WO2007120207A2 - PROCÉDÉ DE FABRICATION DE REVÊTEMENTS EN MÉTAL AMORPHE RÉSISTANTS À LA CORROSION À PARTIR DE POUDRES DE MÉTAL AMORPHE PULVÉRISÉES AU GAZ PRÉSENTANT DES TAUX DE REFROIDISSEMENT CRITIQUES RELATIVEMENT ÉLEVÉS, PAR OPTIMISATION DE LA DIMENSION GRANULOM&Ea - Google Patents

PROCÉDÉ DE FABRICATION DE REVÊTEMENTS EN MÉTAL AMORPHE RÉSISTANTS À LA CORROSION À PARTIR DE POUDRES DE MÉTAL AMORPHE PULVÉRISÉES AU GAZ PRÉSENTANT DES TAUX DE REFROIDISSEMENT CRITIQUES RELATIVEMENT ÉLEVÉS, PAR OPTIMISATION DE LA DIMENSION GRANULOM&Ea Download PDF

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Publication number
WO2007120207A2
WO2007120207A2 PCT/US2006/044196 US2006044196W WO2007120207A2 WO 2007120207 A2 WO2007120207 A2 WO 2007120207A2 US 2006044196 W US2006044196 W US 2006044196W WO 2007120207 A2 WO2007120207 A2 WO 2007120207A2
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WO
WIPO (PCT)
Prior art keywords
amorphous
metal
particles
deposition
spray
Prior art date
Application number
PCT/US2006/044196
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English (en)
Other versions
WO2007120207A3 (fr
Inventor
Joseph C. Farmer
Jeffery J. Haslam
Nancy Yang
Enrique J. Lavernia
Julie Schoenung
Leo Ajdelsztajn
Larry Kaufman
Craig A. Blue
John H. Perepezko
Original Assignee
The Regents Of The University Of California
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 The Regents Of The University Of California filed Critical The Regents Of The University Of California
Publication of WO2007120207A2 publication Critical patent/WO2007120207A2/fr
Publication of WO2007120207A3 publication Critical patent/WO2007120207A3/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • 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

