The method of applying a multilayer coating on the surface of the product

 

(57) Abstract:

The invention relates to the application of protective and decorative coatings on products. The method comprises the following operations: first precipitated at least one layer of the coating on the product by means of electroplating, extract the product is plated with galvanic baths and subjected to drying with pulsed blowing to obtain a surface plated with free from spots, and then precipitated by physical deposition from the gas phase at least one coating layer is deposited from a gas phase, the product is plated. Layers plated selected from copper, Nickel and chromium. Layers with the physical deposition from the gas phase are selected from non-precious refractory metals, non-precious refractory metal alloys, base compositions of refractory metals and compositions of alloys of non-precious refractory metals. The method allows to obtain a multilayer coating of high quality through effective drying with pulsed blowing. 20 C.p. f-crystals, 6 ill.

The invention relates to a method for applying protective and decorative coatings for articles.

The layer deposited from the gas phase, usually protects the product from abrasion and gives it a decorative look. However, the coating layer deposited from the gas phase is usually too thin and usually has a thickness in the range of about 2,54-50,8010-6see due to the very small thickness of the coating deposited from gases is or the result of a process of electroplating, appear on the surface and are underlined by a thin coating deposited from the gas phase. Even small surface roughness, colored or colorless spots that are not visible to the naked eye on the product, plated, become visible after coating deposited from the gas phase.

So, now you want to completely check to make cleaning and drying of each product, which is removed from the electroplating bath. One known method of cleaning products plated consists in passing the articles through the water, which is based on the treatment system and the use of nitrogen drying for drying products. This method is very expensive and not always successful. Another method includes a hand drying and cleaning products. Although manual drying is more effective than drying method based on the use of nitrogen, however, it is rather time-consuming and therefore very expensive. Hand drying also complicates the processing of products with a galvanic coating, which can lead to a fall or collision products with other items from further damage.

Naib is I method of applying a multilayer coating on the surface of the product, known from German patent DE 3006308 A1 (C 23 C 11/00, 22.10.80).

There is a method implemented as follows. Using galvanothermy precipitated at least one layer of electroplating, then the product having at least one layer of the galvanic coating is dried. Subsequently precipitated by physical deposition from the gas phase of at least one layer of at least part of the layer is plated.

However, when the drying plated in accordance with the above method on the surface of the product after evaporation of liquids are traces, i.e. spots, which increase when applied to the surface of the coatings produced by physical deposition from the gas phase, which prevents the obtaining of protective and decorative coatings.

The basis of the invention is to provide a method of applying a multilayer coating on the surface of the product, which would be used in an effective and efficient method for drying products with a galvanic coating that eliminates the disadvantages associated with known currently used methods of cleaning and drying.

The problem is solved in that in the automation of at least one layer of electroplating, drying articles having at least one layer of plated and deposition using physical deposition from the gas phase of at least one layer of at least part of the layer is plated according to the invention, drying is conducted with pulsed blowing to remove products all liquid stains, and the layer deposited from the gas phase, selected from a range, including non-precious refractory metals, refractory alloys and base metals, the composition of non-precious refractory metals and compositions of alloys of non-precious refractory metals, and the composition of non-precious refractory metals and alloys of non-precious refractory metals include nitrides, oxides, carbides, carbonitrides and the reaction products of refractory metals or alloys of refractory metals, oxygen, and nitrogen.

The above method can be used for the deposition of multilayer protective and decorative coating on the product. The method includes a first operation of applying at least one layer using electroplating. The product is plated then removed from the electroplating bath and subjected to drying with pulsed blowing, to whom, designed for deposition from the gas phase, and the product is plated with precipitated from the gas phase at least one coating layer.

Preferably at least part of the surface of the product to precipitate galvanic coating containing at least one layer selected from a range that includes copper, Nickel and chromium. Copper plating includes both alkaline copper plating and acid copper plating. The plating involves the application of a galvanic method, bright Nickel, semi-gloss Nickel and a double layer of Nickel, which consists of bright Nickel and semi-gloss Nickel.

Before the product is plated is subjected to the deposition process from the gas phase to be applied to plating at least one thin coating layer deposited from the gas phase, the product is dried using a pulsed purge to remove any wet spots or stains containing Nickel or chrome.

After drying pulsed blowing at least one coating layer is precipitated by physical deposition from the gas phase in the upper layer plated. The layer or layers deposited from the gas phase, wybitnych refractory metals and compositions of alloys of non-precious refractory metals. Composition of non-precious refractory metals and alloys of non-precious refractory metals include nitrides, oxides, carbides, carbonitrides and the reaction products of refractory metal or alloy of the refractory metal, oxygen and nitrogen.

Recommended refractory metal and alloy of refractory metals to choose from a range that includes zirconium, titanium, alloy zirconium-titanium.

Need as the refractory metal and the alloy of refractory metals to choose zirconium and zirconium alloy-titanium. The next step would be the composition of the refractory metal and the composition of the alloys of refractory metals to choose from a range comprising zirconium nitride, zirconium oxide, reaction products of zirconium, oxygen and nitrogen, titanium nitride, titanium oxide, reaction products of titanium, oxygen and nitrogen, the nitride alloy zirconium-titanium oxide alloy zirconium-titanium, the reaction products of alloy zirconium-titanium, oxygen and nitrogen. Not less advisable when the composition of the refractory metal and the composition of the alloys of refractory metals selected from a range that includes zirconium oxide, zirconium nitride, the reaction products of zirconium, oxygen and nitrogen, nitride alloy zirconium-titanium oxide of an alloy of zirconium, titanium and reaction products of the JV containing at least one layer of copper on at least part of the surface of the product to obtain at least one layer of copper, the galvanised cause galvanic coating at least one layer of Nickel of at least one layer of copper deposited by electroplating method, for obtaining at least one layer of Nickel deposited by galvanic method, and precipitated by plating at least one layer of chromium on said at least one layer of Nickel deposited by galvanic method for obtaining at least one layer of chromium deposited by galvanic method.

