EP2414106B1 - Chromium-free metallic coating, method of forming thereof and composite wire - Google Patents

Chromium-free metallic coating, method of forming thereof and composite wire Download PDF

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Publication number
EP2414106B1
EP2414106B1 EP10756469.2A EP10756469A EP2414106B1 EP 2414106 B1 EP2414106 B1 EP 2414106B1 EP 10756469 A EP10756469 A EP 10756469A EP 2414106 B1 EP2414106 B1 EP 2414106B1
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Prior art keywords
weight
range
aluminum
silicon
nickel
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EP10756469.2A
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German (de)
French (fr)
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EP2414106A4 (en
EP2414106A1 (en
Inventor
Michael W. Seitz
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General Electric Technology GmbH
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General Electric Technology GmbH
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • C23C4/067Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131Wire arc spraying

Definitions

  • This invention relates to chrome-free metal coating compositions and thermal spray wires for producing same.
  • CH 311 869 discloses an alloy composition for use as a magnet.
  • DE 102 59 141 discloses material systems for coating.
  • DE 43 28 732 discloses a process and material for producing a thermally sprayed layer.
  • GB 2 250 030 discloses wire compositions for use in metal spraying.
  • US 2009/0032501 discloses abrasion-resistant weld overlay compositions.
  • US 2008/0098926 discloses composite wires for coating substrates.
  • US 2006/0078749 discloses composite materials.
  • a chromium-free metallic coating precursor in one embodiment of the invention, according to claim 1, there is provided a chromium-free metallic coating precursor.
  • the precursor is provided in the form of a composite wire.
  • a chromium-free metallic coating as can be made from the wire.
  • the chromium-free metallic coating precursor comprises a base metal constituent, a silicon constituent, a titanium constituent, and a boron constituent.
  • the base metal constituent is present in amount of at least 54% by weight.
  • the base metal constituent comprises at least one base metal selected from the group consisting of iron, nickel, cobalt, lead, zinc, copper, tin, and aluminum and always comprises at least 1 % by weight of aluminum, based on mass of the coating precursor.
  • the silicon, titanium and boron constituents are each present in amount between 1 % and 15% by weight.
  • the above constituents are provided in a composite wire in accordance with another embodiment of the invention.
  • the composite wire comprises a metallic outer sheath in the range of 70 to 95% by weight and an inner core of particles in the range of 5 to 30% by weight.
  • the metallic outer sheath comprises at least 70 weight percent of a base metal readily capable of being rolled and drawn into the sheath and comprising at least one of nickel, iron and cobalt, and at least 2 weight percent alloyed aluminum and/or silicon.
  • the inner core of particles comprises, by weight percent, in the range of 15% to 30% titanium, in the range of 15% to 35% silicon, in the range of 20% to 50% boron, and in the range of 0% to 15% carbon.
  • the composite wire is applied by thermal spray technique to produce the metallic chrome-free coating of the invention on a substrate.
  • the chrome-free coating composition usually comprises, in bulk on a weight basis, 70% to 90% of base metal, at least 2% aluminum, 2 to 10% titanium, 2 to 10% silicon, and 2 to 10% boron.
  • the coating is high temperature wear and corrosion resistant.
  • the drawing illustrates pictorially a composite wire in accordance with an embodiment of the invention.
  • the chromium-free metallic coating precursor comprises a base metal constituent, a silicon constituent, a titanium constituent, and a boron constituent, in alloy, mixture or composite form.
  • the base metal constituent is present in amount of at least 54% by weight.
  • the base metal constituent comprises at least one base metal selected the group consisting of iron, nickel, cobalt, lead, zinc, copper, tin, and aluminum and always comprises at least about 1% by weight of aluminum, based on mass of the coating precursor.
  • the silicon, titanium and boron constituents are each present in amount between about 1% and about 15% by weight.
  • the base metal is present in an amount of at least 68% by weight and contains an aluminum and/or silicon component alloyed therein in an amount of at least 2% by weight, based on mass of coating precursor.
  • the silicon, titanium and boron are preferably each present in amount between 2% and 10 percent by weight.
  • the base metal constituent is present in an amount of at least 76% by weight and is selected from at least one of iron, nickel, cobalt, and aluminum.
  • the base metal constituent is a mixture or an alloy, preferably an alloy, and always preferably comprises at least 3% by weight of aluminum, based on mass of coating precursor.
  • the silicon, titanium and boron may be present, preferably as a mass in particle form, in amount between 4% and 7%, preferably as the inside of a composite wire formed from the base metal constituent.
  • the coatings of the present invention can be formed from composite wires as described herein by feeding the wires through a conventional arc spraying apparatus.
  • the composite wire 10 comprises a metallic outer sheath 20 in the range of 70 to 95% by weight and an inner core 30 in the range of 5 to 30% by weight.
  • the composite wire comprises a metallic outer sheath in the range of 75 to 85% by weight and an inner core in the range of 15 to 25% by weight.
  • the metallic outer sheath comprises at least 70 weight percent of a base metal readily capable of being rolled and drawn into the sheath and at least 2 weight percent alloyed aluminum and/or silicon.
  • Aluminum can also be employed exclusively as the base metal.
