WO2001046324A2 - Erosion-resistant coatings for organic matrix composites - Google Patents

Erosion-resistant coatings for organic matrix composites Download PDF

Info

Publication number
WO2001046324A2
WO2001046324A2 PCT/US2000/041502 US0041502W WO0146324A2 WO 2001046324 A2 WO2001046324 A2 WO 2001046324A2 US 0041502 W US0041502 W US 0041502W WO 0146324 A2 WO0146324 A2 WO 0146324A2
Authority
WO
WIPO (PCT)
Prior art keywords
erosion
coating
resistant coating
organic resin
mixtures
Prior art date
Application number
PCT/US2000/041502
Other languages
French (fr)
Other versions
WO2001046324A3 (en
WO2001046324B1 (en
Inventor
Subhash K. Naik
Raymond J. Sinatra
Original Assignee
Rolls-Royce Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rolls-Royce Corporation filed Critical Rolls-Royce Corporation
Priority to EP00992985A priority Critical patent/EP1244544A4/en
Priority to AU49012/01A priority patent/AU4901201A/en
Publication of WO2001046324A2 publication Critical patent/WO2001046324A2/en
Publication of WO2001046324A3 publication Critical patent/WO2001046324A3/en
Publication of WO2001046324B1 publication Critical patent/WO2001046324B1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/042Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/046Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

