the quantity of green and red light reflected on the one hand by a coating of titanium nitride and on the other hand by various standard gold alloys. As before, the nitrogen content of the titanium nitride compound is plotted on the abscissa in an arbitrary unit. Curve 21 represents the quantity of green and red light reflected by the coating of titanium nitride.
  • FIG. 5 represents the quantity of blue and yellow light respectively reflected by a coating of titanium nitride and by various coatings of standard gold alloys.
  • the nitrogen content in titanium nitride has been plotted on the abscissa in an arbitrary unit.
  • Curve 22 represents the amount of blue and yellow light reflected by the titanium nitride coating as a function of its composition.
  • the blue and yellow light reflected by the different alloys is represented by a succession of points.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Physical Vapour Deposition (AREA)

Claims (8)

1. Verfahren zum Beschichten eines Substrates mit einem verschleißfesten, dekorativen Überzug, der auf der Außenfläche eine vorher bestimmte Farbe aufweist, wobei dieses Substrat mindestens einen Teil eines dekorativen und/oder eines Gebrauchsgegenstands, insbesondere einen Bestandteil für die Uhrenindustrie bildet, wobei im Laufe eines ersten Schrittes mindestens eine erste verschleißfeste Schicht mit einer Farbe, die mit der besagten gewünschten Farbe annähernd identisch ist, unter Vakuum auf die Außenfläche des Substrats aufgebracht wird, dadurch gekennzeichnet, daß die besagte erste Schicht mindestens ein Metall enthält, das unter den folgenden Metallen: Titan, Zirkonium, Hafnium, Vanadium, Niobium, Tantal, Chrom, Molybdän, Wolfram, Aluminium, gewählt wird, dem mindestens ein Element beigement wird, das unter den folgenden Elementen: Kohlenstoff, Stickstoff, Sauerstoff, Bor, Silizium, Fluor, Chlor, Schwefel, Phosphor gewählt wird, so daß die Farbe dieser ersten Schicht mit der besagten gewünschten Farbe annähernd identisch ist, daß im Laufe dieses ersten Schrittes der Anteil des beigemengten Elements und die elektrische Polarisation des Substrates von innen nach außen in der Schicht zunehmend gleichzeitig geändert wird, daß im Laufe eines zweiten Schrittes diese erste Schicht durch Beschuß von Ionen unter Vakuum aktiviert wird und eine zweite feine Schicht eines Metalls und/oder einer Metallegierung aufgebracht wird, deren Farbe mit der besagten gewünschten Farbe annähernd identisch ist, daß im Laufe einer ersten Phase des zweiten Schrittes die erste Schicht mit Ionen beschossen wird, ohne ein dekoratives Metall und/oder Legierung aufzubringen, daß im Laufe der zweiten Phase des zweiten Schrittes die erste Schicht weiterhin mit Ionen beschossen wird, wobei gleichzeitig die zweite Schicht gleichzeitig aufgebracht wird und der Beschuß mit Ionen nach und nach vermindert wird, und daß im Laufe eines dritten Schrittes auf dieser zweiten Schicht eine dritte Schicht eines metallenen dekorativen Überzugs mit der genauen gewünschten Farbe galvanisch aufgebracht wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die zweite Schicht mindestens aus einem Edelmetall, das unter den folgenden Edelmetallen: Gold, Platin, Palladium, Rhodium, Silber, Iridium, Osmium, Rhenium, Ruthenium gewählt wird, und/oder aus einer Legierung von Gold mit mindestens einem der folgenden Elemente: Indium, Nickel, Kobalt, Cadmium, Kupfer, Silber, Palladium, Zink, Antimon besteht.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die zweite Schicht eine Dicke zwischen 10 und 1000 nm (100 und 10000 Å) aufweist.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die dritte Schicht, die galvanisch aufgebracht wird, mindestens aus einem Edelmetall, das unter den folgenden Edelmetallen: Gold, Platin, Palladium, Rhodium, Silber, Iridium, Osmium, Rhenium, Ruthenium gewählt wird, und/oder aus einer Legierung von Gold mit einem der folgenden Elemente: Indium, Nickel, Kobalt, Cadmium, Kupfer, Silber, Palladium, Zink, Antimon besteht.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die dritte Schicht eine Dicke zwischen 0,1 und 30 Mikrometer aufweist.
6. Dekorativer und/oder Gebrauchsgegenstand, der mit dem Verfahren nach Anspruch 1 hergestellt ist, der auf mindestens einem Teil seiner Oberfläche einen dekorativen, verschleißfesten Überzug enthält, der auf der Außenfläche eine vorher bestimmte Farbe aufweist, wobei dieser Überzug aus einer ersten Schicht aus einer metallenen verschleißfesten Verbindung, aus einer zweiten Schicht aus einem metallenen verschleißfesten Auftrag und aus einer dritten Schicht aus einem galvanischen Auftrag aus einem Metall oder aus einer Metallegierung besteht, dadurch gekennzeichnet, daß die erste Schicht des Überzugs eine Farbe aufweist, die mit der besagten vorher bestimmten Farbe annähernd identisch ist, und mindestens eine Verbindung aus mindestens einem Metall, das unter den folgenden Metallen: Titan, Zirkonium, Hafnium, Vanadium, Niobium, Tantal, Chrom, Molybdän, Wolfram, Aluminium gewählt wird, und aus mindestens einem Element, das unter den folgenden Elementen: Kohlenstoff, Stickstoff, Sauerstoff, Bor, Silizium, Fluor, Chlor, Schwefel, Phosphor gewählt wird, enthält, daß die zweite Schicht eine Farbe aufweist, die mit der besagten vorher bestimmten Farbe annähernd identisch ist, und mindestens aus einem Edelmetall, das unter den folgenden Edelmetallen: Gold, Platin, Palladium, Rhodium, Silber, Iridium, Osmium, Rhenium, Ruthenium gewählt wird, und/oder aus mindestens einer Legierung von Gold mit einem der folgenden Elemente; Indium, Nickel, Kobalt, Cadmium, Kupfer, Silber, Palladium, Zink, Antimon besteht und daß die dritte Schicht genau die besagte vorher bestimmte Farbe aufweist und mindestens aus einem Edelmetall, das unter den folgenden Edelmetallen: Gold, Platin, Palladium, Rhodium, Silber, Iridium, Osmium, Rhenium, Ruthenium gewählt wird, und/oder aus einer Legierung einer dieser Metalle mit einem oder mehreren anderen Metallen und/oder aus einer Legierung von Gold mit mindestens einem der folgenden Elemente: Indium, Nickel, Kobalt, Cadmium, Kupfer, Silber, Palladium, Zink, Antimon besteht.
7. Gegenstand nach Anspruch 6, dadurch gekennzeichnet, daß die zweite Schicht eine Dicke zwischen 10 und 1000 nm (100 und 10000 Å) aufweist.
8. Gegenstand nach Anspruch 6, dadurch gekennzeichnet, daß die dritte Schicht eine Dicke zwischen 0,1 und 30 Mikrometer aufweist.
EP87900794A 1986-02-04 1987-02-03 Verfahren zum beschichten eines substrates mit einem verschleissfesten, dekorativen überzug und ein gemäss diesem verfahren hergestellter artikel Expired - Lifetime EP0258283B1 (de)

