EP1010777A2 - Article revêtu avec un revêtement multicouche - Google Patents

Article revêtu avec un revêtement multicouche Download PDF

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Publication number
EP1010777A2
EP1010777A2 EP99123321A EP99123321A EP1010777A2 EP 1010777 A2 EP1010777 A2 EP 1010777A2 EP 99123321 A EP99123321 A EP 99123321A EP 99123321 A EP99123321 A EP 99123321A EP 1010777 A2 EP1010777 A2 EP 1010777A2
Authority
EP
European Patent Office
Prior art keywords
titanium
layer
zirconium
compound
inch
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Withdrawn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
EP99123321A
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German (de)
English (en)
Other versions
EP1010777A3 (fr
Inventor
Patrick B. Jonte
William K. Grant
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.)
Masco Corp
Masco Corp of Indiana
Original Assignee
Masco Corp
Masco Corp of Indiana
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 Masco Corp, Masco Corp of Indiana filed Critical Masco Corp
Publication of EP1010777A2 publication Critical patent/EP1010777A2/fr
Publication of EP1010777A3 publication Critical patent/EP1010777A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • 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
    • 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
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • This invention relates to decorative and protective coatings.
  • a coating containing a nickel basecoat and a non-precious refractory metal compound such as zirconium nitride, titanium nitride and zirconium-titanium alloy nitride top coat.
  • a non-precious refractory metal compound such as zirconium nitride, titanium nitride and zirconium-titanium alloy nitride top coat.
  • zirconium compound such as zirconium nitride, or a zirconium alloy compound over the layers containing the titanium compound or titanium alloy compound significantly reduces or eliminates galvanic corrosion.
  • the present invention is directed to a protective and decorative coating for a substrate, particularly a metallic substrate. More particularly, it is directed to a substrate, particularly a metallic substrate such as brass, having on at least a portion of its surface a coating comprised of multiple superposed layers of certain specific types of metals or metal compounds wherein at least one of the layers contains titanium or a titanium alloy.
  • the coating is decorative and also provides corrosion, wear and chemical resistance.
  • the coating provides the appearance of polished brass with a golden hue, i.e. has a golden-brass color tone.
  • an article surface having the coating thereon simulates polished brass with a gold hue.
  • a first layer deposited directly on the surface of the substrate is comprised of nickel.
  • the first layer may be monolithic, i.e., a single nickel layer, or it may consist of two different nickel layers such as a semi-bright nickel layer deposited directly on the surface of the substrate and a bright nickel layer superimposed over the semi-bright nickel layer.
  • Over the nickel layer is a layer comprised of chrome.
  • Over the chrome layer is a strike layer comprised of titanium or titanium alloy.
  • a layer comprised of titanium compound or titanium alloy compound is optionallybstructive nickel.
  • titanium compound or titanium alloy compound layer Over the titanium compound or titanium alloy compound layer is a thin layer comprised of zirconium compound or zirconium alloy compound. This layer functions to reduce or eliminate galvanic corrosion.
  • the substrate 12 can be any plastic, metal or metallic alloy.
  • metal and metal alloy substrates are copper, steel, brass, tungsten, nickel alloys and the like.
  • the substrate is brass.
  • a nickel layer 13 is deposited on the surface of the substrate 12 by conventional and well known electroplating processes. These processes include using a conventional electroplating bath such as, for example, a Watts bath as the plating solution. Typically such baths contain nickel sulfate, nickel chloride, and boric acid dissolved in water. All chloride, sulfamate, and fluoroborate plating solutions can also be used. These baths can optionally include a number of well known and conventionally used compounds such as leveling agents, brighteners, and the like. To produce specularly bright nickel layer at least one brightener from class I and at least one brightener from class II is added to the plating solution. Class I brighteners are organic compounds which contain sulfur.
