EP2820171A1 - Procédé de fabrication d'un substrat revêtu et substrat obtenu de cette façon - Google Patents

Procédé de fabrication d'un substrat revêtu et substrat obtenu de cette façon

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Publication number
EP2820171A1
EP2820171A1 EP13709507.1A EP13709507A EP2820171A1 EP 2820171 A1 EP2820171 A1 EP 2820171A1 EP 13709507 A EP13709507 A EP 13709507A EP 2820171 A1 EP2820171 A1 EP 2820171A1
Authority
EP
European Patent Office
Prior art keywords
substrate
particulate material
metal
magnetic field
electroless plating
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.)
Withdrawn
Application number
EP13709507.1A
Other languages
German (de)
English (en)
Inventor
Alan Macdonald Davidson
John Sharp
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.)
Edinburgh Napier University
Original Assignee
Edinburgh Napier University
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 Edinburgh Napier University filed Critical Edinburgh Napier University
Publication of EP2820171A1 publication Critical patent/EP2820171A1/fr
Withdrawn legal-status Critical Current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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1664—Process features with additional means during the plating process
    • C23C18/1673—Magnetic field
    • 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
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
    • C23C18/18—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
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition
    • 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for the manufacture of a coated substrate, such as an electrode or interconnect for a fuel cell, particularly a solid oxide fuel cell (SOFC), and a substrate manufactured according to the method.
  • a coated substrate such as an electrode or interconnect for a fuel cell, particularly a solid oxide fuel cell (SOFC)
  • SOFC solid oxide fuel cell
  • Fuel cells are electrochemical devices which convert the chemical energy in fuels into electrical energy. Fuel cells comprise at least an electrolyte and two electrodes, namely an anode and a cathode, and may additionally comprise an interconnect. Fuel cells are typically constructed from an electrolyte
  • a flow of a gaseous fuel - typically hydrogen - passes over the anode and an oxygen-containing gas passes over the cathode resulting in ionic transfer through the electrolyte and electronic transfer through an external load.
  • a gaseous fuel - typically hydrogen - passes over the anode and an oxygen-containing gas passes over the cathode resulting in ionic transfer through the electrolyte and electronic transfer through an external load.
  • the ionic transfer occurs in the form of the diffusion of oxide ions into the electrolyte and their migration to the anode where they can combine with the fuel to liberate electrons which pass to an external circuit via an interconnect.
  • PCT/GB2008/003342 allows the deposition of a metal and particulate material onto a many substrate types, including non-conducting substrates.
  • the deposition of the particulate material suspended in the plating solution relies upon its entrainment with the metal as the metal is being plated onto the substrate.
  • the concentration of the particulate material at the substrate is dependent upon the concentration in the electroless plating solution and the effectiveness of any mixing. This can lead to inadequate deposition of the particulate material onto the substrate.
  • the present invention provides a method for the manufacture of a coated substrate which addresses these problems.
  • the present invention provides a method for the manufacture of a coated substrate which improves the deposition of the particulate material. This can provide higher densities of particular material on the coated substrate.
  • It is a further object of the present invention to provide a method which allows the selection of the properties of the coated substrate.
  • the choice of particulate material can provide a variety of properties to the substrate, such a wear, corrosion or thermal resistance.
  • by varying the proportion of the metal to particulate material deposited on the substrate it is possible to alter the electrical conductivity and porosity of the coated substrate.
  • the present invention provides a method for the manufacture of a coated substrate, the method comprising at least the steps of:
  • an electroless plating solution comprising a reducing agent, a metal precursor and a suspension of particulate material, wherein said particulate material is attracted to a magnetic field;
  • the step of generating a magnetic field around the substrate can be carried out before or after the substrate is contacted with an electroless plating solution. Consequently, the "contacting" and “generating” steps described above may also be provided in the reversed order to that given above, or simultaneously.
  • the magnetic field is generated before the contacting step. It will be apparent that the benefits of the invention are achieved when the electroless plating step is carried out in the presence of a magnetic field.
  • the magnetic field may be one or both of a permanent magnetic field, such as the field generated by a permanent magnet, and an electromagnetic field, such as the field generated by an electromagnet.
