WO2013130169A1 - Compositions de revêtement, applications de celles-ci, et procédés de réalisation - Google Patents

Compositions de revêtement, applications de celles-ci, et procédés de réalisation Download PDF

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Publication number
WO2013130169A1
WO2013130169A1 PCT/US2012/070358 US2012070358W WO2013130169A1 WO 2013130169 A1 WO2013130169 A1 WO 2013130169A1 US 2012070358 W US2012070358 W US 2012070358W WO 2013130169 A1 WO2013130169 A1 WO 2013130169A1
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WO
WIPO (PCT)
Prior art keywords
coating layer
substrate
tubing
coating
work piece
Prior art date
Application number
PCT/US2012/070358
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English (en)
Inventor
Justin Lee Cheney
Grzegorz Jan Kusinski
Original Assignee
Chevron U.S.A. Inc.
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
Priority claimed from US13/407,859 external-priority patent/US20130220523A1/en
Priority claimed from US13/407,878 external-priority patent/US9316341B2/en
Application filed by Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Publication of WO2013130169A1 publication Critical patent/WO2013130169A1/fr

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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
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • C23C4/08Metallic material containing only metal elements
    • 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
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129Flame spraying
    • 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
    • C23C4/18After-treatment

Definitions

  • the invention relates generally to a coating for use in corrosive and / or erosive environments, applications employing the coating, and methods to form the coating.
  • Corrosion is a problem for many industries, for example corrosion costs within U.S. refineries alone total $4,000,000,000 annually.
  • As corrosion is a surface phenomenon one method to combat corrosion and extend the lifetime of a work piece is modifying the surface of a corroding part with a thin layer of corrosion resistant material, via weld overlay or thermal spray. For some applications, these solutions are not used often due to costs and / or unsatisfactory performance.
  • US Patent No. 4,382,976 discloses the use of plasma spraying to protect an article with an overlay coating of MCrAlY, formed with a halide activator.
  • the alloy MCrAlY is applied via thermal spray followed a thermal sprayed aluminum alloy, then a heat treatment.
  • 6,682,780 discloses the use of reactive sintering to create solid coatings during a heat treatment process, using two or more separate powders of distinctly different alloys as constituents to form the coating.
  • US Patent No. 2,868,667 discloses a hard surfacing ("hard facing") method of using a two component mixture of soft and hard particles, wherein the soft mixture melts and binds the hard particles to the substrate to be hard faced.
  • brazing is commonly used to join similar or dissimilar metals using a technique that does not melt the base metals to be joined, with the brazing temperatures being lower than the melting points of the base metals, using brazing materials designed to flow across a surface and into tight joints through capillary action. Properly designed brazing alloys form a strong metallurgical bond with the substrate material.
  • Amorphous metals have been disclosed for use as brazing materials to join surfaces in US Patent Nos. 4,410,604; 7,392,930; and 7,455,811; and in US Patent
  • US Patent No. 7,794,783 discloses a method to form a wear-resistant coating by heating a coating material comprising a brazing material and hard particles to a temperature above a solidus temperature of the braze material.
  • a method to form a single-component protective coating comprises: preparing a substrate on the work piece to be coated, the substrate having a melting point of T s ; applying onto the substrate a coating layer from a single-component feedstock, the feedstock is a Fe-based alloy composition containing at least two refractory elements selected from Cr, V, Nb, Mo and W in an amount of up to 30% each and a total concentration of up to 40%, and having a melting point of T m ; and subjecting the coating layer to heat treatment for the coating layer to be heated to a temperature above T m and below T s for at least a portion of the refractory elements to diffuse across an interface between the coating layer and the substrate into the substrate, for the substrate to be alloyed forming a metallurgical bond with coating layer.
  • the coating layer has an adhesion strength of at least 7,000 psi measured according to ASTM D4541.
  • the invention relates to a work piece for use in an abrasive environment.
