EP0221492A2 - Gegenstand mit Verschleissschutzschicht aus Edelmetall - Google Patents

Gegenstand mit Verschleissschutzschicht aus Edelmetall Download PDF

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Publication number
EP0221492A2
EP0221492A2 EP86114909A EP86114909A EP0221492A2 EP 0221492 A2 EP0221492 A2 EP 0221492A2 EP 86114909 A EP86114909 A EP 86114909A EP 86114909 A EP86114909 A EP 86114909A EP 0221492 A2 EP0221492 A2 EP 0221492A2
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EP
European Patent Office
Prior art keywords
layer
precious metal
inclusions
alloy
coating
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.)
Granted
Application number
EP86114909A
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English (en)
French (fr)
Other versions
EP0221492B1 (de
EP0221492A3 (en
Inventor
Eric Saurer
Yves Ruedin
Jean-Paul Randin
Michel Sallin
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.)
Asulab AG
Original Assignee
Asulab 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 Asulab AG filed Critical Asulab AG
Publication of EP0221492A2 publication Critical patent/EP0221492A2/de
Publication of EP0221492A3 publication Critical patent/EP0221492A3/fr
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Publication of EP0221492B1 publication Critical patent/EP0221492B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/005—Coating layers for jewellery
    • A44C27/006—Metallic coatings
    • 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
    • C23C28/021—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 alloy layer
    • 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
    • G04B37/223—Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/938—Vapor deposition or gas diffusion
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12486—Laterally noncoextensive components [e.g., embedded, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12868—Group IB metal-base component alternative to platinum group metal-base component [e.g., precious metal, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12875—Platinum group metal-base component
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12889—Au-base component
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12896—Ag-base component