Not less preferably, when a multilayer coating comprising alternating layers of zirconium or zirconium alloy, titanium and zirconium nitride or nitride of an alloy of zirconium, titanium, precipitated from the gas phase on the zirconium layer, or an alloy of zirconium-titanium, the zirconium nitride or nitride layer alloy zirconium-titanium is precipitated from the gas phase on said multilayer coating.

Even more preferably, when the zirconium oxide or the oxide layer on the zirconium-titanium is precipitated from the gas phase on the zirconium nitride or nitride layer alloy zirconium-titanium.

Next, a layer consisting of reaction products of zirconium or zirconium alloy, titanium, oxygen and nitrogen, are precipitated from the gas the reed zirconium or nitride of an alloy of zirconium, titanium, precipitated from the gas phase on the zirconium layer, or an alloy of zirconium-titanium.

The layer composed of zirconium oxide or oxide of an alloy of zirconium, titanium, precipitated from the gas phase on the zirconium nitride or nitride layer alloy zirconium-titanium.

It is recommended that at least part of the surface of the product to precipitate galvanic coating containing at least one layer selected from a range, including Nickel and chromium.

It is advisable at least one layer selected from a range that includes a refractory metal, an alloy of refractory metals, the composition of the refractory metal and the composition of the alloys of refractory metals, deposition from the gas phase of at least part of at least one layer plated.

The invention is illustrated by reference to the drawings, in which:

Fig. 1 depicts in General form the incision dryer with pulsed blowing;

Fig. 2 depicts a view in cross section (not to scale) side of the substrate having the layers plated;

Fig. 3 depicts a view similar to Fig. 2, but showing another variant embodiment of the invention with a different arrangement of layers plated;

Fig. 5 depicts a view similar to Fig. 4, but showing another variant embodiment of the invention with a different arrangement of the various layers with the physical deposition from the gas phase;

Fig. 6 depicts a view in cross section (not to scale) side of the substrate having the layers plated and physical coating deposited from the gas phase.

Description of the preferred option exercise

The method according to the present invention differs significantly in that it provides for a decorative and protective thin coating layer deposited from the gas phase, galvanic clay that is free from blemishes or defects, such as water stains, stain Nickel and stain chrome. These spots or defects usually occur because of the stains remaining on the surface of the product is plated by a process of electroplating. When a thin coating layer deposited from the gas phase, is applied on top of these spots, they strongly emphasized that a thin coating layer with a physical deposition from the gas phase.

The method according to the present invention includes the following operations: first precipitated at least in part by the opening of the galvanic bath and subjected to drying by pulsed purge to remove any stains from its surface, and applied by physical deposition from the gas phase at least one thin coating layer on a clean and dry surface plated.

Drying by pulse blowing and dryer with a pulse purge described in the European patent N 0486711 provided here as a reference. Dryer with pulsed blowing shown in Fig. 1. Briefly, it includes a housing, same famous and well known to the dryer air circulation. The fan, the heating device and valve for air circulation correspond to the known and traditional designs. Roaming coplowe device is additionally installed on each side of the station. Coplowe device is equipped with a small deployme tubes with a length of about 150 mm and provided with bores 15, which correspond to the direction of air passage. In each small nozzle tube the air is supplied through solenoid valves. Solenoid valves control using a microprocessor, which allows the valves to open one after the other. The intervals of the opening can be adjusted from 20 to 100 MS using a control unit. In the case of broad of dryers valves otkryvaet is I. Nozzle device to move up and down in opposite directions with adjustable speed. The speed is usually about one to two working pass in a minute. Stroke corresponds to the height of the stand plus 50 mm from the top and the bottom.

In the connection, a similar pulse, separate small nozzle tube to the compressed air supply with a nominal pressure of six bar get 15 air jets on the tube. These air jet spray of water droplets on the surfaces. Thanks again blowing surface pulsating air jets and step-by-step to allow transition from one tube to another to allow the tube in a horizontal position on a surface area of approximately 1 cm2form one air jet.

Changing the direction of the passage and blowing out a narrowly focused air jet in the bores, blind holes, notches and edges leads to the suction effect, which allows you to remove the liquid even hollow out parts. This effect is so intense that even deep bore in the hollow parts which are larger inner emptiness and the screw holes good the odes do not degrade the quality of the surface.

Programmable control unit allows selection of the pulse repetition rate, the speed of the moving nozzle device, the number of simultaneously opening valves, the number of passes and the temperature. These parameters can be set for products that must be processed. In dry separately for each passage to regulate the moving speed and the frequency of pulse repetition. Major product after the extraction, you can blow fast enough in a single pass using a focused pulsed air flow. In this case, blown a significant part of the adhering water droplets.

In the next passages travel speed is automatically reduced, and the pulse repetition rate increases. The more powerful pulses of air flow and the longer the valves are in the open state, the significantly better the effect of suction, which results in better drying of the hollow spaces.

As the amount of water blown, that is sprayed, it will dry out only a very thin adsorption layer. Therefore, required only short periods of drying time 2 to 5 min at a temperature of circus which does not leave stains. Thus, products with a galvanic coating can be a thin layer of coating applied to it using a physical deposition from the gas phase and does not require any additional cleaning or drying products plated.

The product may consist of any of the substrate, yielding a galvanic processing, such as metal or plastic. Metals, which may consist of products include brass, zinc, steel and aluminium. Galvanic coating, which precipitated the galvanic method, at least part of the surface of the product may consist of one layer or more than one layer. The preferred plating include copper, including alkaline copper and acid copper, Nickel, including bright Nickel and semi-gloss Nickel, and chrome.