  • the work piece comprises: a metal substrate having a melting point of T s ; a coating layer deposited onto the metal substrate from a single-component feedstock, the feedstock is a Fe-based alloy composition containing at least two refractory elements selected from Cr, V, Nb, Mo and W in an amount of up to 30% each and a total concentration of up to 40%, and having a melting point of T m ; wherein at least a portion of the refractory elements in the coating layer diffuse into the metal substrate for the metal substrate to have a gradient composition, in which the metal substrate is alloyed with at least a portion of the refractory elements for the metal substrate at a depth at least 25 ⁇ from an interface between the coating layer and the substrate to have a concentration of refractory elements of at least 25% of the concentration of refractory elements in the alloy composition .
  • the invention relates to a tubing for use in a corrosive environment with a protective corrosion resistant layer on its interior surface.
  • the tubing comprises: a carrier sheet having two edges, a first side and a second side opposite to the first side having a protective layer deposited thereon, the layer prepared from a single-component feedstock comprising a Fe-based alloy composition having least two refractory elements selected from Cr, V, Nb, Mo and W in an amount of up to 30% each and a total concentration of up to 40%).
  • the carrier sheet is inserted into the tubing for the two edges to overlap and for the first side to form the surface exposed to the corrosive environment, and for the second side with the protective layer to be in contact with the interior surface of the tubing.
  • Figure 2 is diagram illustrating an embodiment of a method for coating interior of a pipe or tubing.
  • Figure 3 is diagram illustrating an embodiment of a method for coating a work piece with the use of a carrier sheet.
  • Figure 4 is a diagram illusrating the coating of a substrate with an embodiment of the brazing alloy as a "button.”
  • Figure 5 A is an optical micrograph and Figure 5B is a scanning electron micrograph showing an embodiment of the interface of a coating formed on a mild steel substrate.
  • Figure 8 A is an optical micrograph and Figure 8B is a scanning electron micrograph showing another embodiment of the interface of a coating formed on a mild steel substrate.
  • Figure 9 is a graph from an energy dispersive spectroscopy (EDS) evaluation showing diffusion of alloying elements across the interface in Figues 8 A - 8B.
  • EDS energy dispersive spectroscopy
  • Figure 10 is another graph from the EDS evaluation showing the chemistry of the phases in the alloy coating of Figures 8A-8B.
  • a "layer” is a thickness of a material that may serve a functional purpose including but not limited to erosion resistance, reduced coefficient of friction, high stiffness, or mechanical support for overlying layers or protection of underlying layers.
  • Coating is comprised of one or more adjacent layers and any included interfaces. Coating also refers to a layer is placed directly on the substrate of the article to be protected. In another embodiment, “coating” refers to the top protective layer.
  • Substrate refers to a portion or the entire surface an article, e.g., a work piece, equipment or portions of an equipment to be protected by a coating of the embodiment.
  • the article (i.e., equipment, work piece) to be coated can be of any shape, e.g., tools, the interior of a structural component such as a pipe, a vessel, or a tank.
  • Refractory elements refers to Cr, V, Nb, Mo, and W, metals that are resistant to heat and wear, with a higher melting temperature than steel.
  • Single component coating refers to coating formed with a single feedstock material whether the feedstock is in the form of a wire or a powder, this is opposed to a multi- component (or two-component) coating formed by two or more distinct alloys (in the form of a wire or powder), or by the brazing of two different materials forming a coating.
  • Interface refers to the initial layer between the coating layer and the substrate layer, wherein subsequently a transition region is formed between the coating layer and the substrate with one or more constituent material composition and/or property value changes from 5% to 95% of the initial values that characterize each of the adjacent layers.
  • the invention relates to brazing methods in which no joining is used, wherein a single-component braze material is melted and flows across the surface of the substrate forming a protective coating.
  • a strong metallurgical bond is created between the substrate and the coating created by the brazing composition.
  • the coating formed by the mechanically bound coating alloy is disclosed with a sufficiently low heat treatment operation to minimize damage the substrate in any manner.