Definitions

  • the present invention relates generally to coatings for organic matrix composite substrates, and more particularly to a method of providing a hard, adherent, erosion- resistant coating on the surface of an organic matrix composite.
  • Synthetic organic resins have increasingly been used to manufacture strong, lightweight components. Since many of these resins can also withstand high operating temperatures, they are particularly useful for the construction of turbine engine components. Examples of commercially available high temperature resins include Epoxy, PMR 15, PMR 25, BMI, PEEU, PEEK and PAM.
  • organic matrix composites are organic resins that include reinforcing components encapsulated in the resin.
  • the reinforcing components provide substantial mechanical strength to the resin.
  • the reinforcing components can be formed as fibers, platelets, whiskers and particulates.
  • Typical examples of materials that can be used as reinforcing components include carbon, glass, quartz, metal, metal oxides and ceramics.
  • Selected OMCs can provide the mechanical strength and thermal stability necessary to replace many heavier metal components in turbine engines; however, components formed with the OMCs are frequently short lived because they wear excessively in the hostile environments in which they are used. Often components are exposed to severe abrasive forces, for example, impaction by sand, rain, hailstones and other particulates entrained in high velocity wind streams. These particles can quickly erode the relatively soft OMC components. The eroded components must be replaced frequently to maintain the performance requirements of many turbines. Otherwise a severely eroded turbine component can disintegrate in use causing potential engine failure.
  • a hard coating to a shaped organic matrix resin could provide an erosion-resistant component useful for gas turbine engines.
  • coating organic resins with a hard metallic or ceramic coating presents unique problems.
  • the coating must be applied to the resin without jeopardizing the shape and structural integrity of a shaped resin.
  • the hard coating must bond and remain bonded to the resin surface.
  • the coating should have good compatibility with the organic resin to minimize stress and, therefore, prevent delamination when the coated component heats up or cools down.
  • the coating should not separate from the resin when the component is subjected to abrasive materials or struck with larger particles.
  • the coating should be sufficiently thin and lightweight to minimize weight, yet sufficiently hard to provide adequate protection. The prior art has not successfully developed such coatings.
  • the present invention addresses that need.
  • a coated article that is lightweight, has an increased usable life span and resists erosion even in high temperature environments.
  • the coated article comprises an organic resin substrate (preferably an organic matrix resin substrate), a high-temperature, erosion- resistant coating, and a bonding layer to secure the coating to the substrate.
  • the erosion-resistant coating is provided as a substantially non-porous layer and comprises a material selected from the group consisting of carbide, boride, nitride, oxide and mixtures thereof.
  • the non-porous layer additionally can comprise materials such as nickel, cobalt, iron, chromium, tungsten, molybdenum, polyester and nylon.
  • the organic resin substrate comprises a polymers selected from the group consisting of polyimide, poly(phenyl sulfide), polybenzoxazole, polycarbonate, polyepoxide, polyphthalamide, polyketone, and mixtures of these polymers. Reinforcing materials such as glass, carbon, quartz, kevlar, metal, metal oxide, ceramic, etc., may be included in the organic resin substrate.
  • the bonding layer preferably comprises zinc, aluminum, silicon, zinc- aluminum, aluminum-silicon, and zinc-silicon compositions, although other materials such as tin, antimony, copper, chromium, titanium, or nickel may also be used alone or in combination with those mentioned above.
  • the method of providing the erosion resistant coating comprises preparing the organic resin surface, applying a metallic bond coating and depositing the erosion- resistant coating to the organic resin.
  • the organic resin can be prepared by grit blasting the resin surface with an abrasive material such as aluminum oxide (Al 2 O 3 ), silicon carbide (SiC), and the like.
  • the coatings are applied while maintaining the temperature of the resin below about 500 °F.
  • FIG. 1 is a graph comparing the amount of mass lost from an organic matrix composite to the amount of dust (sand) consumed.
  • the present invention relates to new erosion-resistant coatings for organic resin substrates.
  • a bond coating layer is preferably used to fix the coating to the substrate.
  • the coatings are useful for making strong yet lightweight composite materials for use in high temperature operating environments.
  • the organic resin substrate can be made from a wide variety of thermally stable resins, such as polyimides, polysulfides, polycarbonates, polyepoxides, polyphthalamides, polyketones, etc. Mixtures of organic resin materials may also be used.
  • the preferred organic resins are sufficiently thermally stable to withstand common techniques used for coatings, such as thermal spray, plating, overlay or CVD.
  • the resin has an operating temperature above about 300 °F, more preferably about 400 °F and most preferably above about 500 °F. (For the purposes of this disclosure, the operating temperature is a minimum temperature that the resin can withstand without significant deformation or loss in structural strength.)
  • the heat deflection temperature (HDT) and the glass transition temperature (Tg) of a resin are two parameters that can be used to determine whether a resin is suitable for the present invention.
  • a resin's HDT can be measured using standard test ASTM D 648-97 "Standard Test Method for Deflection Temperature of Plastics Under Flexural Load.”
  • Organic resins that have an HDT greater than about 300 °F more preferably greater than about 500 °F are suitable for use in this invention.
  • the Tg of a resin can be measured according to ASTM E 1640-94 "Standard Test Method for Assignment of the Glass Transition Temperature by Dynamic Mechanical Analysis.”
  • high temperature resins useful in this invention include polyimide, (bismaleimide), poly(phenyl sulfide), polybenzoxazole, polycarbonate, polyepoxide, polyphthalamide, polyketones, and mixtures of these polymers. Many of these high temperature polymers are readily commercially available. Polyimides such as PMR 15 , PMR 25 and BMI can be obtained from Quantum Composites. A polyphthalamide resin is sold under the trade name AMODEL® by Amoco. A polyketone resin sold under the trade name PEEK. In certain preferred embodiments, the organic resin contains a reinforcing component. The reinforcing component imparts sufficient mechanical strength to the resin for use as structural components such as blades or vanes in gas turbine engines.
  • Reinforcing components such as fibers, platelets, whiskers, and particulates are commonly embedded in resins to provide organic matrix composites. Most commonly used reinforcing components are fibers.
  • the fibers can be chopped fibers, continuous fibers, oriented fibers, woven or nonwoven fibers. Examples of specific materials that can compose the reinforcing components include: carbon, glass, quartz, kevlar, metal, metal oxide and ceramic.
  • the organic matrix composite comprises a polymer designated as PMR 15, or a polymer designated as PMR 25.
  • These resins include a polyimide resin and contain carbon fibers designated as T650-35 chopped carbon fibers embedded therein.
  • the resin designated as PMR 15 has an operating temperature of about 475° to about 525°F.
  • the resin designated as PMR 25 has an operating temperature of about 500 °F to about 600 °F.
  • Other high temperature resins available to the industry can also be used as a substrate in this invention.
  • the erosion-resistant coating which is deposited on the substrate, provides the organic matrix with an outer, wear-resistant surface that protects the substrate from harsh environments and increases the longevity of the coated substrate.
  • the erosion- resistant coating is "over coated” with another coating material such as a polymer, wax. Polyurethane, paint, etc., to improve the erosion-resistant properties.
  • the erosion-resistant coating for this invention includes materials selected from nickel, chromium, cobalt, iron, tungsten, molybdneum, and carbides, borides, nitrides, oxide intermetallics of various metals such as tungsten, aluminum, chromium, nickel, silicon, titanium, zirconium, and boron, and mixtures of these materials - either as stoichiometric components or as composites.
  • materials that are suitable for use in the coating include, but are not limited to: Cr, Mo, BW, Co, Ni, NiCr, WC, Cr 3 C 2 , A1 2 C 3 , TiB 2 , HfC, CrB 2 , SiC, B 4 C, CrN, CBN, TiN, TiAIN, ZrN, CrO 2 , SiO 2 , diamond films, diamond-like carbon structures, and mixtures of these materials.
  • the erosion-resistant coating is deposited on the bond coating to provide a top coating as a monolithic coating.
  • the top coat preferably has a thickness of about 0.1 to about 4 mils.
  • the erosion-resistant coating is provided as a substantially non-porous, non-columnar coating.
  • the erosion-resistant coating has a density greater than about 95%, more preferably greater than about 98%, most preferably greater than about 99%.
  • the uninterrupted surface structure of a non-porous coating provides a more uniform surface that exhibits less tendency to delaminate under abrasive conditions than a columnar-type coating.
  • the bond coating preferably includes a metal such as, for example, zinc, aluminum, aluminum-silicon, chromium, titanium, nickel, silicon, tin, antimony, copper, iron (including stainless steel), silver and mixtures of these metals. Zinc and aluminum-silicon compositions are most preferred.
  • the bond coating layer is in direct contact with both the organic resin and the erosion-resistant coating.
  • the bond coating provides an adhesive layer between the resin and the erosion-resistant coating.
  • the bond coating also provides significant advantages to inhibit debonding from the resin. Debonding is most often exhibited as spallation or delamination where one or more of the coatings separate from the substrate.
  • the bond coating can be formed as a single layer or multiple layers of the above-mentioned metals or mixtures of these metals. When the bond coating is provided as multiple layers, each layer need not contain the same metal or mixtures of metals.