  • the magnetic field can be aligned to attract the particulate material to the substrate.
  • the particulate material In order for the particulate material to be attracted to the magnetic field, and thereby deposit on the substrate in the field, the particulate material should exhibit a magnetic moment.
  • the magnetic moment may be a permanent magnetic moment, such as that present in a ferrimagnetic or ferromagnetic materials or may be an induced magnetic moment, such as that present in a paramagnetic material in a magnetic field. Consequently, the particulate material may comprise one or more of the group selected from a ferrimagnetic material, a ferromagnetic material and a paramagnetic material.
  • the particulate material may also comprise a magnetic additive.
  • the magnetic additive is attracted to a magnetic field and its presence increases the attraction of the particulate material to the magnetic field.
  • the magnetic additive is selected from one or more of the group comprising a ferrimagnetic material, a ferromagnetic material and a paramagnetic material. It will be apparent that the magnetic additive should be a part of, i.e. unitary with, the particulate material, either within or on the surface of a particle of the particulate material.
  • the particulate material may be attracted to the magnetic field by virtue of the magnetic additive.
  • the magnetic additive is preferably a ferromagnetic material, such as nickel.
  • Other magnetic additives include iron and cobalt.
  • the magnetic additive is present on the particulate material as a coating, such as a full or a partial coating. A partial coating does not cover the entire external surface area of the particle of particulate material. Coatings of nickel and/or cobalt are preferred.
  • the magnetic additive particularly a nickel, iron and/or cobalt magnetic additive, may be deposited on the particulate material by an electroless plating process.
  • the magnetic additive may be provided as a metallic coating on the surface of the particles forming the particulate material.
  • the deposition of the magnetic additive on the particulate material may be carried out in a pre- treatment step prior to the electroless plating step which co-deposits metal and particulate material onto the substrate.
  • the pre-treating step comprises depositing a magnetic additive onto a particle to provide the particulate material; and forming an electroless plating solution with the particulate material, a reducing agent and a metal precursor.
  • a metal such as nickel
  • a metal such as nickel
  • the particle to form the particulate material would take the place of the substrate, such that the electroless plating solution may comprise a reducing agent and a metal precursor and the plated metal is the magnetic additive.
  • the pre-treatment may comprise at least the steps of providing a particle or plurality of particles, contacting the particles with an electroless plating solution comprising a reducing agent and a metal precursor and electrolessly plating metal on the particles to form the particulate material.
  • Iron may be deposited on the particulate material in accordance with the method disclosed in Chem. Mater., 2006, 18 (18), pp 4361-4368. Cobalt may be deposited on the particulate material in accordance with the method disclosed in IEEE Transactions on Magnetics, vol. 5, issue 3, pp. 314-317, 1969.
  • the magnetic additive may be in particulate form. In one embodiment, it can be deposited on the particles forming the particulate material by an electroless plating process, such as that described in
  • the particle to form the particulate material would take the place of the substrate and the magnetic additive in particulate for would be the particulate material, such that the electroless plating solution may comprise a reducing agent, a metal precursor and a magnetic additive in particulate form.
  • the magnetic additive in particulate form could be applied to the particle to form the particulate material in a pre-treatment step.
  • the deposition of the magnetic additive on the particulate material may be carried out in a pre-treatment step prior to the electroless plating step which co-deposits metal and particulate material onto the substrate.
  • the pre- treatment may comprise at least the steps of providing a particle or plurality of particles to form the particulate material, contacting the particles with an electroless plating solution comprising a reducing agent, a metal precursor and a magnetic additive in particulate form and electrolessly plating metal from the metal precursor on the particles to form the particulate material, thereby co- depositing the magnetic additive in particulate form to provide a particulate material.
  • the inclusion of a magnetic additive in the particulate material is beneficial when the particle forming the particulate material (i.e. without the magnetic additive) is not attracted to the magnetic field, or is insufficiently attracted to the magnetic field to provide an acceptable coating on the substrate.
  • the particulate material may comprise a particle which is a non-magnetic material i.e. which is not attracted to a magnetic field, or a material which is repelled by a magnetic field, such as a diamagnetic material, and the advantages described herein may still be obtained if a magnetic additive is present.