Definitions

  • the invention relates to an object, in particular a watch case, surmounted by a wear-resistant coating and consisting mainly of a precious metal from the group of gold, silver, rhodium, palladium, platinum, iridium, osmium and ruthenium or an alloy of said precious metal, said coating consisting of a first layer of said precious metal or its alloy, said first layer comprising discrete inclusions of a compound metallic consisting of an oxide, a nitride, a carbide, a boride, a phosphide, a silicide or a fluoride, said inclusions being distributed in a substantially homogeneous manner throughout the thickness of the first layer, said first layer being applied by deposition in vapor phase (CVD or PVD), its thickness being equal to or greater than 0.4 ⁇ m.
  • a wear-resistant coating consisting mainly of a precious metal from the group of gold, silver, rhodium, palladium, platinum, iridium, osm
  • the surface gold layer must be thin (equal to or less than 1 ⁇ m) for the coating to produce the expected effect, namely to make scratches caused by foreign bodies not very visible.
  • the coating described does not allow to reach a real plating containing enough precious metal so that said object can carry the maker's mark.
  • a source for example TiN
  • Another embodiment of the cited invention starts from two separate sources constituted respectively by the noble metal and the metallic compound, these sources being subjected to an evaporation process at increasing, respectively decreasing, speeds.
  • the coatings which are the subject of the two documents cited above, although being different in their composition, have a common characteristic: they both have a layer of precious metal, for example gold, deposited on underlying layers much harder than that of precious metal, for example titanium nitride. If the surface layer is scratched, it will be only slightly deep and the scratch will be only slightly visible, and this all the more if the underlying layer is of a color close to that of the precious metal deposited on the surface.
  • precious metal for example gold
  • Document JP-A-59 185774 describes a plating of a gold alloy deposited in the vapor phase and further comprising hardening agents in the form of nitrides. Thanks to this contribution, the hardness and the corrosion resistance of the plating are improved.
  • Document JP-A-60 114567 proposes the use of a precious metal codeposited with a transparent oxide to form the coating of an object which then has better resistance to wear and scratches.
  • the use of gold is proposed in conjunction with Si0 2 deposited by methods such as vacuum deposition. The method can be applied to watch cases and makes it possible to reduce the gold content to one fifth of a conventional coating while increasing the abrasion resistance.
  • the document JP-A-60 67 654 describes a coating of an object formed of gold or of a gold alloy and of titanium nitride by evaporation under vacuum, for example. This improves the abrasion and scratch resistance of objects such as watches or spectacle frames.
  • Figure 1 is a partial sectional view of the object according to the prior art.
  • Object 1 can be a watch case, a link making up a bracelet or any other item of jewelry.
  • he includes a box body or substrate 2 which can be made of noble metal, common metal (stainless steel, brass) or plastic.
  • the substrate 2 is surmounted by a coating 3 called the first layer.
  • This first layer consists mainly of a precious metal from the group of gold, silver, rhodium, palladium, platinum, iridium, osmium and ruthenium or an alloy of said precious metal, represented by an oblique hatch 4.
  • This layer 3 also includes discrete inclusions of a metallic compound constituted by an oxide, a nitride, a carbide, a boride, a phosphide, a silicide or a fluoride, represented by points 5.
  • discrete means that these are inclusions, that is to say aggregates composed of a large number of molecules without chemical bonds with the precious metal. These inclusions are distributed in a substantially homogeneous manner throughout the thickness of the layer considered.
  • This layer is obtained by vapor deposition, for example by CVD or PVD methods well known in the state of the art. These techniques are described in detail in the documents cited above and there is therefore no need to return to them here.
  • the deposit is applied in a single operation, either from a composite source, or from two sources, one containing the metal, the other the metallic compound.
  • the fine inclusions of metallic compound (of the order of 100 A) are distributed very evenly in the layer. This would not be the case if this layer was galvanically deposited from a bath containing metallic compounds in the form of powders whose dimensions would necessarily be much larger (of the order of 1 ⁇ m). In the latter case the distribution of inclusions in the layer would be less homogeneous because the dimension of these inclusions is of the same order than the thickness of the layer. This would result in a decrease in resistance to wear.
  • the coating comprises only a single first layer of precious metal and inclusions of metallic compound. If it is desired to produce an imitation of plating only, this layer will remain thin and its thickness will be between 0.5 and 1.5 ⁇ m for example. In addition to the metallic compound, this layer will include precious metal in the pure state or in the alloy state.
  • a precious metal alloy instead of pure precious metal, an alloy with a title equal to or greater than that required by legislation.
  • a second layer 6 consisting of a precious metal or an alloy of said precious metal, for example galvanically deposited.
  • a first layer 3 composed of a precious metal or a precious metal alloy 4 and inclusions of metallic compound 5 defined during the description of FIG. 1.