  • Class II brighteners are organic compounds which do not contain sulfur. Class II brighteners can also cause leveling and, when added to the plating bath without the sulfur-containing class I brighteners, result in semi-bright nickel deposits. These class I brighteners include alkyl naphthalene and benzene sulfonic acid. The benzene and naphthalene di- and trisulfonic acids, benzene and naphthalene sulfonamides, and sulfonamides such as saccharin, vinyl and allyl sulfonamides and sulfonic acids.
  • the class II brighteners generally are unsaturated organic materials such as, for example, acetylenic or ethylenic alcohols, ethoxylated and propoxylated acetylenic alcohols, coumarins, and aldehydes. These class I and class II brighteners are well known to those skilled in the art and are readily commercially available. They are described, inter alia, in U.S. Patent No. 4,421,611.
  • the nickel layer 13 can be comprised of a single nickel layer such as, for example, bright nickel, or it can be comprised of two different nickel layers such as a semi-bright nickel layer and a bright nickel layer.
  • layer 14 is comprised of semi-bright nickel while layer 16 is comprised of bright nickel.
  • This duplex nickel deposit provides improved corrosion protection to the underlying substrate.
  • the semi-bright, sulfur free plate 14 is deposited by conventional electroplating processes directly on the surface of substrate 12.
  • the substrate 12 containing the semi-bright nickel layer 14 is then plated in a bright nickel plating bath and the bright nickel layer 16 is deposited on the semi-bright nickel layer 14, also by conventional electroplating processes.
  • the thickness of the nickel layer 13 is generally in the range of from about 2540 nm [100 millionths (0.0001) of an inch], preferably from about 3810 nm [150 millionths (0.00015) of an inch] to about 88900 nm [3500 millionths (0.0035) of an inch].
  • the thickness of the semi-bright nickel layer and the bright nickel layer is a thickness effective to provide improved corrosion protection.
  • the thickness of the semi-bright nickel layer 14 is at least about 1270 nm [50 millionths (0.00005) of an inch], preferably at least about 2540 nm [100 millionths (0.0001) of an inch], and more preferably at least about 3810 nm [150 millionths (0.00015) of an inch].
  • the upper thickness limit is generally not critical and is governed by secondary considerations such as cost and appearance.
  • a thickness of about 38100 nm [1500 millionths (0.0015) of an inch], preferably about 25400 nm [1000 millionths (0.001) of an inch], and more preferably about 19050 nm [750 millionths (0.00075) of an inch] should not be exceeded.
  • the bright nickel layer 16 generally has a thickness of at least about 1270 nm [50 millionths (0.00005) of an inch], preferably at least about 3175 nm [125 millionths (0.000125) of an inch], and more preferably at least about 6350 nm [250 millionths (0.00025) of an inch] .
  • the upper thickness range of the bright nickel layer is not critical and is generally controlled by considerations such as cost.
  • a thickness of about 63500 nm [2500 millionths (0.0025) of an inch], preferably about 50800 nm [2000 millionths (0.002) of an inch], and more preferably about 38100 nm [1500 millionths (0.0015) of an inch] should not be exceeded.
  • the bright nickel layer 16 also functions as a leveling layer which tends to cover or fill in imperfections in the substrate.
  • a layer 22 Disposed over the nickel layer 13, particularly the bright nickel layer, is a layer 22 comprised of chrome.
  • the chrome layer 22 may be deposited on layer 13 by conventional and well known chromium electroplating techniques. These techniques along with various chrome plating baths are disclosed in Brassard, "Decorative Electroplating - A Process in Transition", Metal Finishing, pp. 105-108, June 1988; Zaki, “Chromium Plating", PF Directory, pp. 146-160; and in U.S. Patent Nos. 4,460,438; 4,234,396 and 4,093,522. Chrome plating baths are well known and commercially available. A typical chrome plating bath contains chromic acid or sales thereof, and catalyst ion such as sulfate or fluoride.
  • the catalyst ions can be provided by sulfuric acid or its salts and fluosilicic acid.
  • the baths may be operated at a temperature of about 44.4 - 46.7°C [112 - 116°F].
  • a current density of about 1615 A/m 2 [150 amps per square foot] at about S to 9 volts is utilized.