  • the quantity of magnetic additive in the particulate material should be sufficient to enhance the attraction of the particulate material to the magnetic field, for instance to overcome the repulsion of a component which is repelled by a magnetic field, so that a net attraction to a magnetic field is exhibited by the particulate material.
  • the magnetic field can vary the concentration of the particulate material at different points in the solution. This can not only increase the concentration of the particulate material near the substrate compared to the average concentration of the particulate material in the electroless plating solution, leading to improved particulate material deposition, but also efficiently replace the suspended particulate material removed by deposition in the solution near the substrate from the rest of the solution experiencing a weaker or no applied magnetic field.
  • the concentration of the particulate material in the magnetic field can be increased in proportion with an increase with the intensity of the magnetic field in the solution, enabling real time adjustment of the deposition rate.
  • the method disclosed herein can be used to apply a particulate material imparting an advantageous property to a substrate.
  • wear, thermal or corrosion resistant particulate material can be deposited in order to provide such properties to the substrate.
  • the method can be used with metallic substrates, such as alloys like steel, in which the particulate material would provide a resistant coating.
  • Certain substrates, such as steel, may require pre-treating prior to the electroless plating. For instance, a pre-treatment step such as etching to remove the oxide coating from the surface of a steel substrate can be carried out. This provides improved adhesion of the coated layer.
  • the substrate may be electrically conducting, e.g. an electrode or an
  • interconnect such as a metal or alloy
  • substrate may be electrically nonconducting (i.e. an electrical insulator), such as a ceramic.
  • the method described herein can be particularly useful in coating an electrode, an interconnect, a membrane filter, a pipe, a joint, particularly tubular joints, a valve body, a turbine blade, or other items having a complex shape in which the surface to be coated may not be easily accessible.
  • Such substrates having resistant coatings may have applications in the oil and gas industries, aviation and automotive industries, power generation such as heat exchangers and other fields operating in extreme environments.
  • the method described herein can be carried out to a substrate, such as a pipeline, in situ i.e. after the substrate has been placed in position for use.
  • a resistant coating may be applied to the internal surface of a pipe in a pipeline, by passing the electroless plating solution through the pipe while generating a magnetic field around the pipe, for instance by applying external magnets or electromagnets to the outer surface of the pipe.
  • the external magnets or electromagnets generate a magnetic field around the pipe, attracting the particulate material to its inner surface.
  • the coating may also be applied to a polymeric substrate, particularly a polymer membrane. Polymer membranes are often used in ion exchange and water treatment.
  • the coating may be provided to a polymeric substrate to provide a printed circuit board.
  • the method described herein may also be applied in the field of electronics, to provide nanomaterial aligned structures.
  • a particulate material as disclosed herein will inherently align along the magnetic field lines of the magnetic field generated around the substrate. This effect can lead to the control of the spatial positioning of the particulate material co-deposited on the substrate, and/or control the alignment of a magnetically anisotropic particulate material co- deposited on the substrate.
  • the method of the present invention utilises a plating solution to electrolessly deposit a metal onto the substrate.
  • the plating solution comprises a reducing agent, a metal precursor and a suspension of a particulate material.
  • the suspended particulate material is co-deposited with the metal on the substrate during the electroless plating method.
  • the metal to be deposited is one or more selected from the group consisting of: nickel, cobalt, platinum, rhodium, ruthenium, rhenium and palladium, or an alloy of more than one of these metals.
  • the metal preferably comprises nickel.
  • the metal to be deposited is provided by a metal precursor in the plating solution.
  • the metal precursor is preferably a metal salt, and should be soluble in the plating solution to provide free metal ions.
  • the particulate material may be selected from a wide variety of solids depending upon the desired function.
  • the particulate material may have a particle size in the range from 0.2 to 40 micrometers, particularly if the particulate material is deposited on a substrate for use in a fuel cell.
  • the electroless plating solution may comprise a further particulate material.
