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US20160024628A1 - Chromium free hardfacing materials - Google Patents

Chromium free hardfacing materials Download PDF

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Publication number
US20160024628A1
US20160024628A1 US14/702,569 US201514702569A US2016024628A1 US 20160024628 A1 US20160024628 A1 US 20160024628A1 US 201514702569 A US201514702569 A US 201514702569A US 2016024628 A1 US2016024628 A1 US 2016024628A1
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coating
work piece
article
manufacture
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US14/702,569
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Justin Lee Cheney
Tianho Jiang
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Scoperta Inc
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Scoperta Inc
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Priority to US14/702,569 priority Critical patent/US20160024628A1/en
Publication of US20160024628A1 publication Critical patent/US20160024628A1/en
Abandoned legal-status Critical Current

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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
    • C23C4/125—
    • 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.
  • 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.
  • 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 10K/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 10K/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.
  • 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 10K/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 fine-grained 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 10K/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:
  • 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 156 pm.
  • 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.
  • 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. %.
  • 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. %.
  • 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.
  • ⁇ 1% (or ⁇ about 1%) borides and carbides are formed.
  • ⁇ 0.1% (or ⁇ about 0.1%) 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).
  • 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.
  • 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 G77 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 G77 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 3 , 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 1100K (or about 1100K) for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S (or less than about 10K/S). In some embodiments, 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). In some embodiments, the coating can be ‘readable’ after exposure to 1500K (or 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.
  • Embodiments of alloys disclosed herein can be used in a variety of applications and industries. Some non-limiting examples of applications of use include:
  • Wear resistant sleeves and/or wear resistant hardfacing for slurry pipelines including wear resistant sleeves and/or wear resistant hardfacing for slurry pipelines, mud pump components including pump housing or impeller or hardfacing for mud pump components, ore feed chute components including chute blocks or hardfacing of chute blocks, separation screens including but not limited to rotary breaker screens, banana screens, and shaker screens, liners for autogenous grinding mills and semi-autogenous grinding mills, ground engaging tools and hardfacing for ground engaging tools, wear plate for buckets and dumptruck liners, heel blocks and hardfacing for heel blocks on mining shovels, grader blades and hardfacing for grader blades, stacker reclaimers, siazer crushers, general wear packages for mining components and other communition components.
  • Upstream oil and gas applications including but not limited to the following components and coatings for the following components: Downhole casing and downhole casing, drill pipe and coatings for drill pipe including hardbanding, mud management components, mud motors, fracking pump sleeves, fracking impellers, fracking blender pumps, stop collars, drill bits and drill bit components, directional drilling equipment and coatings for directional drilling equipment including stabilizers and centralizers, blow out preventers and coatings for blow out preventers and blow out preventer components including the shear rams, oil country tubular goods and coatings for oil country tubular goods.
  • Downstream oil and gas applications including but not limited to the following components and coatings for the following components: Process vessels and coating for process vessels including steam generation equipment, amine vessels, distillation towers, cyclones, catalytic crackers, general refinery piping, corrosion under insulation protection, sulfur recovery units, convection hoods, sour stripper lines, scrubbers, hydrocarbon drums, and other refinery equipment and vessels.
  • Process vessels and coating for process vessels including steam generation equipment, amine vessels, distillation towers, cyclones, catalytic crackers, general refinery piping, corrosion under insulation protection, sulfur recovery units, convection hoods, sour stripper lines, scrubbers, hydrocarbon drums, and other refinery equipment and vessels.
  • Pulp and paper applications including but not limited to the following components and coatings for the following components: Rolls used in paper machines including yankee dryers and other dryers, calendar rolls, machine rolls, press rolls, digesters, pulp mixers, pulpers, pumps, boilers, shredders, tissue machines, roll and bale handling machines, doctor blades, evaporators, pulp mills, head boxes, wire parts, press parts, M.G. cylinders, pope reels, winders, vacuum pumps, deflakers, and other pulp and paper equipment.
  • Power generation applications including but not limited to the following components and coatings for the following components: boiler tubes, precipitators, fireboxes, turbines, generators, cooling towers, condensers, chutes and troughs, augers, bag houses, ducts, ID fans, coal piping, and other power generation components.
  • Agriculture applications including but not limited to the following components and coatings for the following components: chutes, base cutter blades, troughs, primary fan blades, secondary fan blades, augers and other agricultural applications.
  • Construction applications including but not limited to the following components and coatings for the following components: cement chutes, cement piping, bag houses, mixing equipment and other construction applications.
  • Machine element applications including but not limited to the following components and coatings for the following components: Shaft journals, paper rolls, gear boxes, drive rollers, impellers, general reclamation and dimensional restoration applications and other machine element applications.
  • Steel applications including but not limited to the following components and coatings for the following components: cold rolling mills, hot rolling mills, wire rod mills, galvanizing lines, continue pickling lines, continuous casting rolls and other steel mill rolls, and other steel applications.
  • Embodiments of alloys disclosed herein can be produced and or deposited in a variety of techniques effectively. Some non-limiting examples of processes include:
  • Thermal spray process including but not limited to those using a wire feedstock such as twin wire arc, spray, high velocity arc spray, combustion spray and those using a powder feedstock such as high velocity oxygen fuel, high velocity air spray, plasma spray, detonation gun spray, and cold spray.
  • Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire.
  • Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.
  • Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire.
  • Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.
  • Casting processes including but not limited to processes typical to producing cast iron including but not limited to sand casting, permanent mold casting, chill casting, investment casting, lost foam casting, die casting, centrifugal casting, glass casting, slip casting and process typical to producing wrought steel products including continuous casting processes.
  • Post processing techniques including but not limited to but not limited to rolling, forging, surface treatments such as carburizing, nitriding, carbonitriding, heat treatments including but not limited to austenitizing, normalizing, annealing, stress relieving, tempering, aging, quenching, cryogenic treatments, flame hardening, induction hardening, differential hardening, case hardening, decarburization, machining, grinding, cold working, work hardening, and welding.
  • surface treatments such as carburizing, nitriding, carbonitriding, heat treatments including but not limited to austenitizing, normalizing, annealing, stress relieving, tempering, aging, quenching, cryogenic treatments, flame hardening, induction hardening, differential hardening, case hardening, decarburization, machining, grinding, cold working, work hardening, and welding.
  • One of the more applicable uses of this technology is in applications where coatings are deposited on-site, in the field, or in locations where proper ventilation, dust collection, and other safety measures cannot be easily met.
  • Some well-known non-limiting examples of these applications include power generation applications such as the coating of boiler tubes, upstream refinery applications such as the coating of refinery vessels, and pulp and paper applications such as the coating and grinding of yankee dryers.
  • the previously disclosed alloy #4, Fe: BAL, Mn: about 5, Mo: about 13, Si: about 10 was produced in the form of a 40 gram trial ingot to verify hardness and thermal spray vitrification potential.
  • the ingot hardness was measured to be 534 Vickers (converting from a Rockwell C measurement).
  • the microstructure of the ingot showed a fully eutectic structure indicating a strong possibility for amorphous or nanocrystalline structure under the rapid cooling rate of the spray process.
  • This material has been selected for manufacture into 1/16′′ cored thermal spray wire for twin wire arc spray trials after slight modification to the alloy #14, Fe: BAL, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2.
  • alloy #5 Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a 40 gram trial ingot to verify hardness and thermal spray vitrification potential.
  • the ingot hardness was measured to be 534 Vickers (converting from a Rockwell C measurement).
  • the microstructure of the ingot showed a fully eutectic structure indicating a strong possibility for amorphous or nanocrystalline structure under the rapid cooling rate of the spray process.
  • This material has been selected for manufacture into 1/16′′ cored thermal spray wire for twin wire arc spray trials after slight modification to alloy #15, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.
  • the previously disclosed alloy #8, Fe: BAL, C: about 0.25, Mn: about 19, Mo: about 7, Si: about 5 was produced in the form of a 40 gram ingot to verify hardness, thermal spray vetrification potential and magnetic permeability.
  • the alloy candidate is being developed as a ‘readable’ coating which requires the alloy to be non-magnetic in the sprayed form.
  • the ingot hardness was measured to be 300 Vickers (converting from a Rockwell C measurement). While this is below the desired hardness threshold, it is well known by those skilled in the art that the rapid cooling process achieved in thermal spray will increase the hardness of the alloy in this form. Thus, it is not unreasonable to expect an increase in hardness in the sprayed form up to the desired level of 400 Vickers.
  • the relative magnetic permeability was measured via a Low-Mu Magnetic Permeability Tester and was determined to be less than 1.01, well below the threshold required to ensure ‘readability’.
  • the previously disclosed alloy #5, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a cored thermal spray wire. This alloy was sprayed using the twin wire arc spray technique, specifically using the parameters shown in
  • Table 3 A series of tests were run to evaluate the alloys performance in reference to standard Cr-bearing thermal spray materials used for hardfacing.
  • the specific alloy of reference is known by the commercial names, Armacor M, TAFA 95MXC, PMet 273, etc. and has an alloy composition of about Fe: BAL, Cr: 29, Si: 1, Mn: 2, B: 4.
  • Table 2 highlights the result of the testing.
  • Alloy #5 has comparable adhesion and abrasion resistance as measure via ASTM G65B testing.
  • alloy #4, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a cored thermal spray wire. This alloy was sprayed using the twin wire arc spray technique using the parameters shown in
  • Alloy #4 replicates the key performance criteria of Armacor M in all key criteria.
  • Alloy #4 represents an exemplary embodiment of this disclosure, additional testing was performed in order to compare other performance criteria specifically as it relates to the coating of yankee dryers, a specific article of manufacture used in paper machines. This testing including corrosion testing, grinding studies, spray characteristics, thorough metallographic evaluation, and evaluation of surface properties as related to surface tension. In all cases, alloy #4 was deemed to have similar or better performance than the Armacor M coating.
  • Corrosion testing was conducted by exposing the coating to saltwater and measuring the voltage against a reference bare steel plate, which could be then used to place the material on the Galvanic Series. Both the Armacor M and Alloy #4 coatings showed significant rust on the coating surface after the 2 week test exposure.
  • the position of the Armacor M coating on the galvanic series is ⁇ 450 to ⁇ 567 and the position of Alloy #4 is ⁇ 510 to ⁇ 640.
  • Increasingly negative values reflect more active potentials, which is less desirable as it indicates reduced corrosion resistance. This represents a ‘similarity’ in that the quantified performance does not vary by more than 25%.
  • the coating In the Yankee dryer application it is desirable for the coating to be hydrophilic, which enables the adsorption of water based organic compounds used in paper making into the surface.
  • the contact angle that a water droplet makes on the surface can be used to quantify the surface tension of the material.
  • the Armacor M water droplet formed a 63.9° angle
  • Alloy #4 formed a 41.5° angle.
  • a smaller angle indicates increased hydrophillicity, which is advantageous because in Yankee dryer applications, a monoammonium phosphate (MAP) water-based solution is typically sprayed onto the coating for paper release properties. It can be advantageous for this water-based solution to immerse itself into the coating structure and stick well to the coating surface, which can be enhanced by having a hydrophilic coating.
  • MAP monoammonium phosphate
  • the above recited ranges can be specific ranges, and not within a particular % of the value. For example, within less than or equal to 10 wt./vol. % of, within less than or equal to 5 wt./vol. % of, within less than or equal to 1 wt./vol. % of, within less than or equal to 0.1 wt./vol. % of, and within less than or equal to 0.01 wt./vol. % of the stated amount.

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Abstract

Disclosed are embodiments of Fe-based alloys for use as a hardfacing material having high hardness while avoiding the use of chromium. The alloys can be twin arc or thermally sprayed as coatings on different types of equipment. In some embodiments, the alloys can be readable even after heating of the alloys.

Description

    INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS
  • Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet as filed with the present application are hereby incorporated by reference under 37 CFR 1.57.
    • BACKGROUND
  • 1. Field
  • The disclosure generally relates to hardfacing materials which can be deposited as hardfacing coatings without the production of Cr, such as hexavalent Cr dust.
  • 2. Description of the Related Art
  • 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. However, chromium is considered undesirable for use in thermal spray applications due to the potential to form hexavalent chromium dust. Hexavalent chromium dust is known to cause cancer.
  • 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
    Alloy Hardness
    30T 97-100 FMB (~250 Vickers)
    38T 23 HRC (~250 Vickers)
    39T 34-47 HRC (~330-470 Vickers)
    35 MXC 30-35 HRC (~290-330 Vickers)
  • There have also been efforts to specifically design Cr-free hardfacing materials for welding processes, such as that shown in 2012/0097658. However, the alloys disclosed in the reference require the formation of borides and carbides. Further, the reference requires the use of boron.
    • SUMMARY
  • Disclosed herein are embodiments of alloy compositions used to produce thermal spray coatings, methods of identifying these compositions, the coatings themselves, and methods of making and using the coatings. Thermal spray coatings according to certain embodiments 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.
  • In some embodiments, the coating can be applied via the twin wire arc spray process.
  • In some embodiments, 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.
  • In some embodiments, 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.
  • In some embodiments, the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an Elcometer™ 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 Elcometer™ 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 10K/s or less.
  • 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.
  • Also disclosed herein are embodiments of 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.
  • In some embodiments, 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.
  • In some embodiments, 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.
  • In some embodiments, 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.
  • In some embodiments, the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an Elcometer™ 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 Elcometer™ 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 10K/s or less.
  • 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.
  • Disclosed herein are embodiments of a work piece having at least one surface, the work piece 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.
  • In some embodiments, 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. In some embodiments, 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. In some embodiments, 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.
  • In some embodiments, the coating can be non-magnetic and the coating thickness can be accurately measured with an Elcometer™ 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 10K/s or less.
  • 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.
  • In some embodiments, 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.
  • Also disclosed herein are embodiments of 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 fine-grained structure of either martensite, ferrite, or austenite.
  • In some embodiments, 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.
  • In some embodiments, 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.
  • In some embodiments, 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.
  • In some embodiments, the coating can be non-magnetic and the coating thickness can be accurately measured with an Elcometer™ 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 10K/s or less. In some embodiments, the coating can comprise a Vickers hardness of at least 500 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. In some embodiments, the coating can be applied via a thermal spray process.
  • 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.
  • In some embodiments, 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.
  • Also disclosed herein are embodiments of a work piece having at least one surface, the work piece 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. In some embodiments, the alloy can have less than 1 vol. % carbides and less than 1 vol. % borides.
    • DETAILED DESCRIPTION
  • Disclosed herein are embodiments of chromium free, iron based alloys, and methods of manufacturing the alloys. In some embodiments, the alloys can have high hardness and can be used as, for example, coatings. In some embodiments, 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. Prior to this disclosure, 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.
  • Specifically, disclosed herein are embodiments of 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.
    • Metal Alloy Composition
  • In some embodiments, 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:
      • Fe: BAL
      • 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)
  • Generally, embodiments of an alloy can be designed using any of the large elements as long as the other elemental ratios are controlled properly. The following atomic sizes, in picometers, were used for the large elements, large atoms defined as atoms which are larger than iron atoms: Mn: 161, Mo: 190, Nb, 198, Ta: 200, Ti: 176, V: 171, W: 193, Zr: 206. Fe has an atomic size of 156 pm. 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.
