EP3874075A2 - Procédé de dépôt autocatalytique d'aluminium - Google Patents

Procédé de dépôt autocatalytique d'aluminium

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Publication number
EP3874075A2
EP3874075A2 EP19880829.7A EP19880829A EP3874075A2 EP 3874075 A2 EP3874075 A2 EP 3874075A2 EP 19880829 A EP19880829 A EP 19880829A EP 3874075 A2 EP3874075 A2 EP 3874075A2
Authority
EP
European Patent Office
Prior art keywords
aluminum
substrate
solution
electroless
electroless deposition
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP19880829.7A
Other languages
German (de)
English (en)
Other versions
EP3874075A4 (fr
Inventor
Mohammed Taha ELSHARKAWI
Amal ESAWI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
American University in Cairo
Original Assignee
American University in Cairo
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 American University in Cairo filed Critical American University in Cairo
Publication of EP3874075A2 publication Critical patent/EP3874075A2/fr
Publication of EP3874075A4 publication Critical patent/EP3874075A4/fr
Pending legal-status Critical Current

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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
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1637—Composition of the substrate metallic substrate
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/1687—Process conditions with ionic liquid
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1889—Multistep pretreatment with use of metal first
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/52—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 reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/243—Chemical after-treatment using organic dyestuffs
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Definitions

  • the present invention relates to a method for electroless deposition of aluminum on a substrate which employs materials which are commercially available at a cost suitable for large scale production quantities.
  • Aluminum coatings are applied to many substrates to impart strength, abrasion resistance corrosion resistance, barrier properties, thermal conductivity and electrical conductivity.
  • the substrate may include, but is not limited to glass, metal, metal oxide, ceramic, organic materials, or polymer and may have any geometry varying from a simple geometry such as a flat sheet to a more complex geometry.
  • Conventional methods for applying aluminum coatings or thin films include methods such as aluminum cladding wherein aluminum and another metal are bonded together by application of pressure at a suitable elevated pressure, thermal or slurry spray methods wherein molten or semi-molten aluminum or an aluminum containing slurry is sprayed onto a substrate, physical or chemical vapor deposition wherein thin aluminum film is produced through condensation of a vaporized form of aluminum under high vacuum or electrolytic deposition (also referred to as electrolytic plating) wherein electrical current is used to reduce dissolved aluminum cations to form an aluminum film on an electrode.
  • electrolytic deposition also referred to as electrolytic plating
  • aluminum cladding is generally limited to flat sheets and difficult to apply to complex geometries.
  • Thermal or slurry spraying also has limitation to the geometry of the substrate and requires line of sight for the coating to be deposited.
  • the spraying methods tend to have non-uniformity issue and the product may contain contaminants from the process and therefore limiting the application of this method.
  • Physical or chemical vapor deposition requires expensive and specialized equipment, is conducted at a high temperature, and is only applicable to selected substrates with simple geometries.
  • Aluminum electrodeposition in an aqueous medium is difficult because the standard reduction potential of aluminum is -1.66E (V) and therefore, water is electrolyzed in favor of electrodeposition of aluminum.
  • Electrolytic deposition of aluminum may be accomplished in a solvent system.
  • this method is only applicable to the deposition of pure aluminum.
  • ionic liquid based aluminum alloy deposition due to the low solution conductivity of aluminum or aluminum alloys, it is often difficult to plate alloy onto complex geometries, and also difficult to produce a coating of uniform thickness.
  • this process requires very high power and is only applicable to conductive substrates. In the case of non-conductive substrates the surface has to be modified with a conductive or catalyst layer prior to the electrolytic deposition.
  • Shitanda et al. (Electrochimica Acta, 54 (2009) 5889-5893) describes a method for electroless aluminum deposition on glass wherein the glass surface is first treated with a catalytic coating in a two stage process. The surface is initially treated with a tin chloride solution and then treated with a palladium chloride solution to prepare a Pd catalyst surface on the glass substrate.
  • EMIC l-ethyl 3-methylImidazolium chloride
  • RTIL Room Temperature Ionic liquid
  • the present inventors have studied this electroless plating process and determined that this method has two significant negative attributes which inhibit its use as an industrial scale process.