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Application Number Priority Date Filing Date Title
AT87900794T ATE65333T1 (de) 1986-02-04 1987-02-03 Verfahren zum beschichten eines substrates mit einem verschleissfesten, dekorativen ueberzug und ein gemaess diesem verfahren hergestellter artikel.

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CH41686A CH667361GA3 (de) 1986-02-04 1986-02-04
CH416/86 1986-02-04

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EP0258283A1 EP0258283A1 (de) 1988-03-09
EP0258283B1 true EP0258283B1 (de) 1991-07-17

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US (1) US4973388A (de)
EP (1) EP0258283B1 (de)
JP (1) JPH0832964B2 (de)
CH (1) CH667361GA3 (de)
WO (1) WO1987004812A1 (de)

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JPS57120685A (en) * 1981-01-16 1982-07-27 Seiko Epson Corp Constitution of gold plating for armor parts for timepiece
JPS57120686A (en) * 1981-01-16 1982-07-27 Seiko Epson Corp Constitution of gold plating for external finishing parts for timepiece
US4737252A (en) * 1981-05-18 1988-04-12 Westinghouse Electric Corp. Method of coating a metallic article of merchandise with a protective transparent film of abrasion-resistance material
JPS5864396A (ja) * 1981-10-13 1983-04-16 Seiko Instr & Electronics Ltd 白色時計用外装部品
JPS58120777A (ja) * 1982-01-11 1983-07-18 Seiko Epson Corp 時計用外装部品
JPS61104097A (ja) * 1984-10-23 1986-05-22 Iwasaki Mekki:Kk 外装部品
US4591418A (en) * 1984-10-26 1986-05-27 The Parker Pen Company Microlaminated coating

Also Published As

Publication number Publication date
JPS63502288A (ja) 1988-09-01
CH667361GA3 (de) 1988-10-14
WO1987004812A1 (fr) 1987-08-13
US4973388A (en) 1990-11-27
JPH0832964B2 (ja) 1996-03-29
EP0258283A1 (de) 1988-03-09

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