MXPA96001823A - Article that has a protective coat that simulates the la - Google Patents
Article that has a protective coat that simulates the laInfo
- Publication number
- MXPA96001823A MXPA96001823A MXPA/A/1996/001823A MX9601823A MXPA96001823A MX PA96001823 A MXPA96001823 A MX PA96001823A MX 9601823 A MX9601823 A MX 9601823A MX PA96001823 A MXPA96001823 A MX PA96001823A
- Authority
- MX
- Mexico
- Prior art keywords
- layer
- comprised
- approximately
- tin
- article
- Prior art date
Links
- 230000001681 protective Effects 0.000 title description 3
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 21
- 239000010974 bronze Substances 0.000 claims abstract description 21
- -1 tin-nickel Chemical compound 0.000 claims abstract description 19
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N Zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims description 23
- 150000003755 zirconium compounds Chemical class 0.000 claims description 11
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 4
- 239000003870 refractory metal Substances 0.000 abstract description 4
- 230000004224 protection Effects 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000007747 plating Methods 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003599 detergent Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000009718 spray deposition Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002363 hafnium compounds Chemical class 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003482 tantalum compounds Chemical class 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L Nickel(II) chloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910006414 SnNi Inorganic materials 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TXKRDMUDKYVBLB-UHFFFAOYSA-N methane;titanium Chemical compound C.[Ti] TXKRDMUDKYVBLB-UHFFFAOYSA-N 0.000 description 1
- UGHSGZIDZZRZKT-UHFFFAOYSA-N methane;zirconium Chemical compound C.[Zr] UGHSGZIDZZRZKT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229940013123 stannous chloride Drugs 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin dichloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Abstract
The present invention relates to an article that is coated with a multilayer coating comprising a layer of tin-nickel alloy deposited on the surface of the article, and a refractory metal compound, preferably of zirconium nitride, deposited on the layer tin-nickel. The coating provides the color of the polished bronze to the article and also provides protection against wear and abrasion.
Description
Ref.22450 ARTICLE THAT HAS A PROTECTIVE COAT THAT SIMULATES THE BRONZE ^
FIELD OF THE INVENTION
The present invention relates to substrates, in particular to bronze substrates, coated with a decorative and multi-layer protective coating.
BACKGROUND OF THE INVENTION
It is a very common practice with several bronze items such as lamps, placemats, candlesticks, door knobs, door handles, shields or ornamental door plates and the like, that the surface of the item is first smoothed and polished until it is obtained an intense gloss and then a protective organic coating, such as one comprised of acrylics, urethanes, epoxies, and the like, is applied on this polished surface. Although this system in general is quite satisfactory, it has the disadvantage that the operation of smoothing and polishing, particularly if the article is of a complex shape, is of an intense work. Also, known organic coatings are not always as durable as desired, particularly in external applications where articles are exposed to the elements and ultraviolet radiation. Therefore, it could be completely advantageous if the brass articles, or indeed other metal articles, could be provided with a coating which provides the article with the appearance of the polished bronze and which also provides resistance to wear. The present invention provides or provides such a coating.
BRIEF DESCRIPTION OF THE INVENTION
The present invention is directed to a metal substrate having a multi-foot layer coating placed or deposited on its surface. More particularly, it is directed to a metal substrate, particularly bronze, which has deposited on its surface multiple overlapping metallic layers of certain specific types of metals or metal compounds. The coating is decorative and also provides resistance against abrasion and wear. The coating provides the appearance of polished bronze. Accordingly, a surface of the article having the coating thereon simulates a polished bronze surface.
A first layer deposited directly on the surface of the substrate is comprised of a tin-nickel alloy. On the layer of the tin-nickel alloy is a top layer comprised of a refractory metal compound such as a zirconium compound, a titanium compound, a hafnium compound or a tantalum compound, preferably a titanium compound or a compound of zirconium such as zirconium nitride. The tin-nickel alloy layer is applied by electroplating. The refractory metal compound such as the zirconium compound layer is applied by vapor deposition such as by reactive ion spray deposition.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a cross-sectional view of a portion of the substrate having the multilayer coating deposited on its surface.