  • a coated system comprising a multiple layer bond coating can be used when necessary to increase the compatibility between the resin and the hard erosion- resistant coating. Application of multiple layers of either the same metal or different metals can decrease the stress created in the coated system as the different materials expand and contract by varying amounts and at different rates upon heating or cooling.
  • the bond coating is formed as a single layer having a coating thickness of about 0.2 mil to about 3 mils.
  • the present invention also provides methods for adhering the hard, erosion- resistant coatings onto the organic resins using a bond coating.
  • the organic resin surface must be properly prepared.
  • the organic resin is abrasively blasted to provide a surface with the proper texture for adhering to the bond coating.
  • the bond coating is then deposited at processing temperatures below about 500 °F using common deposition techniques, such as thermal spray, plating, overlay and chemical vapor deposition processes.
  • the erosion-resistant coating also is applied using processing temperatures below about 500 °F.
  • Typical application processes for the erosion-resistant coating include plasma spray, high velocity oxy/fuel (HVOF), argon shroud plasma spray, sputtering, chemical vapor deposition and cathodic arc-PVD.
  • the resulting coated substrate exhibits enhanced erosion resistance when exposed to abrasive environments. Furthermore, the coated substrate resists spallation and delamination when subjected to repeated thermal cycling between ambient temperatures and about 500 °F.
  • the erosion-resistant coating is formed by first preparing the surface of the organic resin to receive the bond coating. After the resin surface has been prepared the bond coating is applied. Thereafter the hard, erosion-resistant coating is deposited on the bond coating.
  • the surface of the organic resin must be prepared to provide good adhesion to the bond coating. For optimum adhesion, it is important that the surface be textured to provide mechanical interlock with the bond coating, yet the surface must be sufficiently smooth so that scratches, grooves, or furrows are not visible.
  • the resin surface can be prepared by a variety of techniques such as, for example, sanding, abrasive blasting, and chemical methods.
  • Abrasives that can be used with this invention include abrasives commonly known and used in the art. Typically aluminum oxide and silicon carbide abrasives are used.
  • the organic resin is prepared by abrasively blasting its surface using aluminum oxide (Al O 3 ) having an average particle size of about 45 to about 65 mesh, more preferably, about 50 to about 60 mesh.
  • Aluminum oxide having a larger median particle size removes too much of the resin surface, in effect, eroding or wearing away the resin surface. Furthermore, use of large particles gouge the resin surface, plowing deep scratches into the surface, which can compromise the structural integrity of the coated substrate.
  • Use of aluminum oxide having smaller median particle size does not sufficiently roughen the resin surface to adhere to the bond coating.
  • the resin surface most be sufficient rough or coarse to produce a textured surface than can provide a mechanical interlock with the bond coating.
  • the resin material must be carefully grit blasted to produce a "keyed" surface or, irregular surface profile for the sprayed droplets to adhere.
  • the resin's surface can be abrasively blasted using a variety of commercial grit blast spray equipment.
  • a suction gun (model 32850 by Dayton) operating at a pressure of about 15 to 25 psi provides sufficient force to abrasively prepare the resin surface without gouging or eroding away the resin surface.
  • direct pressure spray guns (such as models sold by Empire) also can be used. However, since the direct pressure gun propels particles at approximately three times the velocity as a suction gun operated at the same pressure, the pressure for direct pressure gun must be controlled accordingly.
  • the bond coating can be applied by a variety of techniques commonly used in the art. Examples of application techniques useful for the present invention include: thermal spray, plating, overlay and chemical vapor deposition.
  • the bond coating is applied by maintaining the organic resin at a processing temperature below the resin's deformation temperature.
  • the organic resin is maintained at a temperature below about 500 °F, more preferably below about 400 °F, most preferably below about 350 °F.
  • the temperature of the resin can be controlled by blowing compressed air (or other non-reactive gas) over the backside of the resin surface as the coating is applied.
  • Auxiliary cooling jets which direct forced air toward the resin surface and are attached to or adjacent to the thermal spray gun, can be used simultaneously with the spray gun.
  • the bond coating can be applied by randomly or uniformly interrupting the application process. The short interruptions to allow the resin to cool down.
  • a backing plate temporarily can be added to the surface of the resin opposite the side to be coated.
  • the backing plate provides support for the hot resin and maintains the substrate's shape. If more than one side of the resin is coated, the backing plate can be removed or transferred to a different position on the resin surface.
  • multiple backing plates each backing plate having a different shape that conforms to a portion of the shaped resin's surface, can be used in this invention.
  • the bond coating is applied using a thermal or wire spray technique.
  • This technique provides a coating composed of individual metal or metal containing particles. The particles mechanically interlock with each other to form a solid, dense coating. This dense coating adheres primarily through a mechanical anchoring with the roughened resin surface.
  • the bond coating is supplied to provide a coating thickness that can vary from about 0.2 mm to about 3 mm.
  • a single bond coating is applied; however, if desired, multiple bond coatings can be applied. If multiple bond coatings are applied, each bond coating should have a thickness of about 0.2 mm to about 1.0 mm.
  • the erosion-resistant coating is deposited onto the bond coating.
  • the erosion- resistant coating can be applied using a variety of techniques, which include thermal spray, plating, overlay, chemical vapor deposition, plasma spray, high velocity oxy/fuel, argon shroud plasma spray, sputtering and cathodic arc-PVD.
  • a single layer erosion-resistant coating is deposited.
  • multiple coatings can be deposited.
  • the erosion-resistant coating is deposited to have a coating thickness of between about 0.1 mil and about 4 mils.
  • the process temperature for deposition of the erosion-resistant coating is maintained below about 500 °F, more preferably below about 400 °F, most preferably below about 350 °F.
  • the resin temperature can be controlled as described above for the application of the bond coating.
  • Deposition of the erosion-resistant coating using the methods described above provides a non-porous top coating that is both non-columnar and columnar.
  • the overlay (sputter, cathodic arc, PVD, etc.) and CVD processes deposit columnar structures while the spray and plating processes deposit equinixed or non- columnar structures.
  • the erosion-resistant coating has a much higher density than cast or wrought alloys because it is substantially nonporous.
  • the top coating applied according to the present invention provides a coating having a density of about 95%, more preferably about 98% and still more preferably 99%. This provides a top coating having a porosity less than about 5%, more preferably less than about 2%, and still more preferably less than or equal to about 0.1%.
  • the coated substrates prepared according to the present invention exhibit significantly greater longevity.
  • the adhesion of the coating to the substrate is very good - as demonstrated by the thermal cycling evaluations described below.
  • the abrasion resistance is also excellent - as demonstrated by abrasive impingement testing.
  • a coupon having a surface area 1" x 3" and .100" thick of an organic matrix composite comprising a polyimide sold under the trade name PMR- 15 was mixed with chipped carbon fibers by sheet molding technique and was cleaned by first wiping the resin surface with an appropriate organic solvent, then abrasively blasting the surface with 54 mesh Al 2 O 3 using a suction spray gun operating at a pressure of about 15 to 25 psi. The resulting organic composite surface was textured.
  • the resin coupon was positioned on top of a backing plate of steel.
  • a zinc bond coating was applied using a Sulzer Metco 10E wire gun with a 2AF flow meter.
  • Zinc wire (0.125") was applied to the organic composite surface at a spray distance of 5" to provide a zinc coating thickness of 0.002" to 0.003".
  • the coating was applied in successive passes without stopping. Cooling air was applied to the back surface.
  • a top coating of tungsten carbide and cobalt was applied using a Sulzer Metco 7M plasma spray system with 4MP powder feeder. The application temperature was maintained below about 500 °F. The resulting top coating had a thickness of about 0.002" to about 0.003".
  • thermal shock tests were performed to verify coating adherence. Generally, poorly bonded coatings will tend to exhibit coating spall. All coated specimens were subjected to repeated shock cycling. The coated substrates were heated at a rate of about 50 °F/ minute until they reached 500 °F, then held for one hour, then the hot, coated substrates were cooked to ambient temperature by fan cooling. This heating/cooling cycle was repeated at least ten times.
  • the coated specimens were then subjected to abrasive (sand) impingement tests. It is to be noted that in the erosion tests, the hard top coatings play the primary role of providing erosion resistance. In a similar manner, the bond coatings play the primary role in improving adhesion of hard coating to the OMC substrate in the aforementioned thermal shock tests.
  • Table 2 lists the results of abrasive impingement tests, which were conducted on the uncoated OMC Substrate No. 1, and Coated OMC Substrates Nos. 2 and 5, by blasting the substrate surface with Arizona Road Dust Sand having an average particle size between 30-50 microns at a 30°-impingement angle. The nozzle to specimen distance was maintained at 1.2 inches. The said abrasive was blasted at 80 psi for 60 minutes using a mass of about 40 grams of sand. The results of the erosion tests indicate that the top coatings on Substrate
  • Nos. 2-5 provided a significant improvement in erosion resistance (4-7.5x) when compared to the uncoated Substrate No. 1. It is to be understood that other hard coatings such as TiN, TiAIN, SiC, TiB , diamond-like carbon, etc., will also provide similar benefits in improvement of the useful life span of a coated substrate.

