CN1259591A - Coatings - Google Patents
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- CN1259591A CN1259591A CN 99125848 CN99125848A CN1259591A CN 1259591 A CN1259591 A CN 1259591A CN 99125848 CN99125848 CN 99125848 CN 99125848 A CN99125848 A CN 99125848A CN 1259591 A CN1259591 A CN 1259591A
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- titanium
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- zirconium
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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Abstract
An article having deposited on at least a portion of its surface a decorative and protective multi-layer coating comprising at least one nickel layer, a tin-nickel alloy layer, and sandwich layer comprised of layers comprised of titanium or zirconium-titanium alloy alternating with layers comprised of titanium compound such as titanium nitride or zirconium-titanium alloy compound such as zirconium-titanium nitride. The coating provides abrasion and corrosion protection to the underlying substrate and also protects the substrate from attack by chemicals such as acids and bases while being crack resistant and resistant to galvanic corrosion.
Description
The present invention relates to decorate and protective coating.
At present; to as lamp; tripod; candlestick, water tap, spherical door knob; the habituation of brass wares such as door handle is processed as at first with its surface grinding and the surface applied protectiveness organism coating that is polished to high gloss and is being polished subsequently; as by acrylic acid or the like, urea, the organism coating that Resins, epoxy etc. are formed.The shortcoming of this system need to be polishing and polishing processing, particularly has complicated shape as fruit product, needs highly intensive labour.Also have, known organic coating does not have the ideal wear resistance.
These shortcomings can be by comprising nickel bottom and non-valuable high-temperature resistant metal compound, and as zirconium nitride, the coating of titanium nitride and zirconium-titanium alloy nitride (zirconium-titanium alloy nitride) is improved.But, to have found titanium to occur in the coating, during as titanium nitride or zirconium-titanium alloy nitride, coating can suffer galvanic etching in corrosive atmosphere.This galvanic etching meeting makes coating show as in fact inefficacy.The tin-nickel alloy layer that now has been surprised to find between end nickel dam and top titanium compound or titanium alloy compound layer can reduce or eliminate galvanic etching.At United States Patent (USP) 5,667, disclosed the coating that contains the tin-nickel alloy layer in 904, wherein said tin-nickel alloy layer is between end nickel dam and non-valuable high temperature material top layer.Coating is by nickel dam, tin-nickel alloy layer and comprise zirconium compounds or the top layer of titanium compound constitutes.Though its performance is very good usually, this coating still has several shortcomings.This coating does not have enough against power to chemical action.Its corrosion to bronsted lowry acids and bases bronsted lowry is responsive especially.And being this coating, its another problem breaks sometimes.
The objective of the invention is to eliminate these defectives and a kind of coating is provided, it has the resistance to chemical corrosion of improvement, resistance to breakage, and electrochemically resistant corrosive nature.
The present invention relates to a kind of protection and decorative coating that is used for a basic unit, particularly metal substrate.The present invention relates more specifically to a kind of basic unit, particularly a kind of metal substrate as brass, and minimum have a coating on the one part surface, and this coating comprises the multilayer superimposed layer of some specialty metal or metallic compound.Described coating has ornamental and erosion resistance can also be provided, abrasion resistance and chemical resistant properties.In one embodiment, described coating can provide the outward appearance that has flavous polishing brass, promptly has golden yellow brass tone.Therefore, the product surface with described coating can be simulated the polishing brass with golden yellow tone.
The first layer that directly is coated in substrate surface is made of nickel.Described the first layer can be an individual layer, as single nickel dam, or comprises two different nickel dams, the bright nickel layer as described in being arranged on as a semi-bright nickel layer and that directly is coated in substrate surface above the semi-bright nickel layer.The one deck that is coated in above the nickel dam is tin and nickel alloy layer.At tin with above the nickel alloy layer be interlayer, it is made of the titanium or the titanium alloy layer that are arranged alternately with titanium compound or titanium alloy compound.
The setting of described interlayer should make titanium or titanium alloy layer be positioned on the tin-nickel alloy layer, and promptly as bottom, and titanium compound or titanium alloy compound layer are top layer or outlier.
