Patent Grant
9598775
The present invention relates to a thermally stable and corrosion protective multilayer overlay system suitable for use on turbine engine components, and more particularly, to a smooth thermally stable and corrosion protective multilayer overlay system and method for producing the said overlay system that includes a basecoat layer formed by applying a slurry comprising metal oxide particles dispersed in a phosphate-based binder, a second layer formed by applying a slurry comprising metal oxide pigment particles dispersed in a phosphate-based binder, and an optional seal coat layer formed by applying a slurry comprising a phosphate-based binder that is substantially free of pigments.
The surfaces of turbine engine parts are exposed to the hot gases from the turbine combustion process. Turbine engine superalloy materials are selected based on their high temperature stability and corrosion resistance. Well-known superalloys, for example nickel based superalloys such as Inconel™ 718, Inconel™ 722 and Udimet™ 720 demonstrate good resistance to oxidation and corrosion damage. However even these materials experience degradation under severe conditions at high temperatures. Oxidation and corrosion reactions at the surface of the component parts can cause metal wastage and loss of wall thickness. The loss of metal rapidly increases the stresses on the respective component part and can ultimately result in part failure. Protective overlays are thus applied to these component parts to protect them from degradation by oxidation and corrosion.
Various corrosion-resistant layers and multilayer overlay systems have been suggested and used to protect turbine engine components, particularly compressor rotor blades. Assessment of the prior art overlay systems have revealed general deficiencies in their functional properties and appearance, as well as several possible failure modes.
For example, a prior art commercially available multilayer overlay system is designed for lower service temperatures and provides effective protection up to 1200° F. However this prior art overlay system would be prone to cracking and delamination at elevated operating temperatures (≧˜1300° F.) of newer engines if it were used on such advanced engines.
Other type of possible issues or problems that may be associated with the prior art based overlay systems are the 1 mm to 3 mm diameter round spots (i.e. “white spots”) on some parts coated with the prior art overlay system. As seen in
In view of the above-identified concerns and disadvantages, a need exists for continuous improvements to the surface finish characteristics as well as thermal and corrosive performance of the prior art slurry-based, multilayer overlay systems. While the prior art slurry-based, multilayer overlay systems meet the requirements and specifications of current engine manufacturers, improvements are needed for use with newer, more advanced engines. It would therefore be desirable to provide a multilayer overlay system that improves upon the surface finish characteristics of the prior art overlay systems and possesses improved thermal stability in normal and corrosive environments.
In one aspect the invention may be characterized as an overlay system comprising: (i) a basecoat layer formed by applying a slurry comprising metal or metal oxide pigment particles dispersed in a phosphate-based binder, the basecoat layer having a thickness of between about 0.5 to 3.0 mils; and (ii) a second layer formed by applying a slurry comprising metal oxide pigment particles, preferably chromium oxide pigment particles, dispersed in a phosphate-based binder, wherein the metal oxide pigment particles have enhanced dispersibility due to a narrow particle size distribution and optimized surface area, the second layer having a thickness of between about 0.1 to 1.0 mil; The multilayer overlay system of the present invention demonstrates improved thermal and corrosion stability and surface finish characteristics compared to prior art slurry based multilayer overlay systems.
In yet another aspect the invention may be characterized as an overlay system comprising: (i) a basecoat layer formed by applying a slurry comprising aluminum oxide pigment particles dispersed in a phosphate-based binder, the basecoat layer having a thickness of between about 0.5 to 3.0 mils; (ii) a second layer formed by applying a slurry comprising chromium oxide pigment particles dispersed in a phosphate-based binder, wherein the chromium oxide pigment particles have a narrow particle size distribution with median particle size (characterized as the 50th percentile of the particle size distribution) of between about 0.8 to 2.2 microns and surface area of the particles is greater than or equal to about 4 m 2/g, the second layer having a thickness of between about 0.1 to 1.0 mil; and wherein the surface roughness of the basecoat layer and the second layer in the overlay system is less than or equal to about 30 μin. The multilayer overlay system of the present invention demonstrates improved thermal stability in corrosive and noncorrosive environment, and surface finish characteristics compared to prior art slurry based multilayer overlay systems.