Abstract

This invention is directed to a coated article having an erosion-resistant coating and a method of providing the erosion-resistant coating to the article. The coated article has an increased useful lifespan and will resist erosion even in high-temperature environments. The coated article includes an organic resin substrate, a high-temperature erosion-resistant coating, and a bonding layer to secure the coating to the substrate. The bond coating can comprise a material selected from zinc, aluminum, aluminum-silicon alloy, chromium, titanium, nickel, silicon, tin, antimony, copper, iron, stainless steel, silver, and mixtures thereof. The erosion-resistant coating can be provided as a substantially non-porous layer comprising a material selected from the group of carbides, fluorides, nitrides, oxides and mixtures thereof of materials such as nickel, cobalt, iron, chromium, tungsten, and molybdenum. The organic resin substrate is prepared to receive the erosion-resistant coating by grip-blasting the resin surface. The metallic bond coat is then applied to the resin surface, and an erosion-resistant coating is deposited on the metallic bond coating.

Description

EROSION-RESISTANT COATINGS FOR
ORGANIC MATRIC COMPOSITES
BACKGROUND OF THE INVENTION The present invention relates generally to coatings for organic matrix composite substrates, and more particularly to a method of providing a hard, adherent, erosion- resistant coating on the surface of an organic matrix composite.
There is continued demand from the aeronautical, aerospace and marine industries for lightweight, strong materials to replace heavy metal components. These lightweight components are often used in demanding and hostile environments such as in gas turbine engines to decrease weight, increase fuel efficiency and increase engine performance. For example, replacement of heavy metal blades and vanes in turbine engines provides more economical operation of these engines.
Synthetic organic resins have increasingly been used to manufacture strong, lightweight components. Since many of these resins can also withstand high operating temperatures, they are particularly useful for the construction of turbine engine components. Examples of commercially available high temperature resins include Epoxy, PMR 15, PMR 25, BMI, PEEU, PEEK and PAM.
Some of the most promising organic resins are organic matrix composites (OMC). These composites are organic resins that include reinforcing components encapsulated in the resin. The reinforcing components provide substantial mechanical strength to the resin. The reinforcing components can be formed as fibers, platelets, whiskers and particulates. Typical examples of materials that can be used as reinforcing components include carbon, glass, quartz, metal, metal oxides and ceramics.
Selected OMCs can provide the mechanical strength and thermal stability necessary to replace many heavier metal components in turbine engines; however, components formed with the OMCs are frequently short lived because they wear excessively in the hostile environments in which they are used. Often components are exposed to severe abrasive forces, for example, impaction by sand, rain, hailstones and other particulates entrained in high velocity wind streams. These particles can quickly erode the relatively soft OMC components. The eroded components must be replaced frequently to maintain the performance requirements of many turbines. Otherwise a severely eroded turbine component can disintegrate in use causing potential engine failure.
Application of a hard coating to a shaped organic matrix resin could provide an erosion-resistant component useful for gas turbine engines. However, coating organic resins with a hard metallic or ceramic coating presents unique problems. For example, the coating must be applied to the resin without jeopardizing the shape and structural integrity of a shaped resin. Also, the hard coating must bond and remain bonded to the resin surface. Further, the coating should have good compatibility with the organic resin to minimize stress and, therefore, prevent delamination when the coated component heats up or cools down. Moreover, the coating should not separate from the resin when the component is subjected to abrasive materials or struck with larger particles. In addition, the coating should be sufficiently thin and lightweight to minimize weight, yet sufficiently hard to provide adequate protection. The prior art has not successfully developed such coatings.
A need therefore exists for thin, lightweight, erosion-resistant coatings for organic matrix composites that may be used in high-temperature environments. The present invention addresses that need.
SUMMARY OF THE INVENTION Briefly describing one aspect of the present invention, there is provided a coated article that is lightweight, has an increased usable life span and resists erosion even in high temperature environments. The coated article comprises an organic resin substrate (preferably an organic matrix resin substrate), a high-temperature, erosion- resistant coating, and a bonding layer to secure the coating to the substrate.
The erosion-resistant coating is provided as a substantially non-porous layer and comprises a material selected from the group consisting of carbide, boride, nitride, oxide and mixtures thereof. The non-porous layer additionally can comprise materials such as nickel, cobalt, iron, chromium, tungsten, molybdenum, polyester and nylon. The organic resin substrate comprises a polymers selected from the group consisting of polyimide, poly(phenyl sulfide), polybenzoxazole, polycarbonate, polyepoxide, polyphthalamide, polyketone, and mixtures of these polymers. Reinforcing materials such as glass, carbon, quartz, kevlar, metal, metal oxide, ceramic, etc., may be included in the organic resin substrate.
The bonding layer preferably comprises zinc, aluminum, silicon, zinc- aluminum, aluminum-silicon, and zinc-silicon compositions, although other materials such as tin, antimony, copper, chromium, titanium, or nickel may also be used alone or in combination with those mentioned above. The method of providing the erosion resistant coating comprises preparing the organic resin surface, applying a metallic bond coating and depositing the erosion- resistant coating to the organic resin. The organic resin can be prepared by grit blasting the resin surface with an abrasive material such as aluminum oxide (Al2O3), silicon carbide (SiC), and the like. Preferably, the coatings are applied while maintaining the temperature of the resin below about 500 °F. BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph comparing the amount of mass lost from an organic matrix composite to the amount of dust (sand) consumed.
DETAILED DESCRIPTION OF THE INVENTION
For the purposes of promoting an understanding of the principles of the present invention, reference will now be made to preferred embodiments, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is intended thereby. Any alterations and further modification in the described processes, systems or devices, and any further applications of the principles of the invention as described herein are contemplated as would normally occur to one skilled in the art to which the invention relates. As briefly described above, the present invention relates to new erosion-resistant coatings for organic resin substrates. A bond coating layer is preferably used to fix the coating to the substrate. The coatings are useful for making strong yet lightweight composite materials for use in high temperature operating environments.
The organic resin substrate can be made from a wide variety of thermally stable resins, such as polyimides, polysulfides, polycarbonates, polyepoxides, polyphthalamides, polyketones, etc. Mixtures of organic resin materials may also be used.
The preferred organic resins are sufficiently thermally stable to withstand common techniques used for coatings, such as thermal spray, plating, overlay or CVD. Preferably the resin has an operating temperature above about 300 °F, more preferably about 400 °F and most preferably above about 500 °F. (For the purposes of this disclosure, the operating temperature is a minimum temperature that the resin can withstand without significant deformation or loss in structural strength.)
The heat deflection temperature (HDT) and the glass transition temperature (Tg) of a resin are two parameters that can be used to determine whether a resin is suitable for the present invention. A resin's HDT can be measured using standard test ASTM D 648-97 "Standard Test Method for Deflection Temperature of Plastics Under Flexural Load." Organic resins that have an HDT greater than about 300 °F more preferably greater than about 500 °F are suitable for use in this invention. The Tg of a resin can be measured according to ASTM E 1640-94 "Standard Test Method for Assignment of the Glass Transition Temperature by Dynamic Mechanical Analysis."
Specific examples of high temperature resins useful in this invention include polyimide, (bismaleimide), poly(phenyl sulfide), polybenzoxazole, polycarbonate, polyepoxide, polyphthalamide, polyketones, and mixtures of these polymers. Many of these high temperature polymers are readily commercially available. Polyimides such as PMR 15 , PMR 25 and BMI can be obtained from Quantum Composites. A polyphthalamide resin is sold under the trade name AMODEL® by Amoco. A polyketone resin sold under the trade name PEEK. In certain preferred embodiments, the organic resin contains a reinforcing component. The reinforcing component imparts sufficient mechanical strength to the resin for use as structural components such as blades or vanes in gas turbine engines. Reinforcing components such as fibers, platelets, whiskers, and particulates are commonly embedded in resins to provide organic matrix composites. Most commonly used reinforcing components are fibers. The fibers can be chopped fibers, continuous fibers, oriented fibers, woven or nonwoven fibers. Examples of specific materials that can compose the reinforcing components include: carbon, glass, quartz, kevlar, metal, metal oxide and ceramic.
In the most preferred embodiments the organic matrix composite comprises a polymer designated as PMR 15, or a polymer designated as PMR 25. These resins include a polyimide resin and contain carbon fibers designated as T650-35 chopped carbon fibers embedded therein. The resin designated as PMR 15 has an operating temperature of about 475° to about 525°F. The resin designated as PMR 25 has an operating temperature of about 500 °F to about 600 °F. Other high temperature resins available to the industry can also be used as a substrate in this invention.
Turning now to the erosion-resistant coating, which is deposited on the substrate, the erosion-resistant coating provides the organic matrix with an outer, wear-resistant surface that protects the substrate from harsh environments and increases the longevity of the coated substrate. In some applications the erosion- resistant coating is "over coated" with another coating material such as a polymer, wax. Polyurethane, paint, etc., to improve the erosion-resistant properties.
The erosion-resistant coating for this invention includes materials selected from nickel, chromium, cobalt, iron, tungsten, molybdneum, and carbides, borides, nitrides, oxide intermetallics of various metals such as tungsten, aluminum, chromium, nickel, silicon, titanium, zirconium, and boron, and mixtures of these materials - either as stoichiometric components or as composites. Specific examples of materials that are suitable for use in the coating include, but are not limited to: Cr, Mo, BW, Co, Ni, NiCr, WC, Cr3C2, A12C3, TiB2, HfC, CrB2, SiC, B4C, CrN, CBN, TiN, TiAIN, ZrN, CrO2, SiO2, diamond films, diamond-like carbon structures, and mixtures of these materials.
Preferably, the erosion-resistant coating is deposited on the bond coating to provide a top coating as a monolithic coating. The top coat preferably has a thickness of about 0.1 to about 4 mils. To provide the most effective erosion-resistant surface, the erosion-resistant coating is provided as a substantially non-porous, non-columnar coating. Preferably, the erosion-resistant coating has a density greater than about 95%, more preferably greater than about 98%, most preferably greater than about 99%. The uninterrupted surface structure of a non-porous coating provides a more uniform surface that exhibits less tendency to delaminate under abrasive conditions than a columnar-type coating. Some degree of porosity is present in all coatings; generally, the pores result from air gaps between the metal particles, which compose the coating. Typically, thermally sprayed coatings according to this invention have a density of about 80% to about 99%. This substantially non-porous surface resists pitting and chipping, even when exposed to high-energy impingement from hard particulates such as sand. As indicated above, the erosion-resistant coating is secured to the substrate using a bond coating layer. The bond coating preferably includes a metal such as, for example, zinc, aluminum, aluminum-silicon, chromium, titanium, nickel, silicon, tin, antimony, copper, iron (including stainless steel), silver and mixtures of these metals. Zinc and aluminum-silicon compositions are most preferred. Most preferably, the bond coating layer is in direct contact with both the organic resin and the erosion-resistant coating. Thus, the bond coating provides an adhesive layer between the resin and the erosion-resistant coating. The bond coating also provides significant advantages to inhibit debonding from the resin. Debonding is most often exhibited as spallation or delamination where one or more of the coatings separate from the substrate.
