WO2016160400A1 - Pulvérisation thermique de revêtements de réparation et de protection - Google Patents

Pulvérisation thermique de revêtements de réparation et de protection Download PDF

Info

Publication number
WO2016160400A1
WO2016160400A1 PCT/US2016/023435 US2016023435W WO2016160400A1 WO 2016160400 A1 WO2016160400 A1 WO 2016160400A1 US 2016023435 W US2016023435 W US 2016023435W WO 2016160400 A1 WO2016160400 A1 WO 2016160400A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
graphene oxide
metal
powder
oxide flakes
Prior art date
Application number
PCT/US2016/023435
Other languages
English (en)
Inventor
Sudipta Seal
David Ward
Shashank SARAF
Ankur Gupta
Original Assignee
University Of Central Florida Research Foundation, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University Of Central Florida Research Foundation, Inc. filed Critical University Of Central Florida Research Foundation, Inc.
Priority to US15/561,396 priority Critical patent/US20180105918A1/en
Priority to JP2017550536A priority patent/JP6603729B2/ja
Publication of WO2016160400A1 publication Critical patent/WO2016160400A1/fr

Links

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
    • 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
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating 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
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • 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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • 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
    • C23C4/134—Plasma 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
    • C23C4/18—After-treatment
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes

Definitions

  • the present invention relates in general to the field of graphite, and more particularly, to compositions and methods of thermal spray of repair and protective coatings.
  • Plasma spray is one of the most versatile forms of a thermal spray process. Plasma is capable of spraying all materials that are considered spray able.
  • an arc is formed in between two electrodes in a plasma forming gas, which usually consists of either argon/hydrogen or argon/helium.
  • a plasma forming gas usually consists of either argon/hydrogen or argon/helium.
  • the plasma gas As the plasma gas is heated by the arc, it expands and is accelerated through a shaped nozzle, creating velocities up to MACH 2.
  • Temperatures in the arc zone can approach 36,000°F (19,982°C).
  • Temperatures in the plasma jet can still be 18,000°F (9,982°C) several centimeters from the exit of the nozzle.
  • Powders may be injected after the plasma. This technique is sometimes referred to as remote plasma deposition. It relies on placing the powder in the jet stream where gas is no longer ionized but is a highly energetic species.
  • Cold spraying In the cold spray coating technique, powder particles are accelerated to supersonic velocities (600-1500 m/s) by a carrier gas flowing under large pressure difference (up to 3.5 MPa) through a de Laval type of nozzle and made to impact onto a substrate.
  • Cold spraying has unique advantages, such as: minimal effects on the material sprayed, like oxidation, grain coarsening or phase changes, produces highly dense coatings, and substrate is not affected during the coating process.
  • cold plasma spraying was used to deposit a blend of aluminum powder that was an agglomeration of powders comprising aluminum-silicon and CNTs.
  • the powder feeder used was a Praxair 1264HP.
  • the powder feeder has a maximum pressure capability of 3.4 MPa.
  • the main gas pressure was kept at a pressure of 2.9 MPa with the use of an additional Argon or Nitrogen carrier gas for the powder delivery.
  • the carrier gas was kept O. lMPa to facilitate the injection of the powder into the jet.
  • the nozzle was fixed to a frame and the substrate was fixed onto an X-Y traverse table, the movement of which was programmable by using a computer. Eight layers were sprayed to build up the coating thickness on a 6061 aluminum alloy substrate resulting in improved strength and enhanced corrosion protection.
  • Thermal spray coatings have numerous inherent defects. The coatings lack bulk strength. Development of residual stress lowers the adhesion strength at high thicknesses. High temperatures during deposition create unwanted oxides. The addition of the graphene or graphene oxide has proven to increase cohesion and adhesion strength at large thicknesses in the model composition, Nickel - 5% Aluminum. It has also proven to reduce unwanted (metallic) oxide content within the coatings.
  • thermal spray powders There are hundreds of commercially available thermal spray powders. Many of those powder compositions are approved by the OEM for specific repairs on jet engine components. Many of these specific repairs would benefit from increased strength and wear properties.
  • Plasma spray deposition technology is one that directly translates to large area applications.
  • Carbon nanotubes can be deposited using a plasma spray process to enhance mechanical strength and corrosion protection. This process used carbon nanotubes placed in a polymer suspension. The suspension was then aerosolized in a spray dryer to form micron-scale polymer carbon nanotube composite particles. The composite particles are injected past the peak energy portion of the plasma where the energetic kinetic of the plasma both evaporates the polymer host and accelerates the superheated carbon nanotubes to supersonic speeds prior to impact on the surface of a substrate. The plasma itself also bathes the surface of the substrate with energetic monotonically decaying ionized particles.