In yet another aspect, the invention may be characterized as a method or process for coating a metal substrate comprising the steps of: (i) preparing surface of the metal substrate; (ii) applying a slurry based ceramic pigment filled phosphate-based binder to the metal substrate to form a basecoat layer, the basecoat layer having a thickness of between about 0.5 to 3.0 mils; (iii) curing the coated substrate with the basecoat layer; (iv) preparing a slurry comprising chromium oxide pigment particles dispersed in a phosphate-based binder, wherein the chromium oxide pigment particles have a narrow particle size distribution with median particle size (characterized as the 50th percentile of the particle size distribution) of between about 0.8 to 2.2 microns, and surface area of the particles is greater than or equal to about 4 m 2/g, (v) applying said slurry to the basecoat layer to form a second layer, the second layer having a thickness of between about 0.1 to 1.0 mil; and (vi) curing the coated substrate with the basecoat layer and the second layer. The multilayer overlay system of the present invention demonstrates improved surface finish characteristics and thermal performance compared to prior art slurry based multilayer overlay systems.
In yet a further aspect, the invention may be characterized as a product by process wherein the product is a coating applied by the process comprising the steps of: (i) applying a slurry based alumina oxide pigment filled phosphate-based binder to the metal substrate to form a basecoat layer, the basecoat layer having a thickness of between about 0.5 to 3.0 mils; (ii) preparing a slurry based chromium oxide pigment filled phosphate-based binder wherein the chromium oxide pigment particles have a particle size distribution characterized in that the 50th percentile of the particle size distribution is a diameter of between about 1.0 to 2.0 microns and the 90th percentile of the particle size distribution does not exceed a diameter of about 3.0 microns; and (iii) applying the stable slurry based chromium oxide pigment filled chromate-phosphate binder to the basecoat layer to form a second layer having a thickness of between about 0.1 to 1.0 mil The multilayer overlay system of the present invention demonstrates improved surface finish characteristics and thermal performance compared to prior art slurry based multilayer overlay systems.
The above and other aspects, features, and advantages of the present invention will be more apparent from the following, more detailed description thereof, presented in conjunction with the following drawings, wherein:
It is well known in the art that absolute numbers measured for particle size and particle size distribution for particulate systems, such as pigment powders and pigment containing slurries, are strongly dependent on testing and/or measurement technique and instrumentation. Thus it is very important to emphasize that particle size D50 and D90 numbers of the present invention have been obtained via laser diffraction technique by employing MicroTrac SRA Particle Analyzer as a particle measuring equipment. As used herein, “D50” refers to a median particle size in which 50 percent of particles are smaller and the other 50 percent of the particles are larger than the median size, and “D90” refers to a particle size in which ninety percent of particles are smaller than the particle size.
It is also known in the art that absolute numbers for Surface Area (SA) of pigment powders also depends on measurement technique and instrumentation. Thus it is very important to emphasize that SA numbers of the present invention were obtained by nitrogen gas absorption technique by BET method employing Gemini 2360 V4.01 measuring system.
Slurries were also characterized by their pH, viscosity, specific gravity and solids content. These parameters, together with D50 and D90, were monitored to test stability and aging of the slurries
Other test methods and equipment were used in the present invention. Thickness of the coating layers was measured by FisherScope MMS (Eddy current and magnetic induction probes, depending on the type of the substrate). The surface finish (smoothness Ra) was measured by Mitutoyo Surftest 301 at a 5.1 mm traverse and 0.030″ (0.76 mm) cutoff. The coatings gloss was tested by BYK Gardner Micro-gloss 60°. Coatings adhesion to a substrate and inter-layer adhesion were tested by cross-hatch tape (per ASTM Standard D3359) and bend (90° bend around a 6.4 mm diameter mandrel) tests. Optical microscopy and SEM/EDS analysis were employed for detailed investigation of the coatings surface and cross-section morphology, microstructure and elemental composition.
