WO2013152306A1 - Compositions d'alliage métallique et applications de ceux-ci - Google Patents

Compositions d'alliage métallique et applications de ceux-ci Download PDF

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Publication number
WO2013152306A1
WO2013152306A1 PCT/US2013/035481 US2013035481W WO2013152306A1 WO 2013152306 A1 WO2013152306 A1 WO 2013152306A1 US 2013035481 W US2013035481 W US 2013035481W WO 2013152306 A1 WO2013152306 A1 WO 2013152306A1
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WIPO (PCT)
Prior art keywords
work piece
welding
less
alloy
deposited
Prior art date
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PCT/US2013/035481
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English (en)
Inventor
Grzegorz Jan Kusinski
Justin Lee Cheney
John Hamilton Madok
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 US13/440,732 external-priority patent/US20130266798A1/en
Priority claimed from US13/440,717 external-priority patent/US20130266820A1/en
Application filed by Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Publication of WO2013152306A1 publication Critical patent/WO2013152306A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides

Definitions

  • the invention relates to metal alloys with excellent wear resistant properties suitable for use as coatings in wear-prone environments, and applications employing the alloys for dynamic three-body tribological systems for reduced wear on multiple components of varied hardnesses.
  • Wear is a problem found in many industries and can encompass different mechanisms.
  • abrasion wear such as in a three-body abrasion system
  • a third body e.g., a hard particle such sand
  • the wear rate is primarily governed by the third body wearing, for example in the form of gouging, chipping, grinding, etc., away at the two respective surfaces of the two primary bodies in motion.
  • the wear rate of each moving primary body is related to the tribological mechanisms between it and the third body, and is relatively independent to the material properties of the opposing primary body. This is in contrast to the mechanisms existing in sliding wear, under which conditions the two primary bodies are in contact with each other and the wear rates of each primary body is directly related to the material properties of the opposing body.
  • Conditions of abrasive wear can be damaging as they often involve sand, rock particles, or other extremely hard media wearing away against a surface.
  • Applications which see severe abrasive wear in the prior art typically utilize materials of high hardness, 60 Rc+, encompassing hard metals or carbides. These materials are often not successful in dealing with conditions of sliding wear, in which wear on both bodies is to be minimized. In cases where one body is significantly harder than the other body, the hard body tends to impart high wear rates on the soft body while wearing significantly less itself. Under applications where one material is a softer material, it is not generally suitable to utilize the prior art materials with high hardness such as carbides or other hard metals.
  • a material may pass through several different wear mechanisms during its service lifetime.
  • the sides of the drill pipe must rub against the earth, e.g., sand, rock, etc., and is considered a condition of abrasive wear.
  • the sides of the drill pipe now rub against the metal of the casing under conditions of sliding wear.
  • Disclosures offering solutions to the competing wear mechanisms in oil & gas drilling applications include but are not limited to US Patent Nos. 4,277,108; 4,666,797; 6,117,493; 6,326,582; 6,582,126; 7,219,727; and US Patent Publication No. 2002/0054972.
  • US Publication Nos. 2011/0220415 and 2011/004069 disclose an ultra-low friction coating for drill stem assemblies.
  • US Patent Nos. 6,375,895, 7,361,411, 7,569,286, 20040206726, 20080241584, and 2011/0100720 disclose the use of hard alloys for the competing wear mechanisms.
  • Methods in the prior art to address the competing wear mechanisms include US Patent No. 7,487,840 and US Patent Publication No.
  • US Patent No. 6,861,612 discloses a laser beam to deposit a hard coating.
  • US Patent Publication No. 2007/0209839 disclosed an improved drill pipe design.
  • US20060006151 Al discloses the use of amorphous metals for handbanding applications with the injection of pellets into a hard-facing amorphous metal.
  • the invention is directed to an improved hardfacing alloy composition, and products with exceptional combination of both high metal to metal wear resistance and resistance to abrasion, e.g., handbanded on tool joints and stabilizers, as well as other industrial products.
  • the invention is directed to the protection of tool joint and casing components in drilling operations against both abrasive and sliding wear.