DESCRIPTION OF THE PREFERRED MODALITY
The substrate 12 may be any metal or metal alloy, venerable substrate, such as copper, steel, bronze, tungsten, nickel alloys, and the like. In a preferred embodiment the substrate is bronze. Placed on the surface of the substrate
12 is a layer 20 comprised of a tin-nickel alloy. More specifically, the layer 20 is comprised of a nickel-tin alloy. The layer 20 is deposited on the substrate by conventional and well-known nickel-tin electroplating processes. These processes and plating baths are conventional and well known and are described, inter alia, in U.S. Pat. Nos. 4,033,835; 4,049,508; 3,887,444; 3,772,168 and 3,940,319, all of which is incorporated herein by reference. The tin-nickel alloy layer is preferably comprised of about 60-70 weight percent tin and about 30-40 weight percent nickel, more preferably in approximate 65% tin and 35% nickel form representing the atomic composition of SnNi. The plating bath contains sufficient amounts of nickel and tin to provide a tin-nickel alloy of the composition described above. A commercially available tin-nickel plating process is the NiColloy process available from ATOTECH, and described in its Technical Information Sheet No: NiColloy, 10/30/94, incorporated herein for reference. The thickness of the layer 20 of the tin-nickel alloy is generally at least about 2.54 x 10"cm (10 millionths (0.00001) of an inch), preferably at least about 5.08 x 10" cm (20 millionths (0.00002 ) of one inch), and more preferably at least about 1.27 x 10 -4 cm (50 millon-chasms (0.00005) of an inch). The range of the upper thickness is not critical and generally depends on economic considerations. In general, a thickness of about 0.00508 cm (2,000 millionths (0.002) of an inch), preferably about 0.00254 cm (1,000 millionths (0.001) of an inch), and more preferably about 0.00127 cm (500 millionths (0.0005) ) of one inch), should not be exceeded. Placed on the layer 20 of the tin-nickel alloy is a top layer 24 comprised of the refractory metal compound such as a hafnium compound, a tantalum compound, a titanium compound or a zirconium compound, preferably a titanium compound or a zirconium compound, and more preferably a zirconium compound. The titanium compound is selected from titanium nitride, titanium carbide, and titanium carbonitride, with titanium nitride being preferred. The zirconium compound is selected from zirconium nitride, zirconium carbonitride, and zirconium carbide, with the zirconium nitride which is preferred. The layer 24 provides resistance to abrasion and wear and the desired color or appearance, such as, for example, polished bronze. The layer 24 is deposited on the layer 20 by any of the well known and conventional plating or deposition processes, such as vacuum coating, reactive ion plating, and the like. The preferred method is reactive ion spray plating. Reactive ion spray is well known in the art and in general is similar to ion spray deposition, except that a reactive gas which reacts with the target or dislodged target material is introduced into the chamber. Accordingly, in the case where the zirconium nitride is the top layer 24, the target or target is comprised of zirconium and the nitrogen gas is the reactive gas introduced into the chamber. By controlling the amount of available nitrogen to react with zirconium, the color of zirconium nitride can be made to be similar to that of various shades of bronze or mat. Ion spray techniques and equipment are well known in the art and are described, inter alia, in T. Van Vorous, "Planar Magnetron Sputtepng; A New Industrial Coatmg Technique, "Solid State Technology, December 1976, pp. 62-66, U. Kapacz and S. Schulz," Industrial Application of Decorative Coatings - Principle and Advantages of the Sputter Ion Plating Process "Soc. Vac. Coat., Proc. 34 / a Arn. Techn.Conf., Philadelphia, USA, 1991, 48-61; and U.S. Patent Nos. 4,162,954 and 4,591,418, all of which are incorporated herein by reference. , in the ion spray deposition process, the metal such as the target or titanium or zirconium target, which is the cathode, and the substrate, are placed in a vacuum chamber.The air in the chamber is evacuated to producing vacuum conditions in the chamber An inert gas, such as Argon, is introduced into the chamber.The particles of the gas are ionized and are accelerated to the target or target to dislodge the titanium or zirconium atoms. target or evicted target is then typically deposited as a cover film on the substrate.
The layer 24 has a thickness at least effective to provide resistance to abrasion. In general, this thickness is at least 5.08 x 10"cm (2 millionths (0.000002) of an inch), preferably at least 1016 x 10" cm (4 millionths (0.000004) of an inch), and more preferably at least 1.524. x 10"cm (6 millionths (0.000006) of an inch.) The range of the upper thickness is generally not critical and depends on considerations such as cost.In general, a thickness of approximately 7.62 x 10" cm (30 millionths (0.00003 ) of one inch, preferably approximately 6.35 x 10"cm (25 millionths (0.000025) of an inch), and more preferably in approximately 5.08 x 10" cm (20 millionths (0.000020) of an inch), should not be The zirconium nitride is the preferred coating material because it provides the appearance most similar to polished bronze, so that the invention can be understood more easily, the following example is provided. I do not limit the invention thereto.