One embodiment of the invention is a multi-layered overlay system suitable for use in harsh environments such as environments associated with turbomachinery. The first layer of the multi-layered overlay system, which is in contact with the metal substrate or metal surface of the turbomachinery, is a metal or/and metal oxide pigment filled inorganic binder, preferably a ceramic pigment filled inorganic binder, having a thickness of between about 0.5 to 3.0 mils. More preferably, the first layer or basecoat is aluminum oxide (e.g. alumina) pigment filled phosphate-based binder. Alternatively, the first layer may contain other non-metallic pigments like zirconia, ceria, other mixed metal oxides and/or combinations thereof in lieu of or in addition to the alumina oxide.
The first layer or basecoat may also optionally contain additional additives such as surfactants, wetting agents and other conventional additives. In addition to the ceramic pigment, other particulate metals, such as aluminum, copper, silver, or nickel may be included in the first layer.
The inorganic binder solution associated with the first layer is preferably an acidic phosphate solution, more preferably includes chromate compounds, or the metal salts thereof dissolved in an acidic phosphate compound. These binder solutions are particularly useful because of their ability to polymerize under drying and curing cycle and to form a continuous glassy matrix with good mechanical strength, flexibility, as well as some corrosion and thermal resistance.
The first layer is applied to a thickness of between 0.5 to 3.0 mils with preferable thickness of this first layer being 0.8 to 1.3 mils. The minimum thickness is determined by a very strong correlation between surface roughness (Ra) and thickness of the basecoat layer: sharp decrease in Ra of this basecoat layer, as well as in Ra of the whole multilayer overlay system has been observed when thickness of 0.8 mils of the first layer has been achieved. The maximum thickness of the basecoat layer is generally determined by a targeted or specified thickness of the entire multilayer overlay system. It is customary and desirable not to apply a layer in excess of functional requirement for the overlay system.
Controlling the surface roughness of basecoat layer is important, as it influences the surface roughness of both the second layer and optional seal coat layer. Preferably, the surface roughness (Ra) of the basecoat layer should be 30 μin or less, and more preferably 20 μin or less. If the surface roughness in the basecoat layer is too high (e.g. >30 μin), then higher surface roughness values will likely occur in the second layer and optional seal coat layer. In other words, surface roughness corrections (i.e. downward adjustments) during application of the second layer and an optional seal coat layer are not feasible or capable if the surface roughness of the basecoat layer is too high.
The second layer of the multi-layered overlay system comprises fine metal oxide pigments of prescribed particle size, particle size distribution (PSD) and Surface Area (SA). Preferably, the second layer is a chromium oxide (e.g. Cr2O3) pigment filled phosphate-based binder. Any phosphate-based binder as known in the art may be used. Preferably, the phosphate-based binder is chromate-phosphate. The chromate-phosphate binder of the second layer generally comprises chromate compounds, or the metal salts thereof dissolved in an acidic phosphate compound. The second layer is applied to the first layer to a thickness of between about 0.1 to 1.0 mils.
In the preferred embodiment, the chromium oxide pigment particles have a narrow PSD with median particle size D50 (characterized as the 50th percentile of the PSD) of between about 0.8 to 2.2 microns and oversized particle size D90 (characterized as the 90th percentile of the PSD) not exceeding about 3.0 microns. The preferred SA of the particles is at least 4 m2/g to 5 m2/g and more preferably about 6 m2/g. Properties of chromium oxide pigment particles of the preferred embodiment (denoted as Powder II) are shown in Table 1. By way of comparison, the prior art multilayer overlay system has the second layer comprising chromium oxide pigment particles with median particle size D50 of 2.5 microns, oversize particle size D90 of 3.5 to 3.7 microns and SA of 3.0 to 3.5 m2/g (denoted as Powder I in Table 1)
The corresponding slurries have been prepared employing these powders (five replicate slurry samples for each powder); these slurries are referred below as Slurry A (prior art slurry) and Slurry B (slurry of the present invention). It is important to note that the dispersing of Powder I in the Slurry A required a lengthy ball-milling stage, while Powder II produced a very good dispersion in Slurry B after less than 30 minutes of high shear mixing. Both slurries have been screened through 500 mesh screen prior to the coating application. This obviously simplifies and shortens a slurry production process and thus is an important practical advantage for a large-scale manufacturing.