  • a work piece capable of withstanding service abrasion has at least a portion of its surface protected by a layer comprising an alloy composition having in wt. %: at least one of Cr and Nb of less than 5% each, at least one of Mo and W in an amount of up to 8% each, at least one of B, C, and Si in an amount of 0.5 to 4%, and a total concentration of Cr and Nb of 10%, balance iron, including impurities as trace elements.
  • the layer exhibits a hardness of at least 50 a wear rate of less than 0.5 grams of mass loss as measured according to ASTM G65-04, Procedure A, a wear rate on a contacting secondary body comprising carbon steel of less than 0.005 grams as measured according to modified ASTM G77 wear test.
  • a hardbanding for protecting a work piece in an abrasive environment.
  • the hardbanding comprises: a layer comprising an alloy composition having in wt. %: Cr (0-5%), Nb (2-5%), Mn (0-6%), V (0 - 4%), C (0.25-2%), B (0.75 -3%), at least one of Mo and W (3-8% each) and up to 15% total, Ti (0-1%), Si (0- 1%), with total concentration of Cr and Nb of up to 10%, total concentration of B, C and Si of up to 4%; and balance iron including impurities as trace elements.
  • the layer is deposited onto at least a portion of the work piece by any of laser welding, shielded metal arc welding (SMAW), stick welding, plasma transfer arc welding (PTAW), gas metal arc-welding (GMAW), metal inert gas welding (MIG), submerged arc welding (SAW), open arc welding (OAW), and combinations thereof.
  • SMAW shielded metal arc welding
  • PTAW plasma transfer arc welding
  • GMAW gas metal arc-welding
  • MIG metal inert gas welding
  • SAW submerged arc welding
  • OFAW open arc welding
  • Procedure A a wear rate on a contacting secondary body comprising carbon steel of less than 0.005 grams as measured according to modified ASTM G77 wear test.
  • a method for prolonging a work piece used in an abrasive environment comprises depositing onto at least a surface of the work piece an alloy comprising a composition having in wt. %: at least one of Cr and Nb of less than 5% each, at least one of Mo and W in an amount of up to 8% each, at least one of B, C, and Si in an amount of 0.5 to 4%, and a total concentration of Cr and Nb of 10%, balance iron, including impurities as trace elements.
  • the layer is deposited by any of laser welding, shielded metal arc welding (SMAW), stick welding, plasma transfer arc welding (PTAW), gas metal arc-welding (GMAW), metal inert gas welding (MIG), submerged arc welding (SAW), open arc welding (OAW), and combinations thereof.
  • the deposited alloy exhibits a hardness of at least 50 R c , a wear rate of less than 0.5 grams of mass loss as measured according to ASTM G65-04, Procedure A, a wear rate on a contacting secondary body comprising carbon steel of less than 0.005 grams as measured according to modified ASTM G77 wear test.
  • Figure 1 A is a diagram illustrating and comparing the wear dynamics between a secondary soft body in a prior art coating comprising a metal alloy with a soft matrix and a microstructure of large hard particles contained within.
  • Figure IB a diagram illustrating the wear dynamics of the secondary soft body in an embodiment of a coating of the invention comprising a metal alloy with a soft matrix but smaller particles in the microstructure.
  • Figure 2 A is an unmodified optical micrograph showing the microstructure of an embodiment of the metal alloy.
  • Figure 2B is a color modified optical micrograph of the microstructure in Figure 2 A.
  • Figure 3 is a zoomed-in scanning electron micrograph detailing various specific phases of the metal alloy of Figure 2A
  • Figures 4 A is an unmodified optical micrograph showing the microstructure of second embodiment of the metal alloy.
  • Figure 4B is a color modified optical micrograph of the microstructure in
  • Figure 5 is a zoomed-in scanning electron micrograph detailing various specific phases of the metal alloy of Figure 4A.
  • Figure 6A is a diagram showing the schematic of an embodiment of a testing apparatus for use in measuring case wear.
  • Figure 6B is a side view of the test apparatus in Figure 6A.
  • Figure 7 is a plot comparing casing wear results as measured using a modified ASTM G77 test for samples of an embodiment of the alloy composition and sample alloys in the prior art.
  • Figure 8 is a plot comparing casing wear results (via modified ASTM G77) as well as dry sand abrasion test results (ASTM G65) for the samples in Figure 7.