  • the cost of the ionic liquid EMIC is extremely high and this material is not readily available as a commercial material. Additionally the method employs a two-step catalyzation process that must be optimized according to the type of surface to be plated.
  • a Lewis acid room temperature ionic liquid RTIL
  • the AlCl 3 : NH 2 CONH 2 molar ratio of the AlCl 3 : NH 2 CONH 2 RTIL is from greater than 1 : 1 to 2: 1 and in a special aspect the AlCl 3 : NH 2 CONH 2 molar ratio of the AlCl 3 : NH 2 CONH 2 RTIL is 2: 1.
  • the hydride reducing agent is selected from the group consisting of lithium hydride, lithium aluminum hydride, diisobutyl aluminum hydride and combinations thereof and in a special aspect the hydride reducing agent is lithium aluminum hydride.
  • the aprotic anhydrous solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, dibutyl ether, dioxane, toluene and hexane.
  • the alloy metal salt is dissolved in an aprotic solvent; and added to the RTIL prior to the addition of the hydride reducing agent; wherein the metal salt is selected from the group consisting of a halide salt of zinc, chromium, iron, nickel, tin, lead, copper, silver, gold and combinations thereof.
  • the catalyst metal is selected from the group consisting of iron, palladium, silver, gold, platinum and combinations thereof and in a special aspect the catalyst metal in Pd.
  • the activation of the surface of the substrate to be coated comprises: treating the surface with a colloidal solution of palladium-tin (Pd-Sn) nanoparticles in the presence of HC1 and water to cover the surface of the substrate with a layer of adsorbed catalytic Pd-Sn nanoparticles comprising stannous hydroxide covered on their surface; cleaning the substrate surface from the residues of the colloidal solution; and placing the substrate in an acidic accelerator solution wherein the excess stannous hydroxide layer is removed from the surface of the substrate for an increased catalytic activity.
  • Pd-Sn palladium-tin
  • the substrate surface is non-reactive to Al deposition and/or is non-conductive.
  • the substrate is a nanostructure and in a special aspect the nanostructure is selected from the group consisting of a nanofiber, a nanoparticle, a nanotube, a nano-rod and a quantum dot.
  • the substrate is composed of a polymer selected from the group consisting of ABS, PL A, Nylon, Teflon and PMMA and the AlCl 3 : NH 2 CONH 2 molar ratio is from 1.3: 1 to 1.5: 1.
  • the substrate is a metal coated polymer and the AlCl 3 : NH 2 CONH 2 molar ratio is 2: 1.
  • the substrate is selected from the group of fibers consisting of a glass fiber, an aramid fiber and a carbon fiber.
  • the substrate is selected from the group of yarns consisting of a glass fiber yam, a Kevlar fiber yam and a carbon fiber yam.
  • the substrate is selected from the group consisting of a fullerene, a Bucky paper and a Bucky sheet.
  • the substrate is selected from the group of 2-D materials consisting of graphene, molybdenum disulfide (MOS 2 ), tungsten disulfide (WS 2 ), tungsten diselenide (WSe 2 ), and zinc oxide(ZnO).
  • MOS 2 molybdenum disulfide
  • WS 2 tungsten disulfide
  • WSe 2 tungsten diselenide
  • ZnO zinc oxide
  • the substrate is selected from the group consisting of graphene powder and graphene nanoparticles.
  • the substrate is selected from the group consisting of a ZnO microtube and a ZnO nanowire.
  • the substrate is selected from the group consisting of steel, a steel alloy, glass and a ceramic.
  • the present invention includes a method for coating a substrate with an anodized aluminum oxide layer, comprising: activating the surface of the substrate to be coated by applying a coating of a catalyst metal;
  • a Lewis acid room temperature ionic liquid RTIL
  • the present invention includes aluminum or aluminum alloy coated carbon nanotubes and aluminum or aluminum alloy coated multi-wall carbon nanotubes.
  • Fig. l is a schematic representation of the coating stages of the method according to one embodiment of the invention.
