EP1689578A1 - Composes de phosphate d'aluminium, compositions, materiaux et revetements metalliques connexes - Google Patents

Composes de phosphate d'aluminium, compositions, materiaux et revetements metalliques connexes

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Publication number
EP1689578A1
EP1689578A1 EP03819148A EP03819148A EP1689578A1 EP 1689578 A1 EP1689578 A1 EP 1689578A1 EP 03819148 A EP03819148 A EP 03819148A EP 03819148 A EP03819148 A EP 03819148A EP 1689578 A1 EP1689578 A1 EP 1689578A1
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EP
European Patent Office
Prior art keywords
materials
compound
coating
substrate
compositions
Prior art date
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Application number
EP03819148A
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German (de)
English (en)
Inventor
Sambasivan Sankar
A. Steiner Kimberly
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Applied Thin Films Inc
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Applied Thin Films Inc
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Application filed by Applied Thin Films Inc filed Critical Applied Thin Films Inc
Publication of EP1689578A1 publication Critical patent/EP1689578A1/fr
Withdrawn legal-status Critical Current

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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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed 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
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    • 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
    • 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
    • C23C28/04—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 only coatings of inorganic non-metallic material
    • C23C28/044—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 only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
    • 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
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX 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
    • 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
    • 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
    • C23C28/3455—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 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory 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
    • 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
    • C23C28/347—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 layers adapted for cutting tools or wear applications

Definitions

  • the United States government has certain rights to this invention pursuant to Grant Nos. F49620-00-C-0022 and F4962O-01-C-0014 from AFOSR (Air Force Office of Scientific Research) and subcontract Grant No. DE-FG02-01ER83149, from DOE (Department of Energy) each to Applied Thin Films, Inc.
  • FIELD OF INVENTION The present invention relates to the development of a new amorphous inorganic oxide material, which is microstructurally dense and useful in a number of applications where it can be used in powder, bulk, fiber, and as a thin film or a coating.
  • This invention is also related to surface modification of metals and alloys via application of thin films for providing protection against wear or abrasion, corrosion, and oxidation, over a range of temperatures and harsh environments and for providing suitable high emissivity, non-wetting, and non-stick surfaces.
  • prior art patents related to synthesis of aluminum phosphate materials primarily for use as a catalyst support including crystalline and amorphous forms.
  • Most synthetic methods comprise of using a sol-gel technique with raw materials that include commonly available salts of aluminum and a variety of phosphorous sources including phosphoric acid, ammonium hydrogen phosphates, phosphorous acid, and others. Many of these methods yield highly porous and crystalline forms and few thermally stable amorphous compositions (US Pat. No.
  • metal or alloy surfaces are treated with acids or other chemical agents containing phosphates or chromates which react with metal components of substrates to form metal phosphate or chromate.
  • acids or other chemical agents containing phosphates or chromates which react with metal components of substrates to form metal phosphate or chromate.
  • Similar primer layers are used for applying adherent coatings on metals and alloys.
  • this adds to the cost and imposes additional constraints for matching material properties within the multilayered coating systems. It would be highly desirable to develop a one- step coating process that achieves both good adhesion and provides a substantially pore-free amorphous inorganic layer for corrosion protection and other purposes.
  • Prior art teaches that phosphates are excellent primers to improve the adhesion on metal substrates.
  • phosphate as functional groups for better adhesion to the metal surfaces. See for example US Pat. No. 6,140,410.
  • a phosphate monomer is selected to provide phosphate reactive groups in the main chain of the ultimate phosphated polyurethane resin to improve adhesion of the polyurethane resin to a metal by the formation of P- -OTM 2+ ionic bonds. See for example US Pat. No. 6,221,955.
  • Adhesion between a metal and a polymeric material is enhanced by contacting the metal surface with a non-phosphate adhesion-promoting composition prior to bonding the polymeric material to the metal surface US Pat. No. 6,554,948.
  • an amorphous dense coating that is thermally durable and stable to protect various substrates.
  • the primary advantage of an amorphous coating is that, if developed by a suitable process, it can provide a hermetic seal over a substrate such that access of gas or liquids that can potentially corrode the substrate is avoided.
  • Many methods have been developed to deposit uniform crystalline coatings that are substantially pore or crack-free. Crystalline coatings do not provide hermetic protection from gas or liquid exposures.
  • Silica-based amorphous coatings have been developed and a recent patent prescribes a unique way to deposit such coatings (US Pat. No. 6,162,498).
  • the coating is not durable under certain harsh conditions and are not thermally stable at elevated temperatures or do not serve adequately as a transparent coating on glass due to processing limitations.
  • High temperature stable glassy or vitreous coatings have also been developed by initially coating substrates with a slurry of glass frits and subsequently treating the coated material to high enough temperatures to melt the glass frits and form the vitreous coating.
  • Vitreous enamel coatings have been in existence for many decades with many different compositions. However, they are usually thick and are porous and deform at elevated temperatures. Although hermetic protection may be achieved with this process, the requirement of high temperature processing to melt the glass frits may degrade the substrate and if low melting glass compositions are selected, they may not be durable due to the presence of sodium.
  • 6,403,164 discloses a method to use organic-inorganic hybrid films to provide protection against corrosion and for other uses. Although the deposited films are dense and pore-free, they are not suitable for high temperature applications (above 300°C) and are relatively soft due to presence of organic material in the films. Such films are not wear or abrasion- resistant. Prior art coatings have also included amorphous aluminum phosphate on metals derived from various methods. British Pat. No. 1,451, 145 discloses a method to form hydrated form of aluminum phosphate coatings on metals using a chemical solution method.
  • the films contain residual chlorine (mimmum of one weight %) which is not desirable for many metals and alloys.
  • toxic HCI gas is released (complex contains one mole HCI for every mole of A1P0 ) which is a significant environmental concern.
  • the synthetic process is relatively complex involving isolation of the complex in crystalline form and then dissolving it in appropriate solvents making it difficult to implement in practical applications.
  • the network structure of the material derived under the aforementioned patent does not provide for a robust microstructure and may not be suitable for use especially at elevated temperatures.
  • the material produced in prior-art methods is not microstructurally dense or robust enough to provide the desired protection.
  • none of the prior art methods provide a suitable process or precursor solution that is economical, stable and clear, and can be applied using a variety of well-known techniques such as dip, spray, brush, and flow.
  • none of the processes associated with prior art methods offer the ability to provide good adhesion with substrates that is critically important for most applications.
  • the prior art coatings are either not durable under certain atmospheric conditions or under certain harsh industrial or use environments where materials are subjected to thermal treatments or exposed to corrosive environments.
  • Prior art inorganic coatings are also not completely transparent for use on glass where transmission properties are affected or other substrates where aesthetic property of the substrate (metallic appearance) needs to be preserved.
  • high strength metals such as zirconium and zirconium alloys, titanium and titanium alloys, alloyed steels and others become brittle when exposed to elementary hydrogen. This embrittlement is known to be associated with the penetration of hydrogen atoms into the metal lattice and has been the subject of extensive research.
  • the palladium film is found to be brittle and susceptible to cracking.
  • the process is expensive and produces environmentally toxic byproducts Metals whose position in the voltage series means that they react with water are susceptible to corrosion and require a protective coating that prevents attack by water and/or oxygen.
  • the prior art includes a very wide variety of processes which have not yielded good results.
  • Anodizing of aluminum (Eloxal process) is well known method to form protective alumina films, but the process does not yield pin-hole free alumina films and the associated electrolytic process limits its applicability and also produces environmentally toxic materials.
  • a microstructurally dense form of amorphous aluminophosphate would be very useful for a number of applications.
  • FIG. 1 A chemical structure of aluminophosphorus complexes present in the precursor solution of the inventive compounds, compositions and/or materials.