  • 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. 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.
  • In some embodiments, 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:
      • Fe: BAL, C: 0-0.25 (or about 0 to about 0.25), Mn: 5-19 (or about 5 to about 19), Mo: 7-23 (or about 7 to about 23), Ni: 0-4 (or about 0 to about 4), Si: 5-10 (or about 5 to about 10)
  • In some embodiments, 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.
      • 1. Fe: BAL, Mn: 5 (or about 5), Mo: 23 (or about 23), Si: 10 (or about 10)
      • 2. Fe: BAL, Mn: 5 (or about 5), Mo: 19 (or about 19), Si: 10 (or about 10)
      • 3. Fe: BAL, Mn: 5 (or about 5), Mo: 11 (or about 11), Si: 10 (or about 10)
      • 4. Fe: BAL, Mn: 5 (or about 5), Mo: 13 (or about 13), Si: 10 (or about 10)
      • 5. Fe: BAL, Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 10 (or about 10)
      • 6. Fe: BAL, Al: 2 (or about 2), Mn: 5 (or about 5), Mo: 5 (or about 5), Si: 13 (or about 13)
      • 7. Fe: BAL, Al: 2 (or about 2), Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 15 (or about 15)
      • 8. Fe: BAL, C: 0.25 (or about 0.25), Mn: 19 (or about 19), Mo: 7 (or about 7), Si: (5 or about 5)
      • 9. Fe: BAL, C: 0.25 (or about 0.25), Mn: 5 (or about 5), Mo: 7 (or about 7), Ni: (4 or about 4), Si: 5 (or about 5)
      • 10. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Si: 7 (or about 7)
      • 11. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Ni: 2 (or about 2), Si: 5 (or about 5)
      • 12. Fe: BAL, Mn: 19 (or about 19), Mo: 15 (or about 15), Si: 6 (or about 6)
      • 13. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Ni: 2 (or about 2), Si: 5 (or about 5)
  • In some embodiments, 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. %. Some exemplary examples of aluminum additions, based upon the #4 and #5 base chemistries, are:
      • 14. Fe: BAL, Mn: 5 (or about 5), Mo: 13 (or about 13), Si: 10 (or about 10), Al: 2 (or about 2)
      • 15. Fe: BAL, Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 10 (or about 10), Al: 2 (or about 2)
  • In some embodiments, 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
  • In some embodiments, the alloy can be described by thermodynamic and kinetic criteria. In some embodiments, 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. In some embodiments, the alloys can have a microstructure of ferritic iron. In some embodiments, a primarily single phase fine-grained structure of either martensite, ferrite, or austenite can be formed. In some embodiments, <5% (or <about 5%) borides and carbides are formed. In some embodiments, <1% (or <about 1%) borides and carbides are formed. In some embodiments, <0.1% (or <about 0.1%) borides and carbides are formed. In some embodiments, no borides or carbides are formed.
  • In some embodiments, 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. Thus, 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. For example, in some embodiments, while there is the potential for an amorphous structure, 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.
  • In some embodiments, 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. In some embodiments, the Fe-based alloys can have a composition that is predominantly iron, e.g., at least 50 wt. % iron.
  • Combining the alloys in Table 2 and Table 3 yields 1,141 compositions which meet the criteria. These alloys were compiled through computational searching tools which evaluated 16,362 alloys according to the disclosed criteria. Thus, the alloys disclosed cover only 6.9% of the total explored space explicitly investigated to design an alloy with the disclosed performance parameters.
  • 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.
    Large Melt
    No B Mn Mo Nb Si Ta Ti V W Zr Atom % T
    M1 0 0 10 1 10 0 0 0 0 0 6.1% 1500
    M2 0 0 15 1 9 0 0 0 0 0 9.1% 1500
    M3 0 0 15 1 10 0 0 0 0 0 9.0% 1500
    M4 0 0 20 0 7 0 0 0 0 0 11.8% 1500
    M5 0 0 20 0 8 0 0 0 0 0 11.7% 1500
    M6 0 0 20 0 9 0 0 0 0 0 11.6% 1450
    M7 0 0 20 0 10 0 0 0 0 0 11.5% 1450
    M8 0 0 20 1 7 0 0 0 0 0 12.5% 1500
    M9 0 0 20 1 8 0 0 0 0 0 12.3% 1500
    M10 0 0 20 1 9 0 0 0 0 0 12.2% 1500
    M11 0 0 20 1 10 0 0 0 0 0 12.1% 1500
    M12 0 1 10 0 10 0 0 0 0 0 6.5% 1500
    M13 0 1 10 1 10 0 0 0 0 0 7.1% 1500
    M14 0 1 15 1 8 0 0 0 0 0 10.2% 1500
    M15 0 1 15 1 9 0 0 0 0 0 10.1% 1500
    M16 0 1 15 1 10 0 0 0 0 0 10.0% 1450
    M17 0 1 20 0 7 0 0 0 0 0 12.8% 1500
    M18 0 1 20 0 8 0 0 0 0 0 12.7% 1500
    M19 0 1 20 0 9 0 0 0 0 0 12.6% 1450
    M20 0 1 20 0 10 0 0 0 0 0 12.5% 1450
    M21 0 1 20 1 7 0 0 0 0 0 13.5% 1500
    M22 0 1 20 1 8 0 0 0 0 0 13.4% 1450
    M23 0 1 20 1 9 0 0 0 0 0 13.2% 1500
    M24 0 1 20 1 10 0 0 0 0 0 13.1% 1500
    M25 0 2 10 0 10 0 0 0 0 0 7.4% 1500
    M26 0 2 10 1 9 0 0 0 0 0 8.1% 1500
    M27 0 2 10 1 10 0 0 0 0 0 8.0% 1500
    M28 0 2 15 1 8 0 0 0 0 0 11.2% 1500
    M29 0 2 15 1 9 0 0 0 0 0 11.1% 1500
    M30 0 2 15 1 10 0 0 0 0 0 11.0% 1450
    M31 0 2 20 0 7 0 0 0 0 0 13.9% 1500
    M32 0 2 20 0 8 0 0 0 0 0 13.7% 1450
    M33 0 2 20 0 9 0 0 0 0 0 13.6% 1450
    M34 0 2 20 0 10 0 0 0 0 0 13.5% 1400
    M35 0 2 20 1 6 0 0 0 0 0 14.7% 1500
    M36 0 2 20 1 7 0 0 0 0 0 14.5% 1500
    M37 0 2 20 1 8 0 0 0 0 0 14.4% 1450
    M38 0 2 20 1 9 0 0 0 0 0 14.2% 1500
    M39 0 2 20 1 10 0 0 0 0 0 14.1% 1500
    M40 0 3 10 0 9 0 0 0 0 0 8.5% 1500
    M41 0 3 10 0 10 0 0 0 0 0 8.4% 1500
    M42 0 3 10 1 9 0 0 0 0 0 9.1% 1500
    M43 0 3 10 1 10 0 0 0 0 0 9.0% 1500
    M44 0 3 15 1 7 0 0 0 0 0 12.3% 1500
    M45 0 3 15 1 8 0 0 0 0 0 12.2% 1500
    M46 0 3 15 1 9 0 0 0 0 0 12.1% 1450
    M47 0 3 15 1 10 0 0 0 0 0 12.0% 1500
    M48 0 3 20 0 6 0 0 0 0 0 15.0% 1500
    M49 0 3 20 0 8 0 0 0 0 0 14.7% 1450
    M50 0 3 20 1 6 0 0 0 0 0 15.7% 1500
    M51 0 3 20 1 8 0 0 0 0 0 15.4% 1450
    M52 0 3 20 1 10 0 0 0 0 0 15.1% 1500
    M53 0 4 5 1 10 0 0 0 0 0 7.1% 1500
    M54 0 4 10 0 9 0 0 0 0 0 9.4% 1500
    M55 0 4 10 0 10 0 0 0 0 0 9.3% 1500
    M56 0 4 10 1 8 0 0 0 0 0 10.1% 1500
    M57 0 4 10 1 9 0 0 0 0 0 10.0% 1500
    M58 0 4 10 1 10 0 0 0 0 0 10.0% 1500
    M59 0 4 15 1 7 0 0 0 0 0 13.4% 1500
    M60 0 4 15 1 8 0 0 0 0 0 13.2% 1500
    M61 0 4 15 1 9 0 0 0 0 0 13.1% 1450
    M62 0 4 15 1 10 0 0 0 0 0 13.0% 1500
    M63 0 4 15 2 6 0 0 0 0 0 14.1% 1500
    M64 0 4 20 0 6 0 0 0 0 0 16.1% 1500
    M65 0 4 20 0 7 0 0 0 0 0 15.9% 1450
    M66 0 4 20 0 8 0 0 0 0 0 15.8% 1450
    M67 0 4 20 0 9 0 0 0 0 0 15.6% 1400
    M68 0 4 20 0 10 0 0 0 0 0 15.5% 1400
    M69 0 4 20 1 5 0 0 0 0 0 16.9% 1500
    M70 0 4 20 1 6 0 0 0 0 0 16.8% 1500
    M71 0 4 20 1 7 0 0 0 0 0 16.6% 1450
    M72 0 4 20 1 8 0 0 0 0 0 16.4% 1450
    M73 0 4 20 1 9 0 0 0 0 0 16.3% 1500
    M74 0 4 20 1 10 0 0 0 0 0 16.1% 1500
    M75 0 4 20 2 5 0 0 0 0 0 17.6% 1500
    M76 0 5 5 1 10 0 0 0 0 0 8.0% 1500
    M77 0 5 10 0 8 0 0 0 0 0 10.5% 1500
    M78 0 5 10 0 9 0 0 0 0 0 10.4% 1500
    M79 0 5 10 0 10 0 0 0 0 0 10.3% 1500
    M80 0 5 10 1 8 0 0 0 0 0 11.1% 1500
    M81 0 5 10 1 9 0 0 0 0 0 11.0% 1500
    M82 0 5 10 1 10 0 0 0 0 0 10.9% 1450
    M83 0 5 15 1 6 0 0 0 0 0 14.5% 1500
    M84 0 5 15 1 7 0 0 0 0 0 14.4% 1500
    M85 0 5 15 1 8 0 0 0 0 0 14.2% 1450
    M86 0 5 15 1 9 0 0 0 0 0 14.1% 1450
    M87 0 5 15 1 10 0 0 0 0 0 14.0% 1500
    M88 0 5 15 2 6 0 0 0 0 0 15.2% 1500
    M89 0 5 20 0 5 0 0 0 0 0 17.3% 1500
    M90 0 5 20 0 6 0 0 0 0 0 17.1% 1500
    M91 0 5 20 0 7 0 0 0 0 0 17.0% 1450
    M92 0 5 20 0 8 0 0 0 0 0 16.8% 1450
    M93 0 5 20 0 9 0 0 0 0 0 16.6% 1400
    M94 0 5 20 0 10 0 0 0 0 0 16.5% 1400
    M95 0 5 20 1 5 0 0 0 0 0 18.0% 1500
    M96 0 5 20 1 6 0 0 0 0 0 17.8% 1500
    M97 0 5 20 1 7 0 0 0 0 0 17.6% 1450
    M98 0 5 20 1 8 0 0 0 0 0 17.5% 1500
    M99 0 5 20 1 9 0 0 0 0 0 17.3% 1500
    M100 0 5 20 1 10 0 0 0 0 0 17.1% 1500
    M101 0 5 20 2 5 0 0 0 0 0 18.7% 1500
    M102 4 0 0 0 0 0 0 2 0 6 5.1% 1350
    M103 4 0 0 0 0 0 0 2 2 6 5.7% 1400
    M104 4 0 0 0 0 0 0 2 4 4 5.2% 1500
    M105 4 0 0 0 0 0 0 2 4 6 6.3% 1450
    M106 4 0 0 0 0 0 0 4 0 4 5.9% 1350
    M107 4 0 0 0 0 0 0 4 0 6 7.0% 1350
    M108 4 0 0 0 0 0 0 4 2 2 5.4% 1400
    M109 4 0 0 0 0 0 0 4 2 4 6.5% 1400
    M110 4 0 0 0 0 0 0 4 2 6 7.6% 1350
    M111 4 0 0 0 0 0 0 4 4 2 6.0% 1450
    M112 4 0 0 0 0 0 0 4 4 4 7.1% 1450
    M113 4 0 0 0 0 0 0 4 4 6 8.3% 1450
    M114 4 0 0 0 0 0 0 6 0 0 5.6% 1350
    M115 4 0 0 0 0 0 0 6 0 2 6.7% 1350
    M116 4 0 0 0 0 0 0 6 0 4 7.8% 1350