  • a Graphene or graphene oxide (G/GO) reinforced composite was achieved using thermal spray.
  • the first method uses dry mixing all of the components of the composite material in a mill to form a homogenous dispersion of all of the elements in the powder.
  • the powder is then injected just beyond the plasma into what is referred to as the flame section into the plasma stream.
  • the plasma stream both heats the powder and accelerates it to high velocities.
  • the combination of heated particles traveling at high velocities allows the powders to be deposited on a substrate forming a composite coating.
  • the second approach is to suspend the G/GO in a solvent at a concentration that allows the suspension to be aerosolized and injected into a cooler portion of the plasma gas stream.
  • an inert gas shroud eliminates the super-heated powder from either burning the G/GO in the presence of oxygen and prevents the formation of an unwanted metal oxide phase in the deposited composite.
  • the coatings created by this invention have higher strength and better wear properties than coatings created using only the stock Ni-185 powder.
  • the simple modification of the powder composition increased the mechanical properties of the resulting coatings. Modifying the conventional thermal spray configurations with either the inert shroud or the solution suspension further increases these properties and maximizes the retention of the additive within the coatings.
  • the present invention includes a method of depositing a composite on a surface comprising: providing a surface; providing graphene/graphene oxide flakes; providing metal and/or metal oxide powder; and thermally spraying the graphene/graphene oxide flakes together with the metal and/or metal oxide material on said surface, whereby the resulting composite has enhance mechanical and corrosion resistant properties.
  • the graphene/graphene oxide flakes and the metal and/or metal oxide material are dry mixed together prior to spraying.
  • the metal and/or metal oxide powder is N1/AI2O 3 powder.
  • the graphene/graphene oxide flakes are introduced as an atomization of a suspension separately from the metallic powder.
  • the graphene/graphene oxide flakes are suspended in water or another polar solvent. In another aspect, the concentration of the graphene/graphene oxide flakes suspension is from 0.1% and 0.5% wt. In another aspect, the graphene has an oxidation level > ⁇ % wt. In another aspect, the graphene/graphene oxide flakes are suspended in ethanol or another non-polar solvent. In another aspect, the concentration of the graphene/graphene oxide flakes suspension is from 0.1% and 0.5% wt. In another aspect, the graphene has an oxidation level > ⁇ % wt.
  • the present invention includes a method of depositing a composite on a surface comprising: providing a surface; providing crystalline graphene/graphene oxide flakes suspended in water or another polar solvent; providing metal and/or metal oxide powder; and thermally spraying the crystalline graphene/graphene oxide flakes together with the metal and/or metal oxide material on said surface, whereby the resulting composite has enhance mechanical and corrosion resistant properties.
  • the crystalline graphene/graphene oxide flakes and the metal and/or metal oxide material are dry mixed together prior to spraying.
  • the metal and/or metal oxide powder is N1/AI2O 3 powder.
  • the crystalline graphene/graphene oxide flakes are introduced as an atomization of a suspension separately from the metallic powder.
  • the crystalline graphene/graphene oxide flakes are suspended in water are from 0.1% to 0.5% wt to volume.
  • the concentration of the crystalline graphene/graphene oxide flakes suspension is from 0.1% to 0.5% wt to volume in a polar solvent.
  • the crystalline graphene/graphene oxide flakes has an oxidation level > ⁇ % wt.
  • the graphene flakes are suspended in ethanol or another non-polar solvent.
  • the concentration of the crystalline graphene/graphene oxide flakes suspension is from 0.1% to 0.5% wt.
  • the graphene has an oxidation level >1% wt.
  • FIG. 1 shows a TEM, which shows coatings having a very high efficiency of G/GO retention
  • FIG. 2 is a SEM showing other enhanced properties
  • FIG. 3 shows a tafel plot of the plasma spray composite material.
  • a powder that includes the components of the composite were mixed in a plastic container using a horizontal jar mill, a speed from 20 RPM to 1000RPM preferably 100 RPM, for between 2 and 10 hours but at least 6 hours continuously.
  • the powder constituents include 10: 1 ratio of Nickel to Alumina powder and a small amount (0.05% - 4.0% wt) of the graphene and/or graphene oxide.
  • the graphene and/or graphene oxide is a crystalline graphene and/or graphene oxide.
  • the combined powder (G/GO/AI2O 3 ) is injected into the gas stream beyond the plasma. This region is often referred to as the plasma's flame and consists of a combination of ionized species and highly energetic molecules.
  • An inert, argon gas shroud is used to prevent oxidizing or burning of the G/GO.
  • G/GO can oxidize or burn at temperatures greater than 400°C in the presence of oxygen and prevent the formation of an unwanted metal (nickel) oxide.
  • the insertion of the G/GO/AI2O 3 powder occurs in a region ranging from 0.5 mm to 20 mm down stream from the plasma. The insertion of powder creates a small amount of turbulence in the gas stream inducing additional mixing of the powders. This produces a coating with a uniform distribution of G/GO through out the N1/AI2O 3 deposition.