  • Figure 4. Plot showing comparison of specific weight change between coated and uncoated nickel-based superalloy coupons exposed to 1100°C in air for 100 h with one-hour thermal cycles.
  • Figure 5. X-ray diffraction spectra of coated and uncoated gamma- titanium aluminide alloy showing substantial oxide growth on the uncoated and minimal oxide growth on the coated substrate.
  • FIG. 11 Schematic illustration showing a coating of an inventive compound, composition and/or material (3) with adhesion layer (2) formed and promoted in situ while depositing the film on a metal or alloy substrate (1).
  • Figure 11. A) Powder x-ray diffraction pattern of calcined material from example 2, showing crystalline uminum phosphate and corundum form of alumina.
  • Figure 12. A) 31 P NMR spectrum of solution from example 3, showing a resonance peak at -5.9 ppm, corresponding to aluminophosphate complex.
  • the other peaks correspond to La 2 P 4 0 13 .
  • Fig 16. Powder x-ray diffraction pattern of calcined material from example 11. The peaks near two-theta values of 20.5, 21.5 and 35 are from aluminum phosphate nanocrystals. The peak (labeled "*") near two-theta value of 30 is from tetragonal zirconia. Based on x-ray data, the size of the tetragonal zirconia nanocrystals are estimated to be about 7nm after 1100°C, 0.5h anneal, 26nm after 1200°C, 50h anneal, and 170 nm after 1400°C, lOh anneal in air. Cu K ⁇ radiation used.
  • Fig 17. X-ray diffraction pattern of calcined material from example 12.
  • the peaks near two-theta values of 20.5, 21.5 and 35 are from uminum phosphate nanocrystals.
  • the peaks (labeled "*") near 16 and 26 are from mullite (Al 6 Si 2 0 13 ).
  • the size of the mullite nanocrystals is lOOnm after 1200°C, 50h heat treatment and 170 nm after 1400°C, lOh heat treatment. Cu K ⁇ radiation used.
  • Fig 18. X-ray diffraction pattern of calcined material from example 13.
  • the peak? near 20.5, 21.5 and 35 are from aluminum phosphate nanocrystals.
  • the peaks near 26 and 37 are from anatase titania nanocrystals.
  • the titania nanocrystals are approximately 7nm in diameter.
  • Figure 19 Transmission electron micrograph showing nanoinclusions of glassy carbon in powders of a compound, composition and/or material of this invention.
  • Figure 20 Photograph of half-coated stainless steel coupon after immersion in molten aluminum ( ⁇ 750°C), showing non-wetting character. The dashed line shows the line of immersion in the molten aluminum.
  • Figure 21 X-ray diffraction patterns of 1018 carbon steel heat-treated to 500°C for 30 minutes. (A) Coated with an inventive aluminophosphate; and (B) uncoated.
  • the (*) indicates the substrate; the ( ⁇ ) indicates Fe 3 0 4 ; and the (+) indicates Fe 2 0 3 .
  • Figure 22 Raman spectrum of a coating of an inventive aluminophosphate material on stainless steel. The labled (*) peaks are from an adhesion layer between the coating and the substrate.
  • Figure 23 Grazing angle FTIR spectrum of stainless steel coated with a thin film of an inventive aluminophosphate compound, composition and/or material after exposure to the ambient. The labeled (*) peaks indicate organics absorbed on the coating surface.
  • a further object of the present invention to develop a (preferably transparent) glassy coating system which provides effective corrosion protection for a very wide variety of metallic substrates, preferably in combination with abrasion resistance properties.
  • this object may be achieved by depositing an alumino-phosphate coating on the metal. Owing to the inorganic network, the resultant coatings also possess abrasion resistance properties, which may be strengthened further by incorporating nanoscale particles. Nanoparticles encompass dimensions ranging from about 1 nm to about 500 nm. Another effect of incorporating the nanosized particles is that such coatings remain transparent.
  • the present invention accordingly provides a process for protecting a metallic substrate against corrosion by forming an inorganic glassy oxide film.
  • vitreous layers can be formed on metallic surfaces, which layers may be dimensioned less than about 10 microns.
  • layers can be converted into dense aluminum-phosphate films (for example on stainless steel or steel surfaces).
  • Such films are about a few nanometers to about a few microns in thickness and form a hermetically sealing layer which prevents or drastically reduces, respectively, the access of oxygen to the metallic surface and secures an excellent protection against corrosion even at elevated temperatures.
  • Such layers are furthermore abrasion- resistant.
  • Another objective of the present invention is to develop a stable and microstructurally dense form of aluminophosphate material for use in the aforementioned applications.
  • a further objective of the invention is to develop a low-cost, simple, and versatile chemical-solution based method to develop the amorphous material in the form of powder, coating, fiber, and bulk materials.
  • a yet another objective of the invention is to prepare a suitable clear precursor solution that yields high quality dense coatings of amorphous aluminophosphate.
  • a further objective is to develop suitable precursor solutions such that other additives can be added to the solution such that new amorphous aluminophosphate compositions can be made.
  • the additives can be added in a chemical form such that the solution is clear or the additives can be added in colloidal or powder form to yield a slurry-based solution.
  • a cured material obtained may be in the form of a nanocomposite (nanoparticles, nanocrystals or crystals embedded or encapsulated in the amorphous aluminophosphate matrix) or exist as uniformly-dispersed dopants within the glass matrix.
  • the additives either individually or in conjunction with the aluminophosphate matrix can induce specific functionality useful for many applications.
  • Such "mixed" aluminophosphate compositions can be formed as a powder or a coating or a fiber or as a bulk material. It is another object of the invention to develop films of the inventive compounds, compositions and/or materials with inclusions within the amorphous matrix material for inducing various functions including, but not limited to, optical, chemical, catalytic, physical, mechanical, and electrical properties.
  • inclusions can be produced in-situ during the synthetic process and they may include metals, non-metals, and compounds of any combination of elements.
  • One such example includes formation of carbon as nano- sized inclusions for providing high emissivity and enhances mechanical properties.
  • High emissivity coatings that are durable at elevated temperatures are desirable for a number of applications where thermal protection is desired or such coatings provide energy savings through re- radiating incident heat fluxes in furnaces, ducts, boilers, heat exchangers, and the like.
  • It is an object of the present invention to provide a material having as a feature of its molecular structure, an 0 P-0-Al-0-Al bonding sequence (with organic and other ligands as may be attached to P and Al) regardless of P/Al ratio and any additional metal therein to enhance coating properties or to create nanocrystals that induce or enhance chemical, physical, optical, electrical, mechanical, and thermal properties (nanocomposite coatings). It is an object of the present invention to provide surface modification of metals or alloys with a material coating to provide corrosion or oxidation resistance and/or to induce non-stick properties over a range of temperatures and environments; proven effective with stainless steel, aluminum alloys, nickel-based superalloys, Inconel, and other steel alloys.
  • the inventive compounds, compositions and/or materials and/or related coatings are hermetic; that is, without open porosity or pathway fluid or gaseous ingression, and/or micro-structurally dense; that is, substantially non-porous and/or approaching zero pore volume. It is yet another object of the invention to develop thin films in the range of about 50nm-about 10 microns that are transparent or opaque as desired for any application.
  • stainless steel AUS304 where, in preference to a porous iron or manganese oxide, a dense chromium-rich oxide is formed; note that higher chrome steels are preferred for this reason, but with the material of this invention, even low Cr-containing steels will remain oxidation- resistant due to the promotion of Cr-rich oxide scales; proof of this was obtained with x-ray diffraction and elemental profiles across the scales.
  • nickel-based superalloys where alumina scale is preferentially formed during early stages of oxidation; an order of magnitude difference in oxidation rate is realized due to the presence of these coatings.