If the product consists of brass, it is usually at least one layer of Nickel and a layer of chromium is deposited on a product by galvanic method, with a layer of Nickel is applied directly on the surface of the product, and a layer of chromium is applied on the layer of Nickel. Articles of brass may also be a copper layer, applied directly to its surface. At least one layer of Nickel is then applied galvanic Nickel precipitate at least part of the surface of the substrate product by using conventional and well known processes for electroplating. These processes include using known electroplating baths, such as bath watts (Watts) with the electroplating solution. Usually these baths contain Nickel sulfate, Nickel chloride and boric acid dissolved in water. You can also use all of the electroplating solutions of chlorides, sulfamates and perborates. These baths may optionally include a number of well-known and traditionally used compositions, such as leveling agents, substances, lustering, and the like. To obtain a layer of Nickel gloss of at least one substance, which imparts the sheen of class I and at least one substance, lustering, from class II, type in the electroplating solution. Substances, lustering, class I are organic compounds that contain sulfur. Substances, lustering, class II are organic compounds that do not contain sulfur. Substances, lustering, class II can also align and when added to the electroplating bath without serosoderjaschei substances, lustering, class I to result in the deposition of semi-gloss Nickel. These substances, lustering, class I include alkhalidi and sulfonamides, such as saccharin, vinyl and arylsulfonic and sulfonic acids. Substances, lustering, class II are usually unsaturated organic matter, such as acetylene or ethylene alcohols, ethoxylates and propoxylation alcohols, coumarins and aldehydes. These substances, lustering, class I and class II well known in the art and readily available commercially. In addition, they are described in U.S. patent N 4421611, which is represented here by reference.

A layer of Nickel can present a monolithic layer, which consists, for example, of semi-gloss Nickel or bright Nickel, or it may be a double layer containing the layer, which consists of a half-bright Nickel layer, which is comprised of bright Nickel. The thickness of the layer of Nickel is typically in the range from about 25410-6(0,000254) cm, preferably about 38110-6(0,000381) cm, up to about 8,8910-3(0,00889) see

As is well known in the art, prior to deposition on a substrate a layer of a Nickel substrate is subjected to activation by placing it in the traditional and well-known acid bath.

In one embodiment (Fig. 2) the layer 13 of Nickel actually consists of two different layers voinoi deposition of Nickel allows for increased protection against corrosion of the underlying substrate. Semi-gloss does not contain sulfur layer 14 is then precipitated using traditional processes of electroplating directly on the surface of the substrate 12 products. The substrate 12 containing layer 14 semi-gloss Nickel, then placed in an electroplating bath with a brilliant Nickel, and a layer 16 bright Nickel precipitated on the layer 14 semi-gloss Nickel.

The thickness of the semi-gloss layer of Nickel and a shiny layer of Nickel is equal to the thickness required to provide enhanced corrosion protection. Usually the thickness of the semi-gloss layer of Nickel is at least about 12710-6(0,000127) cm, preferably at least about 25410-6(0,000254) cm and more preferably at least about 38110-6(0,000381) see Upper limit on the thickness of usually non-critical and depends on secondary conditions, such as the cost. Usually, however, the thickness should not exceed about 3,8110-3(0,00381) cm, preferably about 2,5410-3(0,00254) cm and more preferably approximately 1,910-3(0,0019) see Layer 16 bright Nickel typically has a thickness of at least about 12710-6(0,000127) cm, preferably at least about 317,510-6(0,0003175) cm and more preferably at least about 63510-6the basis of cost. Usually, however, the thickness should not exceed values of about 6,3510-3(0,00635) cm, preferably about 5,0810-3(0,00508) cm and more preferably about 3,8110-3(0,00381) see Layer 16 bright Nickel is used as the alignment layer, which is designed to close or fill the defects of the substrate.

In another embodiment of the invention (Fig. 2) the chromium layer 20 is deposited by galvanic method on the layer 13 of Nickel. The chromium layer 20 can precipitate on the layer 13 of Nickel using traditional and well known method galvanic chrome plating. These methods, along with various electroplating baths with chromium, described in Brassard "Decorative plating process in the transition stage, finishing metals, S. 105-108, June 1988 (Brassard, "Decorative Electroplating - A process in Transition", Metal Finishing, p. 105-108, June 1988), Zaki "Chrome plating". Directory PF, S. 146-160 (Zaki, "Chromium Plating" PF Directory, p. 146-160) and in U.S. patent N 4460438, 4234396 and 4093522, which is incorporated herein by reference.

Galvanic baths for plating are well known and commercially available. Typical electroplating bath for plating contains chromic acid or chromium salt and catalysate sulfur and kremneftoristogo acid. Baths can be operated at a temperature of about 44,44-46,66oC. Typically, when the plating current density is approximately 0,161 A/cm2when the voltage of about 5-9 Century

The chromium layer usually has a thickness of at least about 5,0810-6(0,00508) cm, preferably at least about 12,710-6(0,0000127) cm and more preferably at least about 20,3210-6(0,00002032) see Usually the upper range of the thickness is not critical and is determined by secondary factors, such as cost. However, the thickness of the chromium layer in General should not exceed about 152,410-6(0,0001524) cm, preferably about 12710-6(0,000127) cm and more preferably about 101,610-6(0,0001016) see

In another embodiment of the invention (Fig. 3), especially when the product substrate is composed of zinc or brass layer 17 or layers of copper applied by galvanic method at least a portion of the surface 12 of the product. The layer 16 of Nickel is then applied galvanic copper followed plated 20 chromium on the Nickel. The layer of Nickel may be a monolithic layer (Fig. 3) and consist, for example, from bright Nickel, or may be a double layer of Nickel, which is, for example, from bli two different layers of copper, for example, the alkaline layer of copper deposited on the surface of the product, and the acidic layer of copper deposited on the layer of alkaline copper. In the embodiment (Fig. 3) copper coating is a monolithic layer of copper, which consists of acidic copper.