  • the chrome layer 22 serves to provide structural integrity to the vapor deposited layers or reduce or eliminate plastic deformation of the coating.
  • the nickel layer 13 is relatively soft compared to the titanium compound or titanium alloy compound layer 30. Thus, an object impinging on, striking or pressing on layer 30 will not penetrate this relatively hard layer, but this force will be transferred to the relatively soft underlying nickel layer 13 causing plastic deformation of this layer.
  • Chrome layer 22 has a thickness at least effective to provide structural integrity to and reduce plastic deformation of the coating. This thickness is at least about 50.8 nm [2 millionths (0.000002) of an inch], preferably at least about 127 nm [5 millionths (0.000005) of an inch], and more preferably at least about 203.2 nm [8 millionths (0.000008) of an inch]. Generally, the upper range of thickness is not critical and is determined by secondary considerations such as cost.
  • the thickness of the chrome layer should generally not exceed about 1524 nm [60 millionths (0.00006) of an inch], preferably about 1270 nm [50 millionths (0.00005) of an inch], and more preferably about 1016 nm [40 millionths (0.00004) of an inch].
  • a strike layer 28 Disposed over chrome layer 22 is a strike layer 28 comprised of titanium or titanium alloy.
  • the strike layer 28 functions, inter alia, to improve the adhesion of layer 30, comprised of titanium compound or titanium alloy compound, to the chrome layer 22.
  • this thickness is at least about 6.35 nm [0.25 millionths (0.00000025) of an inch], preferably at least about 12.7 nm [0.5 millionths (0.0000005) of an inch], and more preferably at least about 25.4 nm [one millionth (0.000001) of an inch].
  • the upper thickness range is not critical and is generally dependent upon considerations such as cost and appearance.
  • layer 28 should not be thicker than about 1270 nm [50 millionths (0.00005) of an inch], preferably about 381 nm [15 millionths (0.000015) of an inch], and more preferably about 254 nm [10 millionths (0.00001) of an inch].
  • layer 30 comprised of titanium compound or titanium alloy compound.
  • Layer 30 provides wear and abrasion resistance and the desired color or appearance, such as for example a brass color with a golden hue.
  • Layer 30 has a thickness effective to provide abrasion and wear resistance and to provide the requisite color. The color depends on the composition of layer 30. Thus, titanium-zirconium nitride will provide a brass color with a golden hue.
  • Generally layer 30 has a thickness of at least about 50.8 nm [2 millionths (0.000002) of an inch], preferably at least 101.6 nm [4 millionths (0.000004) of an inch], and more preferably at least 152.4 nm [6 millionths (0.000006) of an inch].
  • the upper thickness range is generally not critical and is dependent upon considerations such as cost.
  • a thickness of about 2540 nm [100 millionths (0.0001) of an inch], preferably about 1270 nm [50 millionths (0.00005) of an inch], and more preferably about 762 nm [30 millionths (0.00003) of an inch] should not be exceeded.
  • the metals that are alloyed with the titanium to form the titanium alloy or titanium alloy compound are the non-precious refractory metals. These include zirconium, hafnium, tantalum, and tungsten.
  • the titanium alloys generally comprise from about 10 to about 90 weight percent titanium and from about 90 to about 10 weight percent of another non-precious refractory metal, preferably from about 20 to about 80 weight percent titanium and from about 80 to about 20 weight percent of another refractory metal.
  • the titanium compounds or titanium alloy compounds include the oxides, nitrides, carbides and carbonitrides.
  • layer 30 is comprised of titanium-zirconium alloy nitride and layer 28 is comprised of titanium-zirconium alloy.
  • the titanium-zirconium alloy nitride layer has a brass color with a golden hue.
  • a method of forming layers 28 and 30 is by utilizing well known and conventional vapor deposition techniques such as physical vapor deposition or chemical vapor deposition.
  • Physical vapor deposition processes include sputtering and cathodic arc evaporation.
  • sputtering or cathodic arc evaporation is used to deposit a layer 28 of titanium alloy or titanium followed by reactive sputtering or reactive cathodic arc evaporation to deposit a layer 30 of titanium alloy compound such as titanium-zirconium nitride or titanium compound such as titanium nitride.