  • TBC thermal barrier coating
  • the present coatings can be deposited on MCrAlY type bondcoats and then TBC deposited (preferably by e-beam PVD), whereby the growth of alumina scale during service is limited which will prevent catastrophic failure of TBCs due to spallation; proof of principle already demonstrated with deposition of the inventive compounds, compositions and/or materials on bondcoat showing reduced weight gain from oxidation above 1 lOOC It is an object of the present invention to provide material coatings sufficiently smooth to impart a low-friction surface (friction coefficients below 0.1 were measured on coatings on steel alloys).
  • the inventive compounds, compositions and/or materials may serve as a multifunctional protective coating (nanocrystals within the material coating can be added to improve wear resistance or tailor thermal properties). It is yet another object of the invention to reduce the surface roughness of said substrates which is desired for many applications.
  • the smooth nature of the films of the inventive compounds, compositions and/or materials deposited allows for planarization of most substrates. This will help in enhancing the non- wetting or non-stick nature of surfaces and also induces a low-friction surface with the added benefit of a lower surface energy attributed to the stable oxide surface on a metal/alloy substrate.
  • the inventive compounds, compositions and/or materials conformally cover these defects and eliminates accelerated corrosion.
  • metals and alloys are subjected to extensive surface preparation (which results in labor and material costs and generates waste) which can be reduced or eliminated with the use of such coatings. It is an object of the present invention to provide, due to the non-stick properties, material coatings on metals and alloys that can be used in a number of applications where moving parts are used. Metal shafts, etc. are moved back and forth during service and if there is any debris that sticks to the surface, the motion is affected and eventually leads to failure of the part.
  • the inventive compounds, compositions and/or materials coatings will help in not allowing unwanted debris from sticking to these parts and its smooth nature should improve the sliding characteristics; it may also serve to act as a dielectric or insulation coating for certain applications.
  • the inventive compounds, compositions and/or materials coatings can be deposited on top of alloy coatings to avoid coke deposition. It is an object of the present invention to provide protective coatings for molten material processing; the amorphous, dense, and non-stick nature of the present material is highly suitable for providing a non-stick surface. It can be used as a durable mold-release agent in die-casting.
  • inventive compounds, compositions and/or materials coatings will help make it durable over several cycles which will save time and costs (proven to be an effective non-wetting protective coating for molten aluminum processing with the present coated products lasting twice as long as other coated products.
  • inventive compounds, compositions and/or materials can also be deposited on top of enamel coatings to seal the highly porous structure).
  • the present invention protects against other molten materials as well as molten amatimim, including molten polymers, molten glass and other non-fenous molten metals.
  • the inventive compounds, compositions and/or materials can serve as a suitable dielectric for a number of applications ; the pin-hole free nature of the coating is very attractive for this purpose Dielectric coatings are desired for example on flexible solar cell metal substrates (next generation need).
  • the stability of metals and alloys used in plasma environments in the semiconductor or thin film processing equipment is a major concern. Coatings can be deposited on these metals and alloys to offer that protection. Additionally, it is an object of the invention to provide low dielectric constant films for semiconductors and thermally stable low observable coatings for defense applications.
  • Polymer products are used to deposit a protective coating on these parts (door knobs, etc.), but they are not durable.
  • the inventive compounds, compositions and/or materials are durable and can be transparent such that appearance is not affected.
  • Fuel cells for example, operate in a combination of oxidizing and reducing environments and materials used in their construction should be able to withstand the varying conditions.
  • An inventive compound, composition and/or material, used as a thin film can provide the necessary protection to various materials of construction used in many of these applications requiring harsh environments, especially at elevated temperatures.
  • Molten materials including but not limited to, metal sulfates (sodium sulfate, for example), metal vanadates, molten polymers (hot melt adhesives), molten metal (aluminum, zinc), are used or are present in a broad range of industrial processing environments that degrade metal/alloy components during service.
  • inventive compounds, compositions and/or materials, in thin film form can provide excellent protection due to its thermal stability and demonstrated durability with these corrosive materials. Due to its robust nature (low atom diffusivity), films as thin as 100 nm are sufficient to provide the desired protection. The ability to use such thin films are particularly useful as they do not crack or spall upon thermal cycling. In addition, they protect the underlying substrate from oxidation or conosion which further helps in preventing delamination of the deposited film of the inventive compounds, compositions and/or materials. It is yet another objective of the invention to enable self-absorption of organic on the surface of the films of the inventive compounds, compositions and/or materials deposited on substrates.
  • organic films Due to the presence of certain organic contaminants in the atmosphere, surfaces of the inventive compounds, compositions and/or materials react with such organic materials, under ambient conditions, forming a stable bond with the organic material or its modified form via a self-absorption process. Such organic films further lower the surface energy of the composite structure, thus providing a hydrophobic or non-wetting surface. Organic films can also be deposited over the film of the inventive compounds, compositions and/or materials including, but not limited to, oleic acid and organo-silanes, using simple dip-coating process.
  • the organic layer present is characterized by observation of an organic group on the surface using Fourier transform infra-red spectroscopy (absorption bands at 2994, 2935, 1702, 1396, 1337 and 972 cm “1 are observed which is attributed to an organic group attached to the surface of the inventive compounds, compositions and/or materials).
  • Organic layers can be deposited on the surface of the inventive compounds, compositions and/or materials to promote hydrophilic behavior such that bonding with certain materials are promoted. For example, adhesion of polymers to metals and alloys is poor.
  • the use of the surface of the inventive compounds, compositions and/or materials, as an adhesive and conosion-resistant interlayer on metals to bond with various polymers and ceramics will provide enhanced adhesion.
  • the oxide nature of the surface of the inventive compounds, compositions and/or materials itself can promote direct adhesion with polymers, the adhesion characteristics can be further enhanced by deposition of suitable hydrophilic organic layers on top of the film prior to bonding with polymers or other materials.
  • the surface of the inventive compounds, compositions and/or materials can be tailored with organics to impart a hydrophobic or a hydrophilic character.
  • a microstructurally dense amorphous aluminophosphate material can be prepared using a low-cost precursor of phosphorous pentoxide and hydrated aluminum nitrate, in ethanol or other fluid media. Pyrolysis of the precursor at temperatures above 500C yields a stable microstructurally dense amorphous aluminophosphate material which is resistant to crystallization up to 1400C. More importantly, it was surprisingly found that the precursor solution has excellent film forming and adhesion characteristics to metal & alloy, glass, and ceramic substrates. Without being bound to any theory, it is proposed that the adhesion is primarily promoted by phosphate bonding between the constituents in the precursor solution and the metallic substrate.
  • phosphate bonding is well known for improving adhesion between metal and inorganic and between ceramic materials.
  • the higher curing temperatures utilized in the present invention (above 500C) helps in promoting the adhesion.
  • the phosphorous contained in the precursor at least partially, bonds with the oxide via a phosphate link, which enables good adhesion between the substrate and the deposited film after curing.
  • Prior art methods do not offer this advantage. This leads to a well-adhered film without requiring any special pretreatment or separate deposition of an underlayer to promote adhesion.
  • Embodiments of the aluminophosphate compounds, compositions and/or materials of this invention inventive compounds, compositions and/or materials are available under the Cerablak trademark from Applied Thin Films, Inc.
  • Various considerations relating to this invention are disclosed in US Pat. Nos. 6,036,762 and 6,461,415 and pending patent application nos. 10/266,832 and PCT/USO 1/41790, each of which are incorporated herein in its entirety.
  • Post analysis of metal-coated films with the inventive compounds, compositions and/or materials show characteristics of an "interfacial layer" that is different in its chemical form compared to the substrate or the deposited film.