The process of applying copper electroplating method and bath for the deposition of copper electroplating method are conventional and well known in the art. They include plating acid copper and alkaline copper. In addition, they are described in the U.S. patent N 3725220, 3769179, 3923613, 4242181 and 4877450 listed here as a reference.

Preferably, the copper layer is chosen from alkaline copper and acid copper. The copper layer may be monolithic and may consist of one type of copper, for example from alkaline copper or acidic copper, or may contain two different types of copper layer, such as layer, which consists of alkaline copper, and a layer, which consists of acidic copper.

The thickness of the layer of copper is typically in the range from at least about 25410-6(0,000254) cm, preferably at least about 38110-6(0,000381) cm to about 8,8910-3(0,00889) cm, preferably about 5,0810-3(0,00508) see

When there is a double layer of copper, which Costa least about 12710-6(0,000127) cm, preferably at least about 190,510-6(0,0001905) see the Upper limit of the thickness is usually not critical. Typically, the thickness should not exceed values of about 3,8110-3(0,00381) cm, preferably about 2,5410-3(0,00254) see the thickness of the layer of acidic copper is typically at least about 12710-6(0,000127) cm, preferably at least about 190,510-6(0,0001905) see the Upper limit of the thickness is usually not critical. Typically, the thickness should not exceed values of about 3,8110-3(0,00381) cm, preferably about 2,5410-3(0,00254) see

Some illustrative and non-limiting examples of layers deposited by galvanic method, include layers of substrate/Nickel, such as bright Nickel/chrome, matte/semi-gloss Nickel/bright Nickel/chrome, substrate/Nickel, such as shiny Nickel, matte/semi-gloss Nickel/bright Nickel substrate/copper, such as acidic copper/Nickel, such as bright Nickel/chrome, matte/alkaline copper/acid copper/Nickel, such as bright Nickel/chrome, substrate/copper, such as alkaline copper/semi-gloss Nickel/bright Nickel/chrome, matte/alkaline copper/acid copper/semi-gloss Nickel/b is such as alkaline copper/semi-gloss Nickel/bright Nickel and the substrate/alkaline copper/acid copper/semi-gloss Nickel/bright Nickel.

After the product has layers plated, as shown in Fig. 2 and 3, which are applied to him by galvanic method, it is then subjected to drying with pulsed blowing to blow away any stains, discoloration, moisture or droplets and to obtain a product with a galvanic coating, which has an upper surface without spots. After drying with pulsed blowing the product is plated is placed in a chamber for physical deposition from the gas phase, and one or more thin layers of coating applied by physical deposition from the gas phase to the surface of articles plated.

Layers that are precipitated by physical deposition from the gas phase, are layers of metal and are selected from non-precious refractory metals, alloys of non-precious refractory metals, base compositions of refractory metals and compositions of alloys of non-precious refractory metals. Non-precious refractory metals include hafnium, tantalum, titanium and zirconium. The preferred refractory metals are titanium and zirconium, and the most preferred is zirconium. Alloys of non-precious refractory metal on the bag. Preferred double alloys are double zirconium alloys, and most preferred are double zirconium alloys and titanium.

Compositions of alloys of non-precious refractory metal or metal include nitrides, oxides, carbides and carbonitrides of non-precious refractory metals and alloys of metals. Also included among the compositions of non-precious refractory metal and alloy metals useful in this invention are the reaction products of non-precious refractory metal or metal alloy, oxygen and nitrogen. Examples of these compositions-precious refractory metal include zirconium nitride, zirconium oxide, zirconium carbide, zirconium carbonitride, the reaction products of zirconium, oxygen and nitrogen, titanium nitride, titanium oxide, titanium carbonitride, the reaction products of titanium, oxygen and nitrogen, hafnium nitride, hafnium oxide, hafnium carbonitride, tantalum oxide, tantalum nitride, tantalum carbide, and the like.

The reaction products of non-precious refractory metal such as zirconium, oxygen and nitrogen, contain zirconium oxide, zirconium nitride and oxynitride Zirconia.

Some explanatory and not ogranichivatsya zirconium-titanium, carbide zirconium-titanium, zirconium carbonitride of titanium, nitride, hafnium-zirconium, hafnium oxide-tantalum, tantalum carbide-titanium and the reaction products of alloy zirconium-titanium with oxygen and nitrogen.

Layers, which consist of refractory metals and alloys of refractory metals precipitate at least part of the surface plated using conventional and well known processes, physical vapor deposition, such as ion sputtering, electron beam deposition using a cathode arc sputtering and the like. Methods of ion sputtering and equipment described in T. van Vorous, "planar Sputtering magnetron; new industrial methods of coating", the Technology is solid, December 1976, 62-66 C. (T. Van Vorous, "Planar Magnetron Sputtering; A New Industrial Coating Technique" Solid State Technology, Dec. 1976, p. 62-66); Y. Kapach and S. Schultz, "Industrial application of decorative coatings - principle of operation and advantages of the metallization process using an ion sputtering device". Proceedings of the 34th scientific. -technical. Conf., Philadelphia, USA, 1991, S. 48-61 (U. Kapacz and S. Schulz, "Industrial Application of Decorative Coatings - Principle and Advantages of the Sputter Ion Plating Process", Soc. Vac. Coat., Proc., 34th Am. Tech. Conf. , Philadelphia, USA, 1991, 48-61); D. Vose is 91); P. Boxman and other "Handbook of vacuum arc science and technology", Noyes Pub., 1995 (R. Boxman et al., "Handbook of Vacuum Arc Science and Technology", Noyes Pub. 1995) and U.S. patent N 4162954 and 4591418 listed here as a reference.