In another embodiment of the present invention, at titanium compound or be titanium oxide or titanium oxide alloy layer above the titanium alloy compound layer, or titanium or titanium alloy, the reaction product layer of oxygen and nitrogen.
Figure 1 shows that multilayer coated cross-sectional view not in scale, in the basic unit;
Apply nickel dam 13 by conventionally known electroplating technology on the surface of basic unit 12. These technologies Comprise and adopt traditional electroplate liquid, for example can adopt a kind of Watts liquid (Watts as electroplate liquid Bath). These electroplate liquids generally include the nickelous sulfate that is dissolved in the water, nickel chloride and boric acid. Also can Use all chlorides, sulfamate and boron fluoride hydrochlorate electroplate liquid. These electroplate liquids can Comprise selectively mixture that some are known, that in the past use, such as equal paint, brightener etc. In order to form special minute surface bright nickel layer, should be with a minimum first kind brightener and minimum one second The class brightener adds electroplate liquid. First kind brightener is the organic compound of sulfur-bearing. The Equations of The Second Kind light Agent is the organic compound of sulfur-bearing not. The Equations of The Second Kind brightener also can produce equalization, and is not containing When being added into electroplate liquid in the situation of the first kind brightener of sulphur, can produce semi-bright nickel coating. This A little first kind brighteners comprise Fluhyzon and benzene sulfonic acid. Two and trisulfonic acid of benzene and naphthalene, benzene and naphthalene sulphur Acid amides, and (phenalgin) sulfanilamide (SN), such as benzoic sulfimide, ethene and pi-allyl sulfanilamide (SN) (vinyl and Allyl sulfonamides) and sulfonic acid. The Equations of The Second Kind brightener is generally unsaturated organic material, as Alkynes or olefin(e) acid, ethyoxyl and propoxyl group alkynol, cumarin (coumarin) and aldehyde. These are years old One class and Equations of The Second Kind brightener are known for the experienced technical staff in the art and are easy to Buy. Can consider the document, particularly United States Patent (USP) NO.4 that use in the application, in 421,611 They are described.
The thickness of nickel dam 13 is typically about 100/1000000ths (0.0001) inches, is preferably about hundred 150/10000ths (0.00015) inches to about 3/1000000ths, 500 (0.0035) inches.
In the embodiment that uses two nickel dams, the thickness of semi-bright nickel layer and bright nickel layer should be able to be effective The anti-corrosion protection of improvement is provided. Usually, the thickness of semi-bright nickel layer 14 is minimum is about 1,000,000 / 50 (0.00005) inches, desirable is minimum about 100/1000000ths (0.0001) inches, It more preferably is minimum about 150/1000000ths (0.00015) inches. Upper thickness limit is usually not heavy Want and by secondary conditions, decide such as cost and outward appearance. But usually, thickness should not surpass about hundred 1/10000th, 500 (0.0015) inches, it is desirable to be no more than about 1/1000000th, 000 (0.001) Inch more preferably should be above about 750/1000000ths (0.00075) inches. Bright nickel layer 16 Thickness usually minimum be about 50/1000000ths (0.00005) inches, it is about it is desirable to minimum 125/1000000ths (0.000125) inches, more preferably be minimum about 1,000,000/ 250 (0.00025) inches. The upper thickness limit of bright nickel layer is unimportant and usually by as cost Condition control. But usually, thickness should not surpass about 2/1000000ths, 500 (0.0025) inches, It is desirable to be no more than about 2/1000000ths, 000 (0.002) inch, more preferably should not surpass About 1/1000000th, 500 (0.0015) inches. Bright nickel layer 16 tends to play and covers or fill not The fully effect of the equal coating of basic unit.