The bond coating can be formed as a single layer or multiple layers of the above-mentioned metals or mixtures of these metals. When the bond coating is provided as multiple layers, each layer need not contain the same metal or mixtures of metals. A coated system comprising a multiple layer bond coating can be used when necessary to increase the compatibility between the resin and the hard erosion- resistant coating. Application of multiple layers of either the same metal or different metals can decrease the stress created in the coated system as the different materials expand and contract by varying amounts and at different rates upon heating or cooling. Preferably, the bond coating is formed as a single layer having a coating thickness of about 0.2 mil to about 3 mils.
The present invention also provides methods for adhering the hard, erosion- resistant coatings onto the organic resins using a bond coating. To apply the adherent coatings, the organic resin surface must be properly prepared. Preferably, the organic resin is abrasively blasted to provide a surface with the proper texture for adhering to the bond coating. The bond coating is then deposited at processing temperatures below about 500 °F using common deposition techniques, such as thermal spray, plating, overlay and chemical vapor deposition processes. The erosion-resistant coating also is applied using processing temperatures below about 500 °F. Typical application processes for the erosion-resistant coating include plasma spray, high velocity oxy/fuel (HVOF), argon shroud plasma spray, sputtering, chemical vapor deposition and cathodic arc-PVD.
The resulting coated substrate exhibits enhanced erosion resistance when exposed to abrasive environments. Furthermore, the coated substrate resists spallation and delamination when subjected to repeated thermal cycling between ambient temperatures and about 500 °F.
The erosion-resistant coating is formed by first preparing the surface of the organic resin to receive the bond coating. After the resin surface has been prepared the bond coating is applied. Thereafter the hard, erosion-resistant coating is deposited on the bond coating.
The surface of the organic resin must be prepared to provide good adhesion to the bond coating. For optimum adhesion, it is important that the surface be textured to provide mechanical interlock with the bond coating, yet the surface must be sufficiently smooth so that scratches, grooves, or furrows are not visible. The resin surface can be prepared by a variety of techniques such as, for example, sanding, abrasive blasting, and chemical methods. Abrasives that can be used with this invention include abrasives commonly known and used in the art. Typically aluminum oxide and silicon carbide abrasives are used. Preferably, the organic resin is prepared by abrasively blasting its surface using aluminum oxide (Al O3) having an average particle size of about 45 to about 65 mesh, more preferably, about 50 to about 60 mesh. Use of aluminum oxide having a larger median particle size removes too much of the resin surface, in effect, eroding or wearing away the resin surface. Furthermore, use of large particles gouge the resin surface, plowing deep scratches into the surface, which can compromise the structural integrity of the coated substrate. Use of aluminum oxide having smaller median particle size does not sufficiently roughen the resin surface to adhere to the bond coating. The resin surface most be sufficient rough or coarse to produce a textured surface than can provide a mechanical interlock with the bond coating. The resin material must be carefully grit blasted to produce a "keyed" surface or, irregular surface profile for the sprayed droplets to adhere.
The resin's surface can be abrasively blasted using a variety of commercial grit blast spray equipment. A suction gun (model 32850 by Dayton) operating at a pressure of about 15 to 25 psi provides sufficient force to abrasively prepare the resin surface without gouging or eroding away the resin surface. Alternatively, direct pressure spray guns (such as models sold by Empire) also can be used. However, since the direct pressure gun propels particles at approximately three times the velocity as a suction gun operated at the same pressure, the pressure for direct pressure gun must be controlled accordingly. The bond coating can be applied by a variety of techniques commonly used in the art. Examples of application techniques useful for the present invention include: thermal spray, plating, overlay and chemical vapor deposition. The bond coating is applied by maintaining the organic resin at a processing temperature below the resin's deformation temperature. Preferably the organic resin is maintained at a temperature below about 500 °F, more preferably below about 400 °F, most preferably below about 350 °F. The temperature of the resin can be controlled by blowing compressed air (or other non-reactive gas) over the backside of the resin surface as the coating is applied. Auxiliary cooling jets, which direct forced air toward the resin surface and are attached to or adjacent to the thermal spray gun, can be used simultaneously with the spray gun. In addition or alternatively to the auxiliary cooling jets, the bond coating can be applied by randomly or uniformly interrupting the application process. The short interruptions to allow the resin to cool down. After a short interruption, the coating application is continued until a bond coating having the desired thickness is formed on the resin surface. For resins that deform at temperatures within about 15 °F to about 20 °F of the processing temperature, a backing plate temporarily can be added to the surface of the resin opposite the side to be coated. The backing plate provides support for the hot resin and maintains the substrate's shape. If more than one side of the resin is coated, the backing plate can be removed or transferred to a different position on the resin surface. In addition, multiple backing plates, each backing plate having a different shape that conforms to a portion of the shaped resin's surface, can be used in this invention.
In a preferred embodiment, the bond coating is applied using a thermal or wire spray technique. This technique provides a coating composed of individual metal or metal containing particles. The particles mechanically interlock with each other to form a solid, dense coating. This dense coating adheres primarily through a mechanical anchoring with the roughened resin surface. The bond coating is supplied to provide a coating thickness that can vary from about 0.2 mm to about 3 mm. Preferably, a single bond coating is applied; however, if desired, multiple bond coatings can be applied. If multiple bond coatings are applied, each bond coating should have a thickness of about 0.2 mm to about 1.0 mm.
The erosion-resistant coating is deposited onto the bond coating. The erosion- resistant coating can be applied using a variety of techniques, which include thermal spray, plating, overlay, chemical vapor deposition, plasma spray, high velocity oxy/fuel, argon shroud plasma spray, sputtering and cathodic arc-PVD. Preferably, a single layer erosion-resistant coating is deposited. However, if desired, multiple coatings can be deposited. The erosion-resistant coating is deposited to have a coating thickness of between about 0.1 mil and about 4 mils. As with the application of the bond coating, the process temperature for deposition of the erosion-resistant coating is maintained below about 500 °F, more preferably below about 400 °F, most preferably below about 350 °F. The resin temperature can be controlled as described above for the application of the bond coating.
Deposition of the erosion-resistant coating using the methods described above provides a non-porous top coating that is both non-columnar and columnar. Typically, the overlay (sputter, cathodic arc, PVD, etc.) and CVD processes deposit columnar structures while the spray and plating processes deposit equinixed or non- columnar structures.
Moreover, the erosion-resistant coating has a much higher density than cast or wrought alloys because it is substantially nonporous. For instance, the top coating applied according to the present invention provides a coating having a density of about 95%, more preferably about 98% and still more preferably 99%. This provides a top coating having a porosity less than about 5%, more preferably less than about 2%, and still more preferably less than or equal to about 0.1%.
The coated substrates prepared according to the present invention exhibit significantly greater longevity. The adhesion of the coating to the substrate is very good - as demonstrated by the thermal cycling evaluations described below. The abrasion resistance is also excellent - as demonstrated by abrasive impingement testing.
Reference will now be made to specific examples using the preferred materials and methods described above. It is to be understood that the examples are provided to more completely describe preferred embodiments, and that no limitation to the scope of the invention is intended thereby.
EXAMPLE 1 Preparation of Adherent Tungsten Carbide-Cobalt Coatings
A coupon having a surface area 1" x 3" and .100" thick of an organic matrix composite comprising a polyimide sold under the trade name PMR- 15 was mixed with chipped carbon fibers by sheet molding technique and was cleaned by first wiping the resin surface with an appropriate organic solvent, then abrasively blasting the surface with 54 mesh Al2O3 using a suction spray gun operating at a pressure of about 15 to 25 psi. The resulting organic composite surface was textured.
The resin coupon was positioned on top of a backing plate of steel. A zinc bond coating was applied using a Sulzer Metco 10E wire gun with a 2AF flow meter. Zinc wire (0.125") was applied to the organic composite surface at a spray distance of 5" to provide a zinc coating thickness of 0.002" to 0.003". The coating was applied in successive passes without stopping. Cooling air was applied to the back surface.
A top coating of tungsten carbide and cobalt was applied using a Sulzer Metco 7M plasma spray system with 4MP powder feeder. The application temperature was maintained below about 500 °F. The resulting top coating had a thickness of about 0.002" to about 0.003".
A series of coated coupons were prepared as described above. Specific examples of the coupons and the coatings are listed in Table. 1. TABLE 1
Figure imgf000015_0001
EXAMPLE 2
Thermal Shock Cycling
Prior to erosion testing, thermal shock tests were performed to verify coating adherence. Generally, poorly bonded coatings will tend to exhibit coating spall. All coated specimens were subjected to repeated shock cycling. The coated substrates were heated at a rate of about 50 °F/ minute until they reached 500 °F, then held for one hour, then the hot, coated substrates were cooked to ambient temperature by fan cooling. This heating/cooling cycle was repeated at least ten times.
Evaluation of the resulting substrates under the ten-fold magnification revealed no evidence of spallation or delamination of the bond or hard coating from the surface. This indicated that the bond coats (e.g., Zn, Al-Si, stainless steel composite with polyester, etc.) and topcoats (e.g., WC-Co, Cr3C2 - NiCr, MoAlNi) were compatible with the OMC substrate and yielded good adhesion. It is to be noted that the broad range of bond coat compositions and top coat compositions indicated in this invention also provides an erosion resistant coating system which is compatible with the OMC substrate. EXAMPLE 3 Sand Impingement Tests
After verifying the good adhesion of the erosion resistant coating systems through thermal shock tests, the coated specimens were then subjected to abrasive (sand) impingement tests. It is to be noted that in the erosion tests, the hard top coatings play the primary role of providing erosion resistance. In a similar manner, the bond coatings play the primary role in improving adhesion of hard coating to the OMC substrate in the aforementioned thermal shock tests.
Table 2 lists the results of abrasive impingement tests, which were conducted on the uncoated OMC Substrate No. 1, and Coated OMC Substrates Nos. 2 and 5, by blasting the substrate surface with Arizona Road Dust Sand having an average particle size between 30-50 microns at a 30°-impingement angle. The nozzle to specimen distance was maintained at 1.2 inches. The said abrasive was blasted at 80 psi for 60 minutes using a mass of about 40 grams of sand. The results of the erosion tests indicate that the top coatings on Substrate
Nos. 2-5 provided a significant improvement in erosion resistance (4-7.5x) when compared to the uncoated Substrate No. 1. It is to be understood that other hard coatings such as TiN, TiAIN, SiC, TiB , diamond-like carbon, etc., will also provide similar benefits in improvement of the useful life span of a coated substrate.
TABLE 2 Summary of Erosion Test Results
Figure imgf000017_0001
While the invention has been illustrated and described in detail in the foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only the preferred embodiment has been shown and described and that all changes and modifications that come within the spirit of the invention are desired to be protected.