  • Amorphous metal refers to a metallic material with disordered atomic scale structure. The term can sometimes be used interchangeably with "metallic glass,” or “glassy metal,” or “bulk metallic glass” for amorphous metals having amorphous structure in thick layers of over 1 mm.
  • Casing is defined as a metal pipe or tube used as a lining for a water, oil, or gas well.
  • 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 a base body assembly to be protected, or the hardbanding placed on a base substrate material. In another embodiment, “coating” refers to the top protective layer.
  • a "layer” is a thickness of a material that may serve a specific functional purpose such as reduced coefficient of friction, high stiffness, or mechanical support for overlying layers or protection of underlying layers.
  • Hardband refers to a process to deposit a layer of a special material, e.g., super hard metal, onto drill pipe tool joints, collars and heavy weight pipe in order to protect both the casing and drill string components from wear associated with drilling practices.
  • a special material e.g., super hard metal
  • Hardbanding refers to a layer of superhard material to protect at least a portion of the underlying equipment or work piece, e.g., tool joint, from wear such as casing wear. Hardbanding can be applied as an outermost protective layer, or an intermediate layer interposed between the outer surface of the body assembly substrate material and the buttering layer(s), buffer layer, or a coating. Hardbanding may be used interchangeably with “hardfacing,” a term also commonly used by those skilled in the art.
  • Coating may be used interchangeably with “hardbanding,” referring to the layer of superhard material to protect the underlying equipment.
  • Hard particles refer to any of hard boride, carbide, borocarbide particles.
  • the invention relates to a metal alloy for use in single or multi-stage tribological processes involving multiple bodies of varying hardness, and applications of the metal alloy, e.g., hardbanding applications.
  • the metal alloy for the hardfacing is characterized as having very fine-grained micro structural features.
  • the metal alloy comprises an iron-based (ferritic or martensitic) matrix containing fine-scaled hard boride, carbide, borocarbide particles (e.g., M 2 B or MC, where M is a transition metal) having average particle sizes of greater than 100 nm and less than 5 ⁇ in an amount of less than 30 vol. %.
  • the metal alloy is applied as a coating of Fe-based matrix containing fine-scaled hard particles having a volume fraction of less than 15%.
  • the chromium concentration in the alloy composition is limited to 5 wt. %, as chromium exhibits the tendency to form carbides and borides and can form complex carbides, borides, and boro-carbides including iron due to the very similar atomic sizes between iron and chromium.
  • the composition further comprises at least an alloying element of larger atomic sizes (compared to Cr) selected from Nb, Mo, and W in an amount of up to 8% each.
  • the concentration of the alloying elements is controlled to help limit the formation of transition metal carbides / borides in the matrix, as inhomogeneous hardness level in the microstructure contributes to uneven wear on the coatings formed therefrom.
  • the alloy is an Fe-based alloy having the composition in wt. %: Fe (balance), at least one of Cr and Nb of less than 6% each, at least one of Mo and W in an amount of up to 8% each, at least one of B, C, and Si in an amount of 0.5 to 4%, and a total concentration of Cr and Nb of 11%.
  • the total concentration of Cr and Nb is 10% or less, and the amount of Cr or Nb is 5% or less.
  • the alloy is an Fe-based alloy having the composition in wt. %: Fe (balance), Cr (0-6%), Mn (0-6%), Nb (2-6%), V (0 - 4%), C (0.25-2%), B (0.75 -3%), at least one of Mo and W (3-8% each) up to 15% total, Ti (0-1%), Si (0-1%), with the total concentration of Cr and Nb of up to 11% and total of B, C and Si of up to 4%.
  • the composition contains in wt. %: Fe (balance),
  • the composition contains: Fe (balance), Cr (0-6%>), Mn (0-1%), Nb (4-6%), V (0-1%), C (0-0.5%), B (2 -3%), at least one of Mo and W (2 - 8% each) up to 10% total, Ti (0-0.25%), and Si (0-0.25%), with the total concentration of Cr and Nb of up to 11% and total of B, C and Si of up to 4%.