  • the inner core comprises in the range of 15% to 30% titanium, in the range of 15% to 35% silicon, in the range of 20% to 50% boron, and in the range of 0% to 15% carbon, all in particle, preferably powdered, mixture form.
  • the titanium, silicon and boron may be present as a mixture of compounds containing additional elements.
  • the base metal is a relatively soft elemental metal or alloy, comprising at least one of nickel, iron, or cobalt.
  • Nickel is preferred, and the outer sheath most preferably comprises an alloy of nickel and aluminum.
  • Exemplary materials may comprise in the range of 70 to 98 percent by weight of nickel and in the range of 2 to 30 percent by weight of alloyed aluminum and/or silicon, preferably in the range of 85 to 98 percent by weight of nickel and in the range of 2 to 15 percent by weight alloyed aluminum and/or silicon, and most preferably 90 to 97 percent by weight of nickel and in the range of 3 to 10 percent by weight of alloyed aluminum.
  • the inner core preferably comprises in the range of 20% to 30% titanium, in the range of 20% to 30% silicon, in the range of 30% to 40% boron, and in the range of 0% to 15% carbon.
  • Carbon generally in the form of carbides, can be present if desired in the inner core, but since it is probably not present in the coating composition, at least in amounts which contribute properties, it is not considered material to the coating invention.
  • the titanium and silicon can be provided by a suitable amount of a TiSi source, for example, in the range of 50 to 60% of a TiSi source such as TiSiFe in admixture with a source of boron and optional carbon, for example, B 4 C in an amount of 40 to 50%.
  • the inner core may also contain additional materials.
  • the additional materials may include: carbides, such as tungsten carbide, titanium carbide, vanadium carbide, and the like; oxides, such as aluminum oxide, zirconium oxide, and the like; and borides, such as nickel boride, iron boride, and the like.
  • the inner core may also include additional metal powders, such as aluminum, nickel, or alloy powder, or composite powders, such as tungsten carbide nickel.
  • the inner core can include in the range of 0.1 to 10% molybdenum, 0.1 to 10% tungsten, 0.1 to 10% neodymium, and 0.1 to 10% carbon.
  • metal or metal alloy powders comprising magnesium, phosphorus, vanadium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, tantalum and/or tungsten may be present in the inner core, for example, in the range of 0.1 to 10%.
  • the core components listed above can be alloyed into the sheath, and where this is done, the constituent need not be present in the inner core, or it can be present in a reduced amount.
  • the constituent need not be present in the inner core, or it can be present in a reduced amount.
  • titanium, silicon and boron can be alloyed in the sheath in the amount of 2 to 10% by weight, based on weight of the composite wire.
  • the aluminum component may be present in the inner core, rather than the sheath.
  • the grain size of the powdered inner core will have an effect on the physical properties of the applied coating. Generally, the finer the grains of the powder, the more homogenous the coating will be and generally the better the wear and corrosion properties. However, acquisition costs and manufacturing constraints will limit the lower end of the grain size range.
  • the cored wires may be formed in a conventional manner by placing the mix for forming the inner core, which need not be an agglomerated mix, onto the strip to be made into the outer metallic sheath.
  • the strip can be drawn continuously through a plurality of wire drawing dies to form an outer wire sheath around an inner core.
  • the final outer diameter of the cored wire will depend upon the application for which it is used. For most applications, the cored wire final diameter ranges between about 0.8 mm and about 6.4 mm.
  • Conventional cored wire manufacturing techniques are disclosed in U.S. Patent Nos. 6,156,443 (Dallaire et al. ) and 6,513,728 (Hughes et al. ), both being hereby incorporated by reference.
  • a method of forming a wear resistant and corrosion resistant coating on a substrate is also provided.
  • the method generally includes the steps of providing a composite wire according to an embodiment of the invention and coating a substrate by employing the composite wire in conjunction with thermal spraying techniques to form a fused metallic coating.
  • the inventive wire is not weldable by commonly available techniques, so non-welding methods must be used to form the fused coating.
  • the resulting fused metallic chrome-free coating composition comprises, in bulk on a weight basis, 70% to 90% of base metal, at least 2% aluminum, 2 to 10% titanium, 2 to 10% silicon, and 2 to 10% boron.
  • the base metal is preferably selected from the group consisting of at least one of nickel, iron and cobalt, most preferably nickel.
  • the coating can contain additional constituents if desired, for example, additional constituents selected from the group consisting of 0.1 to 10% iron, 0.1 to 10% molybdenum, 0.1 to 10% tungsten, and 0 to 10% carbon.
  • the coatings according to the present invention are specifically designed for articles subjected to wear and/or corrosion.
  • Such articles include, for example, boiler tubes, hydraulic piston rods, pump casings, rollers in the paper and steel industry, wear plates, journals and shafts, and turbine blades and casings.
  • the coatings are designed to protect boiler tubes against erosion-corrosion related wastage and are applied to the boiler tubes by means of a conventional arc spraying apparatus.
  • arc spraying apparatus employing wires as the feed material.
  • Arc spraying methods and apparatus are well documented in the art, see for example, U.S. Pat. Nos. 6,156,443 (Dallaire, et al. ); 5,837,326 (Dallaire, et al. ); and European Patent No. EP 0 522 438 (Zurecki et al. ) the disclosures of which are incorporated by reference.
  • a composite wire was formed according to the following composition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Nonmetallic Welding Materials (AREA)