Claims

CLAIMSWe claim:
1. A coated article comprising an organic resin substrate, a bond coating and an erosion-resistant coating, wherein said erosion-resistant coating is provided as a substantially non-porous layer comprising a material selected from the group consisting of nickel, cobalt, iron, chromium, tungsten, molybdenum, diamond, diamond-like carbon, polyester nylon, carbides, borides, nitrides, oxides, intermetallics, and mixtures thereof.
2. The coated substrate of claim 1 wherein said non-porous layer comprises carbides, borides, nitrides, oxides and intermetallics of tungsten, aluminum, chromium, nickel, silicon titanium, zirconium boron, and mixtures of these materials.
3. The coated substrate of claim 1 wherein the organic resin includes reinforcing material selected from the group consisting of carbon, glass, quartz, kevlar, metal, metal oxides, ceramics and mixtures thereof.
4. The coated substrate of claim 1 wherein the organic resin comprises a material selected from the group consisting of polyimides, poly(phenyl sulfide)s, polybenzoxazoles, polycarbonates, polyepoxides, polyphthalamides, and polyketones, and mixtures thereof.
5. The coated substrate of claim 1 wherein the bond coating has a coating thickness of about 0.2 to about 3 mils.
6. The coated substrate of claim 1 wherein the bond coating comprises a metal selected from the group consisting of zinc, aluminum, aluminum-silicon alloy, chromium, titanium, nickel, silicon, tin, antimony, copper, iron, stainless steel, silver, and mixtures thereof.
7. The coated substrate of claim 1 wherein the erosion-resistant coating is provided as a substantially non-porous layer comprising a material selected from the group consisting of Cr, Mo, W, Co, Ni, NiCr, WC-Co, Ni-B, Ni- SiC, MoAlNi, TiN-Mo, Cr3C2-NiCr, SiC, B4C, CrN, CBN, TiN, TiAIN, ZrN, CrO2, SiO , diamond films, diamond-like carbon and mixtures thereof.
8. The coated substrate of claim 1 wherein the erosion-resistant coating has a coating thickness of about 0.1 to about 4 mils.
9. The coated substrate of claiml wherein the erosion-resistant coating has a porosity of about about 5 % to about 0.1%.
10. The coated substrate of claim 1 wherein the erosion-resistant coating has a porosity of about 2% to about 0.1%.
11. A method of providing an erosion-resistant coating to a surface of an organic resin, said method comprising: preparing the surface of the organic resin; applying a metallic bond coating to the organic resin; and depositing a substantially non-columnar coating comprising a material selected from the group consisting of carbides, borides, nitrides, oxides and mixtures thereof to provide the erosion-resistant coating.
12. The method of claim 11 wherein the organic resin comprises a polymer is selected from the group consisting of polyimide, poly(phenyl sulfide) polybenzoxazole, polycarbonate, polyepoxide, polyphthalamide, polyketone, and mixtures thereof.
13. The method of claim 11 wherein the organic resin comprises a reinforcing material.
14. The method of claim 11 wherein preparing the surface of the organic resin includes blasting the surface with an abrasive material.
15. The method of claim 11 wherein the abrasive material used to prepare the surface includes Al O3 or SiC particles having an average particle size of about 45 to about 65 mesh.
16. The method of claim 15 wherein the abrasive material used to prepare the surface includes Al2O3 or SiC particles having an average particle size of about 50 to about 60 mesh.
17. The method of claim 11 wherein preparing the surface of the organic resin includes abrasive cleaning the organic resin surface with an abrasive material at a pressure of about 15 to about 25 psig.
18. The method of claim 11 wherein the metallic bond coating includes a metal selected from the group consisting of zinc, aluminum, aluminum-silicon alloy, chromium, titanium, nickel, silicon, tin, antimony, copper, iron, stainless steel, silver, and mixtures thereof.
19. The method of claim 11 wherein applying a metallic bond coating consists of applying a single bond coating.
20. The method of claim 11 wherein the metallic bond coating has an average thickness of about 0.2 mils to about 3 mils.
21. The method of claim 11 wherein the metallic bond coating is applied using a thermal spray technique or wire spray process or plating or CVD process.
22. The method of claim 11 wherein applying the metallic bond coating includes maintaining the organic resin at a temperature below about 500 °F.
23. The method of claim 11 wherein the erosion-resistant coating has an average thickness of about 0.1 mil to about 4 mils.
24. The method of claim 11 wherein the erosion-resistant coating comprises a material selected from the group consisting essentially of Cr, Mo, W, Co, Ni, NiCr, WC-Co, Cr3C2-NiCr, SiC, B4C, CrN, SBN, TiN, TiAlN, ZrN, CrO2, SiO2, diamond films and mixtures thereof.
25. The method of claim 11 wherein the erosion-resistant coating has a porosity of less than about 5%.
26. The method of claim 25 wherein the erosion-resistant coating has a porosity of less than about 2%.
27. The method of claim 11 wherein deposition of the substantially non- columnar coating includes maintaining the organic resin at a temperature below about 500 °F.
28. The method of claim 11 wherein the erosion-resistant coating is deposited using a CVD, thermal spray, electroplating, electroless plating overlay or cathodic arc deposition technique.
29. A method of adhering an erosion-resistant coating to a surface of an organic resin, the method comprising: abrasively blasting the surface of the organic resin with an abrasive material; applying a bond coating to the surface of the organic resin; and depositing an erosion-resistant coating on the bond coating.
30. The method of claim 29 wherein the organic resin comprises a polymer selected from the group consisting of polyimides, poly(arylene sulfide)s, polybenzoxazoles, polycarbonates, polyepoxides, polyphthalamides, and polyketones, and mixtures thereof.
31. The method of claim 29 wherein the organic resin comprises a reinforcing material selected from the group consisting essentially of carbon, glass, quartz, kevlar, metal, metal oxides, and ceramics, and mixtures thereof.
32. The method of claim 29 wherein the abrasive material to includes a material selected from the group consisting of Al2O3 and SiC, and mixtures thereof.
33. The method of claim 32 wherein the abrasive material has a median particle size of about 45 to about 65 mesh.
34. The method of claim 33 wherein the abrasive material has a median particle size of about 50 to about 60 mesh.
35. The method of claim 29 wherein the bond coating includes at least one metal selected from the group consisting of zinc, aluminum, aluminum-silicon alloy, chromium, titanium, nickel, silicon, tin, antimony, copper, iron, stainless steel, silver, and mixtures thereof.
36. The method of claim 29 wherein deposition of the erosion-resistant coating is includes maintaining the organic resin at a temperature below about 500°F.
37. The method of claim 29 wherein the bond coating consists of a single layer.
38. The method of claim 29 wherein the bond coating has an average thickness of about 0.2 mils to about 3 mils.
39. The method of claim 29 wherein the bond coating is applied using a thermal spray technique.
40. The method of claim 29 wherein the erosion-resistant coating has an average thickness of about 0.1 mil to about 4 mils.
41. The method of claim 29 wherein the erosion-resistant coating comprises a material selected from the group consisting essentially Cr, Mo, W, Co, Ni, NiCr, WC-Co, Cr3C2-NiCr, SiC, B4C, CrN, CBN, TiN, TiAlN, ZrN, CrO2, SiO2, diamond films, and diamond-like carbon, and mixtures thereof.
42. The method of claim 29 wherein the erosion-resistant coating is deposited at a process temperature below about 500 °F.
43. The method of claim 29 wherein the erosion-resistant coating is deposited using a CVD, thermal spray, electroplating, electroless plating overlay or HVOF technique.
PCT/US2000/041502 1999-10-25 2000-10-24 Erosion-resistant coatings for organic matrix composites WO2001046324A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP00992985A EP1244544A4 (en) 1999-10-25 2000-10-24 Erosion-resistant coatings for organic matrix composites
AU49012/01A AU4901201A (en) 1999-10-25 2000-10-24 Erosion-resistant coatings for organic matric composites

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42627999A 1999-10-25 1999-10-25
US09/426,279 1999-10-25

Publications (3)

Publication Number Publication Date
WO2001046324A2 true WO2001046324A2 (en) 2001-06-28
WO2001046324A3 WO2001046324A3 (en) 2001-11-15
WO2001046324B1 WO2001046324B1 (en) 2002-01-03