  • the alloy is any of the followings in wt. %, with the total concentration of Cr and Nb of up to 11% and total of B, C and Si of up to 4%.:
  • Alloy 1 Fe (82.68%), Cr (5%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%),
  • Alloy 2 Fe (82.68% ), Cr (5%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn(0.5%), Ti(0.2%), and Si (0.5%);
  • Alloy 3 Fe (80.4%), Cr (5.6%), Nb (4.4%), V (0.6%), C (0.5%), B (1.7%), W (6.6%), Ti (0.2%);
  • Alloy 4 Fe (81%), Cr (5.6%), Nb (4.4%), V (0.6%), C (0.5%), B (1.1%), W (6.6%), Ti (0.2%);
  • Alloy 5 Fe (83.93%), Cr (5%), Nb (4.3%), V (0.5%), C (0.8%), B (1.25%), W (3%), Mn (0.5%), Ti (0.2%), Si (0.5%); [044] Alloy 6: Fe (82.66%), Cr (5%), Nb (4.3%), V (0.5%), C (1%), B (0.82%), W (5%), Ti (0.2%), Si (0.52%);
  • Alloy 7 Fe (79.8%), Cr (5%), Nb (4.3%), C (0.5%), B (2.5%), W (7.5%), Ti (0.25%), Si (0.15%);
  • Alloy 8 Fe (79.3%), Cr (5%), Nb (4.3%), V (0.5%), C (0.5%), B (2.5%), W(7.5%), Ti (0.25%), Si (0.15%);
  • Alloy 9 Fe (80.3%), Cr (5%), Nb (4.3%), V (0.5%), C (0.5%), B (2.5%), W (6.5%), Ti (0.25%), Si (0.15%);
  • Alloy 10 Fe (83.68%), Cr (4%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (0.5%), Ti (0.2%), Si (0.5%);
  • Alloy 11 Fe (84.68%), Cr (3%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (0.5%), Ti (0.2%), Si (0.5%);
  • Alloy 12 Fe (85.68%), Cr (2%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (0.5%), Ti (0.2%), Si (0.5%);
  • Alloy 13 Fe (86.68%), Cr (1%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (0.5%), Ti (0.2%), Si (0.5%);
  • Alloy 14 Fe (87.68%), Cr (0%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (0.5%), Ti (0.2%), Si (0.5%);
  • Alloy 15 Fe (82.18%), Cr (5%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1%), Ti (0.2%), Si (0.5%);
  • Alloy 16 Fe (83.18%), Cr (4%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1%), Ti (0.2%), Si (0.5%);
  • Alloy 17 Fe (84.18%), Cr (3%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1%), Ti (0.2%), Si (0.5%);
  • Alloy 18 Fe (85.18%), Cr (2%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1%), Ti (0.2%), Si (0.5%);
  • Alloy 19 Fe (86.18%), Cr (1%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1%), Ti (0.2%), Si (0.5%);
  • Alloy 20 Fe (87.18%), Cr (0%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1%), Ti (0.2%), Si (0.5%);
  • Alloy 21 Fe (81.68%), Cr (5%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1.5%), Ti (0.2%), Si (0.5%);
  • Alloy 22 Fe (82.68%), Cr (4%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1.5%), Ti (0.2%), Si (0.5%); [061 ] Alloy 23 : Fe (83.68%), Cr (3
  • Alloy 24 Fe (84.68%), Cr (2%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1.5%), Ti (0.2%), Si (0.5%);
  • Alloy 25 Fe (85.68%), Cr (1%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1.5%), Ti (0.2%), Si (0.5%); and
  • Alloy 26 Fe (86.68%), Cr (0%), Nb (4.3%), V (0.5%), C (0.8%), B (2.5%), Mo (3%), Mn (1.5%), Ti (0.2%), Si (0.5%).
  • the alloy incorporates the above elemental constituents a total of 100 wt. %.
  • the alloy may include, may be limited to, or may consist essentially of the above named elements.
  • the alloy may include 2% or less of impurities. Impurities may be understood as elements or compositions that may be included in the alloys due to inclusion in the feedstock components, through introduction in the processing equipment, or by reaction of the alloy compositions with the environment.
  • the alloy After deposition on a substrate, the alloy forms a protective coating having iron rich phases containing embedded hard particles (carbides, borides, and / or
  • the boride phase is represented as M 2 B, wherein M is a transition metal.