Description

    Technical Field
  • This invention relates to chrome-free metal coating compositions and thermal spray wires for producing same.
  • Background Art
  • It was known prior to the invention that it is difficult to avoid chrome in a metal coating that offers high temperature corrosion resistance. Chrome is undesirable during the coating process because it poses human and environmental hazards. CH 311 869 discloses an alloy composition for use as a magnet. DE 102 59 141 discloses material systems for coating. DE 43 28 732 discloses a process and material for producing a thermally sprayed layer. GB 2 250 030 discloses wire compositions for use in metal spraying. US 2009/0032501 discloses abrasion-resistant weld overlay compositions. US 2008/0098926 discloses composite wires for coating substrates. US 2006/0078749 discloses composite materials.
  • Disclosure of Invention
  • In one embodiment of the invention, according to claim 1, there is provided a chromium-free metallic coating precursor. In another embodiment of the invention, according to claim 9, the precursor is provided in the form of a composite wire. In a further embodiment of the invention, according to claim 5, there is provided a chromium-free metallic coating as can be made from the wire.
  • The chromium-free metallic coating precursor comprises a base metal constituent, a silicon constituent, a titanium constituent, and a boron constituent. The base metal constituent is present in amount of at least 54% by weight. The base metal constituent comprises at least one base metal selected from the group consisting of iron, nickel, cobalt, lead, zinc, copper, tin, and aluminum and always comprises at least 1 % by weight of aluminum, based on mass of the coating precursor. The silicon, titanium and boron constituents are each present in amount between 1 % and 15% by weight.
  • The above constituents are provided in a composite wire in accordance with another embodiment of the invention. The composite wire comprises a metallic outer sheath in the range of 70 to 95% by weight and an inner core of particles in the range of 5 to 30% by weight. The metallic outer sheath comprises at least 70 weight percent of a base metal readily capable of being rolled and drawn into the sheath and comprising at least one of nickel, iron and cobalt, and at least 2 weight percent alloyed aluminum and/or silicon. The inner core of particles comprises, by weight percent, in the range of 15% to 30% titanium, in the range of 15% to 35% silicon, in the range of 20% to 50% boron, and in the range of 0% to 15% carbon.
  • The composite wire is applied by thermal spray technique to produce the metallic chrome-free coating of the invention on a substrate. The chrome-free coating composition usually comprises, in bulk on a weight basis, 70% to 90% of base metal, at least 2% aluminum, 2 to 10% titanium, 2 to 10% silicon, and 2 to 10% boron. The coating is high temperature wear and corrosion resistant.
  • Brief Description of Drawings
  • The drawing illustrates pictorially a composite wire in accordance with an embodiment of the invention.
  • Best Mode for Carrying out the Invention
  • In the following description, all percentages given are weight percent, unless otherwise noted. The invention is described in terms of the precursor materials for forming the chrome-free coating, the precursor materials in the form of a composite wire, which is the preferred form of employing the precursor materials, and a coating as made by the wire.
  • The chromium-free metallic coating precursor comprises a base metal constituent, a silicon constituent, a titanium constituent, and a boron constituent, in alloy, mixture or composite form. The base metal constituent is present in amount of at least 54% by weight. The base metal constituent comprises at least one base metal selected the group consisting of iron, nickel, cobalt, lead, zinc, copper, tin, and aluminum and always comprises at least about 1% by weight of aluminum, based on mass of the coating precursor. The silicon, titanium and boron constituents are each present in amount between about 1% and about 15% by weight.
