Classifications

• • 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
  • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
  • C23C4/06—Metallic material
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
  • C23C4/06—Metallic material
  • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
• • 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

• This invention relates to chrome-free metal coating compositions and thermal spray wires for producing same.
• a composite of precursor materials for forming a chromium-free metallic coating In one embodiment of the invention, there is provided a composite of precursor materials for forming a chromium-free metallic coating. In another embodiment of the invention, the precursor materials are provided in the form of a composite wire. In a further embodiment of the invention, 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 about 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 alloyed aluminum and/or silicon, 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 above constituents can be provided in a composite wire in accordance with another embodiment of the invention.
• the composite wire usually comprises a metallic outer sheath in the range of 70 to 95% by weight and an inner core in the range of about 5 to about 30% by weight.
• the metallic outer sheath preferably comprises at least about 70 weight percent of a base metal readily capable of being rolled and drawn into the sheath and at least about 2 weight percent alloyed aluminum and/or silicon.
• the inner core in one embodiment of the invention comprises in the range of about 15% to about 30% titanium, in the range of about 15% to about 35% silicon, in the range of about 20% to about 50% boron, and in the range of 0% to 15% carbon, all preferably in particle form.
• the composite wire can be 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, about 60 to about 90% of base metal, at least about 2% aluminum, about 2 to about 10% titanium, about 2 to about 10% silicon, and about 2 to about 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 about 54% by weight.
• the base metal constituent usually 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 alloyed aluminum and/or silicon, 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 about 68% by weight and contains an aluminum and/or silicon component alloyed therein in an amount of at least about 2% by weight, based on mass of coating precursor.
• the silicon, titanium and boron are each present in amount between about 2% and 10 percent by weight.
• the base metal constituent is present in an amount of at least about 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 comprises at least about 3% by weight of aluminum, based on mass of coating precursor.
• the silicon, titanium and boron are present, preferably as a mass in particle form, in amount between about 4% and about 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 about 5 to about 30% by weight.
• the composite wire comprises a metallic outer sheath in the range of about 75 to about 85% by weight and an inner core in the range of about 15 to about 25% by weight.
• the metallic outer sheath preferably comprises at least about 70 weight percent of a base metal readily capable of being rolled and drawn into the sheath and at least about 2 weight percent alloyed aluminum and/or silicon. Aluminum can also be employed exclusively as the base metal.
• the inner core in one embodiment of the invention comprises in the range of about 15% to about 30% titanium, in the range of about 15% to about 35% silicon, in the range of about 20% to about 50% boron, and in the range of 0% to 15% carbon, all preferably 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 preferably a relatively soft elemental metal or alloy, for example, 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 comprise in the range of about 70 to about 98 percent by weight of nickel and in the range of about 2 to about 30 percent by weight of alloyed aluminum and/or silicon, preferably in the range of about 85 to about 98 percent by weight of nickel and in the range of about 2 to about 15 percent by weight alloyed aluminum and/or silicon, and most preferably about 90 to about 97 percent by weight of nickel and in the range of about 3 to about 10 percent by weight of alloyed aluminum.
• the inner core preferably comprises in the range of about 20% to about 30% titanium, in the range of about 20% to about 30% silicon, in the range of about 30% to about 40% boron, and in the range of 0% to about 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 about 50 to about 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 about 40 to about 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 about 0. 1 to about 10% molybdenum, about 0. 1 to about 10% tungsten, about 0.1 to about 10% neodymium, and about 0. 1 to about 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 about 0. 1 to about 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.
• titanium, silicon and boron can be alloyed in the sheath in the amount of about 2 to about 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 having an outer sheath formed from a metal or alloy, and a powdered inner core, 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 usually comprises, in bulk on a weight basis, about 60 to about 90% of base metal, at least about 2% aluminum, about 2 to about 10% titanium, about 2 to about 10% silicon, and about 2 to about 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 about 0. 1 to about
• 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)
• Nonmetallic Welding Materials (AREA)
• Other Surface Treatments For Metallic Materials (AREA)

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• 2010
  • 2010-03-24 WO PCT/US2010/000858 patent/WO2010110873A1/en active Application Filing
  • 2010-03-24 MX MX2011009089A patent/MX2011009089A/es active IP Right Grant
  • 2010-03-24 CN CN201080013473.5A patent/CN102387870B/zh active Active
  • 2010-03-24 PL PL10756469T patent/PL2414106T3/pl unknown
  • 2010-03-24 CA CA2756033A patent/CA2756033C/en not_active Expired - Fee Related
  • 2010-03-24 KR KR1020117018812A patent/KR101548553B1/ko active IP Right Grant
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