  • the further particulate material may be a nonmagnetic material which is not attracted to a magnetic field. Such non-magnetic further particulate material would not comprise a magnetic additive and could be deposited by entrainment with the plated metal, as described in
  • the particulate material may comprise a plurality of particulate materials.
  • the further particulate material may comprise a plurality of further particulate materials.
  • the particulate material and/or the further particulate material may comprise one or more of the group selected from a surfactant, a pore former, a lubricant, a smart material, a wear resistant material, a corrosion resistant material, a heat resistant material, an anti-microbial additive and a fuel cell electrode material.
  • a magnetic additive may be added to provide the particulate material if the chosen material is not inherently attracted to a magnetic field.
  • a surfactant deposited on the substrate as part of the electroless plating method may be used to improve the ceramic to metal ratio in the coating and also as a pore former.
  • the coated substrate comprising deposited surfactant in the coating can be subjected, after the plating method, to a heating step in which the surfactant is burned off to form pores in the coating.
  • pore formers such as graphite
  • the pore former may be deposited on the substrate as part of the coating, by entrainment with the plated metal and is then removed. The removal process may be a heating operation to burn off the pore former.
  • the pore former may be a biocide which degrades over time to form pores in the parts of the coating which it previously occupied.
  • the pore former may also be a polymer.
  • polar polymers these may be deposited on the substrate by electrostatic deposition. Under electrostatic deposition, the polar polymers deposit in alignment with an applied electrostatic field, and can subsequently be removed to form the pores in the coating, for instance by heating to burn off the polymers.
  • a lubricant may be present as a lubricant particle, such as a particle of polytetrafluoroethylene (PTFE). Such lubricant particles can provide a smooth surface to the coating, and may improve fluid flow over the coated surface of the substrate.
  • PTFE polytetrafluoroethylene
  • a smart material may be present in the electroless plating solution to impart particular properties to the coating on the substrate.
  • the smart material may respond to light, heat, especially temperature, or other physical inputs to provide a smart coating on the substrate.
  • a wear, corrosion and/or temperature resistant material may be provided in the plating solution.
  • An anti-microbial additive may be present as an anti-microbial particle.
  • Such particles may be provided as a soluble glass, which can dissolve out of the coating over time, when the coating is in contact with a suitable solvent, to produce pores in the coating.
  • the particulate material may be an electrode material, such as a SOFC electrode material.
  • the particulate material may be a ceramic.
  • the electrode material may be selected from one or more of the group comprising yttria stabilised zirconia (YSZ), ceria stabilised zirconia (CeSZ), cerium gadolinium oxide (CGO), samarium-doped ceria (SDC), lanthanum nickel ferrite (LNF) and mixed lanthanum and gallium oxides.
  • YSZ yttria stabilised zirconia
  • CeSZ ceria stabilised zirconia
  • CeG cerium gadolinium oxide
  • SDC samarium-doped ceria
  • LNF lanthanum nickel ferrite
  • CeSZ, CGO, LNF and SDC are all particulate materials which are attracted to a magnetic field.
  • YSZ and mixed lanthanum and gallium oxides are not attracted to a magnetic field and would therefore require the presence of a magnetic additive to be used as a particulate material.
  • the co- deposition of the metal and the particulate material on the substrate can form the anode of the fuel cell.
  • the particulate material co-deposited with the metal can be lanthanum strontium manganite (LSM).
  • LSM lanthanum strontium manganite
  • the co-deposition of the metal and LSM particulate material on the substrate can form the cathode of the fuel cell.
  • LSM is a preferred particulate material because it is attracted to a magnetic field.
  • LSM is ferromagnetic at temperatures below 320 K. Consequently, LSM does not require the addition of a magnetic additive. Should the inclusion of a magnetic additive in the particulate material be required, this may be provided within the particles forming the particulate material and/or as a coating on the particles.
  • the magnetic additive may be a partial coating to ensure that the 3 -phase boundary required of the electrode is not lost, as would occur by fully coating the surface of the particles forming the particulate material.
  • a partial coating can be achieved by partially masking the surface of the particles forming the particulate material, prior to depositing the magnetic additive as a coating.
  • the term 'partially masking the surface of the particle' means masking less than 100% of the surface area of a particle, preferably in the range of from 25 to 75% of the surface area of a particle.