Results of the particle sizing of the prepared Slurries A and B, after screening, are presented in Table 2; very good sample-to-sample repeatability for D50 (±0.3 μm) and D90 ((±0.5 μm) was observed. As seen from the data, employing Cr2O3 powder particles with lower median particle size D50 and oversized particle size D90 resulted in the 2nd layer slurry also having a lower median particle size and lower D90 size of oversized particles.
Table 2 also presents roughness and gloss of the parts coated with two-layer overlay system as follows. 2 inch×4 inch steel panels (1010 carbon steel, three replicate panels for each prepared slurry sample) were coated with the base layer (˜25-30 μm thick), dried and cured at 350° C. for 0.5 hr and then air-spayed with the Slurries A (on Group A panels) or B (on Group B panels). The coated panels were then dried and cured at 350° C. for 0.5 hr to form the 2nd layer of a two-layer overlay system. The thickness of the second layer was targeted at 5-7 μm.
As seen from these data, panels that were coated with the Slurry B were consistently smoother and glossier than the panels coated with Slurry A. Optical microscopy data (
These oversized chromium oxide particles caused even stronger “grittiness” appearance in the three-layer overlay system that employs, on top of a 2nd layer, an additional and optional layer of a seal coat; the seal coat layer comprising a chromate-phosphate binder substantially free of pigments. The sealer may be applied over the 2nd layer coating to a minimum thickness of about 0.05 to 0.1 mils (about 1-2.5 μm).
On
Based on the images of
Depending on the size of Cr2O3 oversized particles, their coverage by the seal coat layer varies (e.g. higher degree of coverage for smaller Cr2O3 particles and lower degree of coverage for larger Cr2O3 particles). However, because of the protrusion of the particles from the surface, the seal coat layer on top of the particle always will be thinner than the rest of the matrix. Thus, reducing number and size of oversized Cr2O3 particles in the slurry has an overarching effect on the quality of the whole overlay system.
It was found that employing chromium oxide with particle size and PSD of the present invention allows significantly decreased defects and improved surface finish of the multilayer overlay system, i.e. reduced roughness and increased glossiness.
The 2nd layer may also contain additional additives such as surfactants, corrosion inhibitors, viscosity modifiers, wetting agents and other conventional additives to increase oxidation and corrosion protection of the overlay system as well as to provide improved application and aesthetic properties. In addition to the chromium oxide pigment, other particulate metal oxide pigments may be included in the 2nd layer.
It was also observed that the slurry of the present invention (Slurry B in Table 2) consistently provides enhanced sprayability and more uniform coverage of the 2nd layer over the base layer of the coating system as compared to the prior art slurry (Slurry A in Table 2). This is obviously an important practical advantage in a large-scale production process, especially when complex-shaped parts should be coated and when any edge non-uniformity and “picture framing” of the coating create potential of a service failure through coating cracking and peeling on the edges during curing and service life of a coated part. These visual observations have been confirmed by SEM comparative study of the coating thickness uniformity on two superalloy complex-shaped rectangular parts denoted as Part 4-196 and Part 21-197, where the 2nd layer was applied using Slurries A (prior art) and B (present invention), correspondingly.
