Method for producing a multilayer coating of a nitride-containing compound

Abstract: The invention relates to a wear, erosion and corrosion resistant coating comprising a first layered zone deposited on a substrate which comprises at least one layer of a titanium nitrogen-containing layer contains a nitrogen content varying from 0 to 35 atomic percent, a second layered zone deposited on the first layered zone and which comprises at least two layers of a titanium nitrogen-containing compound with a nitrogen content varying from 38 atomic percent to 54 atomic percent of nitrogen.

Description: Field of the Invention The invention relates to a method for producing a multilayer coating on a substrate comprising placing the substrate to be coated in a chamber to form a first zone disposed on the substrate which comprises at least one layer of a nitrogen-containing titanium layer which has a nitrogen content varying from above 0 to 35 atomic percent, and changing the ratio of nitrogen to titanium to form a second zone comprising at least two layers of a titanium nitride-containing compound in which each layer contains from 38 atomic percent to 54 atomic percent of nitrogen, with the proviso that each layer in the second zone contains between 6 atomic percent and 14 atomic percent of nitrogen different than the amount of nitrogen contained in an adjacent underlayer whereby the outermost layer of the second zone has a nitrogen content less than an adjacent underlayer. Background of the Invention Titanium nitride (TiN) coatings are of interest for wear, erosion and corrosion applications because of their high hardness and good chemical stability. Physical vapor deposition (PVD) and chemical vapor deposition (CVD) processes have been successfully used to deposit thin TiN coatings on metal and alloy components for a variety of engineering applications. The benefits from their excellent wear characteristics are well recognized on TiN coated cutting and forming tools, and their good erosion protection from solid particle impact is evident on TiN coated compressor blades in turbomachines. For corrosion protection, however, relatively little success has been reported and then only in a mildly corrosive environment. The corrosion behavior of TiN coatings depends on their chemistry, microstructure and thickness. A nearly stoichiometric TiN and a N-rich TiN were found to have good corrosion resistance. It was reported in the prior art that a fully dense TiN coating with fine equiaxial grains is superior to many engineering materials in resistance to various corrosive environments. It was also reported that a coating with a columnar structure generally has poor corrosion resistance due to micropores at the boundaries of the columnar grains. In essence, pinholes and micropores in the coating are most detrimental to its corrosion properties. This is because TiN is electrochemically more noble than most engineering materials. Pinholes in the coating may accelerate corrosion in the underlying metal by pitting, crevice or galvanic corrosion mechanisms, particularly in a chloride-containing environment. The corrosion resistance of TiN was also shown to increase with increasing coating thickness due to reducing the occurrence of possible pinholes penetrating through the coating. Typically, it requires a thick coating (20µm) to provide full protection of the base metal from the corrosive media. However, it is difficult to deposit such a thick coating uniformly on engineering components due to their complex configuration and the relatively high intrinsic compressive stress in the coating. Clearly, pinholes prevent the TiN coating from being successfully used for a combined corrosion and wear/erosion application. In addition, pinholes are an inherent structural defect in PVD and CVD type TiN coatings. Many approaches have been utilized to improve the corrosion resistance of TiN coatings by reducing pinhole defects through the use of a metallic intermediate layer or multilayer deposits. U.S. Patent No. 4,226,082 discloses that a Ti+TiN coating with a Ti-rich intermediate layer adjacent to the base metal provides good properties for an ornamental application in a relatively mild wear and corrosive environment. It was reported in an article by Massiani et al. in Surface Coating Technologies 45 (1991) 115, that a TiN coating with a Ti intermediate layer improves corrosion protection over a single layer TiN coating on AISI 430 and AISI 304 stainless steel and Fe substrates in H 2 SO 4 and NaCl solutions. Japanese Patent No. JP-A-5 8,064,380 discloses that a Ti layer laminating alternately with TiN can inhibit the formation of pinholes passing through the coating layer to protect the coated article from localized corrosion attack. EP-A-0 043 781 discloses a