Definitions

  • the present invention relates to corrosion resistant materials and more particularly to forming corrosion resistant amorphous materials.
  • microcrystalline grains i.e., grains having a size on the order of 10 ⁇ 6 meters
  • desired properties of microcrystalline grains can frequently be improved by reducing the grain size to that of nanocrystalline grains (i.e., grains having a size on the order of 10 ⁇ 9 meters). It is generally more problematic to form grains of nanocrystalline grain size than it is to form grains of microcrystalline grain size. Accordingly, it is desirable to develop improved methods for forming nanocrystalline grain size steel materials. Further, as it is frequently desired to have metallic glass structures, it is desirable to develop methods of forming metallic glasses.” [0006] United States Patent Application No. 2003/0051781 by Daniel J.
  • Both microcrystalline grain internal structures and metallic glass internal structures can have properties which are desirable in particular applications for steel.
  • the amorphous character of metallic glass can provide desired properties.
  • some glasses can have exceptionally high strength and hardness.
  • the particular properties of microcrystalline grain structures are preferred. Frequently, if the properties of a grain structure are preferred, such properties will be improved by decreasing the grain size.
  • microcrystalline grains i.e., grains having a size on the order of 10" 6 meters
  • desired properties of microcrystalline grains can frequently be improved by reducing the grain size to that of nanocrystalline grains (i.e., grains having a size on the order of 10 - 9 meters). It is generally more problematic, and not generally possible utilizing conventional approaches, to form grains of nanocrystalline grain size than it is to form grains of microcrystalline grain size.”
  • Corrosion costs the nation billions of dollars every year. There is an immense quantity of material in various structures undergoing corrosion. For example, approximately 345 million square feet of structure aboard naval ships and crafts require costly corrosion control measures. In addition, fluid and seawater piping, ballast tanks, and propulsions systems require costly corrosion control measures. The use of advanced corrosion-resistant materials to prevent the continuous degradation of this massive surface area would be extremely beneficial.
  • the present invention provides a system for the deposition of full- density, pore-free, corrosion-resistant, thermal-spray amorphous-metal coatings for the protection of a less corrosion resistant substrate.
  • the system comprises using particle-size optimization (PSO), and the integrated sensors and physical separation processes required to achieve PSO, to ensure that the amorphous metal particles are small enough to ensure that the critical cooling rate is achieved throughout the amorphous metal particles.
  • PSO particle-size optimization
  • the particle-size optimization system uses small enough amorphous metal powders in the mixed feed to ensure that the critical cooling rate is achieved throughout the amorphous metal particles, even in cases where the critical cooling rate may be relatively high (>1000 K per second). In other embodiments materials with lower critical cooling rates are used ( ⁇ 100 K per second).
  • the corrosion resistant amorphous metal coating of the present invention has application on ships; oil, gas, and water drilling equipment; earth moving equipment; tunnel- boring machinery; pump impellers and shafts; containers for shipment, storage and disposal of spent nuclear fuel; pressurized water and boiling water nuclear reactors; breeder reactors with liquid metal coolant; metal-ceramic armor; projectiles; gun barrels; tank loader trays; rail guns; non-magnetic hulls; hatches; seals; propellers; rudders; planes; and any other use where corrosion resistance is needed.
  • Corrosion costs the nation billions of dollars every year, with an immense quantity of material in various structures undergoing corrosion.
  • approximately 345 million square feet of structure aboard naval ships and crafts require costly corrosion control measures.
  • the use of the corrosion resistant amorphous metal coating of the present invention to prevent the continuous degradation of this massive surface area would be extremely beneficial.
  • the corrosion resistant amorphous metal coating of the present invention could also be used to coat the entire outer surface of containers for the transportation and long-term storage of high-level radioactive waste (HLW) spent nuclear fuel (SNF), or to protect welds and heat affected zones, thereby preventing exposure to environments that might cause stress corrosion cracking.
  • HW high-level radioactive waste
  • SNF spent nuclear fuel
  • FIG. 1 illustrates one embodiment of a system incorporating the present invention.
  • FIG. 2 illustrates another embodiment of a system incorporating the present invention.
  • FIG. 3 illustrates yet another embodiment of a system incorporating the present invention.
  • Corrosion costs the Department of Defense billions of dollars every year, with an immense quantity of material in various structures undergoing corrosion.
  • approximately 345 million square feet of structure aboard naval ships and crafts require costly corrosion control measures.
  • the use of advanced corrosion-resistant materials to prevent the continuous degradation of this massive surface area would be extremely beneficial.
  • the Fe- based corrosion-resistant, amorphous-metal coatings under development may prove of importance for applications on ships.
  • Such materials could also be used to coat the entire outer surface of containers for the transportation and long-term storage of high-level radioactive waste (HLW) spent nuclear fuel (SNF), or to protect welds and heat affected zones, thereby preventing exposure to environments that might cause stress corrosion cracking. In the future, it may be possible to substitute such high-performance iron-based materials for more-expensive nickel-based alloys, thereby enabling cost savings in various industrial applications.
  • HW radioactive waste
  • SNF spent nuclear fuel
  • new and innovative tools and devices will be enabled specifically by this invention, which is a novel composite material or coating with exceptional corrosion resistance, wear resistance, and damage tolerance. Those devices and tools enabled by this material may include: metal-ceramic armor, projectiles, oil and water drilling equipment, earth moving equipment, and tunnel-boring machinery.
  • Such inventions include, but are not limited to: any modified disc cutter for a tunnel boring machine; any modified bit for an "Alpine Pick" using either amorphous metal coatings, bulk amorphous metals, or derivatives thereof, showing advantages over conventional technology.
  • This embodiment is designated generally by the reference numeral 100.
  • raw materials are induction melted and introduced into a gas atomization process.
  • This gas atomization process in turn produces amorphous metal powders 105 with relatively high critical cooling rate (CCR) and a broad distribution of particle sizes.
  • CCR critical cooling rate
  • these powders are then pneumatically conveyed pass a particle size sensing module which communicates with the particle size controller.
  • the controller can then activate the physical separation process 101.
  • the physical separation process 101 separates the amorphous metal powders 105 into an optimum size fraction 102, and a non-optimum size fraction.
  • the optimum size fraction 102 has a size distribution that enables the CCR to be maintained across the entire diameter of each particle or molten droplet, as those particles or droplets undergoes thermal spraying in process 103, thereby enabling the amorphous nature of the particle to be preserved as it is incorporated into the corrosion and wear resistant amorphous metal coating 104.
  • the non-optimum size fraction is then conveyed to a process element for reforming and remelting, thereby achieving recycle and high overall product yield.
  • the coating 104 has many uses, for example, the coating 104 has application on ships; oil, gas, and water drilling equipment; earth moving equipment; tunnel-boring machinery; pump impellers and shafts; containers for shipment, storage and disposal of spent nuclear fuel; pressurized water and boiling water nuclear reactors; breeder reactors with liquid metal coolant; metal-ceramic armor; projectiles; gun barrels; tank loader trays; rail guns; non-magnetic hulls; hatches; seals; propellers; rudders; planes; and any other use where corrosion resistance is needed.
  • FIG. 2 another embodiment illustrates the present invention in greater detail.
  • This embodiment is designated generally by the reference numeral 200.
  • raw materials 201 are induction melted and introduced into the gas atomization process 202.
  • This gas atomization process in turn produces amorphous metal powders 202 with relatively high critical cooling rate (CCR) and a broad distribution of particle sizes.
  • CCR critical cooling rate
  • these powders are then pneumatically conveyed pass the particle size sensing module 204a which communicates with the particle size controller 204b.