  • x-ray diffraction of films deposited on mild steel show peaks corresponding to the formation of iron oxide (Fe 2 0 3 ).
  • the interface layer is indirectly observed.
  • the TEM micrograph of the film deposited on stainless steel does not, for instance, reveal the presence of an interlayer, however, FTIR and Raman spectroscopic analysis show absorption corresponding to bonds that cannot be assigned to either the inventive compounds, compositions and/or materials or the substrate or any oxide that may have formed on the substrate.
  • the final architecture of the coated material can be defined to contain component between the substrate and the aluminophosphate an additional interface or adhesive layer, which may comprise of a continuous phosphate-bonded metal oxide or an oxide layer linked to phosphate groups of the film, or mixtures thereof.
  • additional interface or adhesive layer which may comprise of a continuous phosphate-bonded metal oxide or an oxide layer linked to phosphate groups of the film, or mixtures thereof.
  • the coating due to its low oxygen diffusivity, establishes a lower partial pressure of oxygen at the coating metal interface, at a given temperature, which helps in formation of more stable oxides of alloy constituents. Further evidence of this phenomenon with specific examples are provided herein.
  • a dip-coating process (described in detail below), a thin, dense, smooth, hermetic, transparent, and continuous glassy coating is formed on substrate surfaces.
  • the precursor solution has low enough viscosity such that a uniform film can be deposited on complex-shaped substrates.
  • Specific monomeric or polymeric species in precursor solution facilitate the formation of hermetic and continuous film.
  • Al-rich compositions are more thermally stable in the amorphous form. Stoichiometric or P-rich compositions also yield a dense material, but the thermal stability is limited. However, they may be useful in applications where the temperature limit do not exceed lOOOC. Stoichiometric aluminum phosphate refers to a compound or composition having an aluminuni/phosphorous ratio of about 1/1. Most surprisingly, it was found that the material has very low oxygen diffusivity such that it can serve as an excellent protective coating on substrates susceptible to high temperature oxidation.
  • an ultia-thin dense film of the material at a thickness of about 0.1 micron, more preferably at a thickness of about 0.5 microns, and most preferably a thickness of about 1 micron.
  • Such thin coatings are not prone to cracking and delamination due to thermal expansion mismatch between coating and substrate.
  • the low-cost of the precursor material and deposition process also allows for its deposition as an overcoat or undercoat on conventional coatings. For example, it is well known in the art that thick (few mils) metal alloy coatings (such as MCrAlY) are deposited on substrates used in turbine engines, ethylene cracking furnaces, and the like.
  • inventive compounds, compositions and/or materials will provide a life enhancement of the underlying coating and thereby an enhancement of the substrate at very little additional cost.
  • inventive compounds, compositions and/or materials can be applied in the field during a plant shutdown or during routine maintenance to provide additional protection.
  • Various examples are provided below that demonstrates its ability to protect metals, alloys, and ceramics from conosion and oxidation at elevated temperatures.
  • the present invention includes a composite comprising a metallic substrate, a substantially amorphous, substantially non-porous aluminophosphate film and a component therebetween.
  • a component comprises a phosphate group in bonded interaction with an oxide of a metal component of the substrate.
  • the aluminophosphate film comprises an aluminum content about, less than, or greater than stoichiometric on a molar basis relative to the phosphorous content of the film.
  • the film of such a composite further comprises nanoparticles, such particles including but not limited to carbon, a metal compound and combinations thereof.
  • the substrate can be a steel alloy such that the aforementioned phosphate group is in bonded interaction with an iron oxide, a chromium oxide or a combination thereof, and such bonding interaction promoted, in situ, during curing in formation of the film or coating.
  • the aluminophosphate film of such a composite can have a thickness dimension of about 0.05 micron to about 10 microns. In various embodiments, such a film can be dimensioned from about 0.1 micron to about 1.0 microns.
  • the present invention can also provide a high-temperature stable composition comprising an aluminophosphate compound, substantially amorphous with carbon nanoparticles therein.
  • the aluminophosphate compound of such a composition can vary over a range of stoichiometric relationships.
  • the aluminophosphate compound has an aluminum content greater than stoichiometric on a molar basis relative to the phosphorous content.
  • such a composition can further, optionally, include nanoparticles of a metal compound, as described above.
  • a substantially amorphous aluminophosphate compound is without or substantially absent chloride ion, such absence as can be indicated with chloride levels or concentrations less than those disclosed in the corresponding patents of the prior art.
  • the present invention can also include a method of using an aluminophosphate compound to lower the surface energy of the substrate.
  • Such a method comprises (1) providing a precursor to an aluminophosphate compound, such a precursor further comprising an aluminum salt and phosphorous pentoxide in a fluid medium; (2) applying such a medium to a substrate; and (3) heating the applied medium for a time and at a temperature sufficient to provide a non-wetting, substantially amorphous and substantially non-porous aluminophosphate compound on the substrate.
  • the fluid medium can comprise an alcoholic solution of an aluminum salt and phosphorous pentoxide.
  • Application techniques vary as described herein, but include, without limitation, dip-coating and spraying.
  • the present invention can also include a composite comprising a metallic substrate and a substantially amorphous, substantially non-porous aluminophosphate film on the substrate, such that the composite has a surface energy lower than that initially available through use of such a substrate, alone, such a surface energy as would be understood by those skilled in the art and in accordance with the structural, compositional and or physical relationships described herein.
  • many polymer or organic materials are known to have the lowest surface energy due to the terminating hydrocarbon groups with fluorine- based compounds providing a more enhanced effect in lowering surface energies.
  • Such surfaces provide non-stick non-wetting or hydrophobic property to such surfaces.
  • Polytetra fluoro ethylene (PTFE) is the most well known non-stick material widely used in many applications including cookware.
  • a surface energy value of about 18 mN/m2 has been measured on PTFE surfaces.
  • metal, ceramic, and glass surfaces have relatively higher surface energies with metals and alloys, in general, exhibiting the highest surface energies and glass having the lowest among these groups of materials.
  • Surface modification techniques, including deposition of polymers are routinely used in industry to provide a lower surface energy.
  • Such properties can enable enhanced flow characteristics of fluids (including molten polymers, oils, aqueous and other organic solutions), maintain relatively clean surfaces, and provide a low-friction surface.
  • Polymer coatings are not durable.
  • the Inventive Material deposited as a relatively smooth, substantially non-porous, and amorphous film on steel components yields a low energy surface (-32 mJ/m 2 ). This is relatively close to surface energies of certain polymers such as polypropylene. " With the hard, thermally stable, durable, abrasion- and corrosion- resistant nature of the film, the low surface energy of the Inventive Material can be exploited for a number of applications, including high temperature applications, such as protective films for molten metal processing.
  • Al/P composition means a compound, composition and/or material comprising aluminum and phosphate.
  • such a compound, composition and/or material can be represented with a formula A1P0 4; wherein the aluminum and phosphate components thereof can vary over the range of stoichiometric relationships known to those skilled in the art made aware of this invention.
  • Corrosion means to any change in the metal which leads to oxidation (conversion) to the corresponding metal cation with formation of a species X.
  • species X are generally (optionally hydrated) metal oxides, carbonates, sulphites, sulphates or else sulphides (for example, in the case of the action of H 2 S on Ag).
  • Metallic substrate means any substrate which consists entirely of one or more metals or has at least one metallic layer on its surface.
  • Metal and “metallic” mean not only pure metals but also mixtures of metals and metal alloys, these metals and metal alloys as may be susceptible to corrosion, but for employment in conjunction with this invention. "On” means, in conjunction with a compound, composition and/or material coating of this invention the position or placement of such a compound, composition and/or material coating in relation to a corresponding substrate, notwithstanding one or more layers, components, films and/or coatings therebetween. Accordingly, this invention may be applied with particular advantage to metallic substrates comprising at least one metal from the group consisting of iron, aluminium, magnesium, zinc, silver and copper, although the scope of application of the present invention is not restricted to these metals.