  • the GO/N1/AI2O 3 composite coating has improved microstructure, decreased unwanted (metallic) oxide phases, enhanced mechanical properties, and ware resistance properties.
  • G/GO can be introduced into the composite through an atomization of a suspension of the G/GO material separately from the metallic powder.
  • the G/GO flakes can be suspended in a solution and sonicated to achieve a uniform dispersion.
  • the GO suspension solution is water or another polar solvent where the GO has an oxidation level > ⁇ % wt.
  • the GO suspension solution is ethanol or another non-polar solvent where the GO has and oxidation level ⁇ 1% wt.
  • the concentration of the G/GO suspension was demonstrated from 0.1% and 0.5% wt. Concentrations greater than 1% wt are too viscous to be easily aerosolized.
  • the aerosolized droplets are injected into the gas stream at a flow rate between 5 mL/min and 200 mL/min but nominally at flow rates 40 mL/min and 90 mL/min.
  • the aerosolized droplets are injected into the non-ionized gas stream of the plasma spray system in a region that has sufficient energy to vaporize the liquid but not bum or other wise damage the G/GO additive.
  • the G/GO droplet insertion point occurs in a region ranging from 0.5 mm to 40 mm downstream from the plasma plume.
  • the N1/AI2O 3 powder is inserted to the hottest section of the plasma plume or flame using the conventional method to ensure uniform melting.
  • N1/AI2O 3 powder and G/GO droplets create a small amount of turbulence in the gas stream inducing additional mixing inflight and are deposited simultaneously.
  • the plasma flame/plume is enclosed in an inert gas shroud to prevent the formation of unwanted metal oxides and reduce the combustion of G/GO in air.
  • FIG. 2 shows a tafel plot of the plasma spray composite material.
  • a Graphene or graphene oxide (G/GO) reinforced composite was achieved using thermal spray.
  • Two delivery methods were used to inject the graphene or graphene oxide into the plasma spray system.
  • the first method used dry mixing all of the components of the composite material in a mill to form a homogenous dispersion of all of the elements in the powder.
  • the powder is then injected just beyond the plasma, e.g., into an area of the plasma that is referred to as the flame section, into the plasma stream.
  • the plasma stream both heats the powder and accelerates it to high velocities.
  • the combination of heated particles traveling at high velocities allows the powders to be deposited on a substrate forming a composite coating.
  • the second method used suspends the G/GO in a solvent at a concentration that allows the suspension to be aerosolized and injected into a cooler portion of the plasma gas stream.
  • an inert gas can be added as a shroud that eliminates the super-heated powder from either burning the G/GO in the presence of oxygen and prevents the formation of an unwanted metal oxide phase in the deposited composite.
  • the coatings created by this invention have higher strength and better wear properties than coatings created using only the stock Ni-185 powder.
  • the modification of the powder composition increased the mechanical properties of the resulting coatings. Modifying the conventional thermal spray configurations with either the inert shroud or the solution suspension further increases these properties and maximizes the retention of the additive within the coatings.
  • compositions of the invention can be used to achieve methods of the invention.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises"), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • “comprising” may be replaced with “consisting essentially of or “consisting of.
  • the phrase “consisting essentially of requires the specified integer(s) or steps as well as those that do not materially affect the character or function of the claimed invention.
  • the term “consisting” is used to indicate the presence of the recited integer (e.g., a feature, an element, a characteristic, a property, a method/process step or a limitation) or group of integers (e.g., feature(s), element(s), characteristic(s), propertie(s), method/process steps or limitation(s)) only.
  • A, B, C, or combinations thereof refers to all permutations and combinations of the listed items preceding the term.
  • A, B, C, or combinations thereof is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
  • expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth.
  • BB BB
  • AAA AAA
  • AB BBC
  • AAABCCCCCC CBBAAA
  • CABABB CABABB
  • words of approximation such as, without limitation, "about”, “substantial” or “substantially” refers to a condition that when so modified is understood to not necessarily be absolute or perfect but would be considered close enough to those of ordinary skill in the art to warrant designating the condition as being present.
  • the extent to which the description may vary will depend on how great a change can be instituted and still have one of ordinary skilled in the art recognize the modified feature as still having the required characteristics and capabilities of the unmodified feature.
  • a numerical value herein that is modified by a word of approximation such as "about” may vary from the stated value by at least ⁇ 1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%.
  • compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Landscapes