    M117 4 0 0 0 0 0 0 6 0 6 8.9% 1400
    M118 4 0 0 0 0 0 0 6 2 0 6.2% 1400
    M119 4 0 0 0 0 0 0 6 2 2 7.3% 1400
    M120 4 0 0 0 0 0 0 6 2 4 8.4% 1350
    M121 4 0 0 0 0 0 0 6 2 6 9.6% 1400
    M122 4 0 0 0 0 0 0 6 4 0 6.8% 1450
    M123 4 0 0 0 0 0 0 6 4 2 7.9% 1450
    M124 4 0 0 0 0 0 0 6 4 4 9.1% 1450
    M125 4 0 0 0 0 0 0 6 4 6 10.2% 1450
    M126 4 0 0 0 0 0 0 6 6 0 7.4% 1500
    M127 4 0 0 0 0 0 0 6 6 2 8.6% 1500
    M128 4 0 0 0 0 0 0 6 6 4 9.7% 1500
    M129 4 0 0 0 0 0 0 6 6 6 10.9% 1500
    M130 4 0 0 0 0 0 0 6 6 8 12.1% 1500
    M131 4 0 0 0 0 0 0 6 6 10 13.3% 1500
    M132 4 0 0 0 0 0 0 8 6 6 12.9% 1500
    M133 4 0 0 0 0 0 0 8 6 8 14.1% 1500
    M134 4 0 0 0 0 0 0 8 6 10 15.3% 1500
    M135 4 0 0 0 0 0 0 10 6 6 14.8% 1500
    M136 4 0 0 0 0 0 0 10 6 8 16.0% 1500
    M137 4 0 0 0 0 0 0 10 6 10 17.3% 1500
    M138 0 3 20 0 10 0 0 0 0 0 14.5% 1400
    M139 0 3 20 0 10 0 0 0 0 2 15.8% 1350
    M140 0 3 20 0 10 0 0 0 0 4 17.1% 1350
    M141 0 3 20 0 10 0 0 0 2 0 15.3% 1400
    M142 0 3 20 0 10 0 0 0 2 2 16.6% 1400
    M143 0 3 20 0 10 0 0 0 2 4 18.0% 1400
    M144 0 3 20 0 10 0 0 0 4 0 16.1% 1450
    M145 0 3 20 0 10 0 0 0 4 2 17.5% 1450
    M146 0 3 20 0 10 0 0 0 4 4 18.9% 1450
    M147 0 3 20 0 10 0 0 2 0 0 16.6% 1400
    M148 0 3 20 0 10 0 0 2 0 2 17.9% 1350
    M149 0 3 20 0 10 0 0 2 0 4 19.3% 1350
    M150 0 3 20 0 10 0 0 2 2 0 17.4% 1400
    M151 0 3 20 0 10 0 0 2 2 2 18.8% 1400
    M152 0 3 20 0 10 0 0 2 2 4 20.2% 1400
    M153 0 3 20 0 10 0 0 2 4 0 18.3% 1450
    M154 0 3 20 0 10 0 0 2 4 2 19.7% 1450
    M155 0 3 20 0 10 0 0 2 4 4 21.1% 1450
    M156 0 3 20 0 10 0 0 4 0 0 18.7% 1400
    M157 0 3 20 0 10 0 0 4 0 2 20.1% 1350
    M158 0 3 20 0 10 0 0 4 0 4 21.4% 1350
    M159 0 3 20 0 10 0 0 4 2 0 19.6% 1400
    M160 0 3 20 0 10 0 0 4 2 2 20.9% 1400
    M161 0 3 20 0 10 0 0 4 2 4 22.4% 1400
    M162 0 3 20 0 10 0 0 4 4 0 20.5% 1450
    M163 0 3 20 0 10 0 0 4 4 2 21.9% 1450
    M164 0 3 20 0 10 0 0 4 4 4 23.3% 1450
    M165 0 3 20 0 10 0 2 0 0 0 16.7% 1400
    M166 0 3 20 0 10 0 2 0 0 2 18.0% 1350
    M167 0 3 20 0 10 0 2 0 0 4 19.4% 1350
    M168 0 3 20 0 10 0 2 0 2 0 17.5% 1450
    M169 0 3 20 0 10 0 2 0 2 2 18.9% 1450
    M170 0 3 20 0 10 0 2 0 2 4 20.3% 1450
    M171 0 3 20 0 10 0 2 0 4 0 18.4% 1500
    M172 0 3 20 0 10 0 2 0 4 2 19.8% 1500
    M173 0 3 20 0 10 0 2 0 4 4 21.2% 1500
    M174 0 3 20 0 10 0 2 2 0 0 18.8% 1400
    M175 0 3 20 0 10 0 2 2 0 2 20.2% 1350
    M176 0 3 20 0 10 0 2 2 0 4 21.5% 1350
    M177 0 3 20 0 10 0 2 2 2 0 19.7% 1450
    M178 0 3 20 0 10 0 2 2 2 2 21.1% 1450
    M179 0 3 20 0 10 0 2 2 2 4 22.5% 1450
    M180 0 3 20 0 10 0 2 2 4 0 20.6% 1500
    M181 0 3 20 0 10 0 2 2 4 2 22.0% 1500
    M182 0 3 20 0 10 0 2 2 4 4 23.4% 1500
    M183 0 3 20 0 10 0 2 4 0 0 20.9% 1400
    M184 0 3 20 0 10 0 2 4 0 2 22.3% 1350
    M185 0 3 20 0 10 0 2 4 0 4 23.7% 1350
    M186 0 3 20 0 10 0 2 4 2 0 21.8% 1450
    M187 0 3 20 0 10 0 2 4 2 2 23.2% 1450
    M188 0 3 20 0 10 0 2 4 2 4 24.6% 1400
    M189 0 3 20 0 10 0 2 4 4 0 22.7% 1450
    M190 0 3 20 0 10 0 2 4 4 2 24.2% 1450
    M191 0 3 20 0 10 0 2 4 4 4 25.6% 1450
    M192 0 3 20 0 10 0 4 0 0 0 18.9% 1400
    M193 0 3 20 0 10 0 4 0 0 2 20.3% 1400
    M194 0 3 20 0 10 0 4 0 0 4 21.7% 1400
    M195 0 3 20 0 10 0 4 0 2 0 19.8% 1450
    M196 0 3 20 0 10 0 4 0 2 2 21.2% 1450
    M197 0 3 20 0 10 0 4 0 2 4 22.6% 1450
    M198 0 3 20 0 10 0 4 0 4 0 20.7% 1500
    M199 0 3 20 0 10 0 4 0 4 2 22.1% 1500
    M200 0 3 20 0 10 0 4 0 4 4 23.5% 1500
    M201 0 3 20 0 10 0 4 2 0 0 21.0% 1400
    M202 0 3 20 0 10 0 4 2 0 2 22.4% 1400
    M203 0 3 20 0 10 0 4 2 0 4 23.8% 1400
    M204 0 3 20 0 10 0 4 2 2 0 21.9% 1450
    M205 0 3 20 0 10 0 4 2 2 2 23.3% 1450
    M206 0 3 20 0 10 0 4 2 2 4 24.7% 1450
    M207 0 3 20 0 10 0 4 2 4 0 22.8% 1500
    M208 0 3 20 0 10 0 4 2 4 2 24.3% 1500
    M209 0 3 20 0 10 0 4 2 4 4 25.7% 1500
    M210 0 3 20 0 10 0 4 4 0 0 23.1% 1400
    M211 0 3 20 0 10 0 4 4 0 2 24.5% 1400
    M212 0 3 20 0 10 0 4 4 0 4 25.9% 1400
    M213 0 3 20 0 10 0 4 4 2 0 24.1% 1450
    M214 0 3 20 0 10 0 4 4 2 2 25.5% 1450
    M215 0 3 20 0 10 0 4 4 2 4 26.9% 1450
    M216 0 3 20 0 10 0 4 4 4 0 25.0% 1500
    M217 0 3 20 0 10 0 4 4 4 2 26.4% 1500
    M218 0 3 20 0 10 0 4 4 4 4 27.9% 1500
    M219 0 3 20 0 10 2 0 0 0 0 15.3% 1400
    M220 0 3 20 0 10 2 0 0 0 2 16.6% 1350
    M221 0 3 20 0 10 2 0 0 0 4 18.0% 1350
    M222 0 3 20 0 10 2 0 0 2 0 16.1% 1400
    M223 0 3 20 0 10 2 0 0 2 2 17.5% 1400
    M224 0 3 20 0 10 2 0 0 2 4 18.9% 1400
    M225 0 3 20 0 10 2 0 0 4 0 17.0% 1450
    M226 0 3 20 0 10 2 0 0 4 2 18.4% 1500
    M227 0 3 20 0 10 2 0 0 4 4 19.8% 1500
    M228 0 3 20 0 10 2 0 2 0 0 17.4% 1400
    M229 0 3 20 0 10 2 0 2 0 2 18.8% 1350
    M230 0 3 20 0 10 2 0 2 0 4 20.2% 1350
    M231 0 3 20 0 10 2 0 2 2 0 18.3% 1400
    M232 0 3 20 0 10 2 0 2 2 2 19.7% 1400
    M233 0 3 20 0 10 2 0 2 2 4 21.1% 1400
    M234 0 3 20 0 10 2 0 2 4 0 19.2% 1450
    M235 0 3 20 0 10 2 0 2 4 2 20.6% 1450
    M236 0 3 20 0 10 2 0 2 4 4 22.0% 1450
    M237 0 3 20 0 10 2 0 4 0 0 19.6% 1400
    M238 0 3 20 0 10 2 0 4 0 2 21.0% 1350
    M239 0 3 20 0 10 2 0 4 0 4 22.4% 1350
    M240 0 3 20 0 10 2 0 4 2 0 20.5% 1400
    M241 0 3 20 0 10 2 0 4 2 2 21.9% 1400
    M242 0 3 20 0 10 2 0 4 2 4 23.3% 1400
    M243 0 3 20 0 10 2 0 4 4 0 21.4% 1450
    M244 0 3 20 0 10 2 0 4 4 2 22.8% 1450
    M245 0 3 20 0 10 2 0 4 4 4 24.3% 1450
    M246 0 3 20 0 10 2 2 0 0 0 17.5% 1350
    M247 0 3 20 0 10 2 2 0 0 2 18.9% 1350
    M248 0 3 20 0 10 2 2 0 0 4 20.3% 1350
    M249 0 3 20 0 10 2 2 0 2 0 18.4% 1450
    M250 0 3 20 0 10 2 2 0 2 2 19.8% 1450
    M251 0 3 20 0 10 2 2 0 2 4 21.2% 1450
    M252 0 3 20 0 10 2 2 0 4 0 19.3% 1500
    M253 0 3 20 0 10 2 2 0 4 2 20.7% 1500
    M254 0 3 20 0 10 2 2 0 4 4 22.1% 1500
    M255 0 3 20 0 10 2 2 2 0 0 19.7% 1350
    M256 0 3 20 0 10 2 2 2 0 2 21.1% 1350
    M257 0 3 20 0 10 2 2 2 0 4 22.5% 1350
    M258 0 3 20 0 10 2 2 2 2 0 20.6% 1450
    M259 0 3 20 0 10 2 2 2 2 2 22.0% 1450
    M260 0 3 20 0 10 2 2 2 2 4 23.4% 1450
    M261 0 3 20 0 10 2 2 2 4 0 21.5% 1500
    M262 0 3 20 0 10 2 2 2 4 2 22.9% 1500
    M263 0 3 20 0 10 2 2 2 4 4 24.4% 1500
    M264 0 3 20 0 10 2 2 4 0 0 21.8% 1350
    M265 0 3 20 0 10 2 2 4 0 2 23.2% 1350
    M266 0 3 20 0 10 2 2 4 0 4 24.6% 1350
    M267 0 3 20 0 10 2 2 4 2 0 22.7% 1450
    M268 0 3 20 0 10 2 2 4 2 2 24.2% 1450
    M269 0 3 20 0 10 2 2 4 2 4 25.6% 1450
    M270 0 3 20 0 10 2 2 4 4 0 23.7% 1500
    M271 0 3 20 0 10 2 2 4 4 2 25.1% 1500
    M272 0 3 20 0 10 2 2 4 4 4 26.6% 1450
    M273 0 3 20 0 10 2 4 0 0 0 19.8% 1400
    M274 0 3 20 0 10 2 4 0 0 2 21.2% 1400
    M275 0 3 20 0 10 2 4 0 0 4 22.6% 1400
    M276 0 3 20 0 10 2 4 0 2 0 20.7% 1450
    M277 0 3 20 0 10 2 4 0 2 2 22.1% 1450
    M278 0 3 20 0 10 2 4 0 2 4 23.5% 1450
    M279 0 3 20 0 10 2 4 0 4 0 21.6% 1500
    M280 0 3 20 0 10 2 4 0 4 2 23.0% 1500
    M281 0 3 20 0 10 2 4 0 4 4 24.5% 1500
    M282 0 3 20 0 10 2 4 2 0 0 21.9% 1400
    M283 0 3 20 0 10 2 4 2 0 2 23.3% 1400
    M284 0 3 20 0 10 2 4 2 0 4 24.7% 1400
    M285 0 3 20 0 10 2 4 2 2 0 22.9% 1450
    M286 0 3 20 0 10 2 4 2 2 2 24.3% 1450
    M287 0 3 20 0 10 2 4 2 2 4 25.7% 1450
    M288 0 3 20 0 10 2 4 2 4 0 23.8% 1500
    M289 0 3 20 0 10 2 4 2 4 2 25.2% 1500
    M290 0 3 20 0 10 2 4 2 4 4 26.7% 1500
    M291 0 3 20 0 10 2 4 4 0 0 24.1% 1400
    M292 0 3 20 0 10 2 4 4 0 2 25.5% 1400
    M293 0 3 20 0 10 2 4 4 0 4 26.9% 1400
    M294 0 3 20 0 10 2 4 4 2 0 25.0% 1450
    M295 0 3 20 0 10 2 4 4 2 2 26.4% 1450
    M296 0 3 20 0 10 2 4 4 2 4 27.9% 1450
    M297 0 3 20 0 10 2 4 4 4 0 26.0% 1500
    M298 0 3 20 0 10 2 4 4 4 2 27.4% 1500
    M299 0 3 20 0 10 2 4 4 4 4 28.9% 1500
    M300 0 3 20 0 10 4 0 0 0 0 16.1% 1350
    M301 0 3 20 0 10 4 0 0 0 2 17.5% 1350
    M302 0 3 20 0 10 4 0 0 0 4 18.9% 1350
    M303 0 3 20 0 10 4 0 0 2 0 17.0% 1400
    M304 0 3 20 0 10 4 0 0 2 2 18.4% 1400
    M305 0 3 20 0 10 4 0 0 2 4 19.8% 1450
    M306 0 3 20 0 10 4 0 0 4 0 17.8% 1500
    M307 0 3 20 0 10 4 0 0 4 2 19.3% 1500
    M308 0 3 20 0 10 4 0 0 4 4 20.7% 1500
    M309 0 3 20 0 10 4 0 2 0 0 18.3% 1350
    M310 0 3 20 0 10 4 0 2 0 2 19.7% 1350
    M311 0 3 20 0 10 4 0 2 0 4 21.1% 1350
    M312 0 3 20 0 10 4 0 2 2 0 19.2% 1400
    M313 0 3 20 0 10 4 0 2 2 2 20.6% 1400
    M314 0 3 20 0 10 4 0 2 2 4 22.0% 1400
    M315 0 3 20 0 10 4 0 2 4 0 20.1% 1450
    M316 0 3 20 0 10 4 0 2 4 2 21.5% 1450
    M317 0 3 20 0 10 4 0 2 4 4 23.0% 1450
    M318 0 3 20 0 10 4 0 4 0 0 20.5% 1350