  • the mask is present on the surface of the particle, coating of the magnetic additive is prevented.
  • the mask can then be removed to uncover the surface of the particles of the particulate material.
  • the mask may be applied to the particulate material during a pre- treatment step. If the magnetic additive is applied using an electroless plating method, such as a method discussed herein, a partial mask can be applied to the particles prior to contacting them with an electroless plating solution.
  • the partial mask is applied at the activation step during pre-treating of the particles.
  • the magnetic additive is not distributed uniformly throughout the particulate material. This allows the retention of the 3 -phase boundary by ensuring that not all of the surface of the particulate material is composed of magnetic additive. This can be achieved my mixing the magnetic additive or a precursor thereof with the other components of the particulate material prior to particulate formation.
  • the magnetic additive may be added as a precursor of the magnetic additive as long as this is transformed into the magnetic additive as part of the process of forming the particulate material.
  • a further particulate material which does not comprise a magnetic additive, can be added to the electroless plating solution to provide the coated substrate in addition to the particulate material discussed above. If the further particulate material is an electrode material, it can be deposited on the substrate with the metal and particulate material as part of the plating process. This would provide regions of 3 -phase boundary in the substrate coating, particularly when plated in combination with particulate material comprising a coating of magnetic additive.
  • the substrate may form the electrolyte or the interconnect of the fuel cell.
  • the substrate is a continuous substrate, such as a monolith, rather than a particulate substrate.
  • the substrate can take any shape. For example, it may be planar to conform to planar SOFC design, or it may be cylindrical to conform to tubular SOFC design.
  • the substrate is selected from the group comprising lanthanum chromate, doped lanthanum chromate, doped lanthanum gallate, lanthanum manganate, doped lanthanum manganate, yttria stabilised zirconia (YSZ), ceria stabilised zirconia (CeSZ), cerium gadolinium oxide, samarium- doped ceria, lanthanum nickel ferrite and mixed lanthanum and gallium oxides.
  • the substrate may be a metallic substrate such as chromium-based, iron-based and/or nickel-based alloys or the substrate may be a polymeric substrate depending on the fuel cell design.
  • Lanthanum chromate, doped lanthanum chromate, lanthanum manganate and doped lanthanum manganate are suitable substrate materials for the interconnect of the fuel cell.
  • Yttria stabilised zirconia (YSZ), ceria stabilised zirconia (CeSZ), cerium gadolinium oxide, samarium-doped ceria and mixed lanthanum and gallium oxides are suitable substrate materials for the electrolyte of the fuel cell.
  • the reducing agent in the electroless plating solution should be capable of causing the reduction of the metal in the metal precursor to metal. It is preferred that the reducing agent comprises hypophosphite, but alternatives may be used depending on the metal to be deposited.
  • the hypophosphite is preferably a hypophosphite salt, such as sodium hypophosphite.
  • the electroless plating solution also comprises a solvent.
  • the solvent should be capable of dissolving the reducing agent and metal precursor. It is preferred that the solvent is water.
  • the electroless plating solution may further comprise a surfactant to assist in keeping the particulate material and any further particulate material in suspension in the plating solution.
  • the electroless plating solution is dosed with one or more of the group selected of: the particulate material, any further particulate material, the metal precursor and the reducing agent during the plating step.
  • the concentration of one or more of the group selected of: the particulate material, any further particulate material, the metal precursor and the reducing agent in the plating solution is varied during the plating step.
  • the method of the invention comprises the step of pre- treating the substrate prior to the contacting step.
  • the pre-treating step may comprise one or more steps selected from the group consisting of: degreasing, electrocleaning, etching, masking, activating and rinsing.
  • the pre-treating step is an activating step
  • this may comprise depositing an electroless plating catalyst on the substrate.
  • the electroless plating catalyst is palladium.
  • the activating step may further comprise the step of sensitizing the substrate prior to or at the same time as the deposition of the electroless plating catalyst. This is particularly beneficial in those cases where the substrate is non-conducting, for instance when the substrate is the fuel cell electrolyte such as YSZ.