  • 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)

Abstract

La présente invention concerne un procédé pour le renforcement, au graphène ou à l'oxyde de graphène, d'un revêtement métallique appliqué par pulvérisation thermique. Les propriétés exceptionnelles du graphène et de l'oxyde de graphène les rendent des options particulièrement intéressantes pour accroître les propriétés mécaniques d'une variété de matériaux. Des développements récents relatifs à la fabrication d'oxyde de graphène et de poudres d'oxyde de graphène ont nettement réduit le coût de ces derniers, les rendant viables en tant qu'additifs dans des poudres de pulvérisation thermique destinées à être largement utilisées dans l'industrie.
PCT/US2016/023435 2015-03-27 2016-03-21 Pulvérisation thermique de revêtements de réparation et de protection WO2016160400A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US15/561,396 US20180105918A1 (en) 2015-03-27 2016-03-21 Thermal Spray of Repair and Protective Coatings
JP2017550536A JP6603729B2 (ja) 2015-03-27 2016-03-21 修復及び保護コーティングの溶射

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562139006P 2015-03-27 2015-03-27
US62/139,006 2015-03-27

Publications (1)

Publication Number Publication Date
WO2016160400A1 true WO2016160400A1 (fr) 2016-10-06

Family

ID=57007228

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/023435 WO2016160400A1 (fr) 2015-03-27 2016-03-21 Pulvérisation thermique de revêtements de réparation et de protection

Country Status (3)

Country Link
US (1) US20180105918A1 (fr)
JP (1) JP6603729B2 (fr)
WO (1) WO2016160400A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9758379B2 (en) 2013-03-08 2017-09-12 University Of Central Florida Research Foundation, Inc. Large scale oxidized graphene production for industrial applications
US9828290B2 (en) 2014-08-18 2017-11-28 Garmor Inc. Graphite oxide entrainment in cement and asphalt composite
US9951436B2 (en) 2011-10-27 2018-04-24 Garmor Inc. Composite graphene structures
US10535443B2 (en) 2013-03-08 2020-01-14 Garmor Inc. Graphene entrainment in a host