    M319 0 3 20 0 10 4 0 4 0 2 21.9% 1350
    M320 0 3 20 0 10 4 0 4 0 4 23.3% 1350
    M321 0 3 20 0 10 4 0 4 2 0 21.4% 1400
    M322 0 3 20 0 10 4 0 4 2 2 22.8% 1400
    M323 0 3 20 0 10 4 0 4 2 4 24.3% 1400
    M324 0 3 20 0 10 4 0 4 4 0 22.3% 1450
    M325 0 3 20 0 10 4 0 4 4 2 23.8% 1450
    M326 0 3 20 0 10 4 0 4 4 4 25.3% 1450
    M327 0 3 20 0 10 4 2 0 0 0 18.4% 1350
    M328 0 3 20 0 10 4 2 0 0 2 19.8% 1400
    M329 0 3 20 0 10 4 2 0 0 4 21.2% 1400
    M330 0 3 20 0 10 4 2 0 2 0 19.3% 1450
    M331 0 3 20 0 10 4 2 0 2 2 20.7% 1450
    M332 0 3 20 0 10 4 2 0 2 4 22.2% 1450
    M333 0 3 20 0 10 4 2 0 4 0 20.2% 1500
    M334 0 3 20 0 10 4 2 0 4 2 21.7% 1500
    M335 0 3 20 0 10 4 2 0 4 4 23.1% 1500
    M336 0 3 20 0 10 4 2 2 0 0 20.6% 1350
    M337 0 3 20 0 10 4 2 2 0 2 22.0% 1350
    M338 0 3 20 0 10 4 2 2 0 4 23.4% 1350
    M339 0 3 20 0 10 4 2 2 2 0 21.5% 1450
    M340 0 3 20 0 10 4 2 2 2 2 22.9% 1450
    M341 0 3 20 0 10 4 2 2 2 4 24.4% 1450
    M342 0 3 20 0 10 4 2 2 4 0 22.4% 1500
    M343 0 3 20 0 10 4 2 2 4 2 23.9% 1500
    M344 0 3 20 0 10 4 2 2 4 4 25.4% 1500
    M345 0 3 20 0 10 4 2 4 0 0 22.7% 1350
    M346 0 3 20 0 10 4 2 4 0 2 24.2% 1350
    M347 0 3 20 0 10 4 2 4 0 4 25.6% 1350
    M348 0 3 20 0 10 4 2 4 2 0 23.7% 1450
    M349 0 3 20 0 10 4 2 4 2 2 25.1% 1450
    M350 0 3 20 0 10 4 2 4 2 4 26.6% 1450
    M351 0 3 20 0 10 4 2 4 4 0 24.7% 1500
    M352 0 3 20 0 10 4 2 4 4 2 26.1% 1500
    M353 0 3 20 0 10 4 2 4 4 4 27.6% 1450
    M354 0 3 20 0 10 4 4 0 0 0 20.7% 1400
    M355 0 3 20 0 10 4 4 0 0 2 22.1% 1400
    M356 0 3 20 0 10 4 4 0 0 4 23.5% 1400
    M357 0 3 20 0 10 4 4 0 2 0 21.6% 1500
    M358 0 3 20 0 10 4 4 0 2 2 23.0% 1500
    M359 0 3 20 0 10 4 4 0 2 4 24.5% 1450
    M360 0 3 20 0 10 4 4 0 4 2 24.0% 1500
    M361 0 3 20 0 10 4 4 0 4 4 25.5% 1500
    M362 0 3 20 0 10 4 4 2 0 0 22.9% 1400
    M363 0 3 20 0 10 4 4 2 0 2 24.3% 1400
    M364 0 3 20 0 10 4 4 2 0 4 25.7% 1400
    M365 0 3 20 0 10 4 4 2 2 0 23.8% 1450
    M366 0 3 20 0 10 4 4 2 2 2 25.2% 1450
    M367 0 3 20 0 10 4 4 2 2 4 26.7% 1450
    M368 0 3 20 0 10 4 4 2 4 0 24.8% 1500
    M369 0 3 20 0 10 4 4 2 4 2 26.2% 1500
    M370 0 3 20 0 10 4 4 2 4 4 27.7% 1500
    M371 0 3 20 0 10 4 4 4 0 0 25.0% 1400
    M372 0 3 20 0 10 4 4 4 0 2 26.4% 1400
    M373 0 3 20 0 10 4 4 4 0 4 27.9% 1400
    M374 0 3 20 0 10 4 4 4 2 0 26.0% 1450
    M375 0 3 20 0 10 4 4 4 2 2 27.4% 1450
    M376 0 3 20 0 10 4 4 4 2 4 28.9% 1450
    M377 0 3 20 0 10 4 4 4 4 0 27.0% 1500
    M378 0 3 20 0 10 4 4 4 4 2 28.5% 1500
    M379 0 3 20 0 7 0 0 0 0 0 14.9% 1500
    M380 0 3 20 0 9 0 0 0 0 0 14.6% 1450
    M381 0 3 20 0 11 0 0 0 0 0 14.3% 1400
    M382 0 3 20 0 13 0 0 0 0 0 14.1% 1400
    M383 0 3 20 0 15 0 0 0 0 0 13.8% 1450
    M384 0 3 20 1 7 0 0 0 0 0 15.6% 1450
    M385 0 3 20 1 9 0 0 0 0 0 15.3% 1500
    M386 0 3 20 1 11 0 0 0 0 0 15.0% 1500
    M387 0 3 20 2 5 0 0 0 0 0 16.6% 1500
    M388 0 0 11 0 10 0 0 0 0 0 6.1% 1500
    M389 0 0 13 0 10 0 0 0 0 0 7.2% 1500
    M390 0 0 15 0 9 0 0 0 0 0 8.5% 1500
    M391 0 0 15 0 10 0 0 0 0 0 8.4% 1500
    M392 0 0 17 0 8 0 0 0 0 0 9.8% 1500
    M393 0 0 17 0 9 0 0 0 0 0 9.7% 1500
    M394 0 0 17 0 10 0 0 0 0 0 9.6% 1450
    M395 0 0 19 0 8 0 0 0 0 0 11.1% 1500
    M396 0 0 19 0 9 0 0 0 0 0 11.0% 1500
    M397 0 0 19 0 10 0 0 0 0 0 10.8% 1450
    M398 0 0 21 0 7 0 0 0 0 0 12.5% 1500
    M399 0 0 21 0 8 0 0 0 0 0 12.3% 1500
    M400 0 0 21 0 9 0 0 0 0 0 12.2% 1450
    M401 0 0 21 0 10 0 0 0 0 0 12.1% 1450
    M402 0 0 23 0 7 0 0 0 0 0 13.8% 1500
    M403 0 0 23 0 8 0 0 0 0 0 13.6% 1450
    M404 0 0 23 0 9 0 0 0 0 0 13.5% 1450
    M405 0 0 23 0 10 0 0 0 0 0 13.3% 1400
    M406 0 0 25 0 6 0 0 0 0 0 15.2% 1500
    M407 0 0 25 0 7 0 0 0 0 0 15.1% 1500
    M408 0 0 25 0 8 0 0 0 0 0 14.9% 1450
    M409 0 0 25 0 9 0 0 0 0 0 14.8% 1400
    M410 0 0 25 0 10 0 0 0 0 0 14.6% 1400
    M411 0 0 27 0 6 0 0 0 0 0 16.6% 1500
    M412 0 0 27 0 7 0 0 0 0 0 16.4% 1450
    M413 0 0 27 0 8 0 0 0 0 0 16.3% 1450
    M414 0 0 27 0 9 0 0 0 0 0 16.1% 1400
    M415 0 0 27 0 10 0 0 0 0 0 15.9% 1400
    M416 0 0 29 0 5 0 0 0 0 0 18.2% 1500
    M417 0 0 29 0 6 0 0 0 0 0 18.0% 1500
    M418 0 0 29 0 7 0 0 0 0 0 17.8% 1450
    M419 0 0 29 0 8 0 0 0 0 0 17.6% 1400
    M420 0 0 29 0 9 0 0 0 0 0 17.4% 1400
    M421 0 0 29 0 10 0 0 0 0 0 17.3% 1400
    M422 0 1 11 0 10 0 0 0 0 0 7.0% 1500
    M423 0 1 13 0 9 0 0 0 0 0 8.3% 1500
    M424 0 1 13 0 10 0 0 0 0 0 8.2% 1500
    M425 0 1 15 0 9 0 0 0 0 0 9.5% 1500
    M426 0 1 15 0 10 0 0 0 0 0 9.4% 1500
    M427 0 1 17 0 8 0 0 0 0 0 10.8% 1500
    M428 0 1 17 0 9 0 0 0 0 0 10.7% 1500
    M429 0 1 17 0 10 0 0 0 0 0 10.6% 1450
    M430 0 1 19 0 7 0 0 0 0 0 12.2% 1500
    M431 0 1 19 0 8 0 0 0 0 0 12.1% 1500
    M432 0 1 19 0 9 0 0 0 0 0 12.0% 1450
    M433 0 1 19 0 10 0 0 0 0 0 11.8% 1450
    M434 0 1 21 0 7 0 0 0 0 0 13.5% 1500
    M435 0 1 21 0 8 0 0 0 0 0 13.4% 1450
    M436 0 1 21 0 9 0 0 0 0 0 13.2% 1450
    M437 0 1 21 0 10 0 0 0 0 0 13.1% 1400
    M438 0 1 23 0 6 0 0 0 0 0 14.9% 1500
    M439 0 1 23 0 7 0 0 0 0 0 14.8% 1500
    M440 0 1 23 0 8 0 0 0 0 0 14.6% 1450
    M441 0 1 23 0 9 0 0 0 0 0 14.5% 1450
    M442 0 1 23 0 10 0 0 0 0 0 14.4% 1400
    M443 0 1 25 0 6 0 0 0 0 0 16.3% 1500
    M444 0 1 25 0 7 0 0 0 0 0 16.1% 1450
    M445 0 1 25 0 8 0 0 0 0 0 16.0% 1450
    M446 0 1 25 0 9 0 0 0 0 0 15.8% 1400
    M447 0 1 25 0 10 0 0 0 0 0 15.7% 1400
    M448 0 1 27 0 5 0 0 0 0 0 17.9% 1500
    M449 0 1 27 0 6 0 0 0 0 0 17.7% 1500
    M450 0 1 27 0 7 0 0 0 0 0 17.5% 1450
    M451 0 1 27 0 8 0 0 0 0 0 17.3% 1400
    M452 0 1 27 0 9 0 0 0 0 0 17.1% 1400
    M453 0 1 27 0 10 0 0 0 0 0 17.0% 1400
    M454 0 1 29 0 5 0 0 0 0 0 19.3% 1500
    M455 0 1 29 0 6 0 0 0 0 0 19.1% 1450
    M456 0 1 29 0 7 0 0 0 0 0 18.9% 1450
    M457 0 1 29 0 8 0 0 0 0 0 18.7% 1400
    M458 0 1 29 0 9 0 0 0 0 0 18.5% 1400
    M459 0 1 29 0 10 0 0 0 0 0 18.3% 1400
    M460 0 2 9 0 10 0 0 0 0 0 6.8% 1500
    M461 0 2 11 0 9 0 0 0 0 0 8.1% 1500
    M462 0 2 11 0 10 0 0 0 0 0 8.0% 1500
    M463 0 2 13 0 9 0 0 0 0 0 9.3% 1500
    M464 0 2 13 0 10 0 0 0 0 0 9.2% 1500
    M465 0 2 15 0 8 0 0 0 0 0 10.6% 1500
    M466 0 2 15 0 9 0 0 0 0 0 10.5% 1500
    M467 0 2 15 0 10 0 0 0 0 0 10.4% 1450
    M468 0 2 17 0 7 0 0 0 0 0 11.9% 1500
    M469 0 2 17 0 8 0 0 0 0 0 11.8% 1500
    M470 0 2 17 0 9 0 0 0 0 0 11.7% 1450
    M471 0 2 17 0 10 0 0 0 0 0 11.6% 1450
    M472 0 2 19 0 7 0 0 0 0 0 13.2% 1500
    M473 0 2 19 0 8 0 0 0 0 0 13.1% 1500
    M474 0 2 19 0 9 0 0 0 0 0 13.0% 1450
    M475 0 2 19 0 10 0 0 0 0 0 12.8% 1450
    M476 0 2 21 0 6 0 0 0 0 0 14.7% 1500
    M477 0 2 21 0 7 0 0 0 0 0 14.5% 1500
    M478 0 2 21 0 8 0 0 0 0 0 14.4% 1450
    M479 0 2 21 0 9 0 0 0 0 0 14.2% 1450
    M480 0 2 21 0 10 0 0 0 0 0 14.1% 1400
    M481 0 2 23 0 6 0 0 0 0 0 16.0% 1500
    M482 0 2 23 0 7 0 0 0 0 0 15.8% 1450
    M483 0 2 23 0 8 0 0 0 0 0 15.7% 1450
    M484 0 2 23 0 9 0 0 0 0 0 15.5% 1400
    M485 0 2 23 0 10 0 0 0 0 0 15.4% 1400
    M486 0 2 25 0 5 0 0 0 0 0 17.5% 1500
    M487 0 2 25 0 6 0 0 0 0 0 17.4% 1500
    M488 0 2 25 0 7 0 0 0 0 0 17.2% 1450
    M489 0 2 25 0 8 0 0 0 0 0 17.0% 1400
    M490 0 2 25 0 9 0 0 0 0 0 16.8% 1400
    M491 0 2 25 0 10 0 0 0 0 0 16.7% 1350
    M492 0 2 27 0 5 0 0 0 0 0 18.9% 1500
    M493 0 2 27 0 6 0 0 0 0 0 18.7% 1450
    M494 0 2 27 0 7 0 0 0 0 0 18.6% 1450
    M495 0 2 27 0 8 0 0 0 0 0 18.4% 1400
    M496 0 2 27 0 9 0 0 0 0 0 18.2% 1400
    M497 0 2 27 0 10 0 0 0 0 0 18.0% 1400
    M498 0 2 29 0 5 0 0 0 0 0 20.4% 1500
    M499 0 2 29 0 6 0 0 0 0 0 20.2% 1450
    M500 0 2 29 0 7 0 0 0 0 0 19.9% 1400
    M501 0 2 29 0 8 0 0 0 0 0 19.7% 1400
    M502 0 2 29 0 9 0 0 0 0 0 19.5% 1400
    M503 0 2 29 0 10 0 0 0 0 0 19.3% 1400
    M504 0 3 7 0 10 0 0 0 0 0 6.7% 1500
    M505 0 3 9 0 10 0 0 0 0 0 7.8% 1500
    M506 0 3 11 0 9 0 0 0 0 0 9.1% 1500
    M507 0 3 11 0 10 0 0 0 0 0 9.0% 1500
    M508 0 3 13 0 8 0 0 0 0 0 10.4% 1500
    M509 0 3 13 0 9 0 0 0 0 0 10.3% 1500
    M510 0 3 13 0 10 0 0 0 0 0 10.2% 1450
    M511 0 3 15 0 8 0 0 0 0 0 11.6% 1500
    M512 0 3 15 0 9 0 0 0 0 0 11.5% 1500
    M513 0 3 15 0 10 0 0 0 0 0 11.4% 1450
    M514 0 3 17 0 7 0 0 0 0 0 13.0% 1500
    M515 0 3 17 0 8 0 0 0 0 0 12.8% 1500
    M516 0 3 17 0 9 0 0 0 0 0 12.7% 1450
    M517 0 3 17 0 10 0 0 0 0 0 12.6% 1450
    M518 0 3 19 0 6 0 0 0 0 0 14.4% 1500
    M519 0 3 19 0 7 0 0 0 0 0 14.2% 1500
    M520 0 3 19 0 8 0 0 0 0 0 14.1% 1450
    M521 0 3 19 0 9 0 0 0 0 0 14.0% 1450
    M522 0 3 19 0 10 0 0 0 0 0 13.8% 1400