  • the sensitizing step preferably comprises treating the substrate with a tin (II) chloride solution.
  • a metallic element such as nickel is deposited on the substrate.
  • This deposition can impart electrical conductivity to the coating.
  • an electroplating step may be carried out when sufficient metal has been deposited on the substrate to provide an electrically conducting coating. A thickness of as little as 2 micrometers of the electrolessly plated metal coating on the substrate can provide sufficient conductivity for electroplating to then be carried out.
  • FIG. 1 shows an image of a coated substrate prepared by an electroless deposition process without the generation of a magnetic field
  • Figure 2 shows a scanning electron micrograph of the surface of a coated substrate prepared by an electroless deposition process without the generation of a magnetic field
  • Figure 3 shows an energy dispersive X-ray analysis spectrum of the highlighted area of the coated substrate shown in the micrograph of Figure 2;
  • Figure 4 shows an image of a coated substrate and support wire prepared by an electroless deposition process carried out in a generated magnetic field
  • Figure 5 shows an image of a coated substrate prepared by an electroless deposition process carried out in a generated magnetic field in which the support wire has been removed;
  • Figure 6 shows the experimental set-up involving the generation of a magnetic field in the electroless co-deposition process.
  • Electroless metal deposition refers to the chemical plating of a metal such as nickel, iron, copper or cobalt onto a substrate by chemical reduction in the absence of external electric current.
  • Known electroless plating solutions generally comprise a metal precursor, such as a source of metal ions, and a reducing agent dissolved in a solvent.
  • the solvent is typically water.
  • the electroless plating solution may further comprise a buffer to provide the required solution pH and a complexing agent for the metal ions capable of preventing their precipitation from solution. Other additives such as stabilizers, brighteners, alloying agents, surfactants may also be present in the plating solution.
  • the metal deposition involves the reduction of the metal ions to the metallic form by the action of a reducing agent itself or a derivative of the reducing agent.
  • the reducing agent may be a hypophosphite, an amine borane or a borohydride.
  • deposition is autocatalysed by the metal deposited on the surface of the substrate.
  • nickel may be deposited onto a substrate from an aqueous solution of a nickel (II) and hypophosphite ions according to the following reactions:
  • the reaction product of the hypophosphite and water (absorbed hydrogen, H a bs) reacts with the nickel (II) in the solution, rather than the reducing agent itself.
  • the metal precursor is nickel (II) chloride.
  • the reducing agent is sodium
  • the solvent can be water.
  • hypophosphite may react with the absorbed hydrogen to deposit phosphorous onto the substrate, and produce water and hydroxyl ions as shown in reaction (III): H2PO2- + Habs ⁇ H 2 0 + OH- + P (III).
  • phosphorus may also be deposited with the nickel, forming a phosphorus alloy.
  • Such deposits typically contain 2 -14% by weight
  • an amine borane may be used as the reducing agent.
  • the reduction of nickel (II) chloride by dimethylamine borane is shown in equation (V): (CH 3 ) 2 HNBH 3 + 3H 2 0 + NiCl 2 ⁇ (CH 3 ) 2 NH + H3BO3 + 2H 2 + 2HC1 + Ni
  • the conductive metal can be plated as either an amorphous or a crystalline metal.
  • a suspension of a particulate material is also present in the plating solution.
  • the particulate material has the property of being attracted to a magnetic field.
  • the generation of a magnetic field around the substrate attracts the particulate material to the field and thereby the substrate, increasing the concentration of the particulate material near the substrate.
  • the deposition of the nickel entrains the particulate material suspended in the plating solution resulting in the deposition of the particulate material with the nickel on the substrate.
  • Agitation of the solution for instance using a rotary stirrer, can aid in the mixing of the particulate material. It is preferred that magnetic stirring means is not used, as this may interfere with the magnetic field generated around the substrate to attract the particulate material.
  • the magnetic field may be generated from a permanent magnet, such as a rare earth magnet, or from an electromagnet.
  • a permanent magnet such as a rare earth magnet
  • an electromagnet provides the advantage that the intensity of the magnetic field can be varied in proportion to the current flowing in the electromagnet.