  • Preferably, in the chromium-free coating precursor, the base metal is present in an amount of at least 68% by weight and contains an aluminum and/or silicon component alloyed therein in an amount of at least 2% by weight, based on mass of coating precursor. The silicon, titanium and boron are preferably each present in amount between 2% and 10 percent by weight.
  • Preferably, in the chromium-free coating precursor, the base metal constituent is present in an amount of at least 76% by weight and is selected from at least one of iron, nickel, cobalt, and aluminum. The base metal constituent is a mixture or an alloy, preferably an alloy, and always preferably comprises at least 3% by weight of aluminum, based on mass of coating precursor. The silicon, titanium and boron may be present, preferably as a mass in particle form, in amount between 4% and 7%, preferably as the inside of a composite wire formed from the base metal constituent.
  • The coatings of the present invention can be formed from composite wires as described herein by feeding the wires through a conventional arc spraying apparatus. The composite wire 10 comprises a metallic outer sheath 20 in the range of 70 to 95% by weight and an inner core 30 in the range of 5 to 30% by weight. In a preferred embodiment, the composite wire comprises a metallic outer sheath in the range of 75 to 85% by weight and an inner core in the range of 15 to 25% by weight.
  • The metallic outer sheath comprises at least 70 weight percent of a base metal readily capable of being rolled and drawn into the sheath and at least 2 weight percent alloyed aluminum and/or silicon. Aluminum can also be employed exclusively as the base metal. The inner core comprises in the range of 15% to 30% titanium, in the range of 15% to 35% silicon, in the range of 20% to 50% boron, and in the range of 0% to 15% carbon, all in particle, preferably powdered, mixture form. The titanium, silicon and boron may be present as a mixture of compounds containing additional elements.
  • The base metal is a relatively soft elemental metal or alloy, comprising at least one of nickel, iron, or cobalt. Nickel is preferred, and the outer sheath most preferably comprises an alloy of nickel and aluminum. Exemplary materials may comprise in the range of 70 to 98 percent by weight of nickel and in the range of 2 to 30 percent by weight of alloyed aluminum and/or silicon, preferably in the range of 85 to 98 percent by weight of nickel and in the range of 2 to 15 percent by weight alloyed aluminum and/or silicon, and most preferably 90 to 97 percent by weight of nickel and in the range of 3 to 10 percent by weight of alloyed aluminum.
  • The inner core preferably comprises in the range of 20% to 30% titanium, in the range of 20% to 30% silicon, in the range of 30% to 40% boron, and in the range of 0% to 15% carbon. Carbon, generally in the form of carbides, can be present if desired in the inner core, but since it is probably not present in the coating composition, at least in amounts which contribute properties, it is not considered material to the coating invention. The titanium and silicon can be provided by a suitable amount of a TiSi source, for example, in the range of 50 to 60% of a TiSi source such as TiSiFe in admixture with a source of boron and optional carbon, for example, B4C in an amount of 40 to 50%.
  • The inner core may also contain additional materials. The additional materials may include: carbides, such as tungsten carbide, titanium carbide, vanadium carbide, and the like; oxides, such as aluminum oxide, zirconium oxide, and the like; and borides, such as nickel boride, iron boride, and the like. The inner core may also include additional metal powders, such as aluminum, nickel, or alloy powder, or composite powders, such as tungsten carbide nickel. As an example, the inner core can include in the range of 0.1 to 10% molybdenum, 0.1 to 10% tungsten, 0.1 to 10% neodymium, and 0.1 to 10% carbon. Further, metal or metal alloy powders comprising magnesium, phosphorus, vanadium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, tantalum and/or tungsten may be present in the inner core, for example, in the range of 0.1 to 10%.