Briefly, in the process of deposition by spraying refractory metal such as titanium or zirconium target, which is the cathode in the vacuum chamber is placed a substrate. The air from the chamber is pumped out to create vacuum conditions in the chamber. The camera serves inert gas, such as argon. The gas particles are ionized and accelerated towards the target by bombarding atoms of titanium or zirconium. Detached particles of the target material is then typically deposited as a film coating on a substrate.

When a cathode arc evaporation of an electrical arc (usually several hundred amperes) is lit on the cathode surface of a metal, such as zirconium or titanium. The arc vaporizes the material of the cathode, which then condenses on the substrate, forming the floor.

Reactive sputtering of ions is generally similar to the deposition under ion sputtering except that the camera serves a reactive gas such as oxygen or nitrogen, which reacts with the material scorer of the Oia, and the camera serves the nitrogen gas, which is a reactive gas. By controlling the amount of nitrogen, sufficient to react with the zirconium, it is possible to choose the color of zirconium nitride, for example, similar to brass color with different shades.

Usually the product is plated with precipitated more than one layer, which consists of a refractory metal, an alloy of refractory metals, the composition of the refractory metal and the composition of the alloys of refractory metals. Thus, the product is plated with precipitated from the gas phase layer, which consists, for example, of refractory metal or alloy of refractory metals such as zirconium, then on a layer of zirconium is precipitated by a multilayer structure (a layer with a multilayer structure), which consists of alternating layers of refractory metal or alloy of refractory metals such as zirconium and composition of the refractory metal or the composition of the alloys of refractory metals, such as zirconium nitride, and a multilayer structure precipitated layer, which consists of the reaction products of refractory metal or alloy of refractory metals such as zirconium, oxygen and nitrogen.

In another embodiment, the layer that is Aida, precipitated from the gas phase on the layer of refractory metal or alloy layer of the refractory metal. Layer, which consists of another, the second composition of the refractory metal or composition of the alloys of refractory metals, preferably oxide or the reaction products of refractory metal or alloy of the refractory metal, oxygen and nitrogen, then precipitated from the gas phase on the first layer of the composition of the refractory metal or a layer of the composition of the alloys of refractory metals.

Typically, the layer of refractory metal or alloy layer of the refractory metal has a thickness of at least about 0,63510-6(0,000000635) cm, preferably at least about 1,2710-6(0,00000127) cm and more preferably at least about 2,5410-6(0,00000254) see the Upper range of the thickness is not critical and usually depends on conditions such as the price. However, usually the layer, which consists of a refractory metal or alloy of refractory metals, should not have a thickness of more than about 12710-6(0,000127) cm, preferably about 38,110-6(0,0000381) cm and more preferably about 25,410-6(0,0000254) see

Typically, the layer of refractory metal or alloy layer of the refractory metal, in addition, serves to pavichevich metals, the reaction products of refractory metal or alloy of the refractory metal, oxygen and nitrogen, the product with electroplated. Thus, the layer of refractory metal or alloy layer of the refractory metal usually has a thickness which is at least effective to improve the adhesion layer, which consists of the composition of the refractory metal, the composition of the alloys of refractory metals and reaction products of refractory metal or alloy of the refractory metal, oxygen and nitrogen, the product plated.

In a preferred embodiment of the present invention, the layer of refractory metal is zirconium, titanium or alloy zirconium-titanium, preferably zirconium or zirconium alloy, titanium, and precipitated using a process called physical vapor deposition such as ion sputtering or electron beam evaporation.

Layer, which consists of the composition of the refractory metal, the composition of the alloys of refractory metals or reaction products of refractory metal or composition of the alloys of refractory metals, oxygen, and nitrogen, typically has a thickness that is at least about 5,0810-6(0,00001524) see the Upper range of the thickness is usually not critical and depends on conditions such as the price. Typically, the thickness should not exceed about 76,2010-6(0,0000762) cm, preferably about 63,510-6(0,0000635) cm and more preferably about 50,8010-6(0,0000508) see

This layer usually provides wear resistance, abrasion resistance and the desired color or appearance. This layer preferably consists of zirconium nitride or nitride alloy zirconium-titanium, which has a brass color. The thickness of this layer is at least effective to provide wear resistance, abrasion resistance and the desired color or appearance.

In another embodiment, the invention is a multilayer structure that consists of alternating layers of composition of non-precious refractory metals or compositions of alloys of non-precious refractory metals and non-precious refractory metal or alloy non-precious refractory metals, precipitated on the layer of refractory metal or alloy layer of refractory metal such as zirconium or zirconium alloy-titanium. An exemplary structure of this alternative implementation is shown in Fig. 4, in which position 22 on the and zirconium-titanium, position 26 - layered structure, position 28 - layer composition of non-precious refractory metal or a layer of the composition of alloys of non-precious refractory metals and position 30 to the base layer of refractory metal or alloy layer of non-precious refractory metals.

Non-precious refractory metals and alloys of non-precious refractory metal containing layers 30 include hafnium, tantalum, titanium, zirconium, zirconium alloy, titanium, an alloy of zirconium-hafnium and the like, preferably zirconium, titanium or an alloy of zirconium, titanium, and more preferably zirconium or zirconium alloy-titanium.

Composition of non-precious refractory metals and compositions of alloys of non-precious refractory metal containing layers 28 include the composition of the hafnium, the composition of tantalum, composition of Titan, the composition of zirconium and composition of alloys zirconium-titanium, preferably the composition of the titanium composition of zirconium or compositions of the alloys of zirconium, titanium, and more preferably the compositions of zirconium or compositions of the alloys zirconium-titanium. These compositions are selected from a nitride, carbide or carbonitride, preferably nitride. Thus, the composition based on titanium. A composition based on zirconium selected from zirconium nitride, zirconium carbide and carbonitride, zirconium, preferably of zirconium nitride.