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL3914744T3 (pl) * 2019-01-27 2024-05-06 Lyten, Inc. Urządzenie do wytwarzania materiałów typu covetic
CN110777277B (zh) * 2019-11-11 2020-08-11 沈阳航空航天大学 激光沉积制造氧化石墨烯铝基复合材料及其制备方法
CN111139424B (zh) * 2019-12-31 2021-08-27 陕西斯瑞新材料股份有限公司 一种提高热辐射系数的不锈钢湿氢制备方法及应用
CN111394681A (zh) * 2020-04-24 2020-07-10 中石化石油工程技术服务有限公司 一种mwd仪器外筒表面抗冲蚀石墨烯复合梯度涂层
CN114405797B (zh) * 2021-12-21 2022-10-28 苏州大学 一种基于液料等离子喷涂技术的石墨烯涂层及其喷涂工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110143018A1 (en) * 2009-10-07 2011-06-16 Shufu Peng Methods and systems for making battery electrodes and devices arising therefrom
US20110267673A1 (en) * 2008-01-31 2011-11-03 Ajjer Llc Sealants and conductive busbars for chromogenic devices
US20110281034A1 (en) * 2010-05-12 2011-11-17 Lee James L Layer-by-layer fabrication method of sprayed nanopaper
US20140117745A1 (en) * 2012-10-26 2014-05-01 Trek Bicycle Corp. Enhanced bicycle braking surfaces
US20140272199A1 (en) * 2013-03-14 2014-09-18 Yi-Jun Lin Ultrasonic spray coating of conducting and transparent films from combined graphene and conductive nano filaments

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6052581A (ja) * 1983-09-02 1985-03-25 Hitachi Ltd 耐水蒸気酸化性に優れた金属部材
JPH0745542Y2 (ja) * 1990-11-30 1995-10-18 山村硝子株式会社 製瓶機におけるゴブ案内用通路部材
KR100494239B1 (ko) * 2002-09-11 2005-06-13 한국기계연구원 ＡＩ－ＳｉＣ 복합재료 박판의 제조방법
FR2900351B1 (fr) * 2006-04-26 2008-06-13 Commissariat Energie Atomique Procede de preparation d'une couche nanoporeuse de nanoparticules et couche ainsi obtenue
US8114375B2 (en) * 2008-09-03 2012-02-14 Nanotek Instruments, Inc. Process for producing dispersible nano graphene platelets from oxidized graphite
JP5146402B2 (ja) * 2009-05-19 2013-02-20 トヨタ自動車株式会社 炭素粒子含有被膜の成膜方法、伝熱部材、パワーモジュール、及び車両用インバータ
DE102009026655B3 (de) * 2009-06-03 2011-06-30 Linde Aktiengesellschaft, 80331 Verfahren zur Herstellung eines Metallmatrix-Verbundwerkstoffs, Metallmatrix-Verbundwerkstoff und seine Verwendung
KR101456905B1 (ko) * 2010-02-19 2014-10-31 가부시키가이샤 인큐베이션 얼라이언스 탄소 재료 및 그 제조 방법
JP5569933B2 (ja) * 2010-06-28 2014-08-13 株式会社倉本鉄工所 溶射材料及び該溶射材料を用いたセラミックス粒子分散型ｍｍｃ皮膜
CN102530926A (zh) * 2010-12-10 2012-07-04 东丽纤维研究所（中国）有限公司 一种基于连二亚硫酸盐制备石墨烯的方法
JP5852131B2 (ja) * 2010-12-15 2016-02-03 スルザー メテコ（ユーエス）インコーポレイテッド サスペンションプラズマ溶射用の圧力式液体供給システム
RU2456361C1 (ru) * 2011-01-11 2012-07-20 Федеральное государственное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" Металломатричный композит
ES2540462T3 (es) * 2011-02-16 2015-07-09 Grupo Antolín-Ingeniería, S.A. Proceso para obtener nanoplaquetas de óxido de grafeno y nanoplaquetas de grafeno
JP5995523B2 (ja) * 2012-05-23 2016-09-21 大阪瓦斯株式会社 グラフェンシート水分散体及びその製造方法並びにグラフェン含有構造体
KR102014992B1 (ko) * 2013-03-06 2019-10-21 삼성전자주식회사 해도형 광굴절 고분자 복합체, 상기 해도형 광굴절 고분자 복합체를 포함하는 광굴절 소자 및 광학 장치
US10006141B2 (en) * 2013-06-20 2018-06-26 Baker Hughes, A Ge Company, Llc Method to produce metal matrix nanocomposite
US20150064451A1 (en) * 2013-08-29 2015-03-05 General Electric Company Coating, coating method, and coated article
DE102013014915A1 (de) * 2013-09-11 2015-03-12 Airbus Defence and Space GmbH Kontaktwerkstoffe für Hochspannungs-Gleichstrombordsysteme