On bright nickel layer 16, be coated with tin-nickel alloy layer 20.More particularly, layer 20 alloy by a kind of nickel and tin constitute.Find that surprisingly the tin-nickel alloy layer can reduce or eliminate galvanic etching when titanium appears in the steaming coating.By conventionally known tin-nickel alloy plating process overlay 20 on layer 16.These technologies and electroplate liquid are conventionally known and at document, special United States Patent(USP) Nos. 4,033,835; 4,049,508; 3,887,444; Disclose in 3,772,168 and 3,940,319, all these documents are all in this application with reference to using.The tin-nickel alloy layer preferably is approximately the tin of 50-80 by weight percent and nickel that weight percent is approximately 20-50 constitutes, and better about 65% tin and 35% the nickel of serving as reasons constitutes, and its atom consists of SnNi.Electroplate liquid should contain the nickel of q.s and tin so that the alloy of the tin-nickel with the described composition in front to be provided.
The industrial suitable Ni-COLLOY of tin-nickel electroplating technology for can from ATOTECH, obtaining
TMTechnology, and at its Technical Information Sheet NO:NiColloy, disclosed in 30 days October in 1994, be used in combination in this application.
The thickness of tin-nickel alloy layer 20 should be able to reduce or eliminate galvanic etching effectively.This thickness is usually minimum be about 10/1000000ths (0.00001) inches, it is desirable to minimumly be about 20/1000000ths (0.00002) inches, and better is minimumly is about 50/1000000ths (0.00005) inches.Upper thickness limit is unimportant and depend on economic conditions usually.Usually thickness should not surpass about 2/1000000ths, 000 (0.002) inch, it is desirable to be no more than about 1/1000000th, 000 (0.001) inch, and better is to be no more than about 500/1000000ths (0.0005) inches.
What apply on tin-nickel alloy layer 20 is to comprise layer 30 interlayer 26, and layer 30 comprises by the titanium or the titanium alloy that are arranged alternately with titanium compound or titanium alloy compound layer 28 and constituting.Described this structure in the accompanying drawing, wherein 26 represent interlayers, 28 expression titanium compound or titanium alloy compound layers, 30 expression titanium or titanium alloy layers.
The metal that forms titanium alloy or titanium alloy compound with the titanium fusion is non-valuable refractory metal.These metals comprise zirconium, hafnium, tantalum and tungsten.It is that about 10 to about 90 titanium and weight percent are about 90 to about 10 another kind of non-valuable refractory metal that titanium alloy generally includes weight percent, and preferably weight percent is that about 20 to about 80 titanium and weight percent are about 80 to about 20 another kind of non-valuable refractory metal.Titanium compound or titanium alloy compound comprise oxide compound, nitride, carbide and carbonitride.
In one embodiment, layer 28 is made of titanium-zirconium alloy nitride, and layer 30 is made of titanium-zirconium alloy.In this embodiment, titanium-zirconium alloy nitride layer has and has flavous brassiness.
The thickness of interlayer 26 should provide resistance to abrasion effectively, damage resistant and wearability, and needed color can be provided, as have the brassiness of golden yellow tone.Usually, the mean thickness of layer 26 is about 2/1000000ths (0.000002) inches to about 40/1000000ths (0.00004) inches, it is desirable to minimum for about 4/1000000ths (0.000004) inches to about 35/1000000ths (0.000035) inches, and better be to be minimum about 6/1000000ths (0.000006) inches to about 30/1000000ths (0.00003) inches.
Each layer 28 and the 30 common thickness that have are minimum to be about 0.01/1000000th (0.00000001) inch, and preferred minimum is about 0.25/1000000th (0.00000025) inch, and better is to be minimum about 0.5/1000000th (0.0000005) inch.Usually, the thickness of layer 28 and 30 should not it is desirable to be no more than about 10/1000000ths (0.00001) inches greater than about 15/1000000ths (0.000015) inches, and better is to be not more than about 5/1000000ths (0.000005) inches.