The multilayer structure 26 generally has an average thickness of from about 12710-6(0,000127) cm to about 2,5410-6(0,00000254) cm, preferably from about 101,610-6(0,0001016) cm to about 5,0810-6(0,00000508) cm and more preferably from 76,210-6(0,0000762) cm to about 7,6210-6(0,00000762) cm (310-6(0,000003)").

Each of the layers 28 and 30 typically has a thickness of at least about 0,00510-6(0,000000005) cm, preferably at least about 0,25410-6(0,000000254) cm and more preferably at least about 1,2710-6(0,00000127) see Generally the thickness of the layers 28 and 30 should not exceed about 63,510-6(0,0000635) cm, preferably about 25,410-6(0,0000254) cm and more preferably about 12,710-6(0,0000127) see

The method of forming the multilayer structure 26 based on the use of metallization using ion sputtering and is used for applying a layer 30 of non-precious refractory metal such as zirconium or titanium after metallization using reactive ion sputtering for deposition of the layer 28 nitride base tuk flow of nitrogen gas is changed (pulse method) for metallization using reactive ion sputtering from zero (no gas supply nitrogen) before introducing the necessary amount of nitrogen for to form numerous alternating layers 30 and metal 28 metal nitride in the multilayer structure 26.

The number of alternating layers 30 of the refractory metal layer 28 with the composition of the refractory metal in the multilayer structure 26 is generally at least about 2, preferably at least about 4 and more preferably at least about 6. Typically, the number of alternating layers 30 and 28 of the refractory metal and the composition of the refractory metals in the multilayer structure 26 should not exceed about 50, preferably about 40 and more preferably about 30.

In one embodiment of the invention (Fig. 4) layer 32, which is precipitated from the gas phase on the multilayer structure 26 consists of a base of refractory metals or compositions of alloys of non-precious refractory metal, preferably nitride, carbide or carbonitride and more preferably nitride.

Layer 32 consists of a composition of hafnium, the composition of tantalum, composition of Titan, the composition of the alloy zirconium-titanium or composition of zirconium, preferably of the composition of Titan, the composition of the alloy zirconium-titanium alloy or composition of zirconium and more preferably from composers who arbid titanium and titanium carbonitride, preferably of titanium nitride. A composition based on zirconium selected from zirconium nitride, zirconium carbonitride or carbide of zirconium, preferably of zirconium nitride.

Layer 32 provides durability and abrasion resistance and the desired color or appearance, such as polished brass. Layer 32 is then precipitated onto the layer 26 by any well known and conventional methods of physical vapor deposition such as reactive ion sputtering.

The layer 32 has a thickness at least effective to provide resistance to abrasion and brass color. Typically, this thickness is at least 5,0810-6(0,00000508) cm, preferably at least 10,1610-6(0,00001016) cm and more preferably at least 15,2410-6(0,00001524) see the Upper range of the thickness is usually not critical and depends on conditions such as the price. Typically, the thickness should not exceed about 76,210-6(0,0000762) cm, preferably about 63,510-6(0,0000635) cm and more preferably about 50,810-6(0,0000508) see

The zirconium nitride is a preferred coating material, because he is mostly obespechyvaly consists of the reaction products of non-precious refractory metal or metal alloy, oxygen-containing gas, such as oxygen and nitrogen, are precipitated on the layer 32. Metals that can be used in the practical part of the present invention are metals that allow you to form a metal oxide and a nitride of the metal under suitable conditions, for example using a reactive gas, which consists of oxygen and nitrogen. Metals can be, for example, tantalum, hafnium, zirconium, zirconium alloy, titanium and titanium, preferably titanium, zirconium alloy, titanium and zirconium, and more preferably zirconium and zirconium alloy-titanium.

The reaction products of the metal or metal alloy, oxygen and nitrogen are usually composed of metal or oxide of an alloy of metals, metal or nitride of an alloy of metals and metal or oxynitride alloy metals. Thus, for example, reaction products of zirconium, oxygen and nitrogen containing zirconium oxide, zirconium nitride and oxynitride Zirconia.

Layer 34 can be applied are well known and conventional physical deposition from the gas phase, including reactive ion sputtering of a target of pure metal and gas or target consisting of oxide, nitride and/or metal.

These metal oxides and metal nitrides, including IU, disclosed in U.S. patent N 5367285 provided here as a reference.

Layer 34 containing a metal, oxygen and reaction products of nitrogen, usually has a thickness of at least about 0,25410-6(0,0000000254) cm, preferably at least about 0,38110-6(0,000000381) cm and more preferably at least about 0,50810-6(0,000000508) see Generally the layer of oxynitride metal should not have a thickness of more than about 2,5410-6(0,00000254) cm, preferably about 1,2710-6(0,00000127) cm and more preferably about 1,01610-6(0,000001016) see

In another embodiment (Fig. 5), instead of the layer 34, which consists of the reaction products of refractory metal or alloy of the refractory metal, oxygen and nitrogen and which is applied on the layer 32, a layer 36, which consists of oxide of non-precious refractory metal or oxide of an alloy of refractory metals and which is deposited on layer 32 using a physical deposition from the gas phase. Oxides of refractory metals and oxides of the alloy of refractory metals that make up the layer 36 include, but are not limited to, hafnium oxide, tantalum oxide, zirconium oxide, titanium oxide and an oxide of an alloy of zirconium, titanium, preferably titanium oxide, about what Ethan.