  • the embedded hard particles in the ferritic matrix contain Nb, Cr, and Mo /W with both carbon and / or boron. In another embodiment, the particles are in the form of embedded Nb carbide and Mo-boro carbide precipitate.
  • the fine grained hard particles have an average size of 100 nm - 20 ⁇ in one embodiment; from 1 to 15 ⁇ in a second embodiment; from 5 - 10 ⁇ in a third
  • the hard particles greater than 100 nm are present in an amount of less than 15 vol. % in one embodiment; less than 10 vol. % in a second embodiment; less than 5 vol. % in a third embodiment; and less than 1 vol. % in a fourth embodiment.
  • more than 50% of the hard particles are Nb carbide precipitates having a particle size of 0.5 to 1 ⁇ .
  • the coatings formed from the alloy compositions are characterized as having a relatively uniformly hard microstructure, with precipitates of the same type having particle sizes with standard deviations of less than 25%.
  • the more uniform microstructure allows for a more uniform wear rate across the coating surface.
  • the coatings are subject to slower wear rate compared to coatings of the prior art having larger grain sizes (e.g., 200 nm to 5 ⁇ or from 0.5 - 3 ⁇ ).
  • "large" hard particles > 100 nm
  • Both amorphous metal alloys can be characterized as having hard (>50 R c ) weldments and cast components with compositions comprising a relatively softer matrix with embedded hard particles.
  • the softer matrix [302] is worn away at a much faster rate than the hard [303] particles when the alloy comes into contact with softer secondary bodies [301], exposing the hard particles [303] and effectively forming a rough wear surface [304].
  • Figure IB for an embodiment of a coating of the invention with smaller hard particles [303] microstructure, the smaller hard particles tend to wear away in a smoother profile, limiting the potential for aggressive wear on the softer secondary bodies [301].
  • the alloy may be formed by blending various feedstock materials together, which may then be melted in a hearth or furnace and formed into ingots.
  • the ingots can be re-melted and flipped one or more times, which may increase homogeneity of the ingots.
  • Combinations of powders may be contained in conventional steel sheaths, which when melted may provide the targeted alloy composition.
  • the steel sheaths may include plain carbon steel, low, medium, or high carbon steel, low alloy steel, or stainless steel sheaths.
  • the ingots may then be melted and atomized or otherwise formed into an intermediate or final product.
  • the forming process may occur in a relatively inert
  • Inert gasses may include, for example, argon or helium. If atomized, the alloy may be atomized by centrifugal, gas, or water atomization to produce powders of various sizes, which may be applied to a surface to provide a hard surface.
  • the alloys may be provided in the form of stick, wire, powder, cored wire, etc.
  • the alloys are formed into a stick electrode, e.g., a wire, of various diameters, e.g., 1 - 5 mm.
  • the cored wire may contain flux, which may allow for welding without a cover gas without porosity-forming in the weld deposit.
  • the metal alloys are applied onto a surface using techniques including but not limited to thermal spray coating, weld-overlay, laser cladding, and combinations thereof.
  • the alloys are deposited in the form of wire feedstock employing hardfacing / welding techniques known in the art.
  • the alloys can be applied with mobile or fixed, semi or automatic welding equipment.
  • the alloys are applied using any of laser welding, shielded metal arc welding (SMAW), stick welding, plasma transfer arc welding (PTAW), gas metal arc-welding (GMAW), metal inert gas welding (MIG), submerged arc welding (SAW), or open arc welding (OAW).
  • SMAW shielded metal arc welding
  • PTAW plasma transfer arc welding
  • GMAW gas metal arc-welding
  • MIG metal inert gas welding
  • SAW submerged arc welding
  • OFAW open arc welding
  • the alloy is deposited onto a machined surface or alternatively, a surface blast cleaned to white metal (e.g., ISO 8501-1).
  • a surface blast cleaned to white metal e.g., ISO 8501-1.
  • the depth of the machined surface is grooved for flush type application depends on the welding applicator.
  • the existing hardbanding is first completely removed by gouging, grinding, or using other suitable techniques.
  • the surfaces for deposition are first preheated at a temperature of 275 0 C. or greater, e.g., 275 - 500°C, for 0.01 hours to 100 hours.