  • specific fields of application and examples of the use of the present invention include the following: construction, e.g. support and shuttering material made of steel, face supports, pit props, tunnel and shaft lining constructions, insulating construction elements, composite sheets comprising two metal profile sheets and an insulating metal layer, shutters, framework constructions, roof structures, fittings and supply conduits, steel protection boards, street lighting and street signage, sliding and rolling lattice gratings, gates, doors, windows and their frames and panels, gate seals or door seals made of steel or aluminium, fire doors, tanks, collecting vessels, drums, vats and similar containers made of iron, steel or aluminium, heating boilers, radiators, steam boilers, turbine parts, halls with and without internals, buildings, garages, garden houses, facings made of sheet steel or urninium, profiles for facings, window frames, facing elements, zinc roofs; vehicles,
  • furniture made of steel, aluminium, nickel-silver or copper, shelving units, sanitary installations, kitchen equipment, lighting elements (lamps or lights), solar installations, locks, fittings, door and window handles, cookware, fiyware and bakeware, letterboxes and box-like constructions, reinforced cabinets, strongboxes, sorting, filing and file-card boxes, pen trays, stamp holders, front plates, screens, identification plates, scales; articles of everyday use, e.g. tobacco tins, cigarette cases, compacts, lipstick cases, weapons, e.g. knives and guns, handles and blades for knives or shears and scissor blades, tools, e.g.
  • Articles including metal parts like catalytic converters, photovoltaic cells may be coated with the inventive material.
  • high emissivity coatings may be useftd for protective coatings for metallic thermal protection systems, as well as increasing heat transfer efficiency for industrial and consumer use, such as glass manufacturing, energy and metal manufacturing, as well as duct linings, firewall materials, heat shields for xenon lights, and high temperature filters for liquid non-ferrous metals.
  • DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE INVENTION The inventive compounds, compositions and/or materials is a sol-gel derived amorphous aluminum phosphate-based material.
  • the inventive compounds, compositions and or materials can be synthesized over a wide range of aluminum to phosphorous ratios, including from about 1/1 to about 10/1.
  • inventive compounds, compositions and/or materials is highly inert to chemical attack, thermally stable beyond 1400°C, and is sufficiently transmissive to light in the visible, IR, and UV ranges (200-25 OOnm). High temperature oxidation tests have shown that the inventive compounds, compositions and or materials is also highly impervious to oxygen ingress.
  • inventive compounds, compositions and/or materials can be deposited as a dense, pinhole-free thin coating on substrates using a simple dip, paint, spray, flow or spin coating process at relatively low temperatures (500°C or above) ( Figure 1). It has excellent potential to be scaled up without significant capital investment to produce continuous coatings on a variety of substrates.
  • the inventive compounds, compositions and/or materials is chemically inert (like alumina) and thermally stable material.
  • the inventive compounds, compositions and/or materials is a unique metastable amorphous material stable to temperatures beyond 1200°C. Testing of The inventive compounds, compositions and/or materials has demonstrated the electrical insulating property of the film and the continuity, hermiticity and, protective nature of the coating.
  • the species present in a precursor solution of inventive compounds, compositions and/or materials can be used to derive the properties of the solid inventive compounds, compositions and/or materials. Based on the collective experimental evidence, we believe the principal ingredients of the precursor solution comprise of complexes that contain Al-O-Al linkages.
  • 31 P nuclear magnetic resonance (NMR) spectra of the precursor solutions show at least one of two prominent peaks near -5 ppm and -12 ppm, which is assigned to aluminophosphate complexes (1) and (2) respectively, with a mixture of alcohol and water molecules coordinated to aluminum ( Figure 2).
  • the inventive compounds, compositions and/or materials contains tetrahedral coordination for aluminum, along with "distorted" octahedral aluminum, the intensity of which increases with excess aluminum content. This is unlike the exclusive tetrahedral coordination for aluminum observed in all crystalline polymorphs of A1P0 4 .
  • the 27 A1 NMR data suggests a distorted environment for the tetrahedral Al, whereas the corresponding P NMR shows an undistorted environment for [P0 4 ] groups. Combining these two data we conclude that [P0 4 ] groups are linked only to [A10 4 ] groups which in turn are linked to [A10 6 ] groups.
  • complexes Regardless of the precursor system used, the formation of these complexes appear to yield the inventive compounds, compositions and/or materials. Such complexes may be further modified with other additions (silicon, zirconium, lanthanum, titanium) which can potentially enhance the amorphous characteristics or enhance the thermal stability of these materials.
  • additions silicon, zirconium, lanthanum, titanium
  • coating techniques can be used with the precursor solution, dip-coating, spraying painting and flow coating are most often used. All are low-cost, easy to apply and scale up. We have been using these techniques successfully on various substrates, including metals, alloys, glass, ceramics and others.
  • inventive compounds, compositions and/or materials solutions show good wetting properties and is particularly significant when alcohol (preferably ethanol, but other alcohols including, but not limited to, methanol, isopropanol, butanol can be used as well) is used as the solvent, although good wetting properties can be attained even using aqueous solutions.
  • alcohol preferably ethanol, but other alcohols including, but not limited to, methanol, isopropanol, butanol can be used as well
  • alcohol preferably ethanol, but other alcohols including, but not limited to, methanol, isopropanol, butanol can be used as well
  • Coatings on stainless steel coupons can withstand treatments of 1000°C or more without cracking.
  • the coating composition employed according to the present invention may be applied onto the metallic surface according to conventional coating methods. Examples of techniques which may be employed are dipping, spinning, spraying or brushing. Particularly preferred are dipping and spraying processes.
  • the inventive compounds, compositions and/or materials solution has been applied with a variety of methods and compositions.
  • the inventive compounds, compositions and/or materials has been coated onto a wide variety of substrates, including stainless and mild steel, titanium, nickel, iron, aluminum alloys glass, ceramics and carbon among many other substrates. After application of the coating, it is dried to remove solvent and cured to remove the organics and nitrates (or other salt components from the precursor).
  • the coating can be cured in the furnace or with a portable quartz infrared heat lamp. The coatings cure quickly and are stable.
  • the (final) temperature of the thermal densification must also be determined in consideration of the heat resistance of the metallic surface, said temperature is usually at least 300° C, particularly at least 400° C. and particularly preferred at least 500° C.
  • the metallic surface is sensitive to oxidation, especially at such high temperatures, it is recommended to cany out said thermal densification in an oxygen-free atmosphere, e.g. under nitrogen or argon.
  • an oxygen-free atmosphere e.g. under nitrogen or argon.
  • Metallic or alloy substrates in particular, partially oxidize and form an oxide scale (either partially or a continuous scale depending on substrate composition, chemistry, and surface roughness) which then forms a strong bond with the coating material during the curing process.
  • the precursor solution may enable direct phosphate bonding of the metal surfaces which also helps in improving adhesion.
  • the temperatures, environments, and time of exposure can be adjusted over a wide range to accomplish the various objectives discussed above.
  • Use of higher temperatures and higher partial pressure of oxygen in the ambient is preferred for fast curing suitable for many applications which will also reduce processing cost.
  • the adhesion with substrates can be further improved with altering the Al P ratio according to the substrate composition and oxide scale chemistry.
  • Excellent adhesion have been achieved with a number of alloy substrates including various grades of steel alloys, nickel, Inconel, advanced nickel and titanium alloys, aluminum, copper, titanium, and alloys thereof.