In interlayer, bottom is a layer 30, and promptly this layer is made of titanium or titanium alloy.Bottom 30 is applied on the tin-nickel alloy layer 20.The top layer of interlayer is a layer 28 '.Layer 28 ' is made of titanium compound or titanium alloy compound.Layer 28 ' is a nonferrous layer.That is to say that it can provide color to coating.With regard to titanium-zirconium alloy nitride, for having flavous brassiness.The thickness minimum of layer 28 ' should be able to provide needed color effectively, as has flavous brassiness.Usually, the thickness of layer 28 ' should be substantially equal to the thickness of interlayer remainder.Layer 28 ' is the final layer of layer in 28,30 that comprises interlayer.Usually, the thickness of layer 28 ' is minimum about 2/1000000ths inches, is preferably about 5/1000000ths inches.Usually, thickness should not surpass about 50/1000000ths inches, preferably should be above about 30/1000000ths inches.
A kind of method that forms interlayer 26 is to utilize known traditional traditional steam coating technology, as physical vapor coating or chemical vapors coating.The physics coated technique comprises sputter spraying plating and cathodic arc evaporation.In technology of the present invention, utilize sputter spraying plating or cathodic arc evaporation to apply zirconium-titanium alloy or titanium layer 30, subsequently by reactant gases (cathode) sputtering method reaction cathodic arc evaporation coating zirconium-titanium alloy compound, as nitride or titanium compound, as nitride layer 28.
In order to form interlayer 26, this place's titanium compound and titanium alloy compound are nitride, the flow velocity of nitrogen is (pulsation) that changes during reactant gases (cathode) sputtering method or cathodic arc evaporation, its changing value does not change to introducing between the nitrogen with ideal value zero (having nitrogen introducing or nitrogen to introduce with smaller value), to form a plurality of metal levels that are arranged alternately 30 and metal nitride layer 28 in interlayer 26.
The number of high melting point metal compound layer 28 should be able to reduce or eliminate to break effectively in metal 30 alternating layers and the interlayer 26.It is minimum about 4 that this number is generally, and ideal is for preferably about 6, and better is minimum about 8.Usually, the number of refractory metal 30 and high melting point metal compound 28 alternating layers should not surpass approximately 50 in the interlayer 26, it is desirable to be no more than about 40, and better is to be no more than about 30.
In one embodiment of the invention, overlay 34 on interlayer 26, and it comprises titanium or titanium alloy, or comprise the oxygen of the gas as oxygen, and the reaction product of nitrogen.
Metal or metal alloy, the reaction product of oxygen and nitrogen are made of metal or metal alloy oxide compound and metal or metal alloy nitride usually.Therefore, for example, titanium, the reaction product of oxygen and nitrogen comprises titanium oxide and titanium nitride.These metal oxides and metal nitride and preparation thereof and coating are conventional known, and they are at document, especially at United States Patent (USP) NO.5, disclose in 367,285, and its disclosure content can be in this application with reference to using.
Steam metallizing by known conventional comes overlay 34, and described steam coating technology comprises reactant gases (cathode) sputtering method and cathodic arc evaporation.
In another embodiment of the present invention, replace by titanium or titanium alloy the layer 34 that the reaction product of oxygen and nitrogen constitutes with titanium oxide or titanium alloy oxide skin.These organism and goods thereof are normally known.
By the steam coating technology energy overlay 34 of known conventional, these technology comprise physical vapor coating and chemical vapors coating, for example reactant gases (cathode) sputtering method and cathodic arc evaporation.
Sputtering technology and equipment thereof are disclosed, particularly in document J.Vossen and W.Kern " ThinFilm Processes II ", Academic Press, 1991; R.Boxman etc., " Handbook ofVacuum Arc Science and Technology ", Noyes Pub., 1995; And disclosed in the United States Patent(USP) Nos. 4,162,954 and 4,591,418, these documents use in conjunction with reference in this application.
Briefly, in the sputter coated technique, in vacuum chamber, be provided as refractory metal (as titanium or zirconium) the target utmost point and the basic unit of negative electrode.Extract air in the described chamber out in described chamber, to form vacuum state.With rare gas element, chamber as described in introducing as argon gas.The ionized gas particle also makes it accelerate to the target utmost point with knocking-on titanium or zirconium atom.Subsequently, be coated in the basic unit as coating usually by knocking-on target pole material.