process for producing layers of a titanium nitride-containing coating on a substrate, wherein stoichiometric titanium nitride layers and non-stoichiometric titanium nitride layers are alternatingly formed on the substrate, the layer adjacent to the substrate being stoichiometric titanium nitride. The nitrogen content in the non-stoichiometric titanium nitride TiN x -layers is disclosed by the index x being from above 0.4 to below 1. In EP-A-0 418 001 there is disclosed a method for producing a multilayer coating of at least two layers of a nitride-containing compound, in which coating at least one layer contains at least two atomic percent of nitrogen different than the nitrogen contained in an adjacent layer. Furthermore, EP-A-0 522 873 discloses a wear and erosion resistant coating for substrates having a non-nitrogen titanium-containing outer surface onto which a non-stoichiometric titanium nitride coating is deposited in which the nitrogen content in the titanium nitride coating is from 32.5 to 47 atomic weight percent. The object of the invention is to provide a method for producing a multilayered coating of a titanium nitrogen-containing compound that can effectively eliminate galvanic corrosion attack within the coating layers. The above and further objects and advantages of this invention will become apparent upon consideration of the following description. Summary of the Invention The invention relates to a method for producing a multilayer titanium nitrogen-containing coating on a substrate comprising the steps: (a) placing a substrate to be coated in a chamber containing a titanium based target and a nitrogen-containing gas mixture; (b) evaporating the titanium from the titanium based target to produce a titanium vapor to react with the nitrogen in the nitrogen-containing gas mixture to form a first zone of at least one nitrogen-containing titanium layer of above 0 to 35 atomic percent of nitrogen, preferably of above 0 to 24 atomic percent of nitrogen, on the substrate, wherein if the first zone has more than one nitrogen-containing titanium layer then each nitrogen-containing titanium layer preferably will contain between 2 and 20 atomic percent of nitrogen different than an adjacent underlayer; (c) changing the ratio of nitrogen to titanium in step (b) to form a second zone comprising a titanium nitride-containing layer on the first zone of the coated substrate that has a nitrogen content between 38 and 54 atomic percent of nitrogen; and (d) repeating step (c) at least once to form a multilayer coating of at least two layers in which each layer contains 38 to 54 atomic percent of nitrogen, wherein for wear and erosion characteristics the atomic percent of nitrogen could be from 38 atomic percent to 45 atomic percent while for corrosion characteristics the atomic percent of nitrogen could be from 45 atomic percent to 54 atomic percent of nitrogen, and each layer in the second zone contains between 6 and 14 atomic percent of nitrogen, preferably between 6 and 10 atomic percent of nitrogen, different than the amount of nitrogen contained in an adjacent underlayer, whereby an outermost layer of the second zone has a nitrogen content less than an adjacent underlayer. The ratio of nitrogen to titanium can be changed by altering the current, changing the flow of nitrogen or a combination of both. It has been found that a great difference in free corrosion potential exists between pure titanium and titanium nitride which cause galvanic corrosion attack to the pure titanium layer in a chloride containing media. It has been found in accordance with this invention that a multilayered coating with an arrangement to reduce the electro-chemical potential difference between an adjacent layer can effectively eliminate the potential galvanic corrosion attack in the coating layer as well as the substrate. Table 1 shows the free corrosion potential [mV (SCE)] for various TiN-containing compounds along with titanium and stainless steel. Galvanic Series of TiNx Coatings, Ti, and 17-4 PH in 3.5 wt.% NaCl Solution Materials Free Corrosion Potential mV (SCE) TiN 0.48 -314 TiN 0.63 -178 TiN 0.66 -212 TiN 0.88 -198 TiN 0.89 -129 TiN 0.92 -156 TiN 0.97 -168 TiN 1.0 - 85 Ti -446 17-4 PH -561 One embodiment for producing a multilayer nitride-containing coating on a substrate would comprise the steps: (a) placing a substrate to be coated in a vapor deposition chamber having an anode and containing a titanium-based cathode along with a nitrogen-containing gas mixture; (b) applying a voltage across the cathode and anode to establish a current to effect evaporation of the titanium from the titanium-based cathode to produce a titanium vapor to react with the nitrogen in the nitrogen-containing gas mixture to form a nitrogen-containing titanium