  • the second layer 6 can be pure precious metal if you want a high-grade coating or an alloy at 9, 14, 18 C depending on the title you want to reach.
  • This second embodiment has the advantage of being the cheapest since most of the coating is galvanically deposited, a very common process well known to specialists.
  • FIG. 3 reports spectral reflectivity measurements carried out on several samples using a spectrophotometer.
  • Curve A is that of fine gold (or pure gold)
  • curves B and C are those of standard colors defined respectively by symbols 1N14 and 2N18 of the standards of the Swiss watch industry (NIHS)
  • curve M is that of gold with inclusions according to the invention.
  • Curve M is obtained with inclusions of titanium nitride (TiN) in fine gold, these inclusions representing by volume 5 to 7% of the total volume occupied by the first layer.
  • This curve shows that the reflectivity of the first layer is close to that of the standard colors of layers commonly used in the watch industry (curves B and C) and which are generally obtained by galvanic means.
  • the layer studied here is naturally only an example and it is clear that by varying the percentage of inclusions and / or by replacing TiN with another metallic compound, it will be possible to obtain very different reflectivities and hence the colors related to other standards than those considered above.
  • FIG. 4 is a diagram reporting measurements on the wear resistance of the coated articles according to the invention compared to the wear resistance of a galvanically coated object.
  • it is a gold coating with inclusions at 6% by volume of TiN.
  • the time in hours during which the samples are subjected to the wear test was plotted on the abscissa and the mass of material removed in milligrams (mg) on the ordinate.
  • the samples to be tested are put in a smoothing machine by sliding with ceramic sticks, water and a wetting agent.
  • the abrasive mass and the samples oscillate in several directions and undergo a smoothing pressure which is pulsed.
  • the mass loss of the samples is determined as a function of the treatment time.
  • Such a smoothing machine was described in communication no. 18 entitled: "The wear of watch cases in galvanic gold plated" from the 57th congress of the Swiss Chronometry Society, Montreux 22 and 23 October 1982.
  • the method which has just been described operates by smoothing or rubbing the surface to be examined. It differs in this from a simple hardness measurement with a microdurometer, because we realized that it is not always correct to correlate a hardness measurement and a determination of the resistance to wear.
  • the coating does not have a much higher hardness in the sense that it is usually understood, but rather an excellent resistance to wear if this is measured by simulating the phenomenon of wear. as it occurs naturally.
  • curve A ' represents the mass loss of a sample covered with galvanic fine gold
  • curve M' represents the mass loss of a sample covered with the coating according to the invention, the mass losses being measured according to the method indicated above under identical conditions.
  • the loss of mass therefore the wear is about twice as low for the sample covered according to the invention this characteristic remaining substantially constant throughout the time that the test lasted (240 hours).
  • the work entitled "The clothing of the watch” by JP Renaud, LSRH, Neucaul June 3 and 17, 1975 it has been shown that the reduction in thickness of a layer of galvanic gold alloy grading 18 carats around 2 pm per year for a watch case to wear. This reduction will only be 1 pm for the same period if the watch case is coated with the layer defined by the invention, which represents a remarkable improvement.
  • Decorative coatings generally include a so-called color finishing phase.
  • This important operation generally consists in depositing a layer of gold with a thickness of between 0.5 and 1.5 ⁇ m for 23.5 C. It aims mainly at two goals: that of checking the final color first ( aspect) of the plating, because the underlying plating composed of gold, silver, copper, cadmium can have very variable colors depending on the deposition conditions (different deposition rate of the metals constituting the alloy); that of preventing the color changes in the underlying plating (tarnishing) that would occur over time, changes that are all the more important the lower the titer.
  • the galvanic coloring phase is replaced by a phase pursuing the same goals but deposited in the vapor phase.
  • the wear resistance will be at least doubled, which will lead to a plating of higher quality and better reliability, thanks to the inclusions of metallic compound deposited at the same time as the precious metal.
  • the coating deposited according to the invention must have a total thickness of at least 8 ⁇ m and titrate at least 9 carats.
  • This coating could comprise a second layer of gold alloy with a thickness equal to or greater than 7 ⁇ m, second layer on which is deposited a first layer of thickness reaching at least 1 ⁇ m obtained in the vapor phase and containing gold and nitride inclusions of titanium occupying a volume between 5% and 7% of the total volume occupied by said first layer.
  • the coating according to the invention also has a corrosion resistance which is comparable to that of precious metal without inclusions.
  • tests have been carried out according to conventional methods such as, for example, exposure to salt spray and periodic soaking in artificial sea water or artificial sweat.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Vapour Deposition (AREA)
EP86114909A 1985-11-04 1986-10-27 Gegenstand mit Verschleissschutzschicht aus Edelmetall Expired - Lifetime EP0221492B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8516425A FR2589484A1 (fr) 1985-11-04 1985-11-04 Objet pourvu d'un revetement en metal precieux resistant a l'usure
FR8516425 1985-11-04