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110267673A1 (en) * 2008-01-31 2011-11-03 Ajjer Llc Sealants and conductive busbars for chromogenic devices
US20110143018A1 (en) * 2009-10-07 2011-06-16 Shufu Peng Methods and systems for making battery electrodes and devices arising therefrom
US20110281034A1 (en) * 2010-05-12 2011-11-17 Lee James L Layer-by-layer fabrication method of sprayed nanopaper
US20140117745A1 (en) * 2012-10-26 2014-05-01 Trek Bicycle Corp. Enhanced bicycle braking surfaces
US20140272199A1 (en) * 2013-03-14 2014-09-18 Yi-Jun Lin Ultrasonic spray coating of conducting and transparent films from combined graphene and conductive nano filaments

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9951436B2 (en) 2011-10-27 2018-04-24 Garmor Inc. Composite graphene structures
US9758379B2 (en) 2013-03-08 2017-09-12 University Of Central Florida Research Foundation, Inc. Large scale oxidized graphene production for industrial applications
US10535443B2 (en) 2013-03-08 2020-01-14 Garmor Inc. Graphene entrainment in a host
US9828290B2 (en) 2014-08-18 2017-11-28 Garmor Inc. Graphite oxide entrainment in cement and asphalt composite

Also Published As

Publication number Publication date
US20180105918A1 (en) 2018-04-19
JP6603729B2 (ja) 2019-11-06
JP2018516311A (ja) 2018-06-21

Similar Documents

Publication Publication Date Title
US20180105918A1 (en) Thermal Spray of Repair and Protective Coatings
US9328918B2 (en) Combustion cold spray
Yang et al. Ablation mechanism of HfC-HfO2 protective coating for SiC-coated C/C composites in an oxyacetylene torch environment
US20060222777A1 (en) Method for applying a plasma sprayed coating using liquid injection
US20130095340A1 (en) Hybrid methodology for producing composite, multi-layered and graded coatings by plasma spraying utilizing powder and solution precursor feedstock
EP2528966B1 (fr) Composition abrasable et procédé de fabrication
US20110039024A1 (en) Cold Gas Spraying Method
JP2014522913A5 (fr)
US10745793B2 (en) Ceramic coating deposition
Sun et al. Study on stainless steel 316L coatings sprayed by a novel high pressure HVOF
JP5017675B2 (ja) 皮膜の製造方法
Miranda et al. Atmospheric plasma spray processes: From micro to nanostructures
JP5247049B2 (ja) 部分的に合金化されたジルコニア粉末
JP2007291523A (ja) 溶射により形成されるコーティング及びその形成の方法
Govindarajan et al. Understanding the Formation of Vertical Cracks in Solution Precursor Plasma Sprayed Yttria‐Stabilized Zirconia Coatings
Jazi Advanced plasma spray applications
US20180251881A1 (en) Ceramic coating deposition
Sánchez et al. Characterization of nanostructured ceramic and cermet coatings deposited by plasma spraying
EP2956566A1 (fr) Procede de depot d'un revetement contre la corrosion
US20120251885A1 (en) High power, wide-temperature range electrode materials, electrodes, related devices and methods of manufacture
Yoo et al. Hafnium carbide coatings deposited by suspension vacuum plasma spraying for ultra-high-temperature oxidation barrier on carbon composites
Manjunath et al. Dry Sliding Wear Behaviour of Plasma SprayedAl2O3-30% Mo and Mo Coating
Lu et al. Microstructure analysis of laser remelting for thermal barrier coatings on the surface of titanium alloy
CN114293127B (zh) 复合封严涂层及其制备方法、机械零件和动力装置
CN104862637A (zh) Co-ZrO2-HfO2纳米涂层材料及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16773747

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15561396

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2017550536

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 06/02/2018)

122 Ep: pct application non-entry in european phase

Ref document number: 16773747

Country of ref document: EP

Kind code of ref document: A1