  • Additionally, the core components listed above can be alloyed into the sheath, and where this is done, the constituent need not be present in the inner core, or it can be present in a reduced amount. For example, titanium, silicon and boron can be alloyed in the sheath in the amount of 2 to 10% by weight, based on weight of the composite wire. In similar manner, the aluminum component may be present in the inner core, rather than the sheath.
  • The grain size of the powdered inner core will have an effect on the physical properties of the applied coating. Generally, the finer the grains of the powder, the more homogenous the coating will be and generally the better the wear and corrosion properties. However, acquisition costs and manufacturing constraints will limit the lower end of the grain size range.
  • The cored wires may be formed in a conventional manner by placing the mix for forming the inner core, which need not be an agglomerated mix, onto the strip to be made into the outer metallic sheath. The strip can be drawn continuously through a plurality of wire drawing dies to form an outer wire sheath around an inner core. The final outer diameter of the cored wire will depend upon the application for which it is used. For most applications, the cored wire final diameter ranges between about 0.8 mm and about 6.4 mm. Conventional cored wire manufacturing techniques are disclosed in U.S. Patent Nos. 6,156,443 (Dallaire et al. ) and 6,513,728 (Hughes et al. ), both being hereby incorporated by reference.
  • In addition to the composite wires discussed above, a method of forming a wear resistant and corrosion resistant coating on a substrate is also provided. The method generally includes the steps of providing a composite wire according to an embodiment of the invention and coating a substrate by employing the composite wire in conjunction with thermal spraying techniques to form a fused metallic coating. The inventive wire is not weldable by commonly available techniques, so non-welding methods must be used to form the fused coating.
  • The resulting fused metallic chrome-free coating composition comprises, in bulk on a weight basis, 70% to 90% of base metal, at least 2% aluminum, 2 to 10% titanium, 2 to 10% silicon, and 2 to 10% boron. The base metal is preferably selected from the group consisting of at least one of nickel, iron and cobalt, most preferably nickel. The coating can contain additional constituents if desired, for example, additional constituents selected from the group consisting of 0.1 to 10% iron, 0.1 to 10% molybdenum, 0.1 to 10% tungsten, and 0 to 10% carbon.
  • The coatings according to the present invention are specifically designed for articles subjected to wear and/or corrosion. Such articles include, for example, boiler tubes, hydraulic piston rods, pump casings, rollers in the paper and steel industry, wear plates, journals and shafts, and turbine blades and casings.
  • In one application, the coatings are designed to protect boiler tubes against erosion-corrosion related wastage and are applied to the boiler tubes by means of a conventional arc spraying apparatus. However, it will be appreciated from the description below that the coatings could also be applied to the boiler tubes by other thermal spraying apparatus employing wires as the feed material. Arc spraying methods and apparatus are well documented in the art, see for example, U.S. Pat. Nos. 6,156,443 (Dallaire, et al. ); 5,837,326 (Dallaire, et al. ); and European Patent No. EP 0 522 438 (Zurecki et al. ) the disclosures of which are incorporated by reference.
  • EXAMPLE
  • A composite wire was formed according to the following composition.
  • 16 wt % Core Material:
    • 43 wt% B4C (79 wt% B, 21 wt% C)
    • 57 wt% TiSiFe (44 wt% Ti, 44 wt% Si, 10 wt% Fe, 2 wt% other)
    Core composition (Elemental basis)
    • 34 wt% B
    • 9 wt % C
    • 25 wt % Ti
    • 25 wt% Si
    • 6 wt% Fe
    • 1 wt% other
  • 84 wt% Sheath Material
    • 95 wt% Ni
    • 5 wt% Al
    Composite Wire composition (Elemental basis)
    • 79.8 wt% Ni
    • 4.1 wt% Si
    • 4.1 wt% Al
    • 1.2 wt% Fe
    • 0.7 wt% C
    • 6.1 wt% B
    • 3.8 wt% Ti