  • the preheat may reduce or prevent cracking of the deposited welds.
  • the alloy may be applied to a surface in one or more layers as an overlay.
  • each layer having an individual thickness of 1 mm to 10 mm.
  • the overlay has a total thickness of 1 to 30 mm.
  • the width of the individual hard-band ranges from 5 mm to 40 m. In another embodiment, the width of the total weld overlay ranges from 5 mm to 20 feet.
  • the alloy After deposition on a substrate, the alloy is allowed to cool to form a protective coating.
  • the cooling rate ranges from 100 to 5000 K/s, a rate sufficient for the alloy to produce iron rich phases containing embedded hard particles (e.g., carbides, borides, and / or borocarbides).
  • Grain coarsening is known stage in the growth process of crystals during solidification.
  • the hard phase will begin to nucleate and grow before the matrix phase during the solidification of the alloy.
  • the extended growth period of the hard phases can result in high fraction (e.g., greater than 15%) of larger hard particles in the microstructure.
  • These larger hard particles while beneficially impacting the alloy durability, contribute to additional casing wear in a manner independent of the grain size of the matrix.
  • the growth period of the hard phases in the inventive composition is suppressed or sluggish for a growth mechanism similar to that of ferrite.
  • This causes the growth of both ferrite phase and hard-particle phases to be more closely matched during the solidification, resulting a small fraction of hard particles exceeding 100 nm in size.
  • the ferritic matrix and hard particles in the alloy solidify according to independent mechanisms, resulting in a microstructure consisting of very fine grained hard particles, which are uniformly distributed.
  • This microstructural property imparts uniformity to the micro-hardness of the alloy, which contributes to both enhanced durability and reduced casing wear.
  • the microstructure has a hardness variation of less than 50% as measured using a Vickers indenter between fine grained hard particles and the surrounding matrix in one embodiment; less than 25% in a second embodiment; and less than 15% in a third embodiment.
  • the measured Vickers hardnesses within a cross sectional area of 100 ⁇ x 100 ⁇ in the weld bead have a standard deviation below 250 in one embodiment; less than 150 in a second embodiment; and less than 100 in a third embodiment.
  • a work piece having at least a portion of its surface having a coating or a welded layer of the metal alloy with the fine-grained microstructure is characterized as having a macro-hardness as measured via standard Rockwell C test of greater 50 R C in one embodiment; a macro-hardness in the range of 52-60 R c in a second embodiment; and a hardness of at least 55 R c in a third embodiment.
  • the fine-grained microstructural features in the alloy provide durability and prevent wear on secondary "softer" bodies which come into contact with the work piece protected by the coatings.
  • the component protected by the alloy is characterized as having elevated wear resistance with a dry sand abrasion mass loss (ASTM G65-04 procedure A) of less than 0.5 grams in one embodiment; and less than 0.35 grams in a second embodiment.
  • the elevated wear resistance does not result in significant wear loss on a contacting secondary body, as characterized by a mineral oil metal to metal sliding wear materials loss on the secondary body (modified ASTM G77 wear test) of less than 0.005 grams when the secondary body is a plain carbon steel.
  • the wear loss on a contacting secondary body comprising carbon steel is less than 0.001 g as measured according to modified ASTM G77 wear test.
  • Figure 6A is a diagram illustrating the ASTM G77 wear test and apparatus for use in the modified test to measure material loss on a secondary body.
  • the tool joint material is held against the casing ring at a prescribed side load of 5,000 lb/ft.
  • the tool joint has a weld overlay coating on the contacting surface of the casing, simulating a hardband for oil and gas downhole wear protection.
  • the casing ring is fabricated according to the API Q125 specification and rotates at 197 rpm for 21,600 rotations.
  • the bottom half of the casing is submerged in mineral oil, which is drawn up the surface of the casing ring and acts as lubrication in the test.
  • Mineral oil is used to simulate oil-based drilling muds simulate in the downhole environment. Because it is desired to understand the wear contribution of solely the tool joint and or hardbanding layer on the wear of the casing, oil-based drilling mud is not used to characterize the materials in this modified test. The drilling mud, as it contains sand, would add an additional wear contribution to the casing and affect the accuracy and understanding of the wear mechanism.