Publications (3)

Publication Number Publication Date
EP0221492A2 true EP0221492A2 (de) 1987-05-13
EP0221492A3 EP0221492A3 (en) 1988-04-13
EP0221492B1 EP0221492B1 (de) 1991-05-15

Family

ID=9324553

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86114909A Expired - Lifetime EP0221492B1 (de) 1985-11-04 1986-10-27 Gegenstand mit Verschleissschutzschicht aus Edelmetall

Country Status (6)

Country Link
US (1) US4745035A (de)
EP (1) EP0221492B1 (de)
JP (1) JPS62112783A (de)
DE (1) DE3679280D1 (de)
ES (1) ES2022801B3 (de)
FR (1) FR2589484A1 (de)

Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP0716360A1 (de) 1995-08-30 1996-06-12 Fabrique D'ebauches De Sonceboz S.A Uhrengehäuse mit ausgehöhltem Gehäuseteil und Gehäuseanpassungsmittel sowie eine mit einem solchen Gehäuse ausgerüstete Uhr
EP1548525B2 (de) † 2003-12-23 2017-08-16 Rolex Sa Keramisches Element für Uhrengehäuse und Verfahren zu seiner Herstellung

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FR2699555B1 (fr) * 1992-12-23 1995-02-03 Ebauchesfabrik Eta Ag Objet présentant un revêtement de coloration rosée.
CN1109126C (zh) * 1993-12-28 2003-05-21 西铁城钟表有限公司 白色覆饰件及其生产方法
GB2288351B (en) * 1994-04-08 1998-03-18 Cutting & Wear Resistant Dev Method for facing a substrate
US5840432A (en) * 1995-02-13 1998-11-24 Hitachi Chemical Company, Ltd. Electroconductive paste
FR2752689B1 (fr) * 1996-09-04 1998-10-23 Joaillier Du Vermeil Piece d'orfevrerie, de bijouterie, de joaillerie, d'horlogerie, de decoration ou analogue
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US6007390A (en) * 1998-06-30 1999-12-28 General Motors Corporation Low friction metal-ceramic composite coatings for electrical contacts
US7175686B2 (en) * 2003-05-20 2007-02-13 Exxonmobil Research And Engineering Company Erosion-corrosion resistant nitride cermets
US7211338B2 (en) * 2003-12-19 2007-05-01 Honeywell International, Inc. Hard, ductile coating system
JP4836943B2 (ja) * 2004-05-11 2011-12-14 ザ リージェンツ オブ ザ ユニバーシティー オブ カリフォルニア 二ホウ化オスミウム化合物、工具、表面コーティング材、研磨材、コーティング方法、研磨方法、及び、切削方法
CN102994949A (zh) * 2005-03-31 2013-03-27 西铁城控股株式会社 金色装饰品及其制造方法
JP5016961B2 (ja) * 2007-03-30 2012-09-05 株式会社神戸製鋼所 刃部材
US20100307671A1 (en) * 2009-06-08 2010-12-09 Zoltan David Metal ornamentation method
US9949539B2 (en) 2010-06-03 2018-04-24 Frederick Goldman, Inc. Method of making multi-coated metallic article
CN102477527B (zh) * 2010-11-23 2014-07-30 鸿富锦精密工业（深圳）有限公司 壳体的制作方法及由该方法制得的壳体
DE102010054046B4 (de) * 2010-12-10 2012-10-18 Dot Gmbh Antibakterielle Beschichtung für ein Implantat und Implantat.
US8956510B2 (en) 2011-06-03 2015-02-17 Frederick Goldman, Inc. Coated metallic products and methods for making the same
US8932437B2 (en) 2011-06-03 2015-01-13 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same
EP2667265A1 (de) * 2012-05-22 2013-11-27 The Swatch Group Research and Development Ltd. Hartgelötete Bimetall-Ausstattungselement
JP2015140484A (ja) * 2014-01-30 2015-08-03 セイコーエプソン株式会社 時計用外装部品、時計用外装部品の製造方法および時計
RU2567428C1 (ru) * 2014-05-19 2015-11-10 Общество с ограниченной ответственностью "ИННОВАТЕХПРОМ" ООО "ИННОВАТЕХПРОМ" Защитно-декоративное покрытие изделия и способ его получения (варианты)
USD896378S1 (en) 2016-12-22 2020-09-15 Integra Lifesciences Corporation Bipolar forceps
CH713746A1 (fr) * 2017-04-28 2018-10-31 Montblanc Montre Sa Procédé de dépôt d'un revêtement d'or sur un article et article obtenu par ce procédé.
CN111588151A (zh) * 2020-05-15 2020-08-28 东吴黄金集团有限公司 一种金包银饰品及其制备方法
JP2022188877A (ja) * 2021-06-10 2022-12-22 セイコーエプソン株式会社 時計部品、時計