  • the coating as formed with the alloy composition of the invention is characterized as being fully protective of the substrate, exhibit minimal or no through-porosity or dilution, providing the work piece with corrosive and/or erosive resistant characteristics.
  • Alloy Compositions The alloy composition is designed using computational metal l urgical techniques for forming a protective coating characterized as having a melting point that is sufficiently below the melting temperature of a typical substrate to be protected, e.g., mild steel or carbon steel with a melting point T m of 2600 - 2800° F.
  • the alloy composition has a T m in the range of 2140 - 2240°F.
  • the alloy composition contains at least two refractory elements selected from Cr, V, Nb, Mo and W each in an amount of up to 30% each and a total concentration of up to 40%.
  • the alloy has a composition in weight %: 10 - 30% Cr and at least a refractory element selected from V, Nb, Mo and W in an amount of up to 20% each; balance of Fe and unavoidable impurities.
  • Refractory elements have been identified as key elements to reducing the corrosion rate, specifically the sulphidation rate, of iron alloys. However, silicon and aluminum have also been demonstrated as elements which can significantly improve sulfur related corrosion performance.
  • the alloy composition further contains at least one of Al and Si, in an amount of up to 10% each.
  • the alloy composition is a steel alloy having a plurality of components as defined in weight percent as: Fe (55-65%), Cr (0-30%), R (4-30%), Si (0- 10%), B (0-3%), and Al (0-20%), with R is at least a refractory element selected from V, Mo, Nb, and W.
  • the alloy composition comprises any of the following chemistries, given in weight percent:
  • Alloy 1 Fe - 60.8%, Cr - 22.1%, Mo - 9.5%, Si - 3.6%, B - 2.8%, Al - 1.1%;
  • Alloy 2 Fe - 60.8%, Cr - 22.1%, Nb - 4.8%, V - 4.8%, Si - 3.6%, B - 2.8%, Al - 1.1%;
  • Alloy 3 Fe - 56.8%, Cr - 21.6%, Mo - 12.8%, Si - 5.6%, B - 2.2%, Al - 1.1%;
  • Alloy 4 Fe - 61.7%, Cr - 12%, Nb - 5%, V - 5%, Si - 3.6%, B - 2.75%, Al -
  • Alloy 5 Fe - 61.7%, Cr -17%, Nb - 5%,V- 5%, Si - 3.6%, B- 2.75%, Al - 5% ;
  • Alloy 6 Fe - 65.9%, Cr - 24.6%, Mo - 4.6%, Si - 1.5%, Mn-1.2%, B - 2.2%;
  • Alloy 7 Fe - 65.9%, Cr - 24.6%, V - 4.6%, Si - 1.5%, Mn-1.2%, B - 2.2%.
  • the alloy composition forms a coating layer with a composition gradient across the thickness of the coating as illustrated in Figure 1 , which compositional gradient can act to reduce stresses during thermal cycling and / or add composition control of the coating layer to protect the underlying substrate.
  • the depth of the performance layer as well as the concentration of the refractory elements alloyed into the substrate can be effectively controlled.
  • the specific elements that diffuse into the substrate as well as the elements or phases in the gradient layer can also be controlled, as smaller elements, i.e., Fe, Cr, V, etc. can more easily diffuse into the substrate leaving behind relatively larger refractories (i.e., W, Nb, Mo).
  • the larger refractory elements in one embodiment form thermally insulating phases such as carbides, borides, silicides, or oxides to provide enhanced corrosion resistance through refractory enrichment in the matrix of the gradient layer adjacent to the interface.
  • the relatively large refractory (i.e., W, Nb, Mo) content in the coating layer increases at least 5% due to the selective diffusion of smaller elements over the interface and into the substrate during the heat treatment operation.
  • the relatively larger refractory content increases by at least 10%.
  • the relatively large refractory content increases by at least 30%.