  • Annealing the coated materials to even higher temperatures provide further improvements in adhesion, however, extensive oxidation of the substrate may lead to thick enough oxide scales which may result in cracking or spallation at the oxide scale/substrate interfaces.
  • Annealing to ultra-high temperatures (above 1000C) may result in some loss of phosphorous, depending on the environment, however, the dense nature of the coating is still maintained such that protection is still considered good. Further description of the oxidation mechanism on steel and advanced alloys are provided below with specific examples attached. Aluminum and its alloys, due to their heat sensitivity can also be cured with other surface heating techniques such as laser heating, IR lamps, and the like.
  • compositional or microstractural changes occurring within the substrate may affect its physical and mechanical properties.
  • curing of coating on aluminum alloys have been accomplished using a furnace at temperatures ranging from 500-550°C.
  • Such coated alloys have shown good performance in salt spray tests demonstrating good corrosion protection.
  • the application of a coating of an inventive compound, composition and/or material can be combined with the tempering process, typically used to harden metals and alloys. This will help in reducing the number of processing steps required to make the final article for a given application.
  • the coating composition applied on the metallic surface will subsequently be thermally densified to form a vitreous layer.
  • the thermal densification Prior to said thermal densification a conventional drying operation of the coating composition at room temperature and or slightly elevated temperature will usually be carried out. It remains to be noted that the thermal densification may optionally also be effected by IR, UV or laser heat sources. Also, it is possible to produce structured coatings by selective action of heat thereon. Slurries have also been made by dispersing a powder in a solution of an inventive compound, composition and/or material. Slurry coatings were made to increase the thickness or functionality of the coating. Different powders were mixed into the solution. Slurry coatings can be applied by any of the above coating methods. When synthesized as a powder, the inventive compounds, compositions and/or materials contain nanoinclusions of glassy carbon completely embedded in the amorphous material.
  • High emissivity coatings can be made by making a coating from a slurry of black compounds, compositions and/or material particles of this invention dispersed in solution or a suitable medium.
  • the inventive compounds, compositions and/or materials may also be used as a protective binder for pigments. It is also possible to synthesize such compounds, compositions and/or materials without carbon inclusions with appropriate selection of precursor formulations.
  • the low-cost associated with the present invention and coating technology allows for combined options to be considered. It is expected that the inventive compounds, compositions and/or materials can enhance the oxidation resistance behavior of a wide range of alloys, even alloys with high oxidation resistance.
  • inventive compounds, compositions and or materials can be deposited on weld areas where morphological non-uniformities and compositional variations are bound to exist.
  • inventive compounds, compositions and or materials are also amenable to field repair, or could be applied during shut-downs where deposits on wash walls or other areas are cleaned.
  • Spraying is a suitable process for depositing inventive compounds, compositions and or materials coatings, and could be used as a field-repair process. Examination of coated substrates under lOOOx magnification, using an optical microscope shows the continuous character of the coating. Compliance of coatings of the inventive compounds, compositions and/or materials on steel foil has been demonstrated where the foil has been bent (>120 degrees) several times without any sign of delamination, thus demonstrating excellent adherence of the thin film.
  • Thin coatings are often preferred to avoid delamination from thermal treatments, for ease of application at lower costs and their compliance even in case of large CTE match between the substrate and the coating. If an insulating layer is required, thicker coatings are preferred for providing adequate electrical insulation and for providing the desired diffusion barrier characteristics during deposition of functional overlayers. Since the inventive compounds, compositions and/or materials are extremely inert to chemical attack, and has a low dielectric constant, it should serve as an excellent insulation and diffusion barrier around 500°C even at thickness of about 2000- 5000A. A dielectric breakdown strength of 190V has been measured for the inventive compounds, compositions and/or materials as a 100 - 500 nm thick film on stainless steel. Such dielectric constants can range from 3.3 - 5.6.
  • inventive compounds, compositions and/or materials significantly limit the oxidation of metal/alloy substrates, and limit corrosion as well.
  • the present invention appears to change the chemistry of the growing oxide scale.
  • the invention can be used to minimize the effects of accelerated conosion due to surface roughness, and eliminates corrosion pitting, which is often observed on oxidized, metal/alloy substrates.
  • a function of the inventive compounds, compositions and/or materials coating is in the early stages of oxidation where it protects sharp edges, planarizes the surface, and defects in an alloy surface. The ability to protect nickel-based alloys at temperatures over 1000°C for over lOOh has been successfully demonstrated.
  • the coated materials were tested for 20 thermal cycles where subsequent surface examination showed the inventive compounds, compositions and/or materials was effective in its protection and, more importantly, no additional cracking or spallation was observed.
  • the inventive compounds, compositions and/or material were used to coat a ⁇ -titanium aluminide alloy, and heat treated, with an uncoated alloy for lOOh at 815°C.
  • the uncoated alloy showed extensive growth of rutile titania and corundum alumina on the surface.
  • the coated alloy showed significantly reduced oxide growth, as seen by x-ray diffraction (Figure 5). All these studies combined suggest the inventive compounds, compositions and/or materials have excellent potential for use in protecting alloys intended for use a wide variety of elevated temperature applications.
  • inventive compounds, compositions and/or materials coatings have been shown to protect alloys against oxidation. Not wishing to be bound by any theory, it is believed that during the very early stages of oxidation a low P ⁇ 2 is established at the alloy such that only oxides stable in low P 02 environments are formed (usually chromia for steels or alumina for nickel- aluminum based alloys).
  • a piece of type-304 stainless steel was half-coated with the inventive compounds, compositions and/or materials and heat treated to 1000°C for 10 hours in air. The coated half shows a dense, uniform, chromia-rich scale, while the uncoated half shows a non-uniform scale with deep pits of non-protective iron-rich oxide (Figure 6).
  • inventive compounds, compositions and/or materials provide significant benefits by modifying the growing oxide. Irrespective of the selection of the alloy, issues related to roughness or surface defects are bound to be of concern, and may require special pretreatments which can be expensive, environmentally unfriendly, and will generate waste. Surface- related defects affected the oxidation behavior for the uncoated materials. Despite the high quality finish, these factors dominated the oxidation behavior. For the intended applications, alloy materials may be fabricated using a wrought process which is certain to create surface defects, and this issue must be addressed.
  • the simplicity and versatility of the inventive compounds, compositions and/or materials coating process and the inexpensive nature of the precursor solution may make it cheaper to deposit a compound, composition and/or material coating of this invention rather than performing many other, more expensive pretreatment of alloy surfaces.
  • growth of thick alumina scale between the bondcoat and ceramic coating leads to premature failure of the TBCs.
  • Compounds, compositions and/or materials coatings of this invention can be deposited on McrAlY type bondcoats and then TBC deposited (preferably by e-beam PVD), whereby the growth of alumina scale during service is limited which will prevent catastrophic failure of TBCs due to spallation.
  • a standard practice used in turbine manufacturing is to preoxidize the bondcoat material (MCrAlY type compositions) to improve the adhesion with the thermal barrier coating to be applied.
  • reducing environments are used to promote the preferential formation of alumina scales (as opposed to spinel and other oxides), see for example US Pat. No. 5,856,027 Murphy.
  • Such treatments in inert or vacuum significantly increases the cost of production and limits the production efficiency.
  • a thin film deposited on MCrAlY can promote the formation of alumina scale even if it is annealed in ambient air.
  • sealing of defects by the coating may provide an added benefit.
  • the presence of the oxidation-resistant glassy film may provide enhanced protection of the substrate during subsequent use.
  • inventive compounds, compositions and or materials can protect metals and alloys against corrosion from molten sulfates, encountered in combustion applications. Its compatibility with the trisulfates vary depending on the Al P stoichiometry whereby Al-rich compositions appear to be more compatible.