    M523 0 3 21 0 6 0 0 0 0 0 15.7% 1500
    M524 0 3 21 0 7 0 0 0 0 0 15.6% 1500
    M525 0 3 21 0 8 0 0 0 0 0 15.4% 1450
    M526 0 3 21 0 9 0 0 0 0 0 15.2% 1400
    M527 0 3 21 0 10 0 0 0 0 0 15.1% 1400
    M528 0 3 23 0 5 0 0 0 0 0 17.2% 1500
    M529 0 3 23 0 6 0 0 0 0 0 17.1% 1500
    M530 0 3 23 0 7 0 0 0 0 0 16.9% 1450
    M531 0 3 23 0 8 0 0 0 0 0 16.7% 1450
    M532 0 3 23 0 9 0 0 0 0 0 16.5% 1400
    M533 0 3 23 0 10 0 0 0 0 0 16.4% 1400
    M534 0 3 25 0 5 0 0 0 0 0 18.6% 1500
    M535 0 3 25 0 6 0 0 0 0 0 18.4% 1450
    M536 0 3 25 0 7 0 0 0 0 0 18.2% 1450
    M537 0 3 25 0 8 0 0 0 0 0 18.0% 1400
    M538 0 3 25 0 9 0 0 0 0 0 17.9% 1400
    M539 0 3 25 0 10 0 0 0 0 0 17.7% 1350
    M540 0 3 27 0 5 0 0 0 0 0 20.0% 1500
    M541 0 3 27 0 6 0 0 0 0 0 19.8% 1450
    M542 0 3 27 0 7 0 0 0 0 0 19.6% 1400
    M543 0 3 27 0 8 0 0 0 0 0 19.4% 1400
    M544 0 3 27 0 9 0 0 0 0 0 19.2% 1350
    M545 0 3 27 0 10 0 0 0 0 0 19.0% 1400
    M546 0 3 29 0 4 0 0 0 0 0 21.7% 1500
    M547 0 3 29 0 5 0 0 0 0 0 21.5% 1500
    M548 0 3 29 0 6 0 0 0 0 0 21.2% 1450
    M549 0 3 29 0 7 0 0 0 0 0 21.0% 1400
    M550 0 3 29 0 8 0 0 0 0 0 20.8% 1400
    M551 0 3 29 0 9 0 0 0 0 0 20.6% 1400
    M552 0 3 29 0 10 0 0 0 0 0 20.4% 1400
    M553 0 4 7 0 10 0 0 0 0 0 7.6% 1500
    M554 0 4 9 0 9 0 0 0 0 0 8.8% 1500
    M555 0 4 9 0 10 0 0 0 0 0 8.8% 1500
    M556 0 4 11 0 9 0 0 0 0 0 10.0% 1500
    M557 0 4 11 0 10 0 0 0 0 0 9.9% 1500
    M558 0 4 13 0 8 0 0 0 0 0 11.3% 1500
    M559 0 4 13 0 9 0 0 0 0 0 11.2% 1500
    M560 0 4 13 0 10 0 0 0 0 0 11.1% 1450
    M561 0 4 15 0 7 0 0 0 0 0 12.7% 1500
    M562 0 4 15 0 8 0 0 0 0 0 12.6% 1500
    M563 0 4 15 0 9 0 0 0 0 0 12.5% 1450
    M564 0 4 15 0 10 0 0 0 0 0 12.3% 1450
    M565 0 4 17 0 7 0 0 0 0 0 14.0% 1500
    M566 0 4 17 0 8 0 0 0 0 0 13.8% 1450
    M567 0 4 17 0 9 0 0 0 0 0 13.7% 1450
    M568 0 4 17 0 10 0 0 0 0 0 13.6% 1400
    M569 0 4 19 0 6 0 0 0 0 0 15.4% 1500
    M570 0 4 19 0 7 0 0 0 0 0 15.3% 1500
    M571 0 4 19 0 8 0 0 0 0 0 15.1% 1450
    M572 0 4 19 0 9 0 0 0 0 0 15.0% 1450
    M573 0 4 19 0 10 0 0 0 0 0 14.8% 1400
    M574 0 4 21 0 6 0 0 0 0 0 16.8% 1500
    M575 0 4 21 0 7 0 0 0 0 0 16.6% 1450
    M576 0 4 21 0 8 0 0 0 0 0 16.4% 1450
    M577 0 4 21 0 9 0 0 0 0 0 16.3% 1400
    M578 0 4 21 0 10 0 0 0 0 0 16.1% 1400
    M579 0 4 23 0 5 0 0 0 0 0 18.3% 1500
    M580 0 4 23 0 6 0 0 0 0 0 18.1% 1500
    M581 0 4 23 0 7 0 0 0 0 0 17.9% 1450
    M582 0 4 23 0 8 0 0 0 0 0 17.7% 1400
    M583 0 4 23 0 9 0 0 0 0 0 17.6% 1400
    M584 0 4 23 0 10 0 0 0 0 0 17.4% 1350
    M585 0 4 25 0 5 0 0 0 0 0 19.7% 1500
    M586 0 4 25 0 6 0 0 0 0 0 19.5% 1450
    M587 0 4 25 0 7 0 0 0 0 0 19.3% 1450
    M588 0 4 25 0 8 0 0 0 0 0 19.1% 1400
    M589 0 4 25 0 9 0 0 0 0 0 18.9% 1350
    M590 0 4 25 0 10 0 0 0 0 0 18.7% 1350
    M591 0 4 27 0 4 0 0 0 0 0 21.3% 1500
    M592 0 4 27 0 5 0 0 0 0 0 21.1% 1500
    M593 0 4 27 0 6 0 0 0 0 0 20.9% 1450
    M594 0 4 27 0 7 0 0 0 0 0 20.7% 1400
    M595 0 4 27 0 8 0 0 0 0 0 20.5% 1400
    M596 0 4 27 0 9 0 0 0 0 0 20.2% 1350
    M597 0 4 27 0 10 0 0 0 0 0 20.0% 1400
    M598 0 4 29 0 4 0 0 0 0 0 22.8% 1500
    M599 0 4 29 0 5 0 0 0 0 0 22.5% 1450
    M600 0 4 29 0 6 0 0 0 0 0 22.3% 1450
    M601 0 4 29 0 7 0 0 0 0 0 22.1% 1400
    M602 0 4 29 0 8 0 0 0 0 0 21.8% 1400
    M603 0 4 29 0 9 0 0 0 0 0 21.6% 1400
    M604 0 4 29 0 10 0 0 0 0 0 21.4% 1400
    M605 0 5 5 0 10 0 0 0 0 0 7.4% 1500
    M606 0 5 7 0 10 0 0 0 0 0 8.6% 1500
    M607 0 5 9 0 9 0 0 0 0 0 9.8% 1500
    M608 0 5 9 0 10 0 0 0 0 0 9.7% 1500
    M609 0 5 11 0 8 0 0 0 0 0 11.1% 1500
    M610 0 5 11 0 9 0 0 0 0 0 11.0% 1500
    M611 0 5 11 0 10 0 0 0 0 0 10.9% 1450
    M612 0 5 13 0 7 0 0 0 0 0 12.5% 1500
    M613 0 5 13 0 8 0 0 0 0 0 12.3% 1500
    M614 0 5 13 0 9 0 0 0 0 0 12.2% 1450
    M615 0 5 13 0 10 0 0 0 0 0 12.1% 1450
    M616 0 5 15 0 7 0 0 0 0 0 13.7% 1500
    M617 0 5 15 0 8 0 0 0 0 0 13.6% 1500
    M618 0 5 15 0 9 0 0 0 0 0 13.4% 1450
    M619 0 5 15 0 10 0 0 0 0 0 13.3% 1450
    M620 0 5 17 0 6 0 0 0 0 0 15.1% 1500
    M621 0 5 17 0 7 0 0 0 0 0 15.0% 1500
    M622 0 5 17 0 8 0 0 0 0 0 14.8% 1450
    M623 0 5 17 0 9 0 0 0 0 0 14.7% 1450
    M624 0 5 17 0 10 0 0 0 0 0 14.6% 1400
    M625 0 5 19 0 6 0 0 0 0 0 16.5% 1500
    M626 0 5 19 0 7 0 0 0 0 0 16.3% 1450
    M627 0 5 19 0 8 0 0 0 0 0 16.1% 1450
    M628 0 5 19 0 9 0 0 0 0 0 16.0% 1400
    M629 0 5 19 0 10 0 0 0 0 0 15.8% 1400
    M630 0 5 21 0 5 0 0 0 0 0 18.0% 1500
    M631 0 5 21 0 6 0 0 0 0 0 17.8% 1500
    M632 0 5 21 0 7 0 0 0 0 0 17.6% 1450
    M633 0 5 21 0 8 0 0 0 0 0 17.4% 1450
    M634 0 5 21 0 9 0 0 0 0 0 17.3% 1400
    M635 0 5 21 0 10 0 0 0 0 0 17.1% 1400
    M636 0 5 23 0 5 0 0 0 0 0 19.4% 1500
    M637 0 5 23 0 6 0 0 0 0 0 19.2% 1450
    M638 0 5 23 0 7 0 0 0 0 0 19.0% 1450
    M639 0 5 23 0 8 0 0 0 0 0 18.8% 1400
    M640 0 5 23 0 9 0 0 0 0 0 18.6% 1400
    M641 0 5 23 0 10 0 0 0 0 0 18.4% 1350
    M642 0 5 25 0 4 0 0 0 0 0 21.0% 1500
    M643 0 5 25 0 5 0 0 0 0 0 20.8% 1500
    M644 0 5 25 0 6 0 0 0 0 0 20.5% 1450
    M645 0 5 25 0 7 0 0 0 0 0 20.3% 1400
    M646 0 5 25 0 8 0 0 0 0 0 20.1% 1400
    M647 0 5 25 0 9 0 0 0 0 0 19.9% 1350
    M648 0 5 25 0 10 0 0 0 0 0 19.7% 1350
    M649 0 5 27 0 4 0 0 0 0 0 22.4% 1500
    M650 0 5 27 0 5 0 0 0 0 0 22.2% 1450
    M651 0 5 27 0 6 0 0 0 0 0 22.0% 1450
    M652 0 5 27 0 7 0 0 0 0 0 21.7% 1400
    M653 0 5 27 0 8 0 0 0 0 0 21.5% 1350
    M654 0 5 27 0 9 0 0 0 0 0 21.3% 1350
    M655 0 5 27 0 10 0 0 0 0 0 21.1% 1400
    M656 0 5 29 0 4 0 0 0 0 0 23.9% 1500
    M657 0 5 29 0 5 0 0 0 0 0 23.6% 1450
    M658 0 5 29 0 6 0 0 0 0 0 23.4% 1400
    M659 0 5 29 0 7 0 0 0 0 0 23.1% 1400
    M660 0 5 29 0 8 0 0 0 0 0 22.9% 1400
    M661 0 5 29 0 9 0 0 0 0 0 22.7% 1400
    M662 0 5 29 0 10 0 0 0 0 0 22.4% 1400
    M663 0 5 5 0 10 1 1 1 1 1 10.8% 1450
    M664 0 5 5 0 10 0 0 0 1 0 7.7% 1500
    M665 0 5 5 0 10 0 0 0 2 0 8.1% 1500
    M666 0 5 5 0 10 0 0 0 3 0 8.4% 1500
    M667 0 5 5 0 10 0 0 0 4 0 8.8% 1500
    M668 0 5 5 0 10 0 0 1 0 0 8.4% 1500
    M669 0 5 5 0 10 0 0 1 1 0 8.8% 1500
    M670 0 5 5 0 10 0 0 1 2 0 9.1% 1500
    M671 0 5 5 0 10 0 0 1 3 0 9.4% 1500
    M672 0 5 5 0 10 0 0 1 4 0 9.8% 1500
    M673 0 5 5 0 10 0 0 2 0 0 9.4% 1500
    M674 0 5 5 0 10 0 0 2 1 0 9.8% 1500
    M675 0 5 5 0 10 0 0 2 2 0 10.1% 1500
    M676 0 5 5 0 10 0 0 2 3 0 10.5% 1500
    M677 0 5 5 0 10 0 0 2 4 0 10.8% 1500
    M678 0 5 5 0 10 0 0 3 0 0 10.4% 1500
    M679 0 5 5 0 10 0 0 3 1 0 10.8% 1500
    M680 0 5 5 0 10 0 0 3 2 0 11.1% 1500
    M681 0 5 5 0 10 0 0 3 3 0 11.5% 1500
    M682 0 5 5 0 10 0 0 3 4 0 11.9% 1500
    M683 0 5 5 0 10 0 0 4 0 0 11.4% 1500
    M684 0 5 5 0 10 0 0 4 1 0 11.8% 1500
    M685 0 5 5 0 10 0 0 4 2 0 12.2% 1500
    M686 0 5 5 0 10 0 0 4 3 0 12.5% 1500
    M687 0 5 5 0 10 0 0 4 4 0 12.9% 1500
    M688 0 5 5 0 10 0 1 0 0 0 8.5% 1500
    M689 0 5 5 0 10 0 1 0 1 0 8.8% 1500
    M690 0 5 5 0 10 0 1 0 2 0 9.2% 1500
    M691 0 5 5 0 10 0 1 0 3 0 9.5% 1500
    M692 0 5 5 0 10 0 1 0 4 0 9.9% 1500
    M693 0 5 5 0 10 0 1 1 0 0 9.5% 1500
    M694 0 5 5 0 10 0 1 1 1 0 9.8% 1500
    M695 0 5 5 0 10 0 1 1 2 0 10.2% 1500
    M696 0 5 5 0 10 0 1 1 3 0 10.5% 1500
    M697 0 5 5 0 10 0 1 1 4 0 10.9% 1500
    M698 0 5 5 0 10 0 1 2 0 0 10.5% 1500
    M699 0 5 5 0 10 0 1 2 1 0 10.8% 1500
    M700 0 5 5 0 10 0 1 2 2 0 11.2% 1500
    M701 0 5 5 0 10 0 1 2 3 0 11.6% 1500
    M702 0 5 5 0 10 0 1 2 4 0 11.9% 1500
    M703 0 5 5 0 10 0 1 3 0 0 11.5% 1500
    M704 0 5 5 0 10 0 1 3 1 0 11.8% 1500
    M705 0 5 5 0 10 0 1 3 2 0 12.2% 1500
    M706 0 5 5 0 10 0 1 3 3 0 12.6% 1500
    M707 0 5 5 0 10 0 1 3 4 0 12.9% 1450
    M708 0 5 5 0 10 0 1 4 0 0 12.5% 1500
    M709 0 5 5 0 10 0 1 4 1 0 12.9% 1500
    M710 0 5 5 0 10 0 1 4 2 0 13.2% 1500
    M711 0 5 5 0 10 0 1 4 3 0 13.6% 1500
    M712 0 5 5 0 10 0 1 4 4 0 14.0% 1450
    M713 0 5 5 0 10 0 2 0 0 0 9.5% 1500
    M714 0 5 5 0 10 0 2 0 1 0 9.9% 1500
    M715 0 5 5 0 10 0 2 0 2 0 10.2% 1500
    M716 0 5 5 0 10 0 2 0 3 0 10.6% 1450
    M717 0 5 5 0 10 0 2 0 4 0 10.9% 1450
    M718 0 5 5 0 10 0 2 1 0 0 10.5% 1500
    M719 0 5 5 0 10 0 2 1 1 0 10.9% 1500
    M720 0 5 5 0 10 0 2 1 2 0 11.3% 1500
    M721 0 5 5 0 10 0 2 1 3 0 11.6% 1450
    M722 0 5 5 0 10 0 2 1 4 0 12.0% 1450
    M723 0 5 5 0 10 0 2 2 0 0 11.5% 1500
    M724 0 5 5 0 10 0 2 2 1 0 11.9% 1500
    M725 0 5 5 0 10 0 2 2 2 0 12.3% 1500
    M726 0 5 5 0 10 0 2 2 3 0 12.6% 1450
    M727 0 5 5 0 10 0 2 2 4 0 13.0% 1450
    M728 0 5 5 0 10 0 2 3 0 0 12.5% 1500