  • the alloy composition as cored wire, solid wire, or powder feedstock, can be applied onto the substrate of the equipment (work piece) using a variety of methods including but not limited to welding, kinetic spray, physical vapor deposition (PVD), chemical vapor deposition (CVD), and thermal spray.
  • the alloy can be applied as a single layer, or as a plurality of layers, with a total thickness of 0.5 to 150 mils (12.7 - 3810 ⁇ ) in one embodiment; from 1 to 100 mils (254 - 2540 ⁇ ) in a second embodiment; and from 5 to 50 mils (127 - 1270 ⁇ ) in a third embodiment.
  • the surface is given an anchor profile abrasive blast ranging from 0.5 mils (0.0254 mm) to 6 mils (0.1524 mm) to provide initial profile for the thermal sprayed coating to better mechanically bond to the substrate.
  • the alloy composition is deposited via the thermal spray technique, which allows for quick a quick application (e.g., 25 lbs/hr or more) of a thick coating of material onto the substrate in a controlled and measurable manner.
  • the thermal spray coating can be any of conventionally sprayed flame, arc wire, plasma, or HVOF (high velocity oxy fuel) techniques.
  • the heat treatment step a sufficient amount of heat is applied to melt the alloy composition for a coating with a thickness substantially close to the original thickness.
  • the equipment with the alloy coating is heat treated in a commercial vacuum furnace.
  • the heat treatment can be local using techniques including but not limited to induction heating, combustion burner, electric resistance heaters, etc.
  • the heat treatment ranges from 10 - 60 minutes in one embodiment, and from 15 to 45 minutes in a second embodiment, wherein the alloy is fused onto the base metal substrate and for the alloy flow across the substrate surface, eliminating coating porosity and the possibility of uncoated exposed surfaces.
  • the heat treatment is via induction heating due to its rapid and controllable heat treatment potential, melting the alloy
  • composition to form a fully protective layer at temperatures below the melting temperature of the substrate are provided.
  • an apparatus scheme as illustrated in Figure 3 is employed.
  • a steel tubing 901 is fed into position on top of a moving conveyer or rollers 903, for its interior to by coated (throughout its length) in the spray zone by spray assembly 905.
  • the mechanical assembly in one embodiment has one or more spray guns 906 connected to the assembly, which may be stationary or rotating, spraying the coating alloy 907 onto the interior surface of the tubing.
  • the mechanical assembly traverses along the length of the tubing via an arm assembly 902 to spray the entire interior length of the tubing.
  • Control of the mechanical assembly can be separate from the spray guns 906 in a containerized spray booth 904.
  • the heat treatment operation takes place at one end of the pipe using techniques known in the art, e.g., induction coil 908, causing the brazed coating to fuse onto the substrate forming a protective layer.
  • a carrier sheet in another embodiment to provide coating protection for interiors of relatively long and relatively small diameter tubing, or for interior of equipment difficult geometries, the use of a carrier sheet is employed as illustrated in Figure 2.
  • the carrier sheet can be of the same or different composition from the substrate to be coated, having a sufficient thickness that allows the carrier sheet to bend and conform to the shape of the equipment to be protected.
  • the carrier sheet has a surface area that is slightly larger than the surface area of the substrate to be coated with the alloy composition.
  • the carrier sheet has a thickness ranging from 0.5 - 100 mils. In a second embodiment, a thickness of 5 - 50 mils. In one embodiment, the carrier sheet comprises carbon steel. In another embodiment, the carrier sheet comprises stainless steel. After the carrier sheet is coated with the alloy composition, it is then placed onto the equipment to be coated with adjacent or slightly overlapping edges, with the alloy coating surface to be in intimate contact with the substrate to be protected. In a heat treatment step, the brazing material preferably melts and diffuses into the substrate to be coated.