  • Fig. 2 is a schematic representation of the experimental procedure of the example.
  • Fig. 3 shows a chemical equation description of the Al deposition according to an embodiment of the invention.
  • Fig. 4A shows a TEM image of CNTs coated with Al as prepared in the example.
  • Fig. 4B shows a SEM image of CNTs coated with Al as prepared in the example.
  • Fig. 5 A shows a TEM image of the surface morphology of CNTs coated with Al as prepared in the example.
  • Fig. 5B shows a SEM of the surface morphology of CNTs coated with Al as prepared in the example.
  • Fig. 6 shows an EDX spectrum of CNTs coated with Al as prepared in the example.
  • Fig. 7 shows and XRD diffraction pattern of CNTs coated with Al as prepared in the example.
  • Fig. 8 shows a Raman analysis of CNTs coated with Al as prepared in the example.
  • Al deposition occurs not only by reduction of the Al 2 Cl 7 ion but also via reduction of an ion derivative of the AlCly NH 2 CONH 2 RTIL shown as [AlCl 2 (urea) n ] + and by catalyzed decomposition of the LiAlH 4.
  • the process could be scaled up to industrial levels in a cost effective manner without affecting the quality of aluminum coatings.
  • a one-step colloidal palladium surface catalyzation process was adopted to render the surfaces to be electroless plated catalytic prior to the electroless plating process.
  • the colloidal palladium resulted in a major cut in the optimization time for the catalyzation step of the entire electroless plating process compared to the conventional two-step system.
  • the method may be universally applied to a wide variety of substrates of different chemical composition, size and geometries.
  • a method for electroless deposition of aluminum or an aluminum alloy on a substrate surface comprises:
  • a coating of a catalyst metal activating the surface of the substrate to be coated by applying a coating of a catalyst metal; preparing a mixture of urea (NH 2 CONH 2 ) and anhydrous aluminum chloride (AlCl 3 ) wherein a molar ratio of AlCl 3 : NH 2 CONH 2 is greater than 1 : 1 to obtain a Lewis acid room temperature ionic liquid (RTIL);
  • a catalyst metal preparing a mixture of urea (NH 2 CONH 2 ) and anhydrous aluminum chloride (AlCl 3 ) wherein a molar ratio of AlCl 3 : NH 2 CONH 2 is greater than 1 : 1 to obtain a Lewis acid room temperature ionic liquid (RTIL);
  • the AlCl 3 : NH 2 CONH 2 ratio may vary from greater than 1 : 1 to 2: 1. As the ratio increases toward 2: 1 the Lewis acidity of the RTIL increases and the ratio may be adjusted within the described limits to provide a Lewis acidity compatible with the substrate to be plated.
  • the AlCl 3 : NH 2 CONH 2 molar ratio may be 2: 1.
  • the hydride reducing agent may be selected from the group consisting of lithium hydride, lithium aluminum hydride, diisobutylaluminum hydride and combinations thereof.
  • the hydride reducing agent may be lithium aluminum hydride (LiAlH 4 ).
  • the hydride reducing agent may be dissolved in an aprotic anhydrous solvent to be added to the AlCl 3 : NH 2 CONH 2 RTIL.
  • the aprotic anhydrous solvent may be one or more of tetrahydrofuran (THF), diethyl ether, dibutyl ether, dioxane, toluene and hexane.
  • THF tetrahydrofuran
  • the electroless mixture may be further diluted with one or more of these aprotic anhydrous solvents to lower the viscosity.
  • An aluminum alloy plating may be obtained by dissolving an anhydrous alloy metal salt in the AlCl 3 : NH 2 CONH 2 RTIL prior to addition of the solution of the hydride reducing agent solution.
  • the alloy metal salt may be first dissolved in one or more of the listed aprotic anhydrous solvents and the obtained solution added to the AlCl 3 : NH 2 CONH 2 RTIL.
  • any solvent soluble salt may be useful, halide salts (F, Cl, Br and I) may be preferred and chloride salts may be most preferred.