    M729 0 5 5 0 10 0 2 3 1 0 12.9% 1500
    M730 0 5 5 0 10 0 2 3 2 0 13.3% 1450
    M731 0 5 5 0 10 0 2 3 3 0 13.7% 1450
    M732 0 5 5 0 10 0 2 3 4 0 14.0% 1450
    M733 0 5 5 0 10 0 2 4 0 0 13.5% 1500
    M734 0 5 5 0 10 0 2 4 1 0 13.9% 1500
    M735 0 5 5 0 10 0 2 4 2 0 14.3% 1450
    M736 0 5 5 0 10 0 2 4 3 0 14.7% 1450
    M737 0 5 5 0 10 0 2 4 4 0 15.1% 1450
    M738 0 5 5 0 10 0 3 0 0 0 10.6% 1500
    M739 0 5 5 0 10 0 3 0 1 0 11.0% 1450
    M740 0 5 5 0 10 0 3 0 2 0 11.3% 1450
    M741 0 5 5 0 10 0 3 0 3 0 11.7% 1450
    M742 0 5 5 0 10 0 3 0 4 0 12.0% 1450
    M743 0 5 5 0 10 0 3 1 0 0 11.6% 1500
    M744 0 5 5 0 10 0 3 1 1 0 12.0% 1450
    M745 0 5 5 0 10 0 3 1 2 0 12.3% 1450
    M746 0 5 5 0 10 0 3 1 3 0 12.7% 1450
    M747 0 5 5 0 10 0 3 1 4 0 13.1% 1450
    M748 0 5 5 0 10 0 3 2 0 0 12.6% 1450
    M749 0 5 5 0 10 0 3 2 1 0 13.0% 1450
    M750 0 5 5 0 10 0 3 2 2 0 13.3% 1450
    M751 0 5 5 0 10 0 3 2 3 0 13.7% 1450
    M752 0 5 5 0 10 0 3 2 4 0 14.1% 1450
    M753 0 5 5 0 10 0 3 3 0 0 13.6% 1450
    M754 0 5 5 0 10 0 3 3 1 0 14.0% 1450
    M755 0 5 5 0 10 0 3 3 2 0 14.3% 1450
    M756 0 5 5 0 10 0 3 3 3 0 14.7% 1450
    M757 0 5 5 0 10 0 3 3 4 0 15.1% 1450
    M758 0 5 5 0 10 0 3 4 0 0 14.6% 1450
    M759 0 5 5 0 10 0 3 4 1 0 15.0% 1450
    M760 0 5 5 0 10 0 3 4 2 0 15.4% 1450
    M761 0 5 5 0 10 0 3 4 3 0 15.7% 1450
    M762 0 5 5 0 10 0 3 4 4 0 16.1% 1450
    M763 0 5 5 0 10 0 4 0 0 0 11.7% 1450
    M764 0 5 5 0 10 0 4 0 1 0 12.0% 1450
    M765 0 5 5 0 10 0 4 0 2 0 12.4% 1450
    M766 0 5 5 0 10 0 4 0 3 0 12.7% 1450
    M767 0 5 5 0 10 0 4 0 4 0 13.1% 1450
    M768 0 5 5 0 10 0 4 1 0 0 12.7% 1450
    M769 0 5 5 0 10 0 4 1 1 0 13.0% 1450
    M770 0 5 5 0 10 0 4 1 2 0 13.4% 1450
    M771 0 5 5 0 10 0 4 1 3 0 13.8% 1450
    M772 0 5 5 0 10 0 4 1 4 0 14.1% 1450
    M773 0 5 5 0 10 0 4 2 0 0 13.7% 1450
    M774 0 5 5 0 10 0 4 2 1 0 14.0% 1450
    M775 0 5 5 0 10 0 4 2 2 0 14.4% 1450
    M776 0 5 5 0 10 0 4 2 3 0 14.8% 1450
    M777 0 5 5 0 10 0 4 2 4 0 15.2% 1450
    M778 0 5 5 0 10 0 4 3 0 0 14.7% 1450
    M779 0 5 5 0 10 0 4 3 1 0 15.0% 1450
    M780 0 5 5 0 10 0 4 3 2 0 15.4% 1450
    M781 0 5 5 0 10 0 4 3 3 0 15.8% 1450
    M782 0 5 5 0 10 0 4 3 4 0 16.2% 1450
    M783 0 5 5 0 10 0 4 4 0 0 15.6% 1450
    M784 0 5 5 0 10 0 4 4 1 0 16.0% 1450
    M785 0 5 5 0 10 0 4 4 2 0 16.4% 1450
    M786 0 5 5 0 10 0 4 4 3 0 16.8% 1450
    M787 0 5 5 0 10 0 4 4 4 0 17.2% 1450
    M788 0 5 7 0 10 0 0 0 1 0 8.9% 1500
    M789 0 5 7 0 10 0 0 0 2 0 9.2% 1500
    M790 0 5 7 0 10 0 0 0 3 0 9.6% 1500
    M791 0 5 7 0 10 0 0 0 4 0 9.9% 1500
    M792 0 5 7 0 10 0 0 1 0 0 9.6% 1500
    M793 0 5 7 0 10 0 0 1 1 0 9.9% 1500
    M794 0 5 7 0 10 0 0 1 2 0 10.3% 1500
    M795 0 5 7 0 10 0 0 1 3 0 10.6% 1500
    M796 0 5 7 0 10 0 0 1 4 0 11.0% 1500
    M797 0 5 7 0 10 0 0 2 0 0 10.6% 1500
    M798 0 5 7 0 10 0 0 2 1 0 10.9% 1500
    M799 0 5 7 0 10 0 0 2 2 0 11.3% 1500
    M800 0 5 7 0 10 0 0 2 3 0 11.7% 1500
    M801 0 5 7 0 10 0 0 2 4 0 12.0% 1450
    M802 0 5 7 0 10 0 0 3 0 0 11.6% 1500
    M803 0 5 7 0 10 0 0 3 1 0 12.0% 1500
    M804 0 5 7 0 10 0 0 3 2 0 12.3% 1500
    M805 0 5 7 0 10 0 0 3 3 0 12.7% 1500
    M806 0 5 7 0 10 0 0 3 4 0 13.1% 1450
    M807 0 5 7 0 10 0 0 4 0 0 12.6% 1500
    M808 0 5 7 0 10 0 0 4 1 0 13.0% 1500
    M809 0 5 7 0 10 0 0 4 2 0 13.3% 1500
    M810 0 5 7 0 10 0 0 4 3 0 13.7% 1450
    M811 0 5 7 0 10 0 0 4 4 0 14.1% 1450
    M812 0 5 7 0 10 0 1 0 0 0 9.6% 1500
    M813 0 5 7 0 10 0 1 0 1 0 10.0% 1500
    M814 0 5 7 0 10 0 1 0 2 0 10.3% 1500
    M815 0 5 7 0 10 0 1 0 3 0 10.7% 1450
    M816 0 5 7 0 10 0 1 0 4 0 11.0% 1450
    M817 0 5 7 0 10 0 1 1 0 0 10.6% 1500
    M818 0 5 7 0 10 0 1 1 1 0 11.0% 1500
    M819 0 5 7 0 10 0 1 1 2 0 11.4% 1450
    M820 0 5 7 0 10 0 1 1 3 0 11.7% 1450
    M821 0 5 7 0 10 0 1 1 4 0 12.1% 1450
    M822 0 5 7 0 10 0 1 2 0 0 11.7% 1500
    M823 0 5 7 0 10 0 1 2 1 0 12.0% 1500
    M824 0 5 7 0 10 0 1 2 2 0 12.4% 1450
    M825 0 5 7 0 10 0 1 2 3 0 12.7% 1450
    M826 0 5 7 0 10 0 1 2 4 0 13.1% 1450
    M827 0 5 7 0 10 0 1 3 0 0 12.7% 1500
    M828 0 5 7 0 10 0 1 3 1 0 13.0% 1500
    M829 0 5 7 0 10 0 1 3 2 0 13.4% 1450
    M830 0 5 7 0 10 0 1 3 3 0 13.8% 1450
    M831 0 5 7 0 10 0 1 3 4 0 14.2% 1450
    M832 0 5 7 0 10 0 1 4 0 0 13.7% 1500
    M833 0 5 7 0 10 0 1 4 1 0 14.0% 1450
    M834 0 5 7 0 10 0 1 4 2 0 14.4% 1450
    M835 0 5 7 0 10 0 1 4 3 0 14.8% 1450
    M836 0 5 7 0 10 0 1 4 4 0 15.2% 1450
    M837 0 5 7 0 10 0 2 0 0 0 10.7% 1500
    M838 0 5 7 0 10 0 2 0 1 0 11.1% 1450
    M839 0 5 7 0 10 0 2 0 2 0 11.4% 1450
    M840 0 5 7 0 10 0 2 0 3 0 11.8% 1450
    M841 0 5 7 0 10 0 2 0 4 0 12.1% 1450
    M842 0 5 7 0 10 0 2 1 0 0 11.7% 1450
    M843 0 5 7 0 10 0 2 1 1 0 12.1% 1450
    M844 0 5 7 0 10 0 2 1 2 0 12.4% 1450
    M845 0 5 7 0 10 0 2 1 3 0 12.8% 1450
    M846 0 5 7 0 10 0 2 1 4 0 13.2% 1450
    M847 0 5 7 0 10 0 2 2 0 0 12.7% 1450
    M848 0 5 7 0 10 0 2 2 1 0 13.1% 1450
    M849 0 5 7 0 10 0 2 2 2 0 13.5% 1450
    M850 0 5 7 0 10 0 2 2 3 0 13.8% 1450
    M851 0 5 7 0 10 0 2 2 4 0 14.2% 1450
    M852 0 5 7 0 10 0 2 3 0 0 13.7% 1450
    M853 0 5 7 0 10 0 2 3 1 0 14.1% 1450
    M854 0 5 7 0 10 0 2 3 2 0 14.5% 1450
    M855 0 5 7 0 10 0 2 3 3 0 14.9% 1450
    M856 0 5 7 0 10 0 2 3 4 0 15.2% 1450
    M857 0 5 7 0 10 0 2 4 0 0 14.7% 1450
    M858 0 5 7 0 10 0 2 4 1 0 15.1% 1450
    M859 0 5 7 0 10 0 2 4 2 0 15.5% 1450
    M860 0 5 7 0 10 0 2 4 3 0 15.9% 1450
    M861 0 5 7 0 10 0 2 4 4 0 16.3% 1450
    M862 0 5 7 0 10 0 3 0 0 0 11.8% 1450
    M863 0 5 7 0 10 0 3 0 1 0 12.1% 1450
    M864 0 5 7 0 10 0 3 0 2 0 12.5% 1450
    M865 0 5 7 0 10 0 3 0 3 0 12.9% 1450
    M866 0 5 7 0 10 0 3 0 4 0 13.2% 1450
    M867 0 5 7 0 10 0 3 1 0 0 12.8% 1450
    M868 0 5 7 0 10 0 3 1 1 0 13.1% 1450
    M869 0 5 7 0 10 0 3 1 2 0 13.5% 1450
    M870 0 5 7 0 10 0 3 1 3 0 13.9% 1450
    M871 0 5 7 0 10 0 3 1 4 0 14.3% 1450
    M872 0 5 7 0 10 0 3 2 0 0 13.8% 1450
    M873 0 5 7 0 10 0 3 2 1 0 14.2% 1450
    M874 0 5 7 0 10 0 3 2 2 0 14.5% 1450
    M875 0 5 7 0 10 0 3 2 3 0 14.9% 1450
    M876 0 5 7 0 10 0 3 2 4 0 15.3% 1450
    M877 0 5 7 0 10 0 3 3 0 0 14.8% 1450
    M878 0 5 7 0 10 0 3 3 1 0 15.2% 1450
    M879 0 5 7 0 10 0 3 3 2 0 15.6% 1450
    M880 0 5 7 0 10 0 3 3 3 0 15.9% 1450
    M881 0 5 7 0 10 0 3 3 4 0 16.3% 1450
    M882 0 5 7 0 10 0 3 4 0 0 15.8% 1450
    M883 0 5 7 0 10 0 3 4 1 0 16.2% 1450
    M884 0 5 7 0 10 0 3 4 2 0 16.6% 1450
    M885 0 5 7 0 10 0 3 4 3 0 17.0% 1450
    M886 0 5 7 0 10 0 3 4 4 0 17.4% 1450
    M887 0 5 7 0 10 0 4 0 0 0 12.8% 1450
    M888 0 5 7 0 10 0 4 0 1 0 13.2% 1450
    M889 0 5 7 0 10 0 4 0 2 0 13.6% 1450
    M890 0 5 7 0 10 0 4 0 3 0 14.0% 1450
    M891 0 5 7 0 10 0 4 0 4 0 14.3% 1450
    M892 0 5 7 0 10 0 4 1 0 0 13.8% 1450
    M893 0 5 7 0 10 0 4 1 1 0 14.2% 1450
    M894 0 5 7 0 10 0 4 1 2 0 14.6% 1450
    M895 0 5 7 0 10 0 4 1 3 0 15.0% 1450
    M896 0 5 7 0 10 0 4 1 4 0 15.4% 1450
    M897 0 5 7 0 10 0 4 2 0 0 14.8% 1450
    M898 0 5 7 0 10 0 4 2 1 0 15.2% 1450
    M899 0 5 7 0 10 0 4 2 2 0 15.6% 1450
    M900 0 5 7 0 10 0 4 2 3 0 16.0% 1450
    M901 0 5 7 0 10 0 4 2 4 0 16.4% 1450
    M902 0 5 7 0 10 0 4 3 0 0 15.8% 1450
    M903 0 5 7 0 10 0 4 3 1 0 16.2% 1450
    M904 0 5 7 0 10 0 4 3 2 0 16.6% 1450
    M905 0 5 7 0 10 0 4 3 3 0 17.0% 1400
    M906 0 5 7 0 10 0 4 3 4 0 17.4% 1450
    M907 0 5 7 0 10 0 4 4 0 0 16.8% 1450
    M908 0 5 7 0 10 0 4 4 1 0 17.2% 1450
    M909 0 5 7 0 10 0 4 4 2 0 17.6% 1450
    M910 0 5 7 0 10 0 4 4 3 0 18.0% 1400
    M911 0 5 7 0 10 0 4 4 4 0 18.4% 1450
    M912 0 5 9 0 10 0 0 0 1 0 10.1% 1500
    M913 0 5 9 0 10 0 0 0 2 0 10.4% 1450
    M914 0 5 9 0 10 0 0 0 3 0 10.8% 1450
    M915 0 5 9 0 10 0 0 0 4 0 11.2% 1450
    M916 0 5 9 0 10 0 0 1 0 0 10.7% 1500
    M917 0 5 9 0 10 0 0 1 1 0 11.1% 1500
    M918 0 5 9 0 10 0 0 1 2 0 11.5% 1450
    M919 0 5 9 0 10 0 0 1 3 0 11.8% 1450
    M920 0 5 9 0 10 0 0 1 4 0 12.2% 1450
    M921 0 5 9 0 10 0 0 2 0 0 11.8% 1500
    M922 0 5 9 0 10 0 0 2 1 0 12.1% 1450
    M923 0 5 9 0 10 0 0 2 2 0 12.5% 1450
    M924 0 5 9 0 10 0 0 2 3 0 12.9% 1450
    M925 0 5 9 0 10 0 0 2 4 0 13.2% 1450
    M926 0 5 9 0 10 0 0 3 0 0 12.8% 1500
    M927 0 5 9 0 10 0 0 3 1 0 13.2% 1450
    M928 0 5 9 0 10 0 0 3 2 0 13.5% 1450
    M929 0 5 9 0 10 0 0 3 3 0 13.9% 1450
    M930 0 5 9 0 10 0 0 3 4 0 14.3% 1450
    M931 0 5 9 0 10 0 0 4 0 0 13.8% 1500
    M932 0 5 9 0 10 0 0 4 1 0 14.2% 1450
  • In some embodiments, 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.