The layer 36 has a thickness of at least about 0,25410-6(0,000000254) cm, preferably at least about 0,38110-6(0,000000381) cm and more preferably at least about 0,50810-6(0,000000508) see Usually metal or layer 36 of oxide alloy metals should not have a thickness of more than about 5,0810-6(0,0000058) cm, preferably about 3,8110-6(0,00000381) cm and more preferably about 2,5410-6(0,00000254) see

In Fig. 6 shows a substrate 12 of a product having a brilliant layer 16 of Nickel, which is applied on its surface is galvanized, and the chromium layer 20, which is applied to the layer 16 with a bright Nickel electroplating method. After drying the substrate by pulsed blowing products 12, which has layers 16 and 20 galvanic coating on the chromium layer, which is deposited by galvanic method, precipitated by physical deposition from the gas phase layer 22, which consists of zirconium, multi-layered structure 26, which consists of alternating layers 28 and 30, which are composed of zirconium nitride and zirconium layer 32, which consists of zirconium nitride, and the layer 34, which consists of the reaction products of zirconium, oxygen and nitrogen.

For a better understanding of the invention, the er

Brass valves are placed in a known bath-dissolving cleaner containing standard and well-known soap solutions, detergents, dispersing agents and the like, which is maintained at pH of 8.9-9.2 and a temperature of 82,22-93,33oC for about 10 minutes Brass valves are then placed in a known bath with supersonic alkaline cleaner. Bath with supersonic alkaline cleaner that has a pH of 8.9-9.2 and maintained at a temperature of approximately 71,11-82,22oC, contains the traditional and well-known soap solutions, detergents, dispersing agents and the like. After supersonic cleaning valves are rinsed and placed in a known bath with alkaline electrochemical. The temperature in the bath electroacoustical supported within about 60 82,22oC, pH of approximately 10,5-11,5 and contains a standard and well-known detergents. The cranes then twice rinsed and placed into a known bath with acid activator. Bath with acid activator has approximately pH 2.0 to 3.0 at ambient temperature and contains fluoride soda on the basis of the acid salt.

The cranes then twice rinsed and placed in g is th usual well-known bath, in which the temperature is maintained around 54,44-65,56oC and a pH of approximately 4.0 and containing with NISO4, NiCl2boric acid and substances, giving luster. A layer of bright Nickel with an average thickness of approximately 1,01610-3(0,001016) cm precipitated on the surface of the faucet. Cranes with the galvanised brilliant Nickel rinsed three times and then placed about 7 min in known commercially available electroplating bath with hexavalent chromium, equipped with well-known equipment for electroplating chromium. Bath with hexavalent chromium is a standard and well-known bath that contains about 239,67 g/l chromic acid. The bath also contains traditional and well-known chromium electroplating additives. In the tub support temperature of about 44,44-46,66oC and used catalyst with a mixture of sulfate/fluoride. The ratio of chromic acid to sulfate is about 200: 1. The chromium layer thickness of about 25,410-4(0,0000254) cm is applied to the surface of the glossy layer of Nickel. Cranes are completely rinsed in deionized water.

Taps plated is placed on the stand, and the last Yeisk patent EP 0486711 A1. Dryer blowing are a number of small nozzles that emit a pulsating air flow 5,62 kg/cm2. In the dryer keep the temperature 100oC. Taps plated left in the dryer with pulsed blowing 210 when moving the stand through the dryer with a speed of 0.12 m/s leave the Stand motionless for 37 C and then move again. The pulse duration of approximately 20 milliseconds. Cranes removed from the dryer with pulsed blowing and placed in the tank for plating using a cathode arc spraying. The tank has a generally cylindrical housing containing a vacuum chamber, which is adapted for pumping air through the pump. And a source of argon gas connected to the chamber through the control valve, which allows you to change the flow rate of argon gas supplied into the chamber. In addition, the source gas of argon connect the camera using an adjustable valve to change the flow rate of nitrogen supplied to the camera.

In the center of the camera set cylindrical cathode and is connected to the negative terminal of the source of DC power. The positive output of the power source podseivat on the rollers, 16 of which are mounted on the ring around the outside of the cathode. The ring rotates around the cathode, while each roller also rotates around its own axis, which results in the so-called planetary motion, which provides a homogeneous material with the cathode for numerous valves mounted around each roller. The ring is usually rotates at a speed of a few revolutions per minute, while each roller makes a few revolutions per rotation of the ring. The rollers are electrically isolated from the camera and rotating contacts so that you in the process of coating applied to the substrate bias voltage.

A vacuum chamber pumped to a pressure of about 510-3mbar and heated to a temperature of about 150oC.

Taps plated then subjected to a plasma-arc clearing at high bias voltage, in which the (negative) bias voltage value of about 500 V is applied to the taps plated on the cathode ignite and maintain an arc with a current of about 500 A. cleaning time is approximately 5 minutes

Argon gas is injected with soon is the woman about 10,1610-6(0,00001016) cm, put on chrome taps for 3 minutes Process a cathode arc deposition contains the following operations: served direct current to the cathode in order to reach the value of passing current of about 500 And serves argon gas into the reservoir to maintain the pressure at about 110-2mbar, and rotate the valves planetary method, which is described above.

After deposition of a layer of zirconium on the layer of zirconium put a multilayer structure. In the vacuum chamber periodically introducing a stream of nitrogen, with the proceeds arc discharge at a current of about 500 A. the flow Rate of nitrogen is modified pulse method, i.e. it changes periodically from a maximum value of the velocity of flow required for complete reaction of the zirconium atoms incident upon the substrate, and the formation of zirconium nitride, to the minimum value of the flow velocity, is equal to zero or has a small value, are not sufficient to fully react with all of the zirconium. The period of pulsation of the flow of nitrogen is about 1 to 2 minutes (from 30 s to 1 min, after completion). The total time for pulsed deposition is approximately 15 minutes, allowing you to get in the multilayer structure 10 to 15 layers with t the STU came in response nitride, zirconium metal, zirconium (or substochiometric ZrN with much lower nitrogen content).