  • the controller can then activate the physical separation process 205.
  • the physical separation process 205 separates the amorphous metal powders 203 into an optimum size fraction 206, and a non-optimum size fraction 209.
  • the optimum size fraction 206 has a size distribution than enables the CCR to be maintained across the entire diameter of each particle or molten droplet, as those particles or droplets undergoes thermal spraying in process 207, thereby enabling the amorphous nature of the particle to be preserved as it is incorporated into the corrosion and wear resistant amorphous metal coating 208.
  • the non-optimum size fraction 209 is then conveyed to process element 210 for reforming and remelting, thereby achieving recycle and high overall product yield. These integrated process steps avoid the incorporation of devitrified particles into the thermal spray coating 210, thereby compromising coating performance.
  • the coating 208 has many uses, for example, the coating 208 has application on ships; oil, gas, and water drilling equipment; earth moving equipment; tunnel-boring machinery; pump impellers and shafts; containers for shipment, storage and disposal of spent nuclear fuel; pressurized water and boiling water nuclear reactors; breeder reactors with liquid metal coolant; metal-ceramic armor; projectiles; gun barrels; tank loader trays; rail guns; nonmagnetic hulls; hatches; seals; propellers; rudders; planes; and any other use where corrosion resistance is needed.
  • FIG. 3 another embodiment of the present invention is illustrated. This embodiment of the present invention is designated generally by the reference numeral 300.
  • the system 300 provides deposition of amorphous-metal coatings.
  • particle-size optimization PSO
  • step 302 critical cooling rate is achieved throughout the amorphous metal particles.
  • step 303 the amorphous metal is used in a spray process.
  • step 305 the spray process produces the coating.
  • Corrosion costs the nation billions of dollars every year, with an immense quantity of material in various structures undergoing corrosion. For example, in addition to fluid and seawater piping, ballast tanks, and propulsions systems, approximately 345 million square feet of structure aboard naval ships and crafts require costly corrosion control measures. The use of the corrosion resistant amorphous metal coating of the present invention to prevent the continuous degradation of this massive surface area would be extremely beneficial.
  • the corrosion resistant amorphous metal coating of the present invention can also be used to coat the entire outer surface of containers for the transportation and long-term storage of high-level radioactive waste (HLW) spent nuclear fuel (SNF), or to protect welds and heat affected zones, thereby preventing exposure to environments that might cause stress corrosion cracking.
  • HW high-level radioactive waste
  • SNF spent nuclear fuel
  • the coating 104 is formed by spray processing 103 as illustrated in FIG. 1.
  • the spray processing 103 can be thermal spray processing or cold spray processing.
  • the coating 104 is produced using particle-size optimization to ensure that the amorphous metal particles are small enough to ensure that the critical cooling rate is achieved throughout the amorphous metal particles.
  • the particle-size optimization method uses small enough amorphous metal powders in the mixed feed to ensure that the critical cooling rate is achieved throughout the amorphous metal particles, even in cases where the critical cooling rate may be relatively high ( ⁇ IOOO K per second).
  • ⁇ IOOO K per second In cases where materials with lower critical cooling rates can be used ( ⁇ 100 K per second), it may be possible to achieve similar results without application of PSO.
  • Predictive computational codes used for the prediction of the optimum particle size for producing thermal spray coatings from amorphous metals without devitrification. These codes are based upon the simultaneous solution of differential equations that: (1) quantify the devitrification kinetics within amorphous metal particles of various sizes, based upon kinetic measurements from wedge casting, differential scanning calorimetry, and differential thermal analysis; (2) quantify the temperature history within amorphous particles of various sizes, based upon transient heat transfer calculations within the spray gun, sub-sonic or hypersonic spray, and at the surface being sprayed; (3) quantify softening within the sprayed particles, and account for the deformation and flow of particles at the surface being sprayed.
  • Ceramics may include compatible metal oxides, carbides, nitrides and other materials.
  • any full-density, pore-free, corrosion-resistant, thermal-spray or cold- spray amorphous-metal protective coating where post-spray high-density infrared fusing (HDIF) to achieve lower porosity and higher density than otherwise possible, thereby enhancing corrosion resistance and damage tolerance of the metal-ceramic composite coating.
  • HDIF high-density infrared fusing
  • any full-density, pore-free, corrosion-resistant, thermal-spray or cold- spray amorphous-metal protective coating where post-spray high-density infrared fusing (HDIF) to achieve lower porosity and higher density to achieve enhanced metallurgical bonding, and to control damage tolerance through controlled devitrification of the amorphous metal matrix.
  • Predictive computational codes (design tool) used for the prediction of the optimum light flux for producing thermal spray coatings from amorphous metals without devitrification, or with controlled levels of devitrification for achieving desired mechanical properties.
  • Enabling particle-size classification processes for separation of optimally sized amorphous metal particles from a broader particle size distribution. Such processes will separate amorphous-metal particles based upon their differences in aerodynamic drag, which are size dependent. Differential motion can be induced in amorphous metal particles that are suspended in an inert gas atmosphere by first imparting an electrostatic charge to the particles, and then subjecting them to an electrostatic force. Capture of desired particle sizes can be triggered with optical sensors based upon optical single particle analyzers or multi-color laser Doppler velocimetry. [0038] Enabling particle-size classification processes for separation of optimally sized amorphous metal particles from a broader particle size distribution.
  • Such processes will separate amorphous-metal particles based upon the size-dependent differences aerodynamic drag in a cyclonic flow field. Differential motion can be induced in amorphous metal particles by entraining them in a cyclonic separator. The capture of desired particle sizes can be triggered with optical sensors based upon either optical single particle analyzers or multi-color laser Doppler velocimetry. [0039] Enabling particle-size classification processes for separation of optimally sized amorphous metal particles from a broader particle size distribution. Such processes will separate amorphous-metal particles based upon the differences in magnetic properties of fully amorphous and completely, or partially devitrified iron-based amorphous metal particles, and the application of an external magnetic field.
  • Differential motion can be induced in amorphous metal particles by entraining them in a magnetic separator.
  • the capture of desired particle sizes can be triggered with optical sensors based upon magnetic sensors, optical single particle analyzers or multicolor laser Doppler velocimetry.
  • a novel induction-heated spray process for producing full-density, pore-free, corrosion-resistant, thermal-spray amorphous-metal coatings for the protection of a less corrosion resistant substrate.
  • ambient- temperature particles entrained in an ambient-temperature flowing gas, and then passed coaxially through an induction coil, where the oscillating electric field (frequency of 1 to 100 kHz) couples directly to the amorphous metal particles, without direct heating of the carrier gas.
  • This particle-specific heating allows more rapid cooling of the amorphous metal particles than possible in processes where the gas is used to heat the particles.
  • the same processing can be applied to ceramic particles, provided that a higher frequency is used (1 to 10 GHz).
  • any new and innovative tools and devices enabled specifically by the aforementioned metal-ceramic composite materials and coatings, which have exceptional corrosion resistance, wear resistance, and damage tolerance may include, but are not limited to: containers for the shipment, long-term storage, and disposal of spent nuclear fuel (SNF) and high-level radioactive waste (HLW); ground support systems for underground tunnels; pressure vessels, piping and heat exchangers for the chemical process industry, fossil power plants, and nuclear power plants; pump shafts and impellers; valve seats; propellers, rudders, shafts and bearings for marine applications; non-sparking trays and racks for munitions; gun barrels; projectiles; armor; rail guns; etc.
  • SNF spent nuclear fuel
  • HW high-level radioactive waste