layer of a desired nitrogen content on the substrate; (c) changing the ratio of nitrogen to titanium in step (b) to form another titanium nitride containing layer on the coated substrate that has a nitrogen content of a specific atomic percent of nitrogen different than the nitrogen contained in the previously deposited coating; and (d) repeating step (c) at least once to form a multilayer coating of at least three layers. Preferably, the nitrogen-containing gas mixture could be argon-nitrogen; krypton nitrogen; helium-nitrogen; xenon-nitrogen; neon-nitrogen or the like. The multilayer coating can be deposited by using conventional process techniques such as chemical vapor deposition and physical vapor deposition such as arc evaporation processes, dc and rf magnetron sputtering, reactive ion plating and the like. The changing of the ratio of nitrogen to titanium for the alternate lamellar layers will interrupt the grain growth process of the coating compound so that the grain size of the compound is no larger than the thickness of the individual layers. The thickness of the individual layers can vary greatly as for example between 0.1 to 5 microns thick, preferably about 1 micron thick. In accordance with this invention, the number of layers of a titanium nitride-containing compound forming the second zone of the coating of this invention can vary from two up to any number desired for a particular application. Generally, 5 to 40 layers of the coating would be suitable for most applications employing turbomachines that operate in a dust environment. For most applications, 15 to 40 layers would be preferable. Preferably the thickness of the first zone could be between 1 and 5 microns thick, preferably between 3 and 5 microns thick and the thickness of the second zone could be between 3 and 35 microns thick, preferably between 8 and 35 microns thick. Preferably, the total thickness of the first layered zone and the second layered zone should be between 6 to 40 microns. The multilayer coating of this invention is ideally suited for coating substrates made of materials such as titanium, aluminum, nickel, cobalt, iron, manganese, copper, alloys thereof and the like. As recited above, pinholes and micropores are generally inherent structural defects in PVD and CVD types of TiN coatings. These defects, however, may not be completely eliminated. The subject invention relates to a multilayer coating to enhance the overall corrosion and wear/erosion performance, by reducing the occurrence of interconnecting pinholes and micropores through the layered structure of the coating and reducing the galvanic corrosion in the coating and the base metal. To accomplish this, a Ti(N) layer with a microstructure of graded nitrogen content or multilayer with varying nitrogen content from 0 to 35 atomic percent nitrogen should be used as an intermediate layer between the TiN x layered coating (second zone) and the base metal. In such an arrangement using an intermediate layer, the free corrosion potential differences between Ti(N), TiN x coating, and the base metal are greatly reduced and thus galvanic corrosion can be prevented. The outermost TiN x layer which is exposed to the corrosion/wear/erosion environment should have a nitrogen content less than the adjacent TiN x layer. The difference in nitrogen content between each of the layers in the second zone should be between 6 atomic percent and 14 atomic percent. Therefore, the outer layer is chemically more active (anode) compared to the adjacent layer (cathode). As a result, the corrosion will be confined in the outermost layer even with the presence of pinholes. EXAMPLE Cyclic polarization studies are carried out to evaluate the pitting corrosion behavior of monolayer TiN coatings and multilayer TiN/TiN x coatings on a 17-4 PH substrate (stainless steel) in a 3.56 wt% NaCl solution at 25°C. The thicknesses of the stoichiometric monolayer TiN coatings were 2, 8 and 15.4 µm. Pitting corrosion of the 17-4 PH substrate occurred in all the TiN coated samples. The critical pitting potential of the TiN coating and the coating including the Ti underlayer, E pit (TiN) and E pit (TiN+Ti) respectively, increased with increasing total coating thickness. Multilayer TiN/TiN x coatings with various coating thicknesses from 7.1 to 18.5 µm and various layer thicknesses from 0.7 to 2.8 µm were investigated. A typical cyclic polarization curve without occurrence of pitting corrosion for a multilayer coatings with 14.2 µm coating thickness and 1.6 µm layer thickness was noted. An active/passive transition occurred at a critical current density of 0.12 mA cm -2 and potential -80 mV (SCE), followed by passivation at a potential greater than -10 mV (SCE). The active/passive transition probably was a result of the dissolution of corrosion products from the surface of the coating which led to the formation of pinholes within the coating layers. This is a distinct polarization characteristic for a multilayer TiN/TiN x coating in a 3.56 wt.