Claims (17)

  1. A chromium-free metallic coating precursor comprising
    at least 54% by weight of at least one base metal selected from the group consisting of iron, nickel, cobalt, lead, zinc, copper, tin, and aluminum, said coating precursor always comprising at least 1% by weight of aluminum,
    between 1% and 15% by weight of silicon, between 1% and 15% by weight of titanium, and between 1% and 15% by weight of boron.
  2. A chromium-free metallic coating precursor as in claim 1 comprising at least 68% by weight of at least one base metal selected from the group consisting of iron, nickel, cobalt, lead, zinc, copper, tin, and aluminum, said base metal always comprising at least 2% by weight of alloyed aluminum and/or silicon,
    between 2% and 10% by weight of silicon, between 2% and 10% by weight of titanium, and between 2% and 10% by weight of boron.
  3. A chromium-free metallic coating precursor as in claim 1 comprising at least 76% by weight of at least one base metal selected from the group consisting of iron, nickel, cobalt, and aluminum, said base metal always comprising at least 3% by weight of alloyed aluminum,
    between 3% and 7% by weight of silicon, between 3% and 7% by weight of titanium, and between 3% and 7% by weight of boron.
  4. A chromium-free metallic coating precursor as in claim 1 comprising an alloy of nickel, iron and/or cobalt with aluminum and a mass of silicon, titanium and boron-containing particles.
  5. A fused chromium-free metallic coating composition comprising, in bulk on a weight basis, 70% to 90% by weight of at least one base metal selected from the group consisting of iron, nickel, cobalt, lead, zinc, copper, tin, and aluminum, said metallic coating composition always comprising at least 2% by weight of aluminum, 2% to 10% by weight of titanium, 2% to 10% by weight of silicon, and 2% to 10% by weight of boron.
  6. A fused chromium-free metallic coating composition as in claim 5 comprising in the range of from 2% to 10% by weight of aluminum.
  7. A fused chromium-free metallic coating composition as in claim 6 wherein the at least one base metal is selected from the group consisting of nickel, iron and cobalt.
  8. A fused chromium-free metallic coating composition as in claim 7 wherein the base metal comprises nickel, said composition further comprising, in bulk on a weight basis, at least one additional constituent selected from the group consisting of 0. 1 % to 10% by weight of iron, 0. 1% to 10% by weight of molybdenum, and 0.1% to 10% by weight of tungsten.
  9. A composite wire containing no chromium for producing a wear resistant and corrosion resistant coating on a substrate, said composite wire comprising a metallic outer sheath in the range of 70 to 95% by weight and an inner core of particles in the range of 5 to 30% by weight, wherein the metallic outer sheath comprises at least 70 weight percent of a base metal and at least 2 weight percent of alloyed aluminum and/or silicon, wherein the base metal comprises at least one of nickel, iron, and cobalt, and wherein the inner core of particles comprises in the range of 15% to 30% by weight of titanium, in the range of 15% to 35% by weight of silicon, in the range of 20% to 50% by weight of boron, and in the range of 0% to 15% by weight of carbon.
  10. A composite wire as in claim 9 wherein the outer sheath comprises an alloy of nickel and aluminum and/or silicon.
  11. A composite wire as in claim 9 wherein the outer sheath comprises in the range of 85 to 98 percent by weight of nickel and in the range of 2 to 15 percent by weight of alloyed aluminum and/or silicon.
  12. A composite wire as in claim 11 wherein the outer sheath comprises in the range of 90 to 97 percent by weight of nickel and in the range of 3 to 10 percent by weight of alloyed aluminum.
  13. A composite wire as in claim 9 wherein the inner core of particles comprises in the range of 20% to 30% by weight of titanium, in the range of 20% to 30% by weight of silicon, in the range of 30% to 40% by weight of boron, and in the range of 0% to 15% by weight of carbon.
  14. A composite wire as in claim 13 wherein the inner core of particles comprises a mixture of in the range of 50% to 60% by weight of a TiSi source and in the range of 40% to 50% by weight of B4C.
  15. A composite wire as in claim 9 comprising a metallic outer sheath in the range of 80 to 90% by weight and an inner core of particles in the range of 10 to 20% by weight.
  16. A composite wire as in claim 9 further comprising in the range of 0.1% to 10% by weight of molybdenum, 0.1% to 10% by weight tungsten, and 0.1% to 10% by weight of carbon.
  17. A method of forming a wear resistant and corrosion resistant coating on a substrate comprising the steps of: providing a composite wire according to claim 9 and employing the wire to form the coating, wherein the step of employing the wire to form the coating comprises thermally spraying the wire onto the substrate.
EP10756469.2A 2009-03-24 2010-03-24 Chromium-free metallic coating, method of forming thereof and composite wire Active EP2414106B1 (en)