  • the alloy element may be any metal which alloys with aluminum and preferably may be one or more selected from zinc, chromium, iron, nickel, tin, lead, copper, silver and gold.
  • the substrate When the substrate is a metal activation of the surface may not be necessary. However, when the substrate surface is not reactive to electroless Al deposition and/or not conductive, the surface may be activated with application of a metal catalyst.
  • the catalyst metal may be selected from the group consisting of iron, palladium, silver, gold, platinum and combinations thereof. In one preferred aspect the catalyst may be palladium.
  • the activation of the surface of the substrate to be coated comprises: treating the surface with a colloidal solution of palladium-tin (Pd-Sn) nanoparticles in the presence of HC1 and water to cover the surface of the substrate with a layer of adsorbed catalytic Pd-Sn nanoparticles comprising stannous hydroxide covered on their surface; cleaning the substrate surface from the residues of the colloidal solution; and placing the substrate in an acidic accelerator solution wherein the excess stannous hydroxide layer is removed from the surface of the substrate for an increased catalytic activity.
  • Pd-Sn nanoparticles and subsequent plating of aluminum is shown in Fig. 1. This method is based upon the description of Cohen et al. (The Chemistry of Palladium-Tin Colloid Sensitizing Processes, J. Colloid Interface Sci. 1976, 55 (1), 156-162).
  • the substrate surface need not be functionalized to promote application of the Pd-Sn nanoparticles.
  • a layer of colloidal Pd-Sn nanoparticles is coated to the substrate surface (Carbon nanotubes in Fig. 1).
  • the initial coating contains an excess amount of stannous hydroxide which is removed by treatment with an aqueous acid solution known as accelerator solution.
  • the acid may be any inorganic acid capable of dissolving and removing stannous hydroxide and may be selected from H 2 S0 4 , HC1, HBF 4 and NH 4 BF 4.
  • the substrate may be a metal wherein application of a catalyst layer is not necessary or a non-reactive surface where catalytic activation is necessary.
  • substrates where catalytic activation is necessary include non-metal nanostructures including nanofibers, nanoparticles, nanotubes, nano-rods and quantum dots.
  • Al coating of carbon nanotubes, including and multi-wall carbon nanotubes (MWCNT) is described in the Example and supporting analytical information shown in Figs. 4-8 as described in the Example.
  • the method may also be applied to single walled carbon nanotubes (SWCNT).
  • the method for electroless deposition of Al or an Al alloy may be employed to coat polymers including ABS, PLA, polyamides, polyimides such as Kapton films, Teflon, fluorinated sulfones, polyethylene oxide and PMMA.
  • Polyelectrolytes such as poly(ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS) may also be coated. Due to the potential for polymer degradation in a strong Lewis environment, the AlCl 3 : NH 2 CONH 2 molar ratio employed in the coating of these materials may be from 1.3: 1 to 1.5: 1. However, if the polymer is already metal coated, thus protected from the AlCl 3 Lewis acidity, the AlCl 3 : NH 2 CONH 2 molar ratio employed in the coating may be 2: 1.
  • substrates that may be coated or plated according to the present invention include fibers, such as glass fibers, aramid fibers and carbon fibers; yams, such as glass fiber yams, Kevlar fiber yams and carbon fiber yarns; allotropes of carbon such as fullerenes, Bucky paper and Bucky sheets; graphene powder; graphene nanoparticles, NMC532/graphite; hollow carbon nanospheres; Li 2 FeSi0 4 /C nanospheres polystyrene nanospheres; ZnO microtubes; ZnO nanowires; silver nanowires and 2-D materials such as graphene, molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ), tungsten diselenide (WSe 2 ), zinc phthalocyanine (ZnPc) and zinc oxide( ZnO).
  • fibers such as glass fibers, aramid fibers and carbon fibers
  • yams such as glass fiber
  • LLZO Li conducting lanthanum zirconate ceramic structures
  • substrates may include amorphous, polycrystalline, and single crystalline silicon, amorphous and polycrystalline silicon germanium (SiGe), silicon dioxide, silicon doped with any of antimony, phosphorous, arsenic, boron, gallium and indium as well as very large scale integration (VLSI) semi conducting surfaces, complimentary metal-oxide-semiconductors (CMOS), P-type semi conductor, N-type semi conductor, PN junctions, PNP junctions and NPN junctions.