Family

ID=23690124

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/041502 WO2001046324A2 (en) 1999-10-25 2000-10-24 Erosion-resistant coatings for organic matrix composites

Country Status (3)

Country Link
EP (1) EP1244544A4 (en)
AU (1) AU4901201A (en)
WO (1) WO2001046324A2 (en)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1707649A2 (en) * 2005-04-01 2006-10-04 The General Electric Company Method for coating surfaces with a mixture.
GB2459372A (en) * 2008-04-21 2009-10-28 Zircotec Ltd Organic substrate with thermally sprayed coating
US7776404B2 (en) * 2006-11-30 2010-08-17 General Electric Company Methods for forming thermal oxidative barrier coatings on organic matrix composite substrates
DE102009013129A1 (en) * 2009-03-13 2010-09-16 Mtu Aero Engines Gmbh Plastic component with erosion protection layer for applications with erosive stress
CN102560394A (en) * 2010-12-27 2012-07-11 鸿富锦精密工业(深圳)有限公司 Coated part and manufacturing method thereof
US8231958B2 (en) * 2007-10-09 2012-07-31 United Technologies Corporation Article and method for erosion resistant composite
CN103422047A (en) * 2012-05-14 2013-12-04 中国科学院上海硅酸盐研究所 Preparation method for boron carbide-molybdenum composite coating layer
CN103725058A (en) * 2013-11-25 2014-04-16 铜陵天河特种电磁线有限公司 Synthesized wire enamel with high temperature resistance and preparation method of synthesized wire enamel
EP2733231A1 (en) * 2012-11-16 2014-05-21 The Boeing Company Thermal spray coated reinforced polymer composites
WO2015006487A1 (en) * 2013-07-09 2015-01-15 United Technologies Corporation Erosion and wear protection for composites and plated polymers
US20150030459A1 (en) * 2012-02-02 2015-01-29 Siemens Aktiengesellschaft Turbomachine component with a parting joint, and a steam turbine comprising said turbomachine component
US9139908B2 (en) 2013-12-12 2015-09-22 The Boeing Company Gradient thin films
CN106119764A (en) * 2016-08-15 2016-11-16 合肥科德电力表面技术有限公司 A kind of preparation method of water smoke cooling arc spraying coating
CN106282886A (en) * 2016-09-27 2017-01-04 郑州科源耐磨防腐工程有限公司 A kind of High Speed Electric Arc Spraying liquid metal ceramic coating and preparation method thereof
EP2438204A4 (en) * 2009-06-02 2017-01-25 Integran Technologies Inc. Metal-coated polymer article of high durability and vacuum and/or pressure integrity
CN107254650A (en) * 2017-07-04 2017-10-17 安徽威龙再制造科技股份有限公司 A kind of fan blade surface repairing method
US9873947B2 (en) 2012-12-19 2018-01-23 Mabe, S.A. De C.V. Easy clean coating applied on stainless steel metallic surfaces used in the manufacture of household appliances
EP3266607A4 (en) * 2015-03-04 2018-02-14 Tocalo Co., Ltd. Fiber-reinforced resin structure and method for producing fiber-reinforced resin structure
CN107779805A (en) * 2017-10-22 2018-03-09 陈海银 Stabilizing roller surface abrasion resistance, corrosion-resistant finishes preparation method
CN109112460A (en) * 2018-08-30 2019-01-01 昆明理工大学 A kind of preparation method of thermal spraying refractory ceramics coating
US10227704B2 (en) 2013-07-09 2019-03-12 United Technologies Corporation High-modulus coating for local stiffening of airfoil trailing edges
CN109468573A (en) * 2018-12-27 2019-03-15 沈阳工业大学 A method of preparing the wear-resistant coating of soldering transition zone using electric arc spraying
CN112251709A (en) * 2020-10-21 2021-01-22 长春理工大学光电信息学院 Laminated heat-resistant electronic film and preparation method thereof
US10927843B2 (en) 2013-07-09 2021-02-23 Raytheon Technologies Corporation Plated polymer compressor
US11267576B2 (en) 2013-07-09 2022-03-08 Raytheon Technologies Corporation Plated polymer nosecone
US11268526B2 (en) 2013-07-09 2022-03-08 Raytheon Technologies Corporation Plated polymer fan
CN115305434A (en) * 2022-08-11 2022-11-08 福建阿石创新材料股份有限公司 Method for preparing ceramic coating on surface of thin-wall protective cover and protective cover with coating
US11691388B2 (en) 2013-07-09 2023-07-04 Raytheon Technologies Corporation Metal-encapsulated polymeric article

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115537701A (en) * 2022-09-29 2022-12-30 清研瀚高科技(北京)有限公司 Manufacturing method of special rough metal plate for tire detection

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787229A (en) * 1971-02-17 1974-01-22 Union Carbide Corp Low-friction, wear-resistant material
US3930807A (en) * 1973-04-25 1976-01-06 Canon Kabushiki Kaisha Plastic molding having satin finish type metallic luster
US4022585A (en) * 1975-04-21 1977-05-10 General Dynamics Corporation Method for sealing composites against moisture and articles made thereby
US4029838A (en) * 1975-09-24 1977-06-14 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Hybrid composite laminate structures
US4765860A (en) * 1983-05-06 1988-08-23 Susumu Ueno Method of making a flexible base plate for printed circuit board
US5039571A (en) * 1987-10-14 1991-08-13 Akzo Nv Metal-resin laminate reinforced with S2-glass fibres
US5236773A (en) * 1991-10-25 1993-08-17 The United States Of America As Represented By The Secretary Of The Navy Fire-resistant barriers for composite materials

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL250277A (en) * 1959-04-08 1900-01-01
DE3136283C1 (en) * 1981-09-12 1983-02-03 Nukem Gmbh, 6450 Hanau Process for metallizing carbon fiber reinforced plastic parts
US4612216A (en) * 1983-07-01 1986-09-16 The Dow Chemical Company Method for making duplex metal alloy/polymer composites
US4510208A (en) * 1983-07-01 1985-04-09 The Dow Chemical Company Duplex metal alloy/polymer compositions
US4961994A (en) * 1987-12-16 1990-10-09 General Electric Company Protective coated composite material
US5126205A (en) * 1990-05-09 1992-06-30 The Perkin-Elmer Corporation Powder of plastic and treated mineral
DE4343904C3 (en) * 1993-12-22 1999-11-04 Mtu Muenchen Gmbh Component made of fiber-reinforced composite material with a protective layer against erosion

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787229A (en) * 1971-02-17 1974-01-22 Union Carbide Corp Low-friction, wear-resistant material
US3930807A (en) * 1973-04-25 1976-01-06 Canon Kabushiki Kaisha Plastic molding having satin finish type metallic luster
US4022585A (en) * 1975-04-21 1977-05-10 General Dynamics Corporation Method for sealing composites against moisture and articles made thereby
US4029838A (en) * 1975-09-24 1977-06-14 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Hybrid composite laminate structures
US4765860A (en) * 1983-05-06 1988-08-23 Susumu Ueno Method of making a flexible base plate for printed circuit board
US5039571A (en) * 1987-10-14 1991-08-13 Akzo Nv Metal-resin laminate reinforced with S2-glass fibres
US5236773A (en) * 1991-10-25 1993-08-17 The United States Of America As Represented By The Secretary Of The Navy Fire-resistant barriers for composite materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1244544A2 *