According to the specifications of these components, total thickness of the applied coating system is tested in one location on one side of the rectangular part. Thus, to investigate the coating thickness uniformity over the part length from one end to the other, a vertical cross-section has been made right through this testing location; the samples were mounted in epoxy, polished and examined by SEM. Coating thickness measurements were taken on 1000× and 2000× magnifications in the locations shown in
The above-described multi-layer overlay system has been successfully used to provide high quality overlay which protect metal and metal alloy surfaces from oxidation and corrosion, particularly at high or moderately high temperatures. Most importantly, it was unexpectedly found that the present multilayer overlay system exhibits a dramatic improvement in thermal stability as compared to the prior art overlay. This improved thermal performance of the entire multilayer overlay system generally occurs where the 2nd layer of the multilayer overlay system is applied with a slurry employing chromium oxide pigment particles with median particle size D50 of between about 0.8 to 2.2 microns, preferably between 1.2 and 1.8 microns, oversized particles size D90 not exceeding about 3.0 microns, preferably not exceeding of about 2.0 to 2.8 micron, whereas SA of the particles is at least 4 m2/g and more preferably at least 6 m2/g.
As shown in
It was also unexpectedly found that the present multilayer overlay system exhibits a dramatic improvement of hot corrosion stability, as evidenced in a test conducted at about 1400° F. for 600 hours while exposed to corrosive environment of CaSO4+carbon black mixture. As seen in
The slurry composition for the basecoat layer may be applied in a conventional way to the metal or metal alloy surface to be coated. Generally, it is desirable to degrease the part to be coated, blast with abrasive, and apply the layer by any suitable means, such as by spraying, brushing, dipping, dip spinning, etc., The coated substrate is then dried and subsequently cured at a temperature of about 340° C. to 350° C. for 15 to 30 minutes or longer. Curing may be performed at higher or lower temperatures if desired. The slurry is preferably applied in at least two coats or passes, each pass depositing a layer of about 0.1 mils to 0.25 mils in thickness, and more preferably a total of four coats or more to achieve a total thickness of the basecoat of between about 0.5 mils to about 3.0 mils. Drying of the basecoat is preferably performed at about 80° C. for 15 to 30 minutes. Curing of the basecoat preferably occurs at 345° C. (650° F.) for about 30 minutes. Higher humidity conditions of 50% humidity or more for application of the basecoat layer is also preferred.
The slurry composition for the 2nd layer may be applied to the basecoat layer by any suitable means, such as by spraying, brushing, dipping, dip spinning, etc. The intermediate layer is then dried and subsequently cured at a temperature of about 340° C. to 350° C. for 15 to 30 minutes or longer. The slurry is preferably applied in one to four coats or passes, each pass or coat depositing a layer of between about 0.1 mils to 0.25 mils in thickness to achieve a total thickness of the 2nd layer of between about 0.1 mils to about 1.0 mils. Drying of the 2nd layer is generally performed at about 80° C. (175° F.) for 15 to 30 minutes followed by curing of the 2nd layer at 345° C. (650° F.) for about 30 minutes.
Optionally, the seal coat slurry composition is then applied over the 2nd layer to a minimum thickness of about 0.05 to 0.1 mils. The seal coat slurry is preferably applied in two or more coats or layers, each coat between about 0.02 mils to 0.25 mils in thickness to achieve a minimum thickness of the seal coat of about 0.05 to 0.1 mils. Drying of the seal coat layer is generally performed at about 80° C. for 15 to 30 minutes followed by its curing at 345° C. (650° F.) for about 30 minutes.
From the foregoing, it should be appreciated that the present invention thus provides a slurry based multilayer overlay system comprising a basecoat layer formed from a slurry based ceramic pigment filled chromate-phosphate binder, a 2nd layer formed from a slurry based metal oxide pigment or ceramic oxide pigment filled chromate-phosphate binder, and, optionally, a sealcoat layer formed from a chromate-phosphate binder substantially free of pigments. Various modifications, changes, and variations of the present methods will be apparent to a person skilled in the art and it is to be understood that such modifications, changes, and variations are to be included within the purview of this application and the spirit and scope of the claims.
This application claims priority to U.S. provisional application Ser. No. 61/496,270 filed Jun. 13, 2011 and 61/504,865 filed Jul. 6, 2011, the disclosures of which are incorporated by reference herein.
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| 20130004712 A1 | Jan 2013 | US |
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| 61496270 | Jun 2011 | US | |
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