  • the coating in one embodiment is suitable for use in hard bodies wear applications.
  • the material loss in coatings is typically caused by abrasive wear of the harder abrading particles.
  • the material loss in this process one should increase the hardness of the coating and / or increasing the amount of comparably hard particles (comparable as related to the abradable particles themselves) or phases within the coating.
  • the alloys contain a sufficient amount of hard particles and display a sufficient hardness property for the protected equipment under these conditions.
  • the coating is also suitable for use in soft bodies wear applications, wherein the coating material wears away against a soft body under conditions of sliding wear.
  • the material loss in the coating is primarily associated with the loss of soft materials due to contact and relative motion with the relatively harder material in the coating.
  • the controlled amount of hard phases in the coating minimizes material losses with the hard materials essentially machining away against the soft body contained within.
  • the alloys are particularly useful for oil & gas applications, e.g., for work pieces employed in subterraneous drilling operations as coating for drill stem assemblies, exposed outer surface of a bottom hole assembly, coatings for tubing coupled to a bottom hole assembly, coatings for casings, hardbanding on at least a portion of the exposed outer surface of the body, and as coatings for oil and gas well production devices as disclosed in US Patent Publication No. 2011/0042069A1, the disclosure is included herein by reference in its entirety. Examples include devices for use in drilling rig equipment, marine riser systems, tubular goods, wellhead, formation and sandface completions, lift equipment, etc. Specific examples include drillpipe tool joints, drill collars, casings, risers, and drill strings.
  • the coating can be on a least a portion of the inner surface of the work piece, at least a portion of the outer surface, or combinations thereof, preventing tool joint wear (due to the high inherent durability) and preventing casing wear (due to the minimal wear caused by these alloys on softer materials).
  • the coatings provide protection in operations with wear from vibration (stick-slip and torsional) and abrasion during straight hole or directional drilling, allowing for improved rates of penetration and enable ultra-extended reach drilling with existing equipment.
  • the tool joint In a tool joint application, the tool joint (intermediate hardness) comes into contact with sand and rock (high hardness) and the casing (low hardness). Under such conditions, the sand and rock wear away creating material loss and damage on the tool joint, whereas the tool joint wears away at the casing creating material loss and damage. The multiple wear interactions reduce the lifetime in the drill pipe (tool joint) and the casing.
  • the metal alloys When used as a protective coating, the metal alloys effectively: a) minimize the loss of coating material caused by the harder abrading particles with an increased hardness of the coating and / or with an increase in the amount of comparably hard particles (comparable as related to the abradable particles themselves) or phases within the coating; and b) minimize the loss of material on the casing (soft coating) due to contact and relative motion with the relatively harder coating material, by limiting the hardness of the coating material of the tool joint with controlled amount of hard phases within the coating, thus decreasing the overall coefficient of friction between the two materials.
  • the alloys can also be used as coatings in may other industries, e.g., drilling, mining, quarrying, processing of minerals, and construction.
  • the alloys are used for structural members in building and bridges.
  • the alloys can also be used for earth moving and dredging equipment and components such as bucket teeth, gravel pump parts, crusher hammers, conveyor chains, gear teeth, and metal to metal sliding parts in the industry.
  • the coating can be applied as raised (“proud”) or flush ("recessed") hardbanding.
  • the coating can be applied on used equipment, e.g., pipe with no previous hardbanding, or to be hardbanded on new work pieces.
  • the coating can be deposited over pre-existing weld deposits, such as tungsten carbide deposits and many other previous hard- facing and hard-banding deposits.
  • the old hardbanding on the equipment is first removed before the application of the alloy.
  • Example 1 An alloy composition of Alloy 1 (Fe - 82.68%, Cr - 5%, Nb - 4.3%, V - 0.5%, C - 0.8%, B - 2.5%, Mo - (3%, Mn - 0.5%, Ti - 0.2%, and Si - 0.5%) was produced in the form of a 1/16" cored wire.