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1840737B (en) * 2005-04-01 2010-12-15 通用电气公司 Reflective and resistant coatings and methods for applying to composite structures
EP1707649A3 (en) * 2005-04-01 2006-12-13 The General Electric Company Method for coating surfaces with a mixture.
EP1707649A2 (en) * 2005-04-01 2006-10-04 The General Electric Company Method for coating surfaces with a mixture.
US7776404B2 (en) * 2006-11-30 2010-08-17 General Electric Company Methods for forming thermal oxidative barrier coatings on organic matrix composite substrates
US8231958B2 (en) * 2007-10-09 2012-07-31 United Technologies Corporation Article and method for erosion resistant composite
US11421313B2 (en) 2008-04-21 2022-08-23 Zircotecip Limited Article and a method of making an article
GB2459372A (en) * 2008-04-21 2009-10-28 Zircotec Ltd Organic substrate with thermally sprayed coating
EP2285999A2 (en) 2008-04-21 2011-02-23 Zircotec Limited An article comprising an organic material at least at a surface and a thermally sprayed layer thereon, and a method of making the article
WO2009130229A2 (en) 2008-04-21 2009-10-29 Zircotec Limited An article and a method of making an article
GB2459372B (en) * 2008-04-21 2013-03-06 Zircotec Ltd An article and a method of making an article
DE102009013129A1 (en) * 2009-03-13 2010-09-16 Mtu Aero Engines Gmbh Plastic component with erosion protection layer for applications with erosive stress
EP2438204A4 (en) * 2009-06-02 2017-01-25 Integran Technologies Inc. Metal-coated polymer article of high durability and vacuum and/or pressure integrity
CN102560394A (en) * 2010-12-27 2012-07-11 鸿富锦精密工业(深圳)有限公司 Coated part and manufacturing method thereof
US9995178B2 (en) * 2012-02-02 2018-06-12 Siemens Aktiengesellschaft Turbomachine component with a parting joint, and a steam turbine comprising said turbomachine component
US20150030459A1 (en) * 2012-02-02 2015-01-29 Siemens Aktiengesellschaft Turbomachine component with a parting joint, and a steam turbine comprising said turbomachine component
CN103422047A (en) * 2012-05-14 2013-12-04 中国科学院上海硅酸盐研究所 Preparation method for boron carbide-molybdenum composite coating layer
CN103819705A (en) * 2012-11-16 2014-05-28 波音公司 Thermal spray coated reinforced polymer composites
JP2014111364A (en) * 2012-11-16 2014-06-19 Boeing Co Thermal spray coated reinforced polymer composites
EP3388544A1 (en) * 2012-11-16 2018-10-17 The Boeing Company Thermal spray coated reinforced polymer composites
EP3388543A1 (en) * 2012-11-16 2018-10-17 The Boeing Company Thermal spray coated reinforced polymer composites
CN103819705B (en) * 2012-11-16 2018-09-04 波音公司 The enhancing polymer composites of thermal spraying
EP2733231A1 (en) * 2012-11-16 2014-05-21 The Boeing Company Thermal spray coated reinforced polymer composites
US10060019B2 (en) 2012-11-16 2018-08-28 The Boeing Company Thermal spray coated reinforced polymer composites
US9873947B2 (en) 2012-12-19 2018-01-23 Mabe, S.A. De C.V. Easy clean coating applied on stainless steel metallic surfaces used in the manufacture of household appliances
US10214824B2 (en) 2013-07-09 2019-02-26 United Technologies Corporation Erosion and wear protection for composites and plated polymers
US10927843B2 (en) 2013-07-09 2021-02-23 Raytheon Technologies Corporation Plated polymer compressor
US11691388B2 (en) 2013-07-09 2023-07-04 Raytheon Technologies Corporation Metal-encapsulated polymeric article
US11268526B2 (en) 2013-07-09 2022-03-08 Raytheon Technologies Corporation Plated polymer fan
WO2015006487A1 (en) * 2013-07-09 2015-01-15 United Technologies Corporation Erosion and wear protection for composites and plated polymers
US10227704B2 (en) 2013-07-09 2019-03-12 United Technologies Corporation High-modulus coating for local stiffening of airfoil trailing edges
US11267576B2 (en) 2013-07-09 2022-03-08 Raytheon Technologies Corporation Plated polymer nosecone
CN103725058A (en) * 2013-11-25 2014-04-16 铜陵天河特种电磁线有限公司 Synthesized wire enamel with high temperature resistance and preparation method of synthesized wire enamel
US9139908B2 (en) 2013-12-12 2015-09-22 The Boeing Company Gradient thin films
US20180073121A1 (en) * 2015-03-04 2018-03-15 Tocalo Co., Ltd. Fiber-reinforced resin structure and method for producing fiber-reinforced resin structure
EP3266607A4 (en) * 2015-03-04 2018-02-14 Tocalo Co., Ltd. Fiber-reinforced resin structure and method for producing fiber-reinforced resin structure
CN106119764A (en) * 2016-08-15 2016-11-16 合肥科德电力表面技术有限公司 A kind of preparation method of water smoke cooling arc spraying coating
CN106282886A (en) * 2016-09-27 2017-01-04 郑州科源耐磨防腐工程有限公司 A kind of High Speed Electric Arc Spraying liquid metal ceramic coating and preparation method thereof
CN107254650A (en) * 2017-07-04 2017-10-17 安徽威龙再制造科技股份有限公司 A kind of fan blade surface repairing method
CN107779805A (en) * 2017-10-22 2018-03-09 陈海银 Stabilizing roller surface abrasion resistance, corrosion-resistant finishes preparation method
CN109112460A (en) * 2018-08-30 2019-01-01 昆明理工大学 A kind of preparation method of thermal spraying refractory ceramics coating
CN109468573B (en) * 2018-12-27 2020-11-10 沈阳工业大学 Method for preparing wear-resistant coating of brazing transition layer by using electric arc spraying
CN109468573A (en) * 2018-12-27 2019-03-15 沈阳工业大学 A method of preparing the wear-resistant coating of soldering transition zone using electric arc spraying
CN112251709A (en) * 2020-10-21 2021-01-22 长春理工大学光电信息学院 Laminated heat-resistant electronic film and preparation method thereof
CN115305434A (en) * 2022-08-11 2022-11-08 福建阿石创新材料股份有限公司 Method for preparing ceramic coating on surface of thin-wall protective cover and protective cover with coating

Also Published As

Publication number Publication date
EP1244544A4 (en) 2003-01-29
AU4901201A (en) 2001-07-03
WO2001046324A3 (en) 2001-11-15
WO2001046324B1 (en) 2002-01-03
EP1244544A2 (en) 2002-10-02

Similar Documents

Publication Publication Date Title
WO2001046324A2 (en) Erosion-resistant coatings for organic matrix composites
KR102630007B1 (en) Turbine gap control coatings and methods
Murthy et al. Abrasive wear behaviour of WC–CoCr and Cr3C2–20 (NiCr) deposited by HVOF and detonation spray processes
US7141110B2 (en) Erosion resistant coatings and methods thereof
EP1398394A1 (en) Cold spraying method for MCrAIX coating
EP2088225A1 (en) Erosion and corrosion-resistant coating system and process therefor
Sidhu et al. Solid particle erosion of HVOF sprayed NiCr and Stellite-6 coatings
EP2226409A2 (en) Erosion and corrosion resistant turbine compressor airfoil and method of making the same
US20080254227A1 (en) Method for Coating a Component
US20100247321A1 (en) Anti-fouling coatings and articles coated therewith
US20080145694A1 (en) Thermal barrier coating system and method for coating a component
EP2256228B1 (en) Layered coating for erosion protection
WO2011100311A1 (en) Abradable ceramic coatings and coating systems
JP2011140715A (en) Erosion and corrosion resistant coating system for compressor
JP2008144272A (en) Environmentally friendly wear resistant carbide coating
EP3647585B1 (en) Hydro-electric turbine component having enhanced life span and method for forming the same
WO2005103331A1 (en) Hard, ductile coating system
Bains et al. Wear between ring and traveler: A pin-on-disc mapping of various detonation gun sprayed coatings
Mohanty et al. Lightweight TiC/Ti wear-resistant coatings for lightweight structural applications
Waldi et al. Quality characterization of HVOF thermal spray coating with NiCr matrix composite for protection application of coal fired boiler tubes
US8974588B2 (en) Coating composition, a process of applying a coating, and a process of forming a coating composition
Houdková et al. Properties of protective NiCr coatings, deposited by Cold Spray technology
Shobha et al. Novel HVAF Coatings for Tribological Behaviour--A Review.
Levy et al. Erosion and Fatigue Behavior of Coated Titanium Alloys for Gas Trubine Engine Compressor Applications
Ksiazek et al. MICROSTRUCTURE, MECHANICAL PROPERTIES AND WEAR BEHAVIOUR OF HVOF SPRAYED Cr3C2-NiCr COATING ON THE Al-Si ALLOY

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

AK Designated states

Kind code of ref document: B1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: B1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

B Later publication of amended claims
WWE Wipo information: entry into national phase

Ref document number: 2000992985

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 2000992985

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 2000992985

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP