WO2016014653A1 - Matériaux de rechargement dur sans chrome - Google Patents

Matériaux de rechargement dur sans chrome Download PDF

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Publication number
WO2016014653A1
WO2016014653A1 PCT/US2015/041514 US2015041514W WO2016014653A1 WO 2016014653 A1 WO2016014653 A1 WO 2016014653A1 US 2015041514 W US2015041514 W US 2015041514W WO 2016014653 A1 WO2016014653 A1 WO 2016014653A1
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coating
work piece
manufacture
article
alloy
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PCT/US2015/041514
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English (en)
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Justin Lee Cheney
Tianho JIANG
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Scoperta, Inc.
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Publication of WO2016014653A1 publication Critical patent/WO2016014653A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying

Definitions

  • the disclosure generally relates to hardfacing materials which can be deposited as hardfacing coatings without the production of Cr, such as hexavalent Cr dust.
  • Thermal spray processing is a technique which can be utilized to deposit a hard wear resistant and/or corrosion resistant layer onto the surface of a component.
  • Thermal spray inherently creates a significant amount of dust due to the fact that about 10-40% or more of the feedstock material does not stick to the component of interest and rebounds of the surface in the form a fine metallic dust.
  • One particular class of thermal spray materials which is used to form wear resistant layers is amorphous and/or nanocrystalline materials.
  • Fe-based amorphous and nanocrystalline materials used in thermal spray contain chromium as an alloying element. Chromium is effective in stabilizing the fine-grained structure, can increase wear resistance through the formation of chromium carbides and/or borides, and is useful in providing a degree of corrosion resistance.
  • Chromium is effective in stabilizing the fine-grained structure, can increase wear resistance through the formation of chromium carbides and/or borides, and is useful in providing a degree of corrosion resistance.
  • chromium is considered undesirable for use in thermal spray
  • Fe-based chromium free thermal spray materials There are several Fe-based chromium free thermal spray materials which have been developed and are used by industry today. Currently available Fe-based Cr-free materials have hardness levels below 500 Vickers, as shown in Table 1, which can make them inapplicable for many different industrial uses. Table 1 : Conventional Fe-based Cr-free materials and reported hardness values
  • Thermal spray coatings may be produced having a hardness above 500 Vickers without the use of chromium as an alloying element.
  • Some embodiments are directed to a work piece having a coating on at least a surface, the work piece comprising a metal surface onto which a coating is applied, the coating comprising an Fe-based alloy without any chromium, wherein the alloy comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.
  • the coating can be applied via the twin wire arc spray process.
  • the coating can comprise, in weight percent, B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W: about 0-6, Zr: about 0-10, wherein B + C + Si is about 4-15, and wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.
  • the coating can comprise Fe and, in weight percent, C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to 10. [0010]
  • the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an ElcometerTM thickness gauge or similar device.
  • the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an ElcometerTM thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less.
  • the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less.
  • an article of manufacture comprising a coating which is Fe-based, without chromium, and possesses a melting temperature of 1500K or below and a large atom concentration of at least 5 atom %, large atoms being of the group Mn, Mo, Nb, Ta, Ti, V, W, and Zr.
  • the coating can comprise a Vickers hardness of at least 400 and an adhesion strength of at least 5,000 psi. In some embodiments, the coating can be applied via the twin wire arc spray process.
  • the coating can comprise, in weight percent, B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W: about 0-6, Zr: about 0-10, wherein B + C + Si is about 4-15, and wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.
  • the coating can comprise Fe and, in weight percent, C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to 10.
  • the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an ElcometerTM thickness gauge or similar device. In some embodiments, the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an ElcometerTM thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less. [0017] In some embodiments, the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less.
  • a work piece having at least one surface comprising a coating applied to the at least one surface, the coating comprising an Fe-based alloy having substantially no chromium, having substantially no carbides, and having substantially no borides, wherein the alloy comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.
  • the coating can comprise Fe and, in weight percent, B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W: about 0-6, Zr: about 0-10, wherein B + C + Si is about 4-15, and wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.
  • the coating can comprise Fe and in weight percent, C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to 10.
  • the coating can comprise one or more of the following compositions in weight percent: Fe, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2; or Fe, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.
  • the coating can be non-magnetic and the coating thickness can be accurately measured with an ElcometerTM thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less.
  • the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less.
  • the coating can be applied via a thermal spray process. In some embodiments, the coating can be applied via a twin wire arc spray process. In some embodiments, the work piece can be a yankee dryer. In some embodiments, the work piece can be a roller used in a paper making machine.
  • an article of manufacture comprising an Fe-based coating having substantially no chromium;, wherein the coating possesses a melting temperature of 1500K or below, wherein the coating possesses a large atom concentration of at least 5 atom %, large atoms being of the group consisting of Mn, Mo, Nb, Ta, Ti, V, W, and Zr, and wherein the coating is a primarily single phase finegrained structure of either martensite, ferrite, or austenite.
  • the coating can comprise, in weight percent B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W: about 0-6, Zr: about 0-10, wherein B + C + Si is about 4-15, and wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.
  • the coating can comprise Fe and in weight percent C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to 10.
  • the coating can comprise one or more of the following compositions in weight percent: Fe, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2; or Fe, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.
  • the coating can be non-magnetic and the coating thickness can be accurately measured with an ElcometerTM thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less.
  • the coating can comprise a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.
  • the coating can be applied via the twin wire arc spray process. In some embodiments, the coating can be applied via a thermal spray process.
  • the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less.
  • the coating can be applied onto a roller used in a paper making machine. In some embodiments, the coating can be applied onto a Yankee Dryer. In some embodiments, the coating can be applied onto a boiler tube.
  • a work piece having at least one surface comprising a coating applied to the at least one surface, the coating comprising an Fe-based alloy having less than 1 wt. % chromium, less than 5 vol. % carbides, and less than 5 vol. % borides, wherein the alloy comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.
  • the alloy can have less than 1 vol. % carbides and less than 1 vol. % borides.
  • the alloys can have high hardness and can be used as, for example, coatings.
  • computational metallurgy can be used to explore alloy compositional ranges where an alloy is likely to form an amorphous or nanocrystalline coating without the use of chromium as an alloying element.
  • Fe-based thermal spray coatings with a hardness above 500 Vickers have used chromium as an alloying element.
  • This disclosure demonstrates embodiments of alloy compositions which can produce thermal spray coatings with hardness values above 500 Vickers, in addition to describing the design techniques successfully used to identify them.
  • alloys which can achieve high hardness levels through mechanisms other than the use of chromium or the formation of carbides and/or borides. Rather, in some embodiments, a very fine-grain structure can be achieved due to melting temperature and large atom criteria disclosed herein.
  • the alloy can be described by a composition in weight percent comprising the following elemental ranges at least partially based on the ranges disclosed in Table 2 and Table 3 :
  • B 0-4 (or about 0 to about 4), C: 0-0.25 (or about 0 to about 0.25), and Si: 0-15 (or about 0 to about 15), where B+C+Si is 4-15 (or about 4 to about 15)
  • Mn 0-25 (or about 0 to about 25), Mo: 0-29 (or about 0 to about 29), Nb: 0-2 (or about 0 to about 2), Ta: 0-4 (or about 0 to about 4), Ti: 0-4 (or about 0 to about 4), V: 0-10 (or about 0 to about 10), W: 0-6 (or about 0 to about 6), Zr: 0-10 (about 0 to about 10), where (Mo+Mn+Nb+Ta+Ti+V+W+Zr) is 5-38 (or about 5 to about 38) 0 Cr (or about 0 Cr)
  • an alloy can be designed using any of the large elements as long as the other elemental ratios are controlled properly.
  • Fe has an atomic size of 156pm.
  • a large atom can be an atom that is larger than Fe.
  • These large atoms can be advantageous as they can increase the viscosity of an alloy in liquid form and thus slow down the crystallization rate of the alloy. As the crystallization rate decreases, the probability of forming an amorphous, nanocrystalline, or fine-grained structure can increase.
  • the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 50 nm or less. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 20 nm or less.
  • the alloy can be described by a composition in weight percent comprising the following elemental ranges at least partially based on a range composed form the alloys selected for manufacture into experimental ingots:
  • the alloy can be described by the specific compositions, which have been produced and experimentally demonstrated amorphous formation potential, in weight percent, comprising the following elements.
  • Fe BAL, Mn: 5 (or about 5), Mo: 23 (or about 23), Si: 10 (or about 10)
  • Fe BAL, Mn: 5 (or about 5), Mo: 19 (or about 19), Si: 10 (or about 10)
  • Fe BAL, Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 10 (or about 10) 6.
  • Fe BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Si: 7 (or about 7)
  • Fe BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Ni: 2 (or about 2), Si: 5 (or about 5)
  • Fe BAL, Mn: 19 (or about 19), Mo: 15 (or about 15), Si: 6 (or about 6)
  • Fe BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Ni: 2 (or about 2), Si: 5 (or about 5)
  • aluminum can be further added to the above alloy ranges and chemistries to improve coating adhesion in the range of up to 5 (or about 5) wt.%.
  • Fe BAL, Mn: 5 (or about 5), Mo: 13 (or about 13), Si: 10 (or about 10), Al: 2 (or about 2)
  • Fe BAL, Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 10 (or about 10), Al: 2 (or about 2)
  • the alloy may contain boron, such as between 0-4 wt. % (including 1, 2, and 3 wt. %) as indicated above. In some embodiments, the alloy may not contain any boron. In some embodiments, boron may act as an impurity and does not exceed 1 wt. %.
  • the Fe content identified in the composition above may be the balance of the composition as indicated above, or alternatively, the balance of the composition may comprise Fe and other elements. In some embodiments, the balance may consist essentially of Fe and may include incidental impurities. In some embodiments, the above alloys may not contain any chromium. In some embodiments, chromium may act as an impurity and does not exceed 1 wt. %. Thermodynamic and Kinetic Criteria
  • the alloy can be described by thermodynamic and kinetic criteria.
  • the thermodynamic criteria can relate to the stability of the liquid phase, e.g., the melting temperature of the alloy.
  • the melting temperature can be calculated via thermodynamic models and is defined as the highest temperature at which liquid is less than 100% of the mole fraction in the material.
  • the kinetic criterion can be related to the viscosity of the liquid and the concentration in atom percent of large atoms. Large atoms are defined as atoms which are larger than iron atoms. Either or both criteria can be used to predict the tendency towards amorphous formation in thermal spray materials.
  • the alloys can have a microstructure of ferritic iron.
  • a primarily single phase fine-grained structure of either martensite, ferrite, or austenite can be formed.
  • ⁇ 5% (or ⁇ about 5%) borides and carbides are formed.
  • ⁇ % (or ⁇ about 1%) borides and carbides are formed.
  • ⁇ A% (or ⁇ about .1%) borides and carbides are formed.
  • no borides or carbides are formed.
  • the melting temperature can be below 1500 K (or below about 1500K). In some embodiments, the melting temperature can be below 1450K (or below about 1450K). In some embodiments, the melting temperature can be below 1400K (or below about 1400K). In general, amorphous formation is encouraged with lower melting temperatures because, typically, as grain size decreases, hardness increases (known as the Hall-Petch relationship). Amorphous alloys effectively have zero grain size, and thus can be the hardest form of the alloy. As amorphous formation potential increases, the alloy, even if it doesn't always become amorphous in every process, will tend towards a smaller grain size.
  • amorphous forming alloys of the disclosure even if they form fine-grained or nanocrystalline structures and not actually an amorphous structure, will tend to be harder.
  • the alloy may end up being crystalline, specifically nanocrystalline, upon application, such as through thermal spray, while still achieving the high hardness levels disclosed herein.
  • the large atom atomic fraction can be above 5 atom % (or above about 5 atom %). In some embodiments, the large atom atomic fraction can be above 7.5 atom % (or above about 7.5 atom %). In some embodiments, the large atom atomic fraction can be above 10 atom % (or above about 10 atom %). In some embodiments, the higher large atom atomic fraction can encourage amorphous formation and increase amorphous formation potential.
  • Table 2 lists the alloy compositions, all Fe-based, in weight percent which can meet the thermodynamic criteria detailed in this disclosure.
  • the Fe-based alloys can have a composition that is predominantly iron, e.g., at least 50 wt. % iron.
  • Table 2 List of alloy compositions with thermodynamic and kinetic parameters which meet disclosed criteria. Large atom % is the total atom % of elements larger than iron and melt T is the melting temperature of the alloy.
  • the alloy can possess a low FCC-BCC transition temperature. This criteria can be related to the likelihood of the alloy to retain an austenitic structure when deposited and thus be 'readable' by certain measuring devices, as discussed further below. Readable coatings can be non-magnetic and thus the thickness can be measured with standard paint thickness gauges. This can be advantageous for many thermal spray applications.
  • the alloy can be described by performance criteria.
  • the performance criteria that can be advantageous to the field of thermal spray hardfacing is the hardness, wear resistance, coating adhesion, and corrosion resistance.
  • the Vickers hardness of the coating can be 400 or above (or about 400 or above). In some embodiments, the Vickers hardness of the coating can be 500 or above (or about 500 or above). In some embodiments, the Vickers hardness can be 550 or above (or about 550 or above).In some embodiments, the Vickers hardness can be 600 or above (or about 600 or above).
  • the specific microstructure disclosed herein can allow for embodiments of the alloys to have high hardness.
  • the adhesion strength of the coating can be 5,000 psi or above (or about 5,000 psi or above). In some embodiments, the adhesion strength of the coating can be 7,500 psi or above (or about 7,500 psi or above). In some embodiments, the adhesion strength of the coating can be 10,000 psi or above (or about 10,000 psi or above).
  • the abrasion resistance of the coating as measured via ASTM G65B testing can be 0.8 grams loss or below (or about 0.8 grams loss or below). In some embodiments, the abrasion resistance of the coating as measured via ASTM G65B testing can be 0.6 grams loss or below (or about 0.6 grams loss or below). In some embodiments, the abrasion resistance of the coating as measured via ASTM G65B testing can be 0.4 grams loss or below (or about 0.4 grams loss or below).
  • the adhesive wear resistance of the coating as measured via ASTM G77 testing can be 2 mm 3 volume loss or below (or about 2 mm 3 volume loss or below). In some embodiments, the adhesive wear resistance of the coating as measured via ASTM Gil testing can be 0.5 mm 3 volume loss or below (or about 0.5 mm 3 volume loss or below). In some embodiments, the adhesive wear resistance of the coating as measured via ASTM Gil testing can be 0.1 mm 3 volume loss or below (or about 0.1 mm 3 volume loss or below).
  • the alloy can exhibit similar performance to conventional Cr-bearing thermal spray materials used for hardfacing.
  • the most exemplary and well used thermal spray hardfacing material possesses a chemical composition of Fe: BAL, Cr: 29, Si: 1, Mn: 2, B: 4, which is generally referred to in the industry as Armacor M.
  • Armacor M possesses the following properties which are relevant to thermal spray hardfacing: adhesion of about 8,000 psi, ASTM G65B mass loss of about 0.37 grams, ASTM G77 volume loss of about 0.07 mm , and position in the galvanic series in saltwater of about -500 mV.
  • Armacor M is primarily made of Fe, Cr, and B, has a high melting temperature, and has no large atoms.
  • the alloys can exhibit similar coating adhesion and abrasive wear resistance as Armacor, where 'similar' equates to within 25% (or within about 25%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, and adhesive wear resistance as Armacor, where 'similar' equates to within 25% (or within about 25%) of the measured performance properties of Armacor M or better.
  • the alloys can exhibit similar coating adhesion, abrasive wear resistance, adhesive wear resistance, and corrosion resistance as Armacor, where 'similar' equates to within 25% (or within about 25%) of the measured performance properties of Armacor M or better.