EXAMPLE 1
The bronze ornamental door shields or plates are placed in a conventional soaking bath, which contains standard and well-known soaps, detergents, deflocculants and the like, which is maintained at a pH of 8.9 - 9.2 and a temperature of 82.2-93.3 ° C (180-200 ° F) for 30 minutes. The bronze ornamental plates or plates are then placed for six minutes in an alkaline, ultrasonic, conventional cleaning bath. The ultrasonic cleaning bath has a pH of 8.9-9.2, is maintained at a temperature of about 71.11-82.2 ° C (160-180 ° F), and contains conventional and well-known soaps, detergents, deflocculants and the like. After the ultrasonic cleaning, the shields or ornamental plates are rinsed and placed in an electrical, alkaline, conventional cleaning bath for about two minutes. The electric cleaning bath contains a submerged, mountable steel anode, 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 detergents and conventional The shields or ornamental plates are then rinsed twice and placed in a conventional acid activator bath for about one minute. The acid activator bath has a "pH of about 2.0-3.0, is at room temperature, and contains an acid salt based on sodium fluoride. The shields or ornamental plates are rinsed twice and placed in a tin-nickel plating bath for approximately 7 1/2 minutes. The bath is maintained at a temperature of about 48.88-60 ° C (120-140 ° F) and at a pH of about 4.5-5.0. The bath contains stannous chloride, nickel chloride, ammonium bifluoride, and other well known and conventional complexing and wetting agents.
A layer of tin-nickel of an average thickness of approximately 5.08 x 10 -4 cm (200 millionths (0.0002) of an inch) is deposited on the surface of the shield or ornamental plate. Ornamental plates or plates plated with a tin-nickel alloy are placed in an ion spray plating container. This container is a stainless steel vacuum vessel sold or marketed by Leybold A.G. from Germany. The container 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 to vary the flow velocity of the argon towards the chamber. In addition, two sources of nitrogen gas are connected to the chamber by an adjustable valve to vary the flow velocity of nitrogen to the chamber. Two pairs of target or magnetron type mountings are mounted in a spaced relationship far into the chamber and connected to the negative outputs of the C power supplies. variable. The targets or targets constitute the cathodes and the wall of the chamber is a common anode for the target or target cathodes. Target or target material comprises zirconium. A carrier or carrier of the substrate, which transports the substrates, that is, to the shields or ornamental plates, is already provided, for example, it can be suspended from the top of the chamber, and is rotated by a variable speed motor to transport to substrates between each pair of target mounts or magnetron target. The carrier or conveyor is conductive and electrically connected to the negative output of a power supply of C.C. variable. The veneered ornamental boards or plates are mounted on the carrier of the substrate in the ion spray plating container. The vacuum chamber is evacuated to a pressure of approximately 5x10 millibars and heated to approximately 400 ° C by means of a radiant electric resistance heater. The target or target material is spray cleaned to remove contaminants from its surface. The spray cleaning is carried out for about half a minute by applying a sufficient amount of energy to the cathodes to achieve a current flow of approximately 18 amps and introducing argon gas at the rate of approximately 200 standard cubic centimeters per minute. A pressure of approximately 3x10"millibars is maintained during the spray cleaning.The shields or ornamental plates are then cleaned by an acid attack process under high pressure.The attack process with acid under low pressure is carried out for approximately five minutes and involves the application of a negative DC potential which is increased over a period of one minute from about 1200 to about 1400 volts to the shields or ornamental plates and applying DC power to the cathodes to achieve a current flow of Approximately 3.6 amps Argon gas is introduced at a rate which increases over a period of one minute from about 800 to about 1000 standard cubic centimeters per minute, and the pressure is maintained at approximately 1.1 x. 10 millibars.The shields or ornamental plates are rotated between the white or target mountings. The agnetron at a speed of one revolution per minute. The ornamental boards or plates are then subjected to an acid-attack cleaning process at elevated pressure for approximately 15 minutes. In the high-pressure acid attack process, the argon gas is introduced into the vacuum chamber at a rate which increases over a period of 10 minutes from about 500 to 650 standard cubic centimeters per minute (ie, at the beginning the flow rate is 500 sccm and after 10 minutes the flow rate is 650 sccm and remains at 650 sccm for the rest of the acid attack process at high pressure), the pressure is maintained at approximately 2 x 10"ilibares, and a negative potential which is increased over