  • Additional substrates suitable for Al or Al coating according to the present invention may include microelectromechanical systems (MEMS), solar cells, and transparent electrodes for solar cells.
  • MEMS microelectromechanical systems
  • solar cells and transparent electrodes for solar cells.
  • Metal salts may also be substrates which may be plated or coated according to the present invention.
  • Examples of such metal salts may include LiS, Mo0 3 , Mn0 2 , LiNio . sMn ! 5 0 4 , indium tin oxide and MnC0 3.
  • the method for electroless deposition of aluminum or an aluminum alloy according to the present invention provides a low cost approach for aluminum or Al alloy electroless plating which is virtually universally applicable to a wide range of substrate materials.
  • the materials employed are inexpensive and readily available in comparison to materials employed in previously described methods.
  • the AlCl 3 : NH 2 CONH 2 RTTL has a wide
  • electrochemical window may be used to plate on non-conductive and non-reactive surfaces. Further, the method may be applied to coat or plate substrates of complex 3 dimensional structure.
  • a further embodiment of the present invention includes a method to coat a substrate with an anodized aluminum oxide layer wherein an Al coated substrate obtained according to the first embodiment and the various aspects thereof may be submerged in an electrolytic solution and an anode current applied to the Al coating to obtain an aluminum oxide coating having an outer barrier layer.
  • Anodization of aluminum is conventionally known and may be conducted in an electrolyte such as chromic acid, sulfuric acid, oxalic acid or phosphoric acid.
  • an electrolyte such as chromic acid, sulfuric acid, oxalic acid or phosphoric acid.
  • a thin aluminum oxide film is formed on the aluminum coating.
  • the thickness of this barrier layer may be from 0.01 - 0.1 nm and may not change throughout the process as it dissolves at the outer side exposed to the electrolyte.
  • the electrochemical field localizes on inhomogeneities of the surface of formed aluminum oxide and the oxide dissolves under the influence of the inhomogeneity of the field thus leading to the growth of pores.
  • the alumina layer may then be dissolved, leaving a regular array of porous aluminum and when anodization is repeated a layer of porous aluminum oxide is obtained.
  • organic or inorganic pigments may be inserted within the aluminum oxide pores to give the aluminum oxide an aesthetic look.
  • the colored substrate may then be inserted in boiling water to seal the pores by forming a transparent outer aluminum hydroxide Al(OH) 3 layer via a method known in industry as“hydration pore closure”.
  • Multi-wall carbon nanotubes were obtained from Thomas Swan Corporation (average diameter of 10-15 nm) were used in the present study.
  • the colloidal palladium-tin solution and the accelerator acids were obtained from Macdermid Enthony ETSA.
  • Aluminum chloride anhydrous was obtained from Alfa-Aeser.
  • ETrea 99.9% was obtained from Lobachemie India.
  • the growth of aluminum on CNTs has taken place in 3 different steps.
  • the first step is the catalytic activation of CNTs by palladium nanoparticles. Then, excess stannous hydroxide was removed from the surface via a group of accelerating acids.
  • CNTs were catalyzed using a colloidal Pd-Sn solution based on the description of Cohen et al. (The Chemistry of Palladium-Tin Colloid Sensitizing Processes, J. Colloid Interface Sci. 1976, 55 (1), 156-162).
  • the colloidal solution was prepared from 62.5 ml of commercial colloidal Pd-Sn concentrate, 50 ml of HC1 (37%), and 137.5 ml of DI water.
  • CNTs of 0.1 g were immersed in the prepared solution and left for 1 -minute sonication agitation and extra 3 to 4 minutes of stir agitation. The CNTs were then filtered using a 0.22 pm PTFE filter membrane on a microfiltration kit.
  • the collected CNTs were then dispersed in what is known industrially as the accelerator solution.
  • the acceleration step is composed of a group of acids beneficial for the removal of excess stannous hydroxide from the surface of palladium nanoparticles coated on CNTs.