After the deposition of multilayer structure, the flow rate of nitrogen is maintained at its maximum value (sufficient for the formation of fully entered into the reaction of zirconium nitride) in the time interval from 5 to 10 min in order to form a thicker "color layer" on top of the multilayer structure. After deposition of a layer of zirconium nitride, an additional stream of oxygen at a rate of about 0.1 l/min served in the time interval from 30 s to 1 min, with a flow rate of nitrogen and oxygen support at their previous values. The result is a thin layer of mixed reaction products (oxinitride Zirconia) with a thickness of approximately 0,508-1,2710-6see the Arc at the end of this last period of deposition extinguish, the vacuum chamber air and remove the substrate with the coating.

1. The method of applying a multilayer coating on the surface of the product, including deposition using galvanothermy at least one layer of the galvanic coating, drying articles having at least one layer of plated and deposition using physical deposition from the gas phase, at least one layer on at least part of the layer with which any liquid stains, and the layer deposited from the gas phase, selected from a range, including non-precious refractory metals, refractory alloys and base metals, the composition of non-precious refractory metals and compositions of alloys of non-precious refractory metals, and the composition of non-precious refractory metals and alloys of non-precious refractory metals include nitrides, oxides, carbides, carbonitrides and the reaction products of refractory metals or alloys of refractory metals, oxygen, and nitrogen.

2. The method according to p. 1, characterized in that at least part of the surface of the product precipitated galvanic coating containing at least one layer selected from a range that includes copper, Nickel, chrome.

3. The method according to p. 2, characterized in that the refractory metal and the alloy of the refractory metal is selected from a range that includes zirconium, titanium, alloy zirconium-titanium.

4. The method according to p. 3, characterized in that the refractory metal and the alloy of the refractory metal is chosen zirconium and zirconium alloy-titanium.

5. The method according to p. 4, characterized in that the composition of the refractory metal and the composition of the alloys of refractory metals selected from a range that includes the nitride reaction of titanium, oxygen and nitrogen, the nitride alloy zirconium-titanium oxide alloy zirconium-titanium, the reaction products of alloy zirconium-titanium, oxygen and nitrogen.

6. The method according to p. 5, characterized in that the composition of the refractory metal and the composition of the alloys of refractory metals selected from a range that includes zirconium oxide, zirconium nitride, the reaction products of zirconium, oxygen and nitrogen, nitride alloy zirconium-titanium oxide of an alloy of zirconium, titanium and the reaction products of alloy zirconium-titanium, oxygen and nitrogen.

7. The method according to p. 4, characterized in that the precipitated galvanic coating containing at least one copper layer, at least part of the surface of the product to obtain at least one layer of copper deposited by galvanic method, applied plating at least one layer of Nickel, at least one layer of copper deposited by electroplating method, for obtaining at least one layer of Nickel deposited by galvanic method, and precipitated by plating at least one layer of chromium on said at least one layer of Nickel deposited by galvanic method, for obtaining at least one layer of chromium, hanesbrands of the series, including refractory metals and alloys of refractory metals, precipitated from the gas phase, at least part of the chromium layer deposited by galvanic method.

9. The method according to p. 8, characterized in that the refractory metal and the alloy of the refractory metal is selected from a range that includes zirconium, titanium and alloy zirconium-titanium.

10. The method according to p. 9, characterized in that the refractory metal and the alloy of the refractory metal is chosen zirconium and zirconium alloy-titanium.

11. The method according to p. 10, characterized in that the multilayer coating comprising alternating layers of zirconium or zirconium alloy, titanium and zirconium nitride or nitride of an alloy of zirconium, titanium, precipitated from the gas phase on the zirconium layer, or an alloy of zirconium-titanium.

12. The method according to p. 11, characterized in that the zirconium nitride or nitride layer alloy zirconium-titanium is precipitated from the gas phase on said multilayer coating.

13. The method according to p. 12, characterized in that the zirconium oxide or the oxide layer on the zirconium-titanium is precipitated from the gas phase on the zirconium nitride or nitride layer alloy zirconium-titanium.

14. The method according to p. 13, characterized in that the layer comprising the reaction products of zirconium or alloy s-titanium.

15. The method according to p. 10, characterized in that the layer comprising zirconium nitride or nitride of an alloy of zirconium, titanium, precipitated from the gas phase on the zirconium layer, or an alloy of zirconium-titanium.

16. The method according to p. 15, characterized in that the layer comprising zirconium oxide or oxide of an alloy of zirconium, titanium, precipitated from the gas phase on the zirconium nitride or nitride layer alloy zirconium-titanium.

17. The method according to p. 15, characterized in that the layer comprising the reaction products of zirconium or zirconium alloy, titanium, oxygen and nitrogen, are precipitated from the gas phase on the zirconium nitride or nitride layer alloy zirconium-titanium.

18. The method according to p. 1, characterized in that at least part of the surface of the product precipitated galvanic coating containing at least one layer selected from a range, including Nickel and chromium.

19. The method according to p. 18, characterized in that at least one layer selected from a range that includes a refractory metal, an alloy of refractory metals, the composition of the refractory metal and the composition of the alloys of refractory metals, precipitated from the gas phase, at least part of at least one layer plated.

20. The method according to p. 19 different and alloy zirconium-titanium.

21. The method according to p. 20, characterized in that the refractory metal and the alloy of the refractory metal is selected from a range that includes zirconium and zirconium alloy-titanium.

 

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1 cl, 1 ex, 1 tbl

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FIELD: metal coats, in particular for gas turbine engines operating at high temperature.

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