Priority Applications (1)

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US21090309P 2009-03-24 2009-03-24
PCT/US2010/000858 WO2010110873A1 (en) 2009-03-24 2010-03-24 Chrome-free coating for substrate

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EP2414106A1 EP2414106A1 (en) 2012-02-08
EP2414106A4 EP2414106A4 (en) 2014-05-14
EP2414106B1 true EP2414106B1 (en) 2020-12-30

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9475154B2 (en) 2013-05-30 2016-10-25 Lincoln Global, Inc. High boron hardfacing electrode
US10767696B2 (en) * 2017-12-29 2020-09-08 Saint-Gobain Performance Plastics Pampus Gmbh Bearing component and method of making and using the same

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH311869A (en) 1951-08-06 1955-12-15 Deutsche Edelstahlwerke Ag Process for making a permanent magnet alloy.
US4039318A (en) * 1976-07-19 1977-08-02 Eutectic Corporation Metaliferous flame spray material for producing machinable coatings
US4741974A (en) * 1986-05-20 1988-05-03 The Perkin-Elmer Corporation Composite wire for wear resistant coatings
IL95930A0 (en) * 1989-10-30 1991-07-18 Lanxide Technology Co Ltd Anti-ballistic materials and methods of making the same
FR2669645A1 (en) 1990-11-22 1992-05-29 Castolin Sa PROCESS FOR PREPARING HIGH ADHERENCE LAYERS
DE4328732C1 (en) 1993-08-26 1995-02-16 Castolin Sa Process for producing a thermally sprayed metal-containing layer and a material for this purpose
US6156443A (en) 1998-03-24 2000-12-05 National Research Council Of Canada Method of producing improved erosion resistant coatings and the coatings produced thereby
US6258185B1 (en) * 1999-05-25 2001-07-10 Bechtel Bwxt Idaho, Llc Methods of forming steel
DE10036262B4 (en) * 2000-07-26 2004-09-16 Daimlerchrysler Ag Process for the preparation of a surface layer and surface layer
US6513728B1 (en) 2000-11-13 2003-02-04 Concept Alloys, L.L.C. Thermal spray apparatus and method having a wire electrode with core of multiplex composite powder its method of manufacture and use
DE10259141A1 (en) 2002-12-18 2004-07-08 Corodur Verschleiss-Schutz Gmbh Material system for thermally coating metallic components subjected to wear and/or corrosion comprises a metallic sleeve made from nickel or nickel alloy and a filler made from vanadium carbides
DE10306919B4 (en) * 2003-02-19 2006-08-17 Daimlerchrysler Ag Composite of intermetallic phases and ceramics, manufacturing process and use
CN100540720C (en) * 2003-06-06 2009-09-16 迈克尔·沃尔特·塞茨 The composite wire material and the using method that are used for coated substrate
US7482061B2 (en) * 2004-11-30 2009-01-27 Momentive Performance Materials Inc. Chromium free corrosion resistant surface treatments using siliconized barrier coatings
FR2886182B1 (en) * 2005-05-26 2009-01-30 Snecma Services Sa SUPERALLIAGE POWDER
US9422616B2 (en) * 2005-08-12 2016-08-23 Kennametal Inc. Abrasion-resistant weld overlay

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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KR20120009422A (en) 2012-02-01
CN102387870B (en) 2015-05-20
WO2010110873A1 (en) 2010-09-30
MX2011009089A (en) 2011-09-27
PL2414106T3 (en) 2021-05-31
CN102387870A (en) 2012-03-21
JP5275509B2 (en) 2013-08-28
CA2756033C (en) 2014-01-28
JP2012521496A (en) 2012-09-13
KR101548553B1 (en) 2015-09-01
EP2414106A1 (en) 2012-02-08
AU2010229319A1 (en) 2011-10-13
AU2010229319B2 (en) 2015-09-17
CA2756033A1 (en) 2010-09-30

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