    • Performance Criteria:
  • In some embodiments, 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.
  • In some embodiments, 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.
  • In some embodiments, 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).
  • In some embodiments, 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).
  • In some embodiments, the adhesive wear resistance of the coating as measured via ASTM G77 testing, hereby incorporated by reference in its entirety, can be 2 mm3 volume loss or below (or about 2 mm3 volume loss or below). In some embodiments, the adhesive wear resistance of the coating as measured via ASTM G77 testing can be 0.5 mm3 volume loss or below (or about 0.5 mm3 volume loss or below). In some embodiments, the adhesive wear resistance of the coating as measured via ASTM G77 testing can be 0.1 mm3 volume loss or below (or about 0.1 mm3 volume loss or below).
  • In some embodiments, 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 mm3, 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.
  • In some embodiments of this disclosure, 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. In some embodiments of this disclosure, 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.
  • In some embodiments of this disclosure, 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. In some embodiments of this disclosure, 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.
  • In some embodiments of this disclosure, 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. In some embodiments of this disclosure, 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.
  • In some embodiments of this disclosure, 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. In some embodiments of this disclosure, 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.
  • In some embodiments, the thermal spray coating can be ‘readable’. A readable coating produces consistent thickness measurements with an Elcometer™ thickness gauge, or similar device, when properly calibrated. Armacor M is not a readable alloy, unlike embodiments of the disclosure, as it is magnetic.
  • As a standard to verify ‘readability’, a 25 mil standard thermal spray coupon is used for measurements. In some embodiments, 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.
  • In some embodiments, consistent measurements according to the above criteria, ±5 mils to actual physical thickness, 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. Thus, in some embodiments, the alloy can remain non-magnetic even after being exposed to heat for a substantial time period.
  • In some embodiments, the coating can be ‘readable’ after exposure to 1100K (or about 1100K) for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S (or less than about 10K/S). In some embodiments, 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). In some embodiments, the coating can be ‘readable’ after exposure to 1500K (or 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.
    No. C Mn Mo Ni Si Large Atom % Trans T Melt T
    M934 0 19 20 0 10 30% 1000 1300
    M935 0 20 19 0 10 31% 1000 1300
    M936 0 20 20 0 10 31% 900 1300
    M937 0 13 11 4 5 20% 800 1500
    M938 0 13 11 5 5 20% 800 1500
    M939 0 13 13 3 5 21% 800 1500
    M940 0 13 13 4 5 21% 800 1500
    M941 0 13 13 5 5 21% 800 1500
    M942 0 13 13 5 6 21% 850 1450
    M943 0 13 15 2 5 22% 800 1500
    M944 0 13 15 3 5 22% 800 1500
    M945 0 13 15 4 5 22% 800 1500
    M946 0 13 15 4 6 22% 850 1450
    M947 0 13 15 5 5 22% 800 1500
    M948 0 13 15 5 6 22% 850 1450
    M949 0 16 7 1 6 20% 850 1500
    M950 0 16 7 2 6 20% 850 1500
    M951 0 16 7 3 6 20% 850 1500
    M952 0 16 7 3 7 20% 900 1500
    M953 0 16 7 4 6 20% 800 1500
    M954 0 16 7 4 7 20% 900 1500
    M955 0 16 7 5 6 20% 800 1500
    M956 0 16 7 5 7 20% 900 1500
    M957 0 16 9 1 6 21% 850 1500
    M958 0 16 9 2 6 21% 800 1500
    M959 0 16 9 2 7 21% 900 1450
    M960 0 16 9 3 6 21% 800 1500
    M961 0 16 9 3 7 21% 900 1450
    M962 0 16 9 4 6 21% 800 1500
    M963 0 16 9 4 7 21% 900 1450
    M964 0 16 9 4 8 21% 1000 1450
    M965 0 16 9 5 5 21% 750 1500
    M966 0 16 9 5 6 21% 800 1500
    M967 0 16 9 5 7 21% 850 1450
    M968 0 16 9 5 8 21% 1000 1450
    M969 0 16 11 0 5 23% 800 1500
    M970 0 16 11 1 5 23% 800 1500
    M971 0 16 11 1 6 22% 850 1500
    M972 0 16 11 1 7 22% 900 1450
    M973 0 16 11 2 5 23% 750 1500
    M974 0 16 11 2 6 22% 800 1500
    M975 0 16 11 2 7 22% 900 1450
    M976 0 16 11 3 5 23% 750 1500
    M977 0 16 11 3 6 22% 800 1500
    M978 0 16 11 3 7 22% 850 1450
    M979 0 16 11 3 8 22% 1000 1400
    M980 0 16 11 4 5 23% 750 1500
    M981 0 16 11 4 6 22% 800 1500
    M982 0 16 11 4 7 22% 850 1450
    M983 0 16 11 4 8 22% 950 1400
    M984 0 16 11 5 5 23% 750 1500
    M985 0 16 11 5 6 22% 800 1500
    M986 0 16 11 5 7 22% 850 1450
    M987 0 16 13 0 5 24% 800 1500
    M988 0 16 13 1 5 24% 750 1500
    M989 0 16 13 1 6 24% 800 1450
    M990 0 16 13 1 7 23% 900 1450
    M991 0 16 13 2 5 24% 750 1500
    M992 0 16 13 2 6 24% 800 1450
    M993 0 16 13 2 7 23% 850 1450
    M994 0 16 13 2 8 23% 950 1400
    M995 0 16 13 3 5 24% 750 1500
    M996 0 16 13 3 6 24% 800 1450
    M997 0 16 13 3 7 23% 850 1450
    M998 0 16 13 4 5 24% 750 1500
    M999 0 16 13 4 6 24% 750 1450
    M1000 0 16 13 5 5 24% 750 1500
    M1001 0 16 15 0 5 25% 750 1450
    M1002 0 16 15 0 6 25% 800 1450
    M1003 0 16 15 0 7 25% 900 1400
    M1004 0 16 15 1 5 25% 750 1450
    M1005 0 16 15 1 6 25% 800 1450
    M1006 0 16 15 1 7 25% 850 1400
    M1007 0 16 15 2 5 25% 750 1450
    M1008 0 16 15 2 6 25% 750 1450
    M1009 0 16 15 3 5 25% 750 1450
    M1010 0 16 15 3 6 25% 750 1450
    M1011 0 16 15 4 5 25% 750 1450
    M1012 0 19 7 0 6 23% 800 1500
    M1013 0 19 7 0 7 22% 900 1450
    M1014 0 19 7 1 6 23% 800 1500
    M1015 0 19 7 1 7 22% 900 1450
    M1016 0 19 7 2 6 23% 750 1500
    M1017 0 19 7 2 7 22% 850 1450
    M1018 0 19 7 2 8 22% 1000 1450
    M1019 0 19 7 3 6 23% 750 1500
    M1020 0 19 7 3 7 22% 850 1450
    M1021 0 19 7 3 8 22% 950 1450
    M1022 0 19 7 4 6 23% 750 1500
    M1023 0 19 7 4 7 22% 850 1450
    M1024 0 19 7 4 8 22% 950 1450
    M1025 0 19 7 5 5 23% 750 1500
    M1026 0 19 7 5 6 23% 750 1500
    M1027 0 19 7 5 7 22% 800 1450
    M1028 0 19 7 5 8 22% 950 1450
    M1029 0 19 9 0 5 24% 750 1500
    M1030 0 19 9 0 6 24% 800 1500
    M1031 0 19 9 0 7 24% 900 1450
    M1032 0 19 9 1 5 24% 750 1500
    M1033 0 19 9 1 6 24% 750 1500
    M1034 0 19 9 1 7 24% 850 1450
    M1035 0 19 9 1 8 24% 1000 1400
    M1036 0 19 9 2 5 24% 750 1500
    M1037 0 19 9 2 6 24% 750 1500
    M1038 0 19 9 2 7 24% 800 1450
    M1039 0 19 9 2 8 24% 950 1400
    M1040 0 19 9 3 5 24% 700 1500
    M1041 0 19 9 3 6 24% 750 1500
    M1042 0 19 9 3 7 24% 800 1450
    M1043 0 19 9 3 8 24% 900 1400
    M1044 0 19 9 4 5 24% 700 1500
    M1045 0 19 9 4 6 24% 750 1500
    M1046 0 19 9 4 7 24% 800 1450
    M1047 0 19 9 5 5 24% 700 1500
    M1048 0 19 9 5 6 24% 750 1500
    M1049 0 19 11 0 5 26% 700 1500
    M1050 0 19 11 0 6 25% 750 1450
    M1051 0 19 11 0 7 25% 850 1450
    M1052 0 19 11 0 8 25% 1000 1400
    M1053 0 19 11 1 5 26% 700 1500
    M1054 0 19 11 1 6 25% 750 1450
    M1055 0 19 11 1 7 25% 800 1450
    M1056 0 19 11 1 8 25% 950 1400
    M1057 0 19 11 2 5 26% 700 1500
    M1058 0 19 11 2 6 25% 750 1450
    M1059 0 19 11 2 7 25% 800 1450
    M1060 0 19 11 3 5 26% 700 1500
    M1061 0 19 11 3 6 25% 750 1450
    M1062 0 19 11 3 7 25% 800 1450
    M1063 0 19 11 4 5 26% 700 1500
    M1064 0 19 11 4 6 25% 750 1450
    M1065 0 19 11 5 5 26% 700 1500
    M1066 0 19 13 0 5 27% 700 1500
    M1067 0 19 13 0 6 27% 750 1450
    M1068 0 19 13 0 7 26% 800 1400
    M1069 0 19 13 1 5 27% 700 1450
    M1070 0 19 13 1 6 27% 750 1450
    M1071 0 19 13 2 5 27% 700 1450
    M1072 0 19 13 3 5 27% 700 1450
    M1073 0 19 15 0 5 28% 700 1450
    M1074 0 19 15 0 6 28% 750 1400
    M1075 0 19 15 1 5 28% 700 1450
    M1076 0 22 7 0 5 26% 700 1500
    M1077 0 22 7 0 6 26% 750 1500
    M1078 0 22 7 0 7 25% 850 1450
    M1079 0 22 7 0 8 25% 1000 1400
    M1080 0 22 7 1 5 26% 700 1500
    M1081 0 22 7 1 6 26% 700 1500
    M1082 0 22 7 1 7 25% 800 1450
    M1083 0 22 7 1 8 25% 950 1400
    M1084 0 22 7 2 5 26% 700 1500
    M1085 0 22 7 2 6 26% 700 1500
    M1086 0 22 7 2 7 25% 800 1450
    M1087 0 22 7 2 8 25% 900 1400
    M1088 0 22 7 3 5 26% 700 1500
    M1089 0 22 7 3 6 26% 700 1500
    M1090 0 22 7 3 7 25% 750 1450
    M1091 0 22 7 4 5 26% 700 1500
    M1092 0 22 7 4 6 26% 700 1500
    M1093 0 22 7 5 5 26% 700 1500
    M1094 0 22 9 0 5 27% 700 1500
    M1095 0 22 9 0 6 27% 700 1450
    M1096 0 22 9 0 7 27% 800 1450
    M1097 0 22 9 0 8 26% 950 1400
    M1098 0 22 9 1 5 27% 700 1500
    M1099 0 22 9 1 6 27% 700 1450
    M1100 0 22 9 1 7 27% 750 1450
    M1101 0 22 9 2 5 27% 700 1500
    M1102 0 22 9 2 6 27% 700 1450
    M1103 0 22 9 3 5 27% 700 1500
    M1104 0 22 9 3 6 27% 700 1450
    M1105 0 22 9 4 5 27% 700 1500
    M1106 0 22 11 0 5 29% 700 1500
    M1107 0 22 11 0 6 28% 700 1450
    M1108 0 22 11 1 5 29% 650 1500
    M1109 0 22 13 0 5 30% 650 1450
    M1110 0 25 7 0 5 29% 650 1500
    M1111 0 25 7 0 6 29% 700 1450
    M1112 0 25 7 0 7 28% 750 1450
    M1113 0 25 7 1 5 29% 650 1500
    M1114 0 25 7 1 6 29% 650 1450
    M1115 0 25 7 2 5 29% 650 1500
    M1116 0 25 7 3 5 29% 650 1500
    M1117 0 25 9 0 5 30% 650 1500
    M1118 0 25 9 0 6 30% 650 1450
    M1119 0 25 9 1 5 30% 650 1500
    M1120 0.25 16 7 3 5 20% 750 1500
    M1121 0.25 16 7 4 5 20% 750 1500
    M1122 0.25 16 7 5 5 20% 750 1500
    M1123 0.25 16 9 0 5 21% 800 1500
    M1124 0.25 19 7 0 5 23% 750 1500
    M1125 0.25 19 7 1 5 23% 750 1500
    M1126 0.25 19 7 2 5 23% 750 1500
    M1127 0.25 19 7 3 5 23% 750 1500
    M1128 0.25 19 7 4 5 23% 700 1500
    M1129 0.25 19 7 5 5 23% 700 1500
    M1130 0.25 19 9 0 5 24% 750 1500
    M1131 0.25 22 7 0 5 26% 700 1500
    M1132 0.25 22 7 1 5 26% 700 1500
    M1133 0.25 22 7 2 5 26% 700 1500
    M1134 0.25 22 7 3 5 26% 700 1500
    M1135 0.25 22 7 4 5 26% 700 1500
    M1136 0.25 22 7 5 5 26% 700 1500
    M1137 0.25 22 9 0 5 27% 700 1500
    M1138 0.25 25 7 0 5 29% 650 1500
    M1139 0.25 25 7 1 5 29% 650 1500
    M1140 0.25 25 7 2 5 29% 650 1500
    M1141 0.25 25 9 0 5 30% 650 1500
    • Applications and Processes for Use:
  • Embodiments of alloys disclosed herein can be used in a variety of applications and industries. Some non-limiting examples of applications of use include:
  • Surface mining applications including but not limited to the following components and coatings for the following components: wear resistant sleeves and/or wear resistant hardfacing for slurry pipelines, mud pump components including pump housing or impeller or hardfacing for mud pump components, ore feed chute components including chute blocks or hardfacing of chute blocks, separation screens including but not limited to rotary breaker screens, banana screens, and shaker screens, liners for autogenous grinding mills and semi-autogenous grinding mills, ground engaging tools and hardfacing for ground engaging tools, wear plate for buckets and dumptruck liners, heel blocks and hardfacing for heel blocks on mining shovels, grader blades and hardfacing for grader blades, stacker reclaimers, siazer crushers, general wear packages for mining components and other communition components.