  • a large carrier sheet can be used for the coating of a plurality of tubings. After being coated with the alloy composition, the carrier sheet is then cut into multiple smaller sheets each with a surface area sufficient to fully cover the interior or exterior of the tubings to be protected. The subsequent heat treatment step can be part of the quench and temper stage of the tubing, in a normal manufacturing process.
  • a flat and thin ductile sheet (“carrier sheet”) 403 is sprayed with the alloy 402 over the entire surface along one side of the sheet.
  • the carrier sheet is a flexible metal sheet, which forms the interior of the tubing and can be subsequently removed or corroded away on its own.
  • the thermal spraying of such a geometry is simple and can be done quickly and in a relatively simple manner as compared to spraying interior pipe surfaces.
  • the sheet 403 is rolled up, and inserted into a piping 404 for the edges of the sheet 403 to overlap, and for the sheet to abut the piping 404 such that the alloy coating 402 is positioned in contact with the interior surface of the pipe.
  • the uncoated side of the sheet is not in contact with the interior piping surface and faces the centerline of the tubing.
  • the pipe 404 is then heat treated with a heat source 405 to a temperature which melts the alloy coating 402 but not the pipe 404 or the sheet 403, forming a protective coating surface which is now sandwiched between the interior pipe walls and the carrier sheet 403.
  • the substrate has a total thickness of at least 10 mils (254 ⁇ ) and at a depth of 50 ⁇ from the interface of the substrate / coating layer, the substrate has a total thickness of at least 10 mils (254 ⁇ ) and at a depth of 50 ⁇ from the interface of the substrate / coating layer.
  • the substrate has a total concentration of refractory elements of at least 10 wt. % at a depth of 50 ⁇ , and a total concentration of at least 5 wt.% at a depth of 100 ⁇ .
  • the coating is characterized as having an adhesion strength of at least 7000 psi (48 MPa) measured according to any of ASTM D4541 and ASTM D7234 in one embodiment; and at least 10,000 psi (70 MPa) in a second embodiment.
  • the adhesion strength here is the average adhesion strength across the coating layer.
  • the coating layer forms a protective solid non-porous coating layer on the underlying substrate that is impermeable to corrosive environments, characterized as showing no pin holes, pitting (0/ m 2 ) in the ferroxyl test according to ASTM A967 Practice E.
  • the coatings and methods for applying coatings are particularly suitable for the protection of work pieces, etc., in any of erosive, corrosive, and abrasive environments.
  • the coating is particularly suitable for use in protecting steel components subject to environments containing sulfur and abrasive sand.
  • the coating further provides protection for the underlying equipment / substrate with any of wear resistance, heat resistance, insulation, shielding, and conductivity characteristics.
  • Mild steel equipment e.g., tubing
  • erosive / corrosive applications including but not to sulfur-containing environments and down-hole exploration.
  • cost and performance can be optimized using the coatings described herein to protect mild steel equipment.
  • Example 1 A number of brazing alloy buttons (15 g each) comprising compositions Alloy 1 - Alloy 7 were fabricated and placed on carbon steel coupons. After heat treatment to a temperature of 1190 - 1225°C (2175 - 2240°F), it was observed that the alloys had melted and flowed across the carbon steel surface and beyond the original point of contact, creating a coating on the coupon surface as illustrated in Figure 4.
  • Example 3 Example 2 was repeated with a 1/16" cored wire formed from an alloy composition of: Fe (65.9%); Cr (24.6%); Mo (4.6%); Si (1.5%); Mn (1.2%) and B (2.2%).
  • Example 4 1/16" cored wire was formed from an alloy composition of: Fe
  • the material was thermal sprayed using the twin wire arc spray technique onto a 0.005" thick 430 stainless steel foil, which was wrapped around a 3.5-4.5" pipe at a thickness of 10-30 mils.
  • the stainless steel foil was hose clamped to the pipe during the spray process at each free end. After the desired thickness was achieved, the hose clamps were removed. The sprayed foil was inserted into a second 3.5-4.5" pipe such that the thermal spray coating was in contact with the inner diameter of the second steel pipe.