  • the alloy was arc-welded onto a 6 5/8" outer diameter box 4137 alloy tool joint pre-heated to 500°F. The joint was rotated at a rotation rate of one full rotation every 2 min and 30 sec. The welding head was moved through the action of an oscillator, resulting in a weld bead approximately 1" wide and 4/32" thick. Three consecutive beads were made, one next to another to produce three adjacent 1" beads for a total thickness of roughly 3". The joint was allowed to cool to room temperature.
  • Example 2 Example 1 was repeated with a different alloy composition
  • Example 3 A number of samples were constructed out of Alloys 1 - 8 by either welding or casting, and examined for carbide concentration and tested for hardness. The results of the tests are presented in Table 1. [099] Table 1
  • Example 4 A wire was produced from Alloy 1 (Fe - 82.68%, Cr - 5%, Nb - 4.3%, V - 0.5%, C - 0.8%, B - 2.5%, Mo - 3%, Mn - 0.5%, Ti - 0.2%, and Si - 0.5%) and used as feedstock for a hardfacing onto a mild steel A36 substrate using a MIG welding system.
  • a number of overlay samples were prepared from 6 alloy compositions as disclosed in US Patent Publication No. 2011/0068152 as comparables (samples A-F) with the compositions of:
  • B Fe - 83.45 % , Cr - 5 %, , Mn - 1 %, Nb - 4.3 %, V - 0.5 %, C - 0.8%, B - 1.25%, Mo - 3 %, Si - 0.4 %, Ti - 0.3 %;
  • C Fe - 88% , Cr - 3 %, , Mn - 1 %, Nb - 4.3 %, V - 0.5 %, C - 0.8%, B - 1 %, Mo - 2 %, Si - 0.4 %, Ti - 0.3 %;
  • E Fe - 73.11 % , Cr - 5.75 %, , Mn - 0.3 %, Nb - 4.3 %, V - 2.78 %, C - 0.85 %, B - 0.94 %, W - 10.8 %, Si - 0.61 %, Ti - 0.2 %;
  • F Fe - 84 % , Cr - 3 %, Mn - 1 %, Nb - 3 %, V - 1.4 %, C - 0.8 %, B - 1.1 %, W - 5 %, Si - 0.4 %, Ti - 0.3 %.

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Abstract

L'invention concerne un procédé pour protéger à l'aide d'un renforcement une pièce de travail destinée à être utilisée dans des environnements abrasifs. La couche est déposée sur au moins une partie de la pièce à protéger. La couche déposée présente une dureté d'au moins 50 Rc, une vitesse d'usure inférieure à 0,5 gramme de perte de masse tel que mesuré selon la procédure A de la norme ASTM G65 -04, un taux d'usure sur un corps secondaire de contact comportant un acier au carbone inférieur à 0,005 gramme tel que mesuré par le test d'usure selon la norme ASTM G77. L'alliage déposé forme une matrice de fer comprenant des particules dures incorporées dans une quantité inférieure à 15% en volume. Les particules dures incorporées ont une taille moyenne de particule se situant dans la plage allant de 100 nm à 5 µm. Dans un mode de réalisation, le dépôt s'effectue par l'intermédiaire d'un soudage.
PCT/US2013/035481 2012-04-05 2013-04-05 Compositions d'alliage métallique et applications de ceux-ci WO2013152306A1 (fr)

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Publication number Priority date Publication date Assignee Title
US11085102B2 (en) 2011-12-30 2021-08-10 Oerlikon Metco (Us) Inc. Coating compositions
EP3234209A4 (fr) * 2014-12-16 2018-07-18 Scoperta, Inc. Alliages ferreux tenaces et résistants à l'usure contenant de multiples phases dures
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US11253957B2 (en) 2015-09-04 2022-02-22 Oerlikon Metco (Us) Inc. Chromium free and low-chromium wear resistant alloys
US11939646B2 (en) 2018-10-26 2024-03-26 Oerlikon Metco (Us) Inc. Corrosion and wear resistant nickel based alloys
WO2020227099A1 (fr) * 2019-05-03 2020-11-12 Oerlikon Metco (Us) Inc. Charge d'alimentation pulvérulente destinée au soudage en vrac résistant à l'usure, conçue pour optimiser la facilité de production
CN112538590A (zh) * 2019-09-21 2021-03-23 刘波 高耐磨挖掘机斗齿及其铸造方法

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