EP2414106B1 - Revêtement sans chrome, procédé de sa production et câble composite - Google Patents

Revêtement sans chrome, procédé de sa production et câble composite 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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German (de)
English (en)
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EP2414106A1 (fr
EP2414106A4 (fr
Inventor
Michael W. Seitz
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General Electric Technology GmbH
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General Electric Technology GmbH
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Priority to PL10756469T priority Critical patent/PL2414106T3/pl
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Publication of EP2414106A4 publication Critical patent/EP2414106A4/fr
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    • 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.
  • 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)
  • Nonmetallic Welding Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (17)

  1. Précurseur de revêtement métallique sans chrome comprenant
    au moins 54 % en poids d'au moins un métal de base choisi dans le groupe constitué de fer, nickel, cobalt, plomb, zinc, cuivre, étain et aluminium, ledit précurseur de revêtement comprenant toujours au moins 1 % en poids d'aluminium,
    entre 1 % et 15 % en poids de silicium, entre 1 % et 15 % en poids de titane, et entre 1 % et 15 % en poids de bore.
  2. Précurseur de revêtement métallique sans chrome selon la revendication 1 comprenant au moins 68 % en poids d'au moins un métal de base choisi dans le groupe constitué de fer, nickel, cobalt, plomb, zinc, cuivre, étain et aluminium, ledit métal de base comprenant toujours au moins 2 % en poids d'aluminium et/ou silicium allié(s),
    entre 2 % et 10 % en poids de silicium, entre 2 % et 10 % en poids de titane, et entre 2 % et 10 % en poids de bore.
  3. Précurseur de revêtement métallique sans chrome selon la revendication 1 comprenant au moins 76 % en poids d'au moins un métal de base choisi dans le groupe constitué de fer, nickel, cobalt et aluminium, ledit métal de base comprenant toujours au moins 3 % en poids d'aluminium allié,
    entre 3 % et 7 % en poids de silicium, entre 3 % et 7 % en poids de titane, et entre 3 % et 7 % en poids de bore.
  4. Précurseur de revêtement métallique sans chrome selon la revendication 1 comprenant un alliage de nickel, de fer et/ou de cobalt avec de l'aluminium et une masse de particules contenant du silicium, du titane et du bore.
  5. Composition fondue de revêtement métallique sans chrome comprenant, en vrac sur une base pondérale, 70 % à 90 % en poids d'au moins un métal de base choisi dans le groupe constitué de fer, nickel, cobalt, plomb, zinc, cuivre, étain et aluminium, ladite composition de revêtement métallique comprenant toujours au moins 2 % en poids d'aluminium, 2 % à 10 % en poids de titane, 2 % à 10 % en poids de silicium, et 2 % à 10 % en poids de bore.
  6. Composition fondue de revêtement métallique sans chrome selon la revendication 5 comprenant dans la plage allant de 2 % à 10 % en poids d'aluminium.
  7. Composition fondue de revêtement métallique sans chrome selon la revendication 6 dans laquelle l'au moins un métal de base est choisi dans le groupe constitué de nickel, fer et cobalt.
  8. Composition fondue de revêtement métallique sans chrome selon la revendication 7 dans laquelle le métal de base comprend du nickel, ladite composition comprenant en outre, en vrac sur une base pondérale, au moins un constituant supplémentaire choisi dans le groupe constitué de 0,1 % à 10 % en poids de fer, 0,1 % à 10 % en poids de molybdène, et 0,1 % à 10 % en poids de tungstène.
  9. Fil composite ne contenant pas de chrome pour produire un revêtement résistant à l'usure et résistant à la corrosion sur un substrat, ledit fil composite comprenant une gaine externe métallique dans la plage de 70 à 95 % en poids et un noyau interne de particules dans la plage de 5 à 30 % en poids, dans lequel la gaine externe métallique comprend au moins 70 pour cent en poids d'un métal de base et au moins 2 pour cent en poids d'aluminium et/ou silicium allié(s), dans lequel le métal de base comprend au moins l'un parmi nickel, fer et cobalt, et dans lequel le noyau interne de particules comprend dans la plage de 15 % à 30 % en poids de titane, dans la plage de 15 % à 35 % en poids de silicium, dans la plage de 20 % à 50 % en poids de bore, et dans la plage de 0 % à 15 % en poids de carbone.
  10. Fil composite selon la revendication 9 dans lequel la gaine externe comprend un alliage de nickel et d'aluminium et/ou de silicium.
  11. Fil composite selon la revendication 9 dans lequel la gaine externe comprend dans la plage de 85 à 98 pour cent en poids de nickel et dans la plage de 2 à 15 pour cent en poids d'aluminium et/ou silicium allié(s).
  12. Fil composite selon la revendication 11 dans lequel la gaine externe comprend dans la plage de 90 à 97 pour cent en poids de nickel et dans la plage de 3 à 10 pour cent en poids d'aluminium allié.
  13. Fil composite selon la revendication 9 dans lequel le noyau interne de particules comprend dans la plage de 20 % à 30 % en poids de titane, dans la plage de 20 % à 30 % en poids de silicium, dans la plage de 30 % à 40 % en poids de bore, et dans la plage de 0 % à 15 % en poids de carbone.
  14. Fil composite selon la revendication 13 dans lequel le noyau interne de particules comprend un mélange dans la plage de 50 % à 60 % en poids d'une source de TiSi et dans la plage de 40 % à 50 % en poids de B4C.
  15. Fil composite selon la revendication 9 comprenant une gaine externe métallique dans la plage de 80 à 90 % en poids et un noyau interne de particules dans la plage de 10 à 20 % en poids.
  16. Fil composite selon la revendication 9 comprenant en outre dans la plage de 0,1 % à 10 % en poids de molybdène, 0,1 % à 10 % en poids de tungstène, et 0,1 % à 10 % en poids de carbone.
  17. Procédé de formation d'un revêtement résistant à l'usure et résistant à la corrosion sur un substrat comprenant les étapes consistant à : fournir un fil composite selon la revendication 9 et employer le fil pour former le revêtement, dans lequel l'étape consistant à employer le fil pour former le revêtement comprend la pulvérisation thermique du fil sur le substrat.
EP10756469.2A 2009-03-24 2010-03-24 Revêtement sans chrome, procédé de sa production et câble composite Active EP2414106B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL10756469T PL2414106T3 (pl) 2009-03-24 2010-03-24 Bezchromowa powłoka metaliczna, sposób formowania takiej powłoki i drutu kompozytowego