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

Abstract

L'invention concerne un système de dépôt par pulvérisation thermique de revêtements en métal amorphe pleine densité, sans porosité et résistants à la corrosion, destinés à protéger un substrat moins résistant à la corrosion. Le système consiste à optimiser la dimension granulométrique (PSO) pour faire en sorte que les particules de métal amorphe soient suffisamment petites pour assurer un taux de refroidissement critique dans toute la masse des particules de métal amorphe.
PCT/US2006/044196 2005-11-14 2006-11-13 PROCÉDÉ DE FABRICATION DE REVÊTEMENTS EN MÉTAL AMORPHE RÉSISTANTS À LA CORROSION À PARTIR DE POUDRES DE MÉTAL AMORPHE PULVÉRISÉES AU GAZ PRÉSENTANT DES TAUX DE REFROIDISSEMENT CRITIQUES RELATIVEMENT ÉLEVÉS, PAR OPTIMISATION DE LA DIMENSION GRANULOM&Ea WO2007120207A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US73679305P 2005-11-14 2005-11-14
US60/736,793 2005-11-14
US11/595,182 US20070107809A1 (en) 2005-11-14 2006-11-09 Process for making corrosion-resistant amorphous-metal coatings from gas-atomized amorphous-metal powders having relatively high critical cooling rates through particle-size optimization (PSO) and variations thereof
US11/595,182 2006-11-09

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Publication Number Publication Date
WO2007120207A2 true WO2007120207A2 (fr) 2007-10-25
WO2007120207A3 WO2007120207A3 (fr) 2008-10-23

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