  • the non-wetting character may be useful in limiting the adhesion of ash particles to the metal/alloy components used in coal-fired combustion systems and other power generation plants.
  • coatings thereof were deposited onto sapphire plates. Sapphire substrates were chosen to avoid the influence of oxide scale on the compatibility test.
  • Sodium sulfate was placed on the coated sapphire pieces and annealed to 900°C, just above the melting point (884°C).
  • Fig 7 shows a coated piece after 120 hrs of exposure.
  • Coatings for enhancing the conosion resistance are suitable, for example, for iron and steel products, especially profiles, strips, plates, sheets, coils, wires and pipes made of iron, of unalloyed, stainless or otherwise-alloyed steel, either bright, zinc-plated or otherwise-plated, semifinished forged goods made of unalloyed, stainless or other alloyed steel; aluminium, especially foils, thin strips, sheets, plates, diecastings, wrought aluminium, or pressed, punched or drawn parts; metallic coatings produced by casting or by electrolytic or chemical processes; and metal surfaces enhanced by coating, glazing or anodic oxidation.
  • Coatings for enhancing the wear resistance are suitable, for example, for jewelry, timepieces and parts thereof, and rings made of gold and platinum.
  • Diffusion barrier layers are suitable, for example, for lead fishing weights, diffusion barriers on stainless steel to prevent heavy metal contamination, water pipes, tools containing nickel or cobalt, or jewelry (anti-allergenic).
  • Surface leveling/frictional wear reducing coats are suitable, for example, for seals, gaskets or guide rings. Steel, iron, aluminum and other alloys corrode readily in a humid and salty environment. The salt fog test is highly accelerated, allowing useful tests in a reasonable amount of time. Coatings of the inventive compounds, compositions and or materials on aluminum and carbon steel coupons have been tested for preliminary evaluation in the salt fog apparatus, and show increased resistance to corrosion compared to aluminum coupons.
  • Fig 8 shows the inventive compounds, compositions and/or materials coated and uncoated coupons after the salt fog test.
  • Non-wetting behavior is helpful to prevent corrosion in a humid/rainy or coastal environment.
  • the inventive compounds, compositions and/or materials show non-wetting behavior to water and other liquids.
  • Non-wetting characteristics are primarily due to the low surface energy associated with the high degree of covalency. It may also serve as an anti-static coating preventing solid particles, such as dust or lint from sticking to its surface. Transmission to light is important for many applications.
  • a glass microscope slide coated with the inventive compounds, compositions and or materials was compared to an uncoated slide.
  • Such compounds, compositions and or materials have been shown to be transmissive to radiation between 200- 2500nm.
  • a coating was put on a sapphire plate, and the transmission properties were compared to an uncoated sapphire piece, cut from the same large plate. Two coated pieces were tested, one with a thicker coating than the other.
  • Fig 9 shows the transmission of the coated vs. uncoated sapphire plates.
  • the inventive compounds, compositions and/or materials could be used a protective coating against coke.
  • inventive compounds, compositions and/or materials relate to their use as a coating for high- temperature protection of metal- or alloy-based thermal protection systems (TPS) to be used in reusable launch vehicles (RLVs).
  • TPS metal- or alloy-based thermal protection systems
  • RLVs reusable launch vehicles
  • Such a material provides both oxidation protection to the underlying substrate and high emissivity characteristics.
  • the powders retain the black or dark color for over 100 hours at 815°C and over 24 hours at 1100°C and retain high emissivity.
  • the present invention has also been demonstrated to protect substrates from attack from molten non-ferrous metals, such as aluminum and zinc, as well as molten polymers.
  • the low surface energy of the inventive compounds, compositions and/or materials allows it to remain non-wetting to these and other materials.
  • inventive compounds, compositions and/or materials can also be used to provide a low friction surface.
  • the friction coefficient of inventive compounds, compositions and or materials coatings on highly polished 440C stainless steel substrates was measured to be around 0.1.
  • inventive compounds, compositions and/or materials show excellent adhesion to metals, alloys and ceramic/glass substrates, upon heat treatment to form the inorganic material. When deposited on a metal or alloy, the heat treatment allows a very thin oxide scale to form on the substrate surface, which enhances the adhesion of such compounds, compositions and/or materials to the substrate.
  • Nanoparticles or nanocrystals of varying chemistries can be embedded or encapsulated into the aluminophosphate amorphous material for inducing various functions including, but not limited to, optical, chemical, catalytic, physical, mechanical, and electrical properties.
  • Example 1 264 g of A1(N0 3 ) 3 -9H 2 0 is dissolved in 300 mL ethanol. In a separate container, 25 g P 2 0 5 (or other soluble phosphate ester) is dissolved in 100 mL ethanol which promotes the formation of phosphate esters and this solution is then added to the aluminum-containing solution.
  • Example 2 19mL triethyl phosphate was mixed with 84 g of A1(N0 3 ) 3 -9H 2 0 in 181 mL of ethanol. After stirring for 30 min, the mixture was dried to form gel powder and annealed to 1100°C for 1 hour in air. The x-ray diffraction pattern obtained shows highly crystalline aluminum phosphate and alumina phases, indicating that this mixture does not form amorphous aluminum-rich aluminum phosphate.
  • Example 3 The solution mixture of Example 2 was refluxed. After various periods, some of the mixture was dried to a gel powder at 150°C for 1 hour and then annealed at 1100°C for 1 hour in air. As the refluxing time increased, the amount of amorphous aluminum phosphate increased. After 3.5 days of reflux, a substantially amorphous phase is formed. The 31 P NMR of the solution showed peaks near -5 ppm, indicating that the aluminum was complexed with the phosphorous ( Figure 12).
  • Example 4 119.28 g A1(N0 3 ) 3 -9H 2 0 was dissolved in 510 niLl-butanol. In a separate beaker, an appropriate molar amount of phosphorous pentoxide was dissolved in 3 lmL of 1-butanol. These two solutions were mixed together to form a 1.75/1 Al/P 1-butanol based solution. The solution was dried to a gel powder at 150°C for 1 hour and then annealed to 1100°C for 1 hour in air. A jet black powder resulted (black color due to the presence of residual carbon encapsulated in amorphous matrix), and the x-ray diffraction pattern indicated that the powder was substantially amorphous.
  • Example 5 Coupons of Inconel 718 were dip-coated with the solution of Example 1, and cured with an IR lamp for 10 min. The coupons were heat treated according to the schedule in Table 1 and examined under optical microscope after 20 cycles. It was noticed that there was no additional cracking of the coating compared to as-deposited coatings which showed some cracking near the edges and few cracks in other areas. This demonstrates that the thin nature of the deposited film of the inventive material is not subject to cracking from thermal stresses even though the thermal expansion mismatch between the substrate and the inventive material is significant.
  • Example 6 A piece of stainless steel was dip-coated into the solution mixture of Example 1. The coupon was dried with flowing air and heated with an IR lamp for a sufficient time to cure the film (remove all of the organics and nitrates) to form substantially inorganic material. The resulting coating was uniform and crack-free.
  • Example 7 A stainless steel coupon was coated using the solution mixture of Example 1 by a roller. The roller was saturated with precursor solution and rolled quickly and firmly across most of the stainless steel coupon. The coupon is then heat treated with an IR lamp (as in Example 6) for sufficient time to remove all organics and nitrates.
  • Example 8 2.2 grams of finely milled (sub-micron to few microns) amorphous aluminum phosphate powder (black in color) derived using processes in the aforementioned Examples was dispersed in 12 mL of ethanol and was added to 12 mL of the solution mixture from Example 1 to form a slurry for application of coatings. This slurry solution was used to coat a piece of type 304 stainless steel as in Example 7 that yielded a composite coating consisting of powder dispersed in the amorphous matrix derived from the solution portion of the slurry.