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FR1074831A (fr) * 1952-02-16 1954-10-08 Heraeus Gmbh W C Revêtement améliorant pour parure métallique, par exemple bracelet, collier, boîtier de montre, etc.
US3481854A (en) * 1967-01-20 1969-12-02 Us Air Force Preparation of thin cermet films by radio frequency sputtering
DE1621347A1 (de) * 1967-10-25 1971-06-03 Siemens Ag Mehrlagige Schichtanordnung,insbesondere aus Aufdampfschichten bestehend
US3606766A (en) * 1969-06-26 1971-09-21 Engelhard Min & Chem Gold finger article composed of compressed and sintered fine gold powder and a refractory oxide
FR2218301A1 (en) * 1973-02-16 1974-09-13 Saint Gobain Semi-reflecting glaze with semi-conductor layer - of pref tin oxide, indium oxide or titanium nitride applied on film of gold, silver or copper
DE2705225C2 (de) * 1976-06-07 1983-03-24 Nobuo Tokyo Nishida Ornamentteil für Uhren usw.
JPS54148182A (en) * 1978-05-13 1979-11-20 Tsuneo Nishida Golddcolor outer decorating part and its manufacture
US4252862A (en) * 1977-06-10 1981-02-24 Nobuo Nishida Externally ornamental golden colored part
JPS6057168B2 (ja) * 1978-03-31 1985-12-13 松下電工株式会社 複合接点
JPS56112473A (en) * 1980-02-08 1981-09-04 Dairiyuu Denshi Sangyo Kk Metallic film for decoration of stainless steel
CH643421B (fr) * 1980-04-10 Asu Composants Sa Procede de depot d'un revetement dur d'un compose d'or, cible de depot pour un tel procede et piece de joaillerie comportant un tel revetement.
JPS56166063A (en) * 1980-05-27 1981-12-19 Citizen Watch Co Ltd Gold sheathing part
US4517217A (en) * 1980-09-09 1985-05-14 Westinghouse Electric Corp. Protective coating means for articles such as gold-plated jewelry and wristwatch components
JPS589975A (ja) * 1981-07-09 1983-01-20 Arakawa Kako Kk 金色腕時計外装部品
ES515502A0 (es) * 1981-09-08 1983-10-16 Johnson Matthey Plc Metodo de produccion de un material metalico compuesto.
JPS58153776A (ja) * 1982-03-05 1983-09-12 Citizen Watch Co Ltd 装飾部品の製造方法およびそれに用いるイオンプレ−テイング装置
JPS59185774A (ja) * 1983-04-04 1984-10-22 Mitsubishi Metal Corp 硬質金合金被覆層の形成方法
JPS6067654A (ja) * 1983-09-22 1985-04-18 Seiko Instr & Electronics Ltd 硬質金合金めつきの製造方法
JPS60114567A (ja) * 1983-11-25 1985-06-21 Seiko Instr & Electronics Ltd 硬質めつき膜の形成方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0716360A1 (de) 1995-08-30 1996-06-12 Fabrique D'ebauches De Sonceboz S.A Uhrengehäuse mit ausgehöhltem Gehäuseteil und Gehäuseanpassungsmittel sowie eine mit einem solchen Gehäuse ausgerüstete Uhr
EP1548525B2 (de) † 2003-12-23 2017-08-16 Rolex Sa Keramisches Element für Uhrengehäuse und Verfahren zu seiner Herstellung

Also Published As

Publication number Publication date
US4745035A (en) 1988-05-17
EP0221492B1 (de) 1991-05-15
FR2589484A1 (fr) 1987-05-07
EP0221492A3 (en) 1988-04-13
DE3679280D1 (de) 1991-06-20
ES2022801B3 (es) 1991-12-16
JPS62112783A (ja) 1987-05-23

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