a period of ten minutes from about 1400 to 2000 volts is applied to the shields or ornamental plates.The shields or ornamental plates are rotated between the target or white magnetron mounts. about one revolution per minute.The pressure in the vessel is maintained at approximately 2x10"millibars. The shields or ornamental plates are then subjected to another cleaning process by acid attack at low pressure, for about five minutes. During this cleaning process by acid attack at low pressure, a negative potential of approximately 1400 volts is applied to the shields or ornamental plates, the energy of C. C. is applied to the cathodes to achieve a current flow of approximately 2.6 amps, and the argon gas is introduced into the vacuum chamber at a rate which increases over a period of five minutes from approximately 800 sccm (standard cubic centimeters per minute) ) to approximately 1000 sccm. The pressure is maintained at _2 about 1.1 x 10 millibars and the shields or ornamental plates are rotated at about one rpm. The target or target material is cleaned again by spraying for about one minute by applying a sufficient amount of energy to the cathodes to achieve a current flow of approximately 18 amps, introducing the argon gas at a speed of approximately 150 sccm, and maintaining a pressure of approximately 3x10"millibars.
During the cleaning process, protections are interposed between the shields or ornamental plates and the target or magnetron mounts, to prevent the deposition of target material on the shields or ornamental plates. The protections are removed and a layer of zirconium nitride having an average thickness of approximately 3.55 x 10"cm (14 millionths (0.000014) of an inch), is deposited on the tin-nickel layer by reactive ion spray for a period of time. A negative potential of approximately 200 volts DC is applied to the shields or ornamental plates while the DC energy is applied to the cathodes to achieve a current flow of approximately 18 amperes. flow velocity of approximately 500 sccm Nitrogen gas is introduced into the vessel from two sources.A source introduces nitrogen at a generally steady flow rate of about 40 sccm.The other source is variable.The variable source is regulated to that maintains a partial ionic current of 6.3 x 10"amps, with the variable flow of nitrogen that is increased or decreased when It is necessary to maintain the partial ionic current at this predetermined value. The pressure in the container is maintained at approximately 7.5 x 10"millibars.The ornamental plates plated with zirconium nitride are then subjected to cooling at low pressure, where the heating is interrupted, the pressure is increased from approximately 1.1 x 10 -2 millibars up to about 2 x 10-1 millibars, and the argon gas is introduced at a rate of 950 sccm This invention can be further developed within the scope of the following claims In accordance with this, the above specification is to be construed as illustrative only of a single operative embodiment of the present invention, rather than interpreted in a strictly limited sense.
It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates. Having described the invention as above, the content contained in the following is claimed as property
Claims (10)
1. An article, which contains or comprises a metallic substrate that has placed on at least a portion of its surface, a coating that simulates bronze, characterized in that it comprises: a layer comprised of the tin-nickel alloy; and a top layer comprised of a zirconium compound or a titanium compound.
2. The article according to claim 1, characterized in that the layer comprised of the zirconium compound or the titanium compound is comprised of the zirconium compound.
3. The article according to claim 2, characterized in that the zirconium compound is comprised of zirconium nitride.
4. The article according to claim 3, characterized in that the metallic substrate is comprised of bronze.
5. The article according to claim 1, characterized in that the metallic substrate is comprised of bronze.
6. An article comprising a substrate having on at least a portion of its surface a coating having a bronze color, characterized in that it comprises: a first layer comprised of the tin-nickel alloy; and an upper layer on at least a portion of the first layer, comprised of a zirconium compound.
7. The article according to claim 6, characterized in that the substrate is comprised of bronze.
8. The article according to claim 7, characterized in that the upper layer is comprised of zirconium nitride.
9. The article according to claim 6, characterized in that the upper layer is comprised of zirconium nitride.
10. The article according to claim 9, characterized in that the substrate is comprised of bronze.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08447149 | 1995-05-22 | ||
US08/447,149 US5654108A (en) | 1995-05-22 | 1995-05-22 | Article having a protective coating simulating brass |
Publications (2)
Publication Number | Publication Date |
---|---|
MX9601823A MX9601823A (en) | 1997-07-31 |
MXPA96001823A true MXPA96001823A (en) | 1997-12-01 |
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