  • the alloys can exhibit similar coating adhesion and abrasive wear resistance as Armacor, where 'similar' equates to within 10% (or within about 10%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, and adhesive wear resistance as Armacor, where 'similar' equates to within 10% (or within about 10%) of the measured performance properties of Armacor M or better.
  • the alloys can exhibit similar coating adhesion, abrasive wear resistance, adhesive wear resistance, and corrosion resistance as Armacor, where 'similar' equates to within 10% (or within about 10%) of the measured performance properties of Armacor M or better.
  • the alloys can exhibit similar coating adhesion and abrasive wear resistance as Armacor, where 'similar' equates to within 1% (or within about 1%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, and adhesive wear resistance as Armacor, where 'similar' equates to within 1% (or within about 1%) of the measured performance properties of Armacor M or better.
  • the alloys can exhibit similar coating adhesion, abrasive wear resistance, adhesive wear resistance, and corrosion resistance as Armacor, where 'similar' equates to within 1% (or within about 1%) of the measured performance properties of Armacor M or better.
  • the alloys can exhibit similar coating adhesion and abrasive wear resistance as Armacor, where 'similar' equates to within 0% (or within about 0%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, and adhesive wear resistance as Armacor, where 'similar' equates to within 0% (or within about 0%) of the measured performance properties of Armacor M or better.
  • the alloys can exhibit similar coating adhesion, abrasive wear resistance, adhesive wear resistance, and corrosion resistance as Armacor, where 'similar' equates to within 0% (or within about 0%) of the measured performance properties of Armacor M or better.
  • the thermal spray coating can be 'readable'.
  • a readable coating produces consistent thickness measurements with an ElcometerTM thickness gauge, or similar device, when properly calibrated.
  • Armacor M is not a readable alloy, unlike embodiments of the disclosure, as it is magnetic.
  • the coating thickness measurement can be accurate to within 5 mils (or within about 5 mils) of the actual physical thickness. In some embodiments, the coating thickness measurement can be accurate to within 3.5 mils (or within about 3.5 mils) of the actual physical thickness. In some embodiments, the coating thickness measurement can be accurate to within 2 mils (or within about 2 mils) of the actual physical thickness.
  • consistent measurements according to the above criteria can be made after the coating has been exposed to heat for an extended period of time.
  • This can be advantageous because when the alloy is heated, there is a potential for a magnetic phase to precipitate out, which would make the alloy non-readable.
  • This can be especially true for amorphous alloys which may be readable in amorphous form, but may crystallize in a different environment due to heat.
  • the alloy can remain non-magnetic even after being exposed to heat for a substantial time period.
  • the coating can be 'readable' after exposure to HOOK (or about HOOK) for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S (or less than about 10K/S).
  • the coating can be 'readable' after exposure to 1300K (or about 1300K) for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S (or less than 10K/S).
  • the coating can be 'readable' after exposure to 1500K (r about 1500K) for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S (or less than about 10K/S). It is expected that increased exposure times above 2 hours will not continue to affect the final 'readability' of these materials.
  • Table 3 List of alloy compositions and thermodynamic and kinetic parameters which meet the criteria described in this disclosure, including the criteria pertained to coating non- magnetism and readability.
  • Large atom % is the total atom % of elements larger than iron, Trans T is the FCC-BCC transition temperature and melt T is the melting temperature of the alloy.

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Abstract

L'invention concerne des modes de réalisation d'alliages à base de Fe destinés à être utilisés en tant que matériau de rechargement dur ayant une dureté élevée tout en évitant l'utilisation de chrome. Les alliages peuvent être pulvérisés à double arc ou thermiquement en tant que revêtements sur différents types d'équipement. Dans certains modes de réalisation, les alliages peuvent être lisibles même après chauffage des alliages.
PCT/US2015/041514 2014-07-24 2015-07-22 Matériaux de rechargement dur sans chrome WO2016014653A1 (fr)

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CA2931842A1 (fr) 2013-11-26 2015-06-04 Scoperta, Inc. Alliage a rechargement dur resistant a la corrosion
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