  • Upstream oil and gas applications including but not limited to the following components and coatings for the following components: Downhole casing and downhole casing, drill pipe and coatings for drill pipe including hardbanding, mud management components, mud motors, fracking pump sleeves, fracking impellers, fracking blender pumps, stop collars, drill bits and drill bit components, directional drilling equipment and coatings for directional drilling equipment including stabilizers and centralizers, blow out preventers and coatings for blow out preventers and blow out preventer components including the shear rams, oil country tubular goods and coatings for oil country tubular goods.
  • Downstream oil and gas applications including but not limited to the following components and coatings for the following components: Process vessels and coating for process vessels including steam generation equipment, amine vessels, distillation towers, cyclones, catalytic crackers, general refinery piping, corrosion under insulation protection, sulfur recovery units, convection hoods, sour stripper lines, scrubbers, hydrocarbon drums, and other refinery equipment and vessels.
  • Pulp and paper applications including but not limited to the following components and coatings for the following components: Rolls used in paper machines including yankee dryers and other dryers, calendar rolls, machine rolls, press rolls, digesters, pulp mixers, pulpers, pumps, boilers, shredders, tissue machines, roll and bale handling machines, doctor blades, evaporators, pulp mills, head boxes, wire parts, press parts, M.G. cylinders, pope reels, winders, vacuum pumps, deflakers, and other pulp and paper equipment.
  • Power generation applications including but not limited to the following components and coatings for the following components: boiler tubes, precipitators, fireboxes, turbines, generators, cooling towers, condensers, chutes and troughs, augers, bag houses, ducts, ID fans, coal piping, and other power generation components.
  • Agriculture applications including but not limited to the following components and coatings for the following components: chutes, base cutter blades, troughs, primary fan blades, secondary fan blades, augers and other agricultural applications.
  • Construction applications including but not limited to the following components and coatings for the following components: cement chutes, cement piping, bag houses, mixing equipment and other construction applications.
  • Machine element applications including but not limited to the following components and coatings for the following components: Shaft journals, paper rolls, gear boxes, drive rollers, impellers, general reclamation and dimensional restoration applications and other machine element applications.
  • Steel applications including but not limited to the following components and coatings for the following components: cold rolling mills, hot rolling mills, wire rod mills, galvanizing lines, continue pickling lines, continuous casting rolls and other steel mill rolls, and other steel applications.
  • Embodiments of alloys disclosed herein can be produced and or deposited in a variety of techniques effectively. Some non-limiting examples of processes include:
  • Thermal spray process including but not limited to those using a wire feedstock such as twin wire arc, spray, high velocity arc spray, combustion spray and those using a powder feedstock such as high velocity oxygen fuel, high velocity air spray, plasma spray, detonation gun spray, and cold spray. Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire. Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.
  • Welding processes including but not limited to those using a wire feedstock including but not limited to metal inert gas (MIG) welding, tungsten inert gas (TIG) welding, arc welding, submerged arc welding, open arc welding, bulk welding, laser cladding, and those using a powder feedstock including but not limited to laser cladding and plasma transferred arc welding. Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire. Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.
  • Casting processes including but not limited to processes typical to producing cast iron including but not limited to sand casting, permanent mold casting, chill casting, investment casting, lost foam casting, die casting, centrifugal casting, glass casting, slip casting and process typical to producing wrought steel products including continuous casting processes.
  • Post processing techniques including but not limited to but not limited to rolling, forging, surface treatments such as carburizing, nitriding, carbonitriding, heat treatments including but not limited to austenitizing, normalizing, annealing, stress relieving, tempering, aging, quenching, cryogenic treatments, flame hardening, induction hardening, differential hardening, case hardening, decarburization, machining, grinding, cold working, work hardening, and welding.
  • One of the more applicable uses of this technology is in applications where coatings are deposited on-site, in the field, or in locations where proper ventilation, dust collection, and other safety measures cannot be easily met. Some well-known non-limiting examples of these applications include power generation applications such as the coating of boiler tubes, upstream refinery applications such as the coating of refinery vessels, and pulp and paper applications such as the coating and grinding of yankee dryers.
    • EXAMPLES
  • The following examples are intended to be illustrative and non-limiting.
    • Example 1
  • The previously disclosed alloy #4, Fe: BAL, Mn: about 5, Mo: about 13, Si: about 10 was produced in the form of a 40 gram trial ingot to verify hardness and thermal spray vitrification potential. The ingot hardness was measured to be 534 Vickers (converting from a Rockwell C measurement). The microstructure of the ingot showed a fully eutectic structure indicating a strong possibility for amorphous or nanocrystalline structure under the rapid cooling rate of the spray process. This material has been selected for manufacture into 1/16″ cored thermal spray wire for twin wire arc spray trials after slight modification to the alloy #14, Fe: BAL, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2.
    • Example 2
  • The previously presented alloy #5, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a 40 gram trial ingot to verify hardness and thermal spray vitrification potential. The ingot hardness was measured to be 534 Vickers (converting from a Rockwell C measurement). The microstructure of the ingot showed a fully eutectic structure indicating a strong possibility for amorphous or nanocrystalline structure under the rapid cooling rate of the spray process. This material has been selected for manufacture into 1/16″ cored thermal spray wire for twin wire arc spray trials after slight modification to alloy #15, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.
    • Example 3
  • The previously disclosed alloy #8, Fe: BAL, C: about 0.25, Mn: about 19, Mo: about 7, Si: about 5 was produced in the form of a 40 gram ingot to verify hardness, thermal spray vetrification potential and magnetic permeability. In this example, the alloy candidate is being developed as a ‘readable’ coating which requires the alloy to be non-magnetic in the sprayed form. The ingot hardness was measured to be 300 Vickers (converting from a Rockwell C measurement). While this is below the desired hardness threshold, it is well known by those skilled in the art that the rapid cooling process achieved in thermal spray will increase the hardness of the alloy in this form. Thus, it is not unreasonable to expect an increase in hardness in the sprayed form up to the desired level of 400 Vickers. The relative magnetic permeability was measured via a Low-Mu Magnetic Permeability Tester and was determined to be less than 1.01, well below the threshold required to ensure ‘readability’.
    • Example 4
  • The previously disclosed alloy #5, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a cored thermal spray wire. This alloy was sprayed using the twin wire arc spray technique, specifically using the parameters shown in
  • Table 3. A series of tests were run to evaluate the alloys performance in reference to standard Cr-bearing thermal spray materials used for hardfacing. The specific alloy of reference is known by the commercial names, Armacor M, TAFA 95MXC, PMet 273, etc. and has an alloy composition of about Fe: BAL, Cr: 29, Si: 1, Mn: 2, B: 4. Table 2 highlights the result of the testing. As shown in Table 4, Alloy #5 has comparable adhesion and abrasion resistance as measure via ASTM G65B testing.
  • TABLE 2
    List of properties of disclosed alloys in relation to Armacor M
    Alloy Adhesion ASTM G65B ASTM G77
    Armacor M 8,000 ± 500 psi 0.37 0.07
    Alloy #4 8,000 ± 500 psi 0.37 0.07
    Alloy #5 8,000 ± 500 psi 0.46 1.55
  • TABLE 3
    Spray parameters used in Example 4 and 5 testing
    Air pressure 60 psi
    Voltage 38 V
    Amperage 125 A
    • Example 5
  • The previously disclosed alloy #4, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a cored thermal spray wire. This alloy was sprayed using the twin wire arc spray technique using the parameters shown in
  • Table 3. Yankee dryers are typically sprayed using this parameter set. A series of tests were run to evaluate the alloys performance in reference to standard Cr-bearing thermal spray materials used for hardfacing similar to that described in Example 4. The preliminary results of this testing are shown in Table 2.
  • As shown, Alloy #4 replicates the key performance criteria of Armacor M in all key criteria. As Alloy #4 represents an exemplary embodiment of this disclosure, additional testing was performed in order to compare other performance criteria specifically as it relates to the coating of yankee dryers, a specific article of manufacture used in paper machines. This testing including corrosion testing, grinding studies, spray characteristics, thorough metallographic evaluation, and evaluation of surface properties as related to surface tension. In all cases, alloy #4 was deemed to have similar or better performance than the Armacor M coating.
  • Corrosion testing was conducted by exposing the coating to saltwater and measuring the voltage against a reference bare steel plate, which could be then used to place the material on the Galvanic Series. Both the Armacor M and Alloy #4 coatings showed significant rust on the coating surface after the 2 week test exposure. The position of the Armacor M coating on the galvanic series is −450 to −567 and the position of Alloy #4 is −510 to −640. Increasingly negative values reflect more active potentials, which is less desirable as it indicates reduced corrosion resistance. This represents a ‘similarity’ in that the quantified performance does not vary by more than 25%.
  • Grinding studies were performed due to its specific relevance to the yankee dryer application. In this application it is desirable for the coating to exhibit faster grinding times, as it reduces the downtime of the paper machine. Grinding times were quantified by removing a specific material thickness and measuring the tie to do so, as shown in
  • Table 4. As shown, Alloy #4 showed reduced grinding time, which is advantageous.
  • TABLE 4
    Grinding Study Measurements
    Thickness Time to Grind (sec)
    Removed Alloy #4 ARM-M % Change
     5 mil 140 s 150 s  7.14%
    10 mil 210 s 210 s    0%
    15 mil 310 s 345 s 11.29%
    20 mil 398 s 488 s 22.61%
  • The characteristics of the spray for both materials was also studied. It was evident that Alloy #4 produced significantly less dust during spraying than Armacor M, which is desirable. Metallographic examination also showed that less oxides were present in the Alloy #4 coating, 7% versus 13% in the Armacor M coating.
  • Finally the surface tension properties of each coating were evaluated. In the Yankee dryer application it is desirable for the coating to be hydrophilic, which enables the adsorption of water based organic compounds used in paper making into the surface. The contact angle that a water droplet makes on the surface can be used to quantify the surface tension of the material. The Armacor M water droplet formed a 63.9° angle, and Alloy #4 formed a 41.5° angle. A smaller angle indicates increased hydrophillicity, which is advantageous because in Yankee dryer applications, a monoammonium phosphate (MAP) water-based solution is typically sprayed onto the coating for paper release properties. It can be advantageous for this water-based solution to immerse itself into the coating structure and stick well to the coating surface, which can be enhanced by having a hydrophilic coating.
  • From the foregoing description, it will be appreciated that an inventive chromium free hardfacing alloy and method of manufacturing are disclosed. While several components, techniques and aspects have been described with a certain degree of particularity, it is manifest that many changes can be made in the specific designs, constructions and methodology herein above described without departing from the spirit and scope of this disclosure.
  • Certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations, one or more features from a claimed combination can, in some cases, be excised from the combination, and the combination may be claimed as any subcombination or variation of any subcombination.
  • Moreover, while methods may be depicted in the drawings or described in the specification in a particular order, such methods need not be performed in the particular order shown or in sequential order, and that all methods need not be performed, to achieve desirable results. Other methods that are not depicted or described can be incorporated in the example methods and processes. For example, one or more additional methods can be performed before, after, simultaneously, or between any of the described methods. Further, the methods may be rearranged or reordered in other implementations. Also, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products. Additionally, other implementations are within the scope of this disclosure.
  • Conditional language, such as “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include or do not include, certain features, elements, and/or steps. Thus, such conditional language is not generally intended to imply that features, elements, and/or steps are in any way required for one or more embodiments.
  • Conjunctive language such as the phrase “at least one of X, Y, and Z,” unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item, term, etc. may be either X, Y, or Z. Thus, such conjunctive language is not generally intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.
  • Language of degree used herein, such as the terms “approximately,” “about,” “generally,” and “substantially” as used herein represent a value, amount, or characteristic close to the stated value, amount, or characteristic that still performs a desired function or achieves a desired result. For example, the terms “approximately”, “about”, “generally,” and “substantially” may refer to an amount that is within less than or equal to 10% of, within less than or equal to 5% of, within less than or equal to 1% of, within less than or equal to 0.1% of, and within less than or equal to 0.01% of the stated amount. If the stated amount is 0 (e.g., none, having no), the above recited ranges can be specific ranges, and not within a particular % of the value. For example, within less than or equal to 10 wt./vol. % of, within less than or equal to 5 wt./vol. % of, within less than or equal to 1 wt./vol. % of, within less than or equal to 0.1 wt./vol. % of, and within less than or equal to 0.01 wt./vol. % of the stated amount.
  • Some embodiments have been described in connection with the accompanying drawings. The figures are drawn to scale, but such scale should not be limiting, since dimensions and proportions other than what are shown are contemplated and are within the scope of the disclosed inventions. Distances, angles, etc. are merely illustrative and do not necessarily bear an exact relationship to actual dimensions and layout of the devices illustrated. Components can be added, removed, and/or rearranged. Further, the disclosure herein of any particular feature, aspect, method, property, characteristic, quality, attribute, element, or the like in connection with various embodiments can be used in all other embodiments set forth herein. Additionally, it will be recognized that any methods described herein may be practiced using any device suitable for performing the recited steps.
  • While a number of embodiments and variations thereof have been described in detail, other modifications and methods of using the same will be apparent to those of skill in the art. Accordingly, it should be understood that various applications, modifications, materials, and substitutions can be made of equivalents without departing from the unique and inventive disclosure herein or the scope of the claims.

Claims (26)

What is claimed is:
1. A work piece having at least one surface, the work piece 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.
2. The work piece of claim 1, wherein the coating comprises 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.
3. The work piece of claim 1, wherein the coating comprises 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.
4. The work piece of claim 1, wherein the coating comprises 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.
5. The work piece of claim 1, wherein the coating is non-magnetic and the coating thickness can be accurately measured with an Elcometer™ 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 10K/s or less.
6. The work piece of claim 1, wherein the coating is amorphous.
7. The work piece of claim 1, wherein the coating is nanocrystalline, as defined by having a grain size of 100 nm or less.
8. The work piece of claim 1, wherein the coating is applied via a thermal spray process.
9. The work piece of claim 1, wherein the coating is applied via a twin wire arc spray process.
10. The work piece of claim 1, wherein the work piece is a yankee dryer.
11. The work piece of claim 1, wherein the work piece is a roller used in a paper making machine.
12. 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 fine-grained structure of either martensite, ferrite, or austenite.
13. The article of manufacture of claim 12, wherein the coating comprises, 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.
14. The article of manufacture of claim 12, wherein the coating comprises 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.
15. The work piece of claim 12, wherein the coating comprises 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.
16. The article of manufacture of claim 12, wherein the coating is non-magnetic and the coating thickness can be accurately measured with an Elcometer™ 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 10K/s or less.
17. The article of manufacture of claim 12, wherein the coating comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.
18. The article of manufacture of claim 12, wherein the coating is applied via the twin wire arc spray process.
19. The article of manufacture of claim 12, wherein the coating is amorphous.
20. The article of manufacture of claim 12, wherein the coating is nanocrystalline, as defined by having a grain size of 100 nm or less.
21. The article of manufacture of claim 12, wherein the coating is applied via a thermal spray process.
22. The article of manufacture of claim 12, wherein the coating is applied onto a roller used in a paper making machine.
23. The article of manufacture of claim 12, wherein the coating is applied onto a Yankee Dryer.
24. The article of manufacture of claim 12, wherein the coating is applied onto a boiler tube.
25. A work piece having at least one surface, the work piece 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.
26. The work piece of claim 25, wherein the alloy has less than 1 vol. % carbides and less than 1 vol. % borides.
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