In cathodic arc evaporation, common electric arc with the hundreds of ampere is applied to the metallic cathode surface as zirconium or titanium.Electric arc makes the cathode material evaporation, and the cathode material of evaporation condenses upon subsequently and forms coating in the basic unit.
Reaction cathodic arc evaporation and reactant gases (cathode) sputtering method are roughly the same with conventional sputter spraying plating and cathodic arc evaporation technology, and its difference is a kind of reactant gases that can react with knocking-on target pole material is introduced in the described vacuum chamber.Therefore, under the situation of titanium oxide as layer 34, negative electrode should be material and should be with oxygen as the reactant gases of introducing described vacuum chamber with the titanium.
Now provide following examples so that can more easily understand the present invention.But these embodiment are property and should not being construed as limiting the present invention as an illustration only.
Embodiment 1
Brass taps is placed on traditional soak cleaning liquid, and this cleaning liquid comprises the general known soap of standard, washing composition, and defloculating agent (defloculant) etc., its pH value should remain on 8.9-9.2 and temperature should keep 145-200 °F in 10 minutes.Subsequently, brass taps is inserted in the known common ultrasonic alkaline clean-out system.The pH value of described ultrasonic alkaline clean-out system is 8.9-9.2, and temperature should remain on about 160-180 °F, and it contains common known soap, washing composition, defloculating agent (defloculant) etc.After ultrasonic cleaning, rinsing tap was also inserted it in a kind of traditional alkaline electro scavenging solution about 50 seconds.The temperature of described electrocleaning liquid should remain on about 140-180 °F, and pH value should remain on 10.5-11.5, and it contains general common washing composition.Subsequently, rinsing tap and putting it in a kind of common acidic activator about 20 seconds.The pH value of described acidic activator is about 2.0-3.0, and its temperature is a room temperature, and it contains Sodium Fluoride base hydrochlorate (sodium fluoridebased acid salt).
Subsequently, rinsing tap and it was inserted in the bright nickel plating bath about 12 minutes.Described bright nickel plating bath is generally a kind of traditional plating bath, and its temperature should remain on about 130-150 °F, and pH value is about 4.0-4.8, and contains NiSO
4, NiCL
2, boric acid and brightening agent.The coating mean thickness is about 400/1000000ths inches bright nickel layer on tap.Rinsing is coated with twice on the tap of bright nickel and put it in the tin-nickel electroplate liquid about 7.5 minutes.The temperature of described electroplate liquid should remain on 120-140 °F, and pH value should be about 4.5-5.0.Described electroplate liquid comprises tin protochloride, nickelous chloride, ammonium acid fluoride and the compound wetting agent of other known routine.At described bright nickel layer surface applied mean thickness is about 200/1000000ths inches tin-nickel layer.Thoroughly rinsing is coated with the tap of nickel and tin-nickel and makes its drying subsequently in deionized water.
To electroplate tap inserts in the cathodic arc evaporation electroplating container.Described container is generally cylindrical housings, and it comprises the vacuum chamber that is suitable for by pump depletion.By the adjustable valve that is used to change gas flow the argon gas body source is linked to each other with described vacuum chamber.
Cylindrical zirconium-titanium alloy negative electrode is set at described vacuum chamber central authorities and links to each other with the cathode end of a variable direct supply.The positive terminal of this power supply links to each other with chamber walls.Described cathode material comprises zirconium and titanium.
To electroplate tap and be arranged on the main shaft, 16 velamens wherein are arranged on one around on the ring outside the negative electrode.Described wholely rotate around negative electrode, every main shaft all also rotates around himself axis simultaneously, thereby forms so-called planetary motion, and this motion can make a plurality of taps around each main shaft setting evenly be exposed to negative electrode.Described ring is usually with the rotational speed of several revolutions per, encircle simultaneously every rotation once each main shaft all rotate several times.Main shaft should and be provided with rotating contact so that applying bias voltage during the coating in basic unit with the insulation of described chamber.
Vacuum chamber is evacuated to pressure and is approximately 5 * 10
-3The millibar and be heated to about 150 ℃.