  • a thicker 25 mil foil was then wrapped into a cylindrical shape and inserted into the assembly (2 nd steel pipe with interior foil) such that the 25 mil foil was actively pressing the foil up against the interior walls due to its tendency to expand into a flat sheet.
  • the entire assembly (2 nd steel pipe + interior sprayed 5 mil foil + 25 mil foil) was inserted into a vacuum furnace and heat treated to a temperature of 1190 °C - 1225°C and held at that elevated temperature for 15-30 min, resulting in the homogenization of the steel plate.
  • the 25 mil interior foil was removed from the center of the pipe and discarded.
  • the 5 mil foil was metallurgically bound to the interior of the pipe allowing with the coating material, providing a corrosion resistant coating against sulfur-containing corrosive species particularly useful for sour service oil and gas upstream applications.
  • Example 5 Example 4 was repeated with a 1/16" cored wire having a composition of Fe (63.4%); Cr (9.4%); Mo (12.5%); B (1.8%); C (2.5%); and W (10.4%), for a pipe having an interior erosion resistant coating against flowing sand particles, particularly useful for oil and gas upstream applications.
  • Example 6 A number of steel coupons were coated with a steel alloy composition of: Fe - 60.8%, Cr - 22.1%, Mo - 9.5%, Si - 3.6%, B - 2.8%, Al - 1.1% (Alloy 1) for coating of 15 mils thick, then heat treated at 1190°C or 1225°C for 30 minutes in a vacuum furnace.
  • Ferroxyl exposure test according to ASTM A967 Practice E was conducted. Permeability in a ferroxyl exposure test is indicated by formation of blue spots on surface of samples, which is the result of the ferroxyl solution penetrating the coating thickness and reacting with the steel substrate. However, the samples showed no permeability to the mild steel substrate with the ferroxyl solution remained yellow during the duration of the test.
  • Example 7 Example 6 was duplicated, but the steel coupons were coated with a nickel alloy having a composition of: Ni - 57%, B - 0.4%, Si - 1%, Cr - 27.6%, Mo - 14%. The coupons showed permeability with the formation of blue spots on the coating surface.
  • Example 6 was duplicated but the coating was not heat treated. Ferroxyl exposure test was carried out with the coupons having as-sprayed coatings. The coupons showed permeability.
  • Example 9 Example 6 was duplicated and the steel coupon was coated with Alloy 3: Fe - 56.8%, Cr - 21.6%, Mo - 12.8%, Si - 5.6%, B - 2.2%, Al - 1.1%. After heat treatment, it was noted that the Cr, Si, and Al species selectively diffused into the steel substrate. However, the Mo due to its large size and preference to react with Si preferentially formed molybdenum disilicide, MoSi 2 and remained in the coating layer. MoSi 2 is a common engineering ceramic which has additional uses beyond its inherent thermal insulating properties, such as high oxidation resistance andhigh temperature strength. The Mo content in the coating layer increased at least 5% as a result of the heat treatment.
  • Example 10 Micro-structural evaluation of a carbon steel coupon formed with a 15 mil thermal sprayed coating of Alloy 1 (Fe - 60.8%, Cr - 22.1%, Mo - 9.5%, Si - 3.6%), B - 2.8%), Al - 1.1%) and fused at 1225°C for 15 minutes.
  • Figure 5A is an optical micrograph
  • Figure 5B is a scanning electron micrograph (SEM).
  • SEM scanning electron micrograph
  • the alloy in fused condition formed a concentrated chromium phase (phase 1) and a concentrated refractory phase (phase 2). These phases form a needle-like structure at the interface and develop into a block- like structure over 100 ⁇ into the alloy coating as shown.
  • Example 11 In this example, micro-structural and EDS evaluations were conducted on a carbon steel coupon formed with a 15 mil thermal spray coating of Alloy 2 (Fe - 60.8%, Cr - 22.1%, Nb - 4.8%, V - 4.8%, Si - 3.6%, B - 2.8%, Al - 1.1%), fused at 1225°C for 15 minutes.