  • the magnetic field may be intensified by the substrate itself, particularly if this is a ferromagnetic material.
  • the magnetic field may produce graduated and/or directional growth of the deposited particulate material on the substrate because of the particulate material's interaction with the field.
  • deposition of the particulate material may follow the lines of magnetic flux, which is proportional to the number of lines of magnetic field on a surface. This can produce a coated substrate with anisotropic properties. For instance, conducting pathways of the deposited metal may be produced extending outwards from the substrate as the coating develops.
  • the deposited nickel and particulate material have an even uniform thickness, even in deep pores and recesses.
  • the uniformity of the coating reproduces the substrate surface finish, which can be roughened to increase its surface area.
  • the coating can be applied as a final production operation and can meet stringent dimensional tolerances.
  • the concentration of metal precursor, reducing agent, particulate material and any further particulate material in the plating solution will decrease as these components are consumed. Consequently, one or more of these components may be added to the plating solution during the plating step.
  • the component may be added to the plating solution at regular or irregular intervals, or continuously.
  • the component is preferably added in the solvent used for the plating solution.
  • the amount of any component added to the plating solution during the plating step may be sufficient to maintain the component at a given average
  • concentration such as the concentration at the start of the plating step.
  • the amount of any component added to the plating solution during the plating step may be varied, or the time interval at which the component is added may be varied in order to adjust the concentration of the component at a particular depth in the co-deposited coating.
  • the concentration of the particulate material co-deposited with the metal may be greatest at the start of the plating step such that the proportion of co-deposited particulate material to metal is greatest nearest to the substrate.
  • the coefficient of thermal expansion (CTE) of the particulate material and substrate are similar, for instance if both the substrate and particulate material comprise YSZ, the CTE of the coating adjacent to the substrate can be more closely matched to the substrate to minimise thermal stresses during cycling and operation.
  • a magnetic additive is required to be added to the YSZ to provide a particulate material which is attracted to the magnetic field.
  • the proportion of the metal co-deposited with the particulate material can be increased in the regions of the coating further from the substrate to provide the requisite electrical conductivity to the anode.
  • increasing the strength of the magnetic field can increase the concentration of particulate material drawn to the substrate, thereby altering the concentration of the particulate material deposited. This can also be used to compensate for a decrease in the total concentration of particulate material in the plating solution as plating progresses.
  • the plating step is typically carried out by immersing the substrate in a plating bath comprising the plating solution.
  • the plating bath is typically heated. It is preferred that the plating bath is heated to a temperature in the range of 80 to 100°C, more preferably 85 to 95°C, most preferably about 90°C to provide an optimum rate of deposition.
  • the plating step may be carried out by contacting only a part of the substrate with the plating solution, for example by immersing only a portion of the substrate in the plating solution.
  • one or more pre-treatment steps may be carried out prior to carrying out the electroless plating step. It is preferred that the substrate is degreased prior to electroless plating, in either aqueous or non-aqueous cleaners utilising either ultrasonic or soak processes.
  • the substrate is a conducting substrate, it can be electrocleaned by methods known in the art.
  • only a part of the substrate is contacted with the plating solution by applying a mask, such as those known in the art of etching, to the substrate in a pre-treatment step. Consequently, the metal and particulate material is only co-deposited in those areas of the substrate not covered by the mask.
  • a mask such as those known in the art of etching
  • the operating properties of a fuel cell anode are closely related to the surface texture.
  • it should have a larger surface area to increase the rate of reaction.
  • the surface area of the anode may be increased by one or both of providing a rougher surface texture and increasing porosity. Combining both of these methods allow the maximisation of the anode surface area to provide efficient reaction kinetics.
  • the co-deposited coating has a uniform thickness, even in deep pores and recesses. Therefore, the surface area of the anode may be increased by one or both of roughening the surface and increasing the porosity of the substrate. This can be achieved by the etching of the substrate surface, for example by wet-phase or dry-phase techniques.
  • Wet-phase etching utilises a liquid etchant, which may be agitated to achieve good process control.
  • solutions comprising one or both of sulphuric and hydrofluoric acid can be used to etch a YSZ substrate.
  • Dry-phase etching utilises a plasma