  • the concentration of the activator solution was 50 g/L.
  • the CNTs were refiltered and collected using teasers.
  • the aluminum chloride urea reaction is an exothermic reaction and excess heat may result in the decomposition of the entire electrolyte. Failure in controlling the exothermic heat of the reaction leads to a great failure in the electroless deposition. For this reason, strict procedures were carried out to prevent the thermal decomposition of the electrolyte by preparing the volume needed on 4 separate parts to reduce the heat created as a result of the exothermic reaction. The previous step was not sufficient in preventing the decomposition. Therefore, the volumetric flask was cooled with a sealed rubber ice bucket that preserved the dry environment of the chamber.
  • An ideal electrolyte has a pale yellow color. If light brown color is observed, this will be a sign of the electrolyte decomposition.
  • Lithium Aluminum Hydride (LiAlH 4 ) (LAH) was dissolved in Toluene, hexane, or diethyl ether and used as a reducing agent. 1.5, 1.9, 2.5, and 5 grams of LAH were tested. The activated CNTs were immersed in the electroless solution using sonication for 5 minutes and magnetic stirring for 10 minutes. The ionic liquid containing CNTs was viscous and could not be filtered without dilution using an organic solvent. This dilatant solvent had to be the same solvent used in diluting the LAH.
  • FIG. 1 A schematic representation of the coating stages is shown in Figure 1 and a schematic representation of the experimental procedures is shown in Figure 2.
  • the Al coating was confirmed using SEM and TEM imaging. Chemical analysis was performed using EDX. Crystal structure of aluminum was confirmed using XRD. Raman analysis was carried out to confirm the existence of CNTs that are coated with aluminum.
  • the aluminum coated MWCNTs were characterized by scanning electron microscopy (SEM) analysis using (LEO SEIPRA 55VP FEG, Zeiss, equipped with Oxford EDS detector), transmission electron microscopy (TEM) using (JEM-2100 LaB6, JEOL, operating at 200 kV and equipped with Gatan SC200B CCD camera), energy dispersive X-ray (EDX) attached to the SEM, X-ray diffraction (XRD) using (Cu Ka, Panalytical Xpert Pro diffractometer).
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • TEM transmission electron microscopy
  • JEM-2100 LaB6, JEOL operating at 200 kV and equipped with Gatan SC200B CCD camera
  • EDX energy dispersive
  • Figure 7 shows the XRD diffraction pattern of aluminum coated CNTs which confirmed the existence the aluminum coat in a crystalline form. As the diffraction depends on how heavy the atom is, it is difficult to observe the CNTs peak at 26° because of their low percentage in the sample as well as the large difference of atomic weight between aluminum and carbon.

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Abstract

L'invention concerne un procédé de dépôt autocatalytique d'aluminium ou d'un alliage d'aluminium sur une surface de substrat. Le procédé comprend les opérations d'activation de la surface du substrat à revêtir par application d'un revêtement d'un métal catalyseur ; de préparation d'un mélange d'urée (NH2CONH2) et de chlorure d'aluminium anhydre (AlCl3), un rapport molaire AlCl3/ NH2CONH2 étant supérieur à 1/1 pour obtenir un liquide ionique à température ambiante d'acide de Lewis (RTIL) contenant éventuellement un sel métallique d'alliage ; de dissolution d'un agent réducteur d'hydrure dans un solvant anhydre aprotique pour obtenir une solution d'hydrure ; de mélange de la solution d'hydrure et l'AlCl3/ NH2CONH2 RTIL pour obtenir une solution D'Al autocatalytique ; d'exposition de la surface activée du substrat à la solution d'Al autocatalytique ; et de retrait de la solution d'Al autocatalytique de la surface de substrat ; un revêtement d'alliage d'Al ou d'Al étant obtenu sur la surface de substrat activée lors de l'exposition de la surface de substrat activée à la solution d'Al autocatalytique.
EP19880829.7A 2018-10-30 2019-10-30 Procédé de dépôt autocatalytique d'aluminium Pending EP3874075A4 (fr)

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