Subsequently, electroplate tap and must stand high bias plasma arc plasma cleaning, wherein on the plating tap, apply about 500 volts of (bearing) bias voltages, on negative electrode, locate to trigger and keep simultaneously roughly 500 amperes electric arc.The time of described cleaning is about 5 minutes.To be enough to keep about 3 * 10
-2The speed of the pressure of millibar imports argon gas.The coating mean thickness is about 4/1000000ths inches zirconium-titanium alloy layer on the tap that is being coated with tin-nickel during lasting 3 minutes.The cathode arc coated technique comprises that anticathode applies direct current to form about 500 amperes electric current, introduces container with argon gas so that the pressure in the container remains on about 1 * 10
-2Millibar, and rotate leading with above-mentioned planetary mode.
Behind coating zirconium-titanium alloy layer, the described interlayer of coating on described zirconium-titanium alloy layer.Periodically nitrogen is introduced vacuum chamber, simultaneously with about 500 amperes of sustained arcs discharge.Make nitrogen flow rate produce pulsation, even it periodically becomes minimum flow velocity from Peak Flow Rate, described Peak Flow Rate should be enough to make the zirconium and the titanium atom that arrive basic unit fully to react to form zirconium-titanium alloy nitride, and described minimum flow velocity equals zero or some smaller value, is not enough to and all zirconiums-titanium alloy complete reaction.The nitrogen gas stream ebb-flow cycle is one to two minute (connected, and closed subsequently in 30 seconds to 1 minute).The whole time of pulsation coating is about 15 minutes, and the result forms 10 layer thicknesses and is about 1/1000000th to 1.5 inch multilayer overlapping layer.In the interlayer coating material between the zirconium-titanium alloy nitride of fully reaction and zirconium-titanium metal alloy the substoichiometric ZrTiN of little many nitrogen contents (or have) alternately.
After having applied described interlayer, nitrogen flow rate should be remained on its maximum value (being enough to fully form the zirconium-titanium alloy nitride of reaction gained) 5-10 minute with after form thicker " color layer " on interlayer top.After having applied zirconium-titanium alloy nitride, another burst Oxygen Flow so that 30 seconds to 1 minute about 0.1 standards of times introducing per minute rise remains on its numerical value in the past with nitrogen and argon gas flow velocity simultaneously.Form a reaction product mixture thin layer (zirconium-titanium alloy oxynitrides), its thickness is about 1,000,000/0.2-0.5 inch.Finally, extinguish arcs during end during this last coating is to the vacuum chamber ventilation and take out coating basic unit.
Though to have described some embodiment of the present invention in order illustrating, to have it should be understood that in overall range of the present invention to form various embodiments and improvement.
Claims (14)
1. one kind comprises the minimum goods that have the basic unit of laminated coating on its part surface, and described goods comprise:
A minimum nickel dam;
Tin and nickel alloy layer;
Titanium or titanium alloy layer;
Interlayer, it comprises titanium compound or the titanium alloy compound layer that is arranged alternately with titanium or titanium alloy layer; And
Titanium compound or titanium alloy compound layer.
2. goods according to claim 1 is characterized in that: described titanium compound is a titanium nitride.
3. goods according to claim 1 is characterized in that: described titanium alloy compound is titanium-zirconium alloy nitride.
4. goods according to claim 3 is characterized in that: described titanium alloy is titanium-zirconium alloy.
5. goods according to claim 1 is characterized in that: a described minimum nickel dam bright nickel constitutes.
6. goods according to claim 5 is characterized in that: described titanium compound is a titanium nitride.
7. goods according to claim 5 is characterized in that: described titanium alloy compound is titanium-zirconium alloy nitride.
8. goods according to claim 7 is characterized in that: described titanium alloy is titanium-zirconium alloy.
9. one kind comprises the minimum goods that have the basic unit of laminated coating on its part surface, and described goods comprise:
The semi-bright nickel layer;
Bright nickel layer;
Tin and nickel alloy layer;
Titanium or titanium alloy layer;
Interlayer, it comprises titanium compound or the titanium alloy compound layer that is arranged alternately with titanium or titanium alloy layer; And
Zirconium compounds or zirconium-titanium alloy compound layer.