% NaCl solution. Table 2 summarizes the cyclic polarization test results of the multilayer and monolayer coatings. The coating thicknesses of the multilayer and monolayer coatings included approximately 1 µm Ti(N) and 1.5 µm Ti underlayers, respectively. The pitting corrosion resistance of the coating system was measured in terms of E pit -E corr . Data show E pit -E corr as a linear function of coating thickness for multilayer coatings and monolayer coatings with and without a Ti underlayer. The result had no direct correlation in a quantitative manner with that in a specific environment in service. However, based on E pit -E corr , for a given coating thickness, the multilayer coating clearly was much more pitting corrosion resistant that the monolayer coating with and without the Ti underlayer. For a given coating thickness, the multilayer TiN/TiN x coating exhibits substantially better protection for the 17-4 PH base metal from pitting corrosion in a chloride environment than a monolayer TiN coating. Although specific embodiments of this invention have been described, it should be understood that various modifications may be made without departing from the scope of the claims. Coating Total No. of Coating Layers Total Coating Thickness (µm) Layer Thickness (µm) E pit -E corr (mV(SCE)) TiN/TiN 0.67 6 8.8 1.3 1073 TiN/TiN 0.67 6 10.6 1.6 1064 TiN/TiN 0.67 6 13.0 2.0 1460 TiN/TiN 0.67 6 18.0 2.8 TiN/TiN 0.67 7 7.1 0.87 708 TiN/TiN 0.67 7 8.0 1.0 966 TiN/TiN 0.67 7 8.8 1.1 1150 TiN/TiN 0.67 7 12.5 1.6 1500 TiN/TiN 0.67 8 10.6 1.2 TiN/TiN 0.67 8 14.2 1.6 TiN/TiN 0.67 11 8.7 0.7 1180 TiN/TiN 0.67 11 18.5 1.6 TiN 1 2.0 2.0 32 TiN 1 8.0 8.0 271 TiN 1 15.4 15.0 572 TiN+Ti 2 3.5 -- 128 TiN+Ti 2 9.5 -- 776 TiN+Ti 2 16.9 -- 1035

Claims: A method for producing a multilayer titanium nitrogen-containing coating on a substrate comprising the steps: (a) placing a substrate to be coated in a chamber containing a titanium based target and a nitrogen-containing gas mixture; (b) evaporating the titanium from the titanium based target to produce a titanium vapor to react with the nitrogen in the nitrogen-containing gas mixture to form a first zone of at least one nitrogen-containing titanium layer of above 0 to 35 atomic percent of nitrogen on the substrate; (c) changing the ratio of nitrogen to titanium in step (b) to form a second zone comprising a titanium nitride-containing layer on the first zone of the coated substrate that has a nitrogen content between 38 and 54 atomic percent of nitrogen; and (d) repeating step (c) at least once to form a multilayer coating of at least two layers in which each layer contains 38 to 54 atomic percent of nitrogen and each layer in the second zone contains between 6 and 14 atomic percent of nitrogen different than the amount of nitrogen contained in an adjacent underlayer, whereby an outermost layer of the second zone has a nitrogen content less than an adjacent underlayer. The method of claim 1 wherein, if the first zone has more than one nitrogen-containing titanium layer, then each nitrogen-containing titanium layer will contain between 2 and 20 atomic percent of nitrogen different than an adjacent underlayer. The method of claim 1 wherein the nitrogen-containing titanium layer in the first zone has a nitrogen content of above 0 to 24 atomic percent. The method of claim 1 wherein the titanium nitride-containing layer in the second zone has a nitrogen content of between 38 and 45 atomic percent. The method of claim 1 wherein each layer in the second zone contains between 6 and 10 atomic percent of nitrogen different than an adjacent underlayer. The method of claim 1 wherein said nitrogen-containing gas mixture is selected from the group consisting of argon-nitrogen; krypton-nitrogen; helium-nitrogen; xenon-nitrogen; and neon-nitrogen. The method of claim 6 wherein said nitrogen-containing gas mixture is argon-nitrogen. The method of claim 1 wherein said substrate is selected from the group consisting of titanium, iron, aluminum, nickel, cobalt, manganese, copper and alloys thereof. The method of claim 8 wherein the substrate is made of titanium. The method of claim 1 wherein the thickness of each layer in said first and second zones is from 0.1 to 5 microns. The method of claim 1 wherein the total thickness of the multilayer coating in the first and second zones is from 6 to 40 microns.

Inventors: JIINJEN ALBERT SUE, JIINJEN, ALBERT SUE
Applicants: PRAXAIR TECHNOLOGY INC, PRAXAIR S.T. TECHNOLOGY, INC.
Application year: 1996
Main classification: C23C14
IPC codes: C23C14, C01B21, C23C28