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US21090309P 2009-03-24 2009-03-24
PCT/US2010/000858 WO2010110873A1 (fr) 2009-03-24 2010-03-24 Revêtement sans chrome pour un substrat

Publications (3)

Publication Number Publication Date
EP2414106A1 EP2414106A1 (fr) 2012-02-08
EP2414106A4 EP2414106A4 (fr) 2014-05-14
EP2414106B1 true EP2414106B1 (fr) 2020-12-30

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EP (1) EP2414106B1 (fr)
JP (1) JP5275509B2 (fr)
KR (1) KR101548553B1 (fr)
CN (1) CN102387870B (fr)
AU (1) AU2010229319B2 (fr)
CA (1) CA2756033C (fr)
MX (1) MX2011009089A (fr)
PL (1) PL2414106T3 (fr)
WO (1) WO2010110873A1 (fr)

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CN109989999A (zh) * 2017-12-29 2019-07-09 圣戈班性能塑料帕姆普斯有限公司 轴承部件及其制备和使用方法

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Also Published As

Publication number Publication date
MX2011009089A (es) 2011-09-27
EP2414106A1 (fr) 2012-02-08
CA2756033A1 (fr) 2010-09-30
EP2414106A4 (fr) 2014-05-14
WO2010110873A1 (fr) 2010-09-30
AU2010229319A1 (en) 2011-10-13
KR101548553B1 (ko) 2015-09-01
AU2010229319B2 (en) 2015-09-17
PL2414106T3 (pl) 2021-05-31
KR20120009422A (ko) 2012-02-01
JP2012521496A (ja) 2012-09-13
CA2756033C (fr) 2014-01-28
CN102387870B (zh) 2015-05-20
JP5275509B2 (ja) 2013-08-28
CN102387870A (zh) 2012-03-21

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