10. goods according to claim 9 is characterized in that: described titanium compound is a titanium nitride.
11. goods according to claim 9 is characterized in that: described titanium alloy compound is titanium-zirconium alloy compound.
12. goods according to claim 11 is characterized in that: described titanium-zirconium compounds is titanium-zirconium alloy nitride.
13. goods according to claim 11 is characterized in that: described titanium alloy is titanium-zirconium alloy.
14. want 12 described goods according to right, it is characterized in that: described titanium alloy is titanium-zirconium alloy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20478098A | 1998-12-03 | 1998-12-03 | |
| US09/204,780 | 1998-12-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1259591A true CN1259591A (en) | 2000-07-12 |
Family
ID=22759413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99125848 Pending CN1259591A (en) | 1998-12-03 | 1999-12-03 | Coatings |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1006214A1 (en) |
| CN (1) | CN1259591A (en) |
| CA (1) | CA2291469A1 (en) |
| FR (1) | FR2786792B1 (en) |
| GB (1) | GB2344354A (en) |
| NL (1) | NL1013706C1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2849449B1 (en) * | 2002-12-27 | 2005-08-05 | Commissariat Energie Atomique | METHOD FOR MAKING A MULTILAYER ANTI-WEAR COATING |
| FR2849620A1 (en) * | 2003-01-07 | 2004-07-09 | Metatherm Sa | MULTILAYER COATING FOR PROTECTING A CORROSION COMPONENT, PROCESS FOR PRODUCING THE SAME, AND COATING COMPRISING SUCH COATING |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3503105A1 (en) * | 1985-01-30 | 1986-07-31 | Leybold-Heraeus GmbH, 5000 Köln | METHOD FOR COATING MACHINE PARTS AND TOOLS WITH CARBIDE MATERIAL AND MACHINE PARTS AND TOOLS PRODUCED BY THE METHOD |
| GB8710296D0 (en) * | 1987-04-30 | 1987-06-03 | British Petroleum Co Plc | Wear resistant multi-layered composite |
| US4904542A (en) * | 1988-10-11 | 1990-02-27 | Midwest Research Technologies, Inc. | Multi-layer wear resistant coatings |
| US5667904A (en) * | 1995-05-22 | 1997-09-16 | Baldwin Hardware Corporation | Article having a decorative and protective coating simulating brass |
| US5552233A (en) * | 1995-05-22 | 1996-09-03 | Baldwin Hardware Corporation | Article having a decorative and protective multilayer coating simulating brass |
| US5948548A (en) * | 1997-04-30 | 1999-09-07 | Masco Corporation | Coated article |
| US5989730A (en) * | 1997-04-30 | 1999-11-23 | Masco Corporation | Article having a decorative and protective multi-layer coating |
| US6033790A (en) * | 1997-04-30 | 2000-03-07 | Masco Corporation | Article having a coating |
-
1999
- 1999-11-23 EP EP99123320A patent/EP1006214A1/en not_active Withdrawn
- 1999-11-25 GB GB9927746A patent/GB2344354A/en not_active Withdrawn
- 1999-11-30 NL NL1013706A patent/NL1013706C1/en not_active IP Right Cessation
- 1999-12-02 CA CA 2291469 patent/CA2291469A1/en not_active Abandoned
- 1999-12-02 FR FR9915197A patent/FR2786792B1/en not_active Expired - Fee Related
- 1999-12-03 CN CN 99125848 patent/CN1259591A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB2344354A (en) | 2000-06-07 |
| EP1006214A1 (en) | 2000-06-07 |
| GB9927746D0 (en) | 2000-01-26 |
| FR2786792B1 (en) | 2002-09-20 |
| FR2786792A1 (en) | 2000-06-09 |
| NL1013706C1 (en) | 2000-06-06 |
| CA2291469A1 (en) | 2000-06-03 |
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