  • Example 9 As-machined graphite samples were coated with the inventive material and annealed, along with an uncoated piece, to 800°C for 2 hours in air. The coated pieces retained their physical dimensions to a substantially greater extent than their uncoated counterparts as seen in Figure 14 suggesting that the inventive material is effective in providing oxidation protection to graphite and carbon-based materials, including composites.
  • Example 10 19.47g P 2 0 5 was dissolved in 200 mL ethanol.
  • Example 12 Analogous to the preceding example, using similar methodology, a silicon-containing solution can be made 8.47 g P 0 5 was dissolved in 90 mL ethanol. In another beaker, 78.6 g Al(N0 3 ) 3 -9H 2 ⁇ was dissolved in 174 mL ethanol. In a third container, 1.7g tetraethylorthosilane was dissolved in 15mL ethanol. All three solutions were mixed together. Some of the solution was dried in a convection oven at 150C. Some of this dried powder was annealed at 1400°C for 10 hours. Crystals of mullite and predominately amorphous aluminum phosphate were identified by x-ray diffraction (Fig 17).
  • Example 13 Analogous to the preceding example, using similar methodology, a titarnum-containing solution can be made 0.2mL nitric acid was mixed with 9.8 4mL deionized water. 2mL titanium isopropoxide was added to this acidified water solution, and a white precipitate resulted. This mixture was added to 86mL of the aluminum phosphate solution from example 1. This mixture was dried at 150°C and annealed at 1000°C for 1 hour. X-ray diffraction indicated the presence of titanium oxide (anatase) and predominately amorphous aluminum phosphate (Figure 18).
  • Example 14 The solution of Example 1 is dried and heat treated to 1100°C for 1 hour.
  • Example 15 The powder of Example 4 is examined in the TEM. Transmission electron microscopy has shown nanoinclusions of glassy carbon embedded in the amorphous matrix of the inventive material. These inclusions are about 2-4 nm by 10 - 40 nm in size ( Figure 19). The inclusions are typical in appearance of glassy carbon and EDS evidence has shown that these particles primarily contain carbon .
  • Example 16 The powder of Example 14 is dispersed in the solution mixture of Example 1. This slurry is painted on an alumina substrate.
  • Example 16 This coating is dried in flowing air until the solvent has evaporated and then heat cured above 500°C .
  • the room temperature total hemispherical emissivity of the coating is 0.917.
  • Example 17 The coating of Example 16 is heat treated in air at 815°C for lOOh.
  • the room temperature total hemispherical emissivity. of the coating is 0.908 suggesting that substantial portion of the nanoinclusions of carbon did not oxidize and was well protected by the substantially pore-free and dense matrix of the inventive material.
  • Example 18 The coating of Example 16 is heat treated in air to 1100°C for 24h.
  • Example 19 Solution mixture of Example 1 was modified via addition of an organic component to enable development of thicker films that are crack-free.
  • a piece of 1018 carbon steel was coated with the aforementioned solution that yielded a relatively thicker coating (> 1 micron average) which was substantially crack- free.
  • the amount of organic additive can be varied to obtain a range of thicknesses for the film deposited.
  • the coated 1018 coupon was subjected to salt fog chamber, per conditions specified in ASTM Bl 17 test along with an uncoated coupon for four days.
  • Example 20 Using the process described in Example 19, a completely inorganic coating that is substantially opaque and dark in appearance can be developed on metallic and other substrates. A piece of stainless steel was coated to yield a black coating. The coating is substantially crack or pore-free, hard and abrasion resistant and may have excellent weathering resistance as compared to conventional black paints. Excellent adhesion is also promoted as described in the specifications of the patent application.
  • Example 21 An alcoholic solution containing silver ions was added to the solution mixture from Example 1. This solution was used to coat a soda-lime glass slide.
  • Example 22 A slurry coating as described in Example 16 was applied to a portion of a stainless steel coupon. The coated sample was immersed in pure molten aluminum at 760°C and retracted. No noticeable wetting of aluminum was observed on the coated portion of the coupon as compared to complete coverage of the uncoated portion immersed in molten aluminum, thus demonstrating the chemical stability and compatibility with molten aluminum and excellent non-wetting characteristics. (See Fig 20.)
  • Example 23 A piece of 1018 carbon steel is dip-coated using the solution mixture of Example 1. This coating is dried in flowing air until the solvent has evaporated and then heat treated at 500°C for 30 minutes in air.
  • Example 26 The sample of Example 20 is immersed and retracted from molten aluminum at 760°C. Significant portion of the coated portion appeared to be completely non-wetting to molten aluminum.
  • Example 27 A piece of steel was partially coated with the solution mixture of Example 1. The coupon was dried with flowing air and heated at 500°C for a sufficient time to cure the film (remove all of the organics and nitrates) to form substantially inorganic material. The surface energy of the coated sample, as well as the uncoated, heat treated sample was measured. The surface energy of the coated material was 31.89 mJ/m 2 .

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Abstract

L'invention concerne des composés d'aluminophosphate, des compositions et des matériaux pouvant être utilisés pour réaliser des revêtements de substrat,
EP03819148A 2003-11-19 2003-11-19 Composes de phosphate d'aluminium, compositions, materiaux et revetements metalliques connexes Withdrawn EP1689578A1 (fr)

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JP4857290B2 (ja) * 2007-01-22 2012-01-18 キヤノン株式会社 光学部材及び光学部材の製造方法
EP1947486B9 (fr) 2007-01-22 2012-03-14 Canon Kabushiki Kaisha Élément optique comportant un revêtement antireflet et son procédé de fabrication
EP2068074A2 (fr) * 2007-10-05 2009-06-10 Koninklijke Philips Electronics N.V. Dispositif générateur de vapeur doté d'un revêtement hydrophile
DE102009039872A1 (de) * 2009-09-03 2011-03-10 Dorma Gmbh + Co. Kg Griff mit Oberflächenbeschichtung und Verfahren zu seiner Herstellung
JP5353931B2 (ja) * 2011-03-25 2013-11-27 株式会社豊田中央研究所 樹脂金属複合材料およびその製造方法
CN102368032A (zh) * 2011-06-28 2012-03-07 苏州方暨圆节能科技有限公司 具有薄膜的铝散热器热管
CN102368033A (zh) * 2011-06-28 2012-03-07 苏州方暨圆节能科技有限公司 具有薄膜的铝散热器翅片
CN103568384B (zh) * 2012-08-10 2017-10-03 赛恩倍吉科技顾问（深圳）有限公司 保护盖及其加工方法
CN104129984B (zh) * 2014-07-21 2016-03-23 哈尔滨工业大学 一种金属表面非晶磷酸铝基耐高温透波陶瓷涂层的制备方法
KR101750963B1 (ko) * 2015-10-20 2017-06-26 세메스 주식회사 집적회로 소자 제조용 이송 장치
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TWI714105B (zh) * 2019-05-29 2020-12-21 中國鋼鐵股份有限公司 皮膜處理液及使用皮膜處理液的鈦鎳合金盤元的抽線預處理方法
CN113025092A (zh) * 2021-03-29 2021-06-25 江西增孚新材料科技有限公司 一种无机防腐涂料及其制备方法
CN113885265B (zh) * 2021-09-25 2024-06-18 中建材玻璃新材料研究院集团有限公司 一种全固态无机电致变色复合膜系智能玻璃组件及其制备方法
CN114477790B (zh) * 2021-12-24 2024-03-15 中建材玻璃新材料研究院集团有限公司 一种玻璃长效疏水涂层及其制备方法
CN114326241B (zh) * 2021-12-27 2024-06-18 中建材玻璃新材料研究院集团有限公司 一种无机电致变色用离子传输层及组件复合膜系制备方法
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