  • Alloy 2 Fe - 60.8%, Cr - 22.1%, Nb - 4.8%, V - 4.8%, Si - 3.6%, B - 2.8%, Al - 1.1%
  • Figure 8A is an optical micrograph
  • Figure 8B is a scanning electron micrograph (SEM).
  • the white phase in the SEM is likely NbB, and the dark phase is likely a V borocarbide phase.
  • the EDS in Figure 9 shows extensive diffusion of Cr and Si into the carbon steel substrate, with elevated levels of Cr (5 wt %) and Si (3 - 4%) at distance of 100 ⁇ into the substrate, expected to provide excellent corrosion resistance properties.

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Abstract

L'invention concerne un procédé permettant de réaliser des couches de protection sur du matériel. L'invention concerne également du matériel, garni d'une couche de revêtement de protection, et destiné à l'utilisation dans des environnements abrasifs, notamment des environnements soufrés. Ce revêtement est réalisé à partir d'un produit de départ mono-composant, notamment une composition d'alliage à base de Fe comprenant au moins deux éléments réfractaires choisis dans le groupe constitué de Cr, V, Nb, Mo et W à raison d'un maximum de 30% pour chacun et une concentration totale n'excédant pas 40%. Dans un mode de réalisation, le revêtement est appliqué par projection à chaud, cette application étant suivie d'un traitement thermique permettant à une partie au moins des éléments réfractaires du revêtement de se fusionner avec le substrat en formant un revêtement métallurgiquement lié. Ce revêtement est doté d'une force d'adhésion d'au moins 7.000 livres par pouce carré mesurée selon ASTM D4541. Cette couche de revêtement est en outre caractérisée en ce qu'elle est imperméable aux environnements corrosifs, ne faisant apparaître aucun trou d'épingle lors du test au ferroxyle selon ASTM A967 Practice E.
PCT/US2012/070358 2012-02-29 2012-12-18 Compositions de revêtement, applications de celles-ci, et procédés de réalisation WO2013130169A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US13/407,859 2012-02-29
US13/407,859 US20130220523A1 (en) 2012-02-29 2012-02-29 Coating compositions, applications thereof, and methods of forming
US13/407,878 US9316341B2 (en) 2012-02-29 2012-02-29 Coating compositions, applications thereof, and methods of forming
US13/407,878 2012-02-29

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Citations (5)

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EP0384054A1 (fr) * 1987-05-11 1990-08-29 Exxon Research And Engineering Company Article résistant à la corrosion
JPH07138727A (ja) * 1993-11-11 1995-05-30 Mitsubishi Heavy Ind Ltd 耐摩耗性皮膜の被覆方法
JPH10195625A (ja) * 1997-01-08 1998-07-28 Toshiba Corp 耐摩耗コーティング部品およびその製造方法
KR100201694B1 (ko) * 1996-09-30 1999-06-15 오상수 경사코팅-확산접합을 이용한 금형부재 제조방법
US20090311103A1 (en) * 2005-06-17 2009-12-17 Hideyuki Arikawa Rotor for steam turbine and method of manufacturing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384054A1 (fr) * 1987-05-11 1990-08-29 Exxon Research And Engineering Company Article résistant à la corrosion
JPH07138727A (ja) * 1993-11-11 1995-05-30 Mitsubishi Heavy Ind Ltd 耐摩耗性皮膜の被覆方法
KR100201694B1 (ko) * 1996-09-30 1999-06-15 오상수 경사코팅-확산접합을 이용한 금형부재 제조방법
JPH10195625A (ja) * 1997-01-08 1998-07-28 Toshiba Corp 耐摩耗コーティング部品およびその製造方法
US20090311103A1 (en) * 2005-06-17 2009-12-17 Hideyuki Arikawa Rotor for steam turbine and method of manufacturing the same

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