  • nitrogen gas is introduced during vapor deposition such as reactive sputtering or reactive cathodic arc evaporation at a desired value or flow rate to form titanium nitride or titanium alloy nitride.
  • Layer 34 is comprised of a zirconium compound or a zirconium alloy compound.
  • the zirconium compounds or zirconium alloy compounds are the oxides, nitrides, carbides and carbonitrides.
  • the metals that are alloyed with zirconium to form the zirconium alloy compounds are the non-precious refractory metal compounds excluding titanium.
  • the zirconium alloy comprises from about 30 to about 90 weight percent zirconium, the remainder being non-precious refractory metal other than titanium; preferably from about 40 to about 90 weight percent zirconium, the remainder being non-precious refractory metal other than titanium; and more preferably from about 50 to about 90 weight percent zirconium, the remainder being non-precious refractory metal other than titanium.
  • Layer 34 may be, for example, zirconium nitride when layer 30 is zirconium-titanium alloy nitride.
  • Layer 34 is very thin. It is thin enough so that it is non-opaque, translucent or transparent in order to allow the color of layer 30 to be seen. It is, however, thick enough to significantly reduce or eliminate galvanic corrosion. Generally layer 34 has a thickness from about 1.778 to 17.78 nm [0.07 millionth to about 0.7 millionth of an inch], preferably from about 5.08 to 7.62 nm [0.2 millionth to about 0.3 millionth of an inch].
  • Layer 34 can be deposited by well known and conventional vapor deposition techniques, including physical vapor deposition and chemical vapor deposition such as, for example, reactive sputtering and reactive cathodic arc evaporation.
  • a refractory metal (such as titanium or zirconium) target which is the cathode
  • the substrate are placed in a vacuum chamber.
  • the air in the chamber is evacuated to produce vacuum conditions in the chamber.
  • An inert gas, such as Argon, is introduced into the chamber.
  • the gas particles are ionized and are accelerated to the target to dislodge titanium or zirconium atoms.
  • the dislodged target material is then typically deposited as a coating film on the substrate.
  • cathodic arc evaporation an electric arc of typically several hundred amperes is struck on the surface of a metal cathode such as zirconium or titanium. The arc vaporizes the cathode material, which then condenses on the substrates forming a coating.
  • Reactive cathodic arc evaporation and reactive sputtering are generally similar to ordinary sputtering and cathodic arc evaporation except that a reactive gas is introduced into the chamber which reacts with the dislodged target material.
  • the cathode is comprised of zirconium and nitrogen is the reactive gas introduced into the chamber.
  • Brass faucets are placed in a conventional soak cleaner bath containing the standard and well known soaps, detergents, defloculants and the like which is maintained at a pH of 8.9 - 9.2 and a temperature of about 62.8 - 93.3°C [145 - 200°F] for 10 minutes.
  • the brass faucets are then placed in a conventional ultrasonic alkaline cleaner bath.
  • the ultrasonic cleaner bath has a pH of 8.9 - 9.2, is maintained at a temperature of about 71.1 - 82.2°C [160 - 180°F], and contains the conventional and well known soaps, detergents, defloculants and the like.
  • After the ultrasonic cleaning the faucets are rinsed and placed in a conventional alkaline electro cleaner bath for about 50 seconds.
  • the electro cleaner bath is maintained at a temperature of about 60 - 82.2°C [140 - 180°F], a pH of about 10.5 - 11.5, and contains standard and conventional detergents.
  • the faucets are then rinsed and placed in a conventional acid activator bath for about 20 seconds.
  • the acid activator bath has a pH of about 2.0 - 3.0, is at an ambient temperature, and contains a sodium fluoride based acid salt.
  • the faucets are then placed in a conventional and standard bright nickel plating bath for about 12 minutes.
  • the bright nickel bath is generally a conventional bath which is maintained at a temperature of about 54.4 - 65.6°C (130 - 150°F], a pH of about 4.0 - 4.8, contains NiSO 4 , NiCL 2 , boric acid, and brighteners.
  • a bright nickel layer of an average thickness of about 10160 nm [400 millionths (0.0004) of an inch] is deposited on the faucets.
  • the bright nickel plated faucets are rinsed three times and then placed in a conventional, commercially available hexavalent chromium plating bath using conventional chromium plating equipment for about seven minutes.
  • the hexavalent chromium bath is a conventional and well known bath which contains about 240 g/L [32 ounces/gallon] of chromic acid.
  • the bath also contains the conventional and well known chromium plating additives.
  • the bath is maintained at a temperature of about 44.4 - 46.7°C [112 - 116° F], and utilizes a mixed sulfate/fluoride catalyst.
  • the chromic acid to sulfate ratio is about 200:1.
  • a chromium layer of about 254 nm [10 millionths of an inch] is deposited on the surface of the bright-nickel layer.
  • the faucets are thoroughly rinsed in deionized water and then dried.
  • the chromium plated faucets are placed in a cathodic arc evaporation plating vessel.
  • the vessel is generally a cylindrical enclosure containing a vacuum chamber, which is adapted to be evacuated by means of pumps.
  • a source of argon gas is connected to the chamber by an adjustable valve for varying the rate of flow of gas.
  • a cylindrical zirconium-titanium alloy cathode is mounted in the center of the chamber and connected to negative outputs of a variable D.C. power supply.
  • the positive side of the power supply is connected to the chamber wall.
  • the cathode material comprises zirconium and titanium.
  • the plated faucets are mounted on spindles, 16 of which are mounted on a ring around the outside of the cathode.
  • the entire ring rotates around the cathode while each spindle also rotates around its own axis, resulting in a so-called planetary motion which provides uniform exposure to the cathode for the multiple faucets mounted around each spindle.
  • the ring typically rotates at several rpm, while each spindle makes several revolutions per ring revolution.
  • the spindles are electrically isolated from the chamber and provided with rotatable contacts so that a bias voltage may be applied to the substrates during coating.
  • the vacuum chamber is evacuated to a pressure of about 5x10 -3 millibar and heated to about 150°C.
  • the electroplated faucets are then subjected to a high-bias arc plasma cleaning in which a (negative) bias voltage of about 500 volts is applied to the electroplated faucets while an arc of approximately 500 amperes is struck and sustained on the cathode.
  • the duration of the cleaning is approximately five minutes.
  • Argon gas is introduced at a rate sufficient to maintain a pressure of about 3x10 - 2 millibars.
  • a layer of zirconium-titanium alloy having an average thickness of about 101.6 nm [4 millionths of an inch] is deposited on the chrome plated faucets during a three minute period.
  • the cathodic arc deposition process comprises applying D.C. power to the cathode to achieve a current flow of about 500 amps, introducing argon gas into the vessel to maintain the pressure in the vessel at about 1x10 -2 millibar, and rotating the faucets in a planetary fashion described above.
  • a thicker zirconium-titanium nitride compound "color layer" is deposited over it.
  • a flow of nitrogen is introduced into the vacuum chamber while the arc discharge continues at approximately 500 amperes.
  • the nitrogen flow rate is set sufficiently high to fully react the zirconium and titanium alloy atoms arriving at the substrate to form zirconium-titanium nitride compound.
  • the total time for deposition is about 30 minutes. The arc is extinguished at the end of this deposition period, the vacuum chamber is vented and the coated substrates removed.
  • a final thin non-optically dense flash layer of zirconium nitride is deposited to provide increased corrosion resistance and to achieve the desired final color.
  • the coated substrate parts are placed into another chamber fitted with cylindrical cathode target composed primarily of zirconium metal.
  • the chamber is evacuated to pressures previously described as well as the parts cleaned again by subjecting them to high-bias arc plasma as described earlier.
  • the cathodic arc deposition process is repeated with nitrogen and argon gas flows set sufficiently high to provide full or nearly full reaction of the zirconium metal to zirconium nitride compound. This flash process is carried out for a one to three minute period. Finally the arc is extinguished, the chamber vented and the coated substrates removed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP99123321A 1998-12-01 1999-11-23 Article revêtu avec un revêtement multicouche Withdrawn EP1010777A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20191898A 1998-12-01 1998-12-01
US201918 1998-12-01

Publications (2)

Publication Number Publication Date
EP1010777A2 true EP1010777A2 (fr) 2000-06-21
EP1010777A3 EP1010777A3 (fr) 2002-07-31

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Country Status (6)

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EP (1) EP1010777A3 (fr)
CN (1) CN1259589A (fr)
CA (1) CA2291363A1 (fr)
FR (1) FR2786506A1 (fr)
GB (1) GB2344355A (fr)
NL (1) NL1013704C1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1624092A1 (fr) * 2004-08-06 2006-02-08 Yamaha Hatsudoki Kabushiki Kaisha Pot d'échappement chromé
US7854831B2 (en) * 2003-03-19 2010-12-21 Blanco Gmbh + Co Kg Method for the manufacture of sanitary fittings with a stainless steel finish
CN102628156A (zh) * 2012-04-09 2012-08-08 上海仟纳真空镀膜科技有限公司 一种pvd超黑涂层

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003268567A (ja) * 2002-03-19 2003-09-25 Hitachi Cable Ltd 導電材被覆耐食性金属材料
CN102544884B (zh) * 2011-12-23 2015-04-01 富士康(昆山)电脑接插件有限公司 电连接器、电连接器壳体及其表面处理的方法
CN109423646A (zh) * 2017-08-24 2019-03-05 华为技术有限公司 一种复合涂层的制备方法以及电子产品制件
CN110106467A (zh) * 2019-06-25 2019-08-09 中国核动力研究设计院 一种核反应堆用高效结合包覆层及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5626972A (en) * 1994-06-02 1997-05-06 Baldwin Hardware Corporation Article having a decorative and protective multilayer coating simulating brass
US5641579A (en) * 1993-02-05 1997-06-24 Baldwin Hardware Corporation Article having a decorative and protective multilayer coating
EP0875596A1 (fr) * 1997-04-30 1998-11-04 Masco Corporation Article pourvu d'un revêtement de protection et de decoration
EP0875600A1 (fr) * 1997-04-30 1998-11-04 Masco Corporation Article revêtu
EP0875602A1 (fr) * 1997-04-30 1998-11-04 Masco Corporation Of Indiana Article revêtu

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6004684A (en) * 1997-04-30 1999-12-21 Masco Corporation Article having a protective and decorative multilayer coating
US5985468A (en) * 1997-04-30 1999-11-16 Masco Corporation Article having a multilayer protective and decorative coating
US5952111A (en) * 1997-04-30 1999-09-14 Masco Corporation Article having a coating thereon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641579A (en) * 1993-02-05 1997-06-24 Baldwin Hardware Corporation Article having a decorative and protective multilayer coating
US5626972A (en) * 1994-06-02 1997-05-06 Baldwin Hardware Corporation Article having a decorative and protective multilayer coating simulating brass
EP0875596A1 (fr) * 1997-04-30 1998-11-04 Masco Corporation Article pourvu d'un revêtement de protection et de decoration
EP0875600A1 (fr) * 1997-04-30 1998-11-04 Masco Corporation Article revêtu
EP0875602A1 (fr) * 1997-04-30 1998-11-04 Masco Corporation Of Indiana Article revêtu

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7854831B2 (en) * 2003-03-19 2010-12-21 Blanco Gmbh + Co Kg Method for the manufacture of sanitary fittings with a stainless steel finish
EP1624092A1 (fr) * 2004-08-06 2006-02-08 Yamaha Hatsudoki Kabushiki Kaisha Pot d'échappement chromé
US7726121B2 (en) 2004-08-06 2010-06-01 Yamaha Hatsudoki Kabushiki Kaisha Engine part
CN102628156A (zh) * 2012-04-09 2012-08-08 上海仟纳真空镀膜科技有限公司 一种pvd超黑涂层

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EP1010777A3 (fr) 2002-07-31
GB2344355A (en) 2000-06-07
GB9927747D0 (en) 2000-01-26
CA2291363A1 (fr) 2000-06-01
CN1259589A (zh) 2000-07-12
NL1013704C1 (nl) 2000-06-06
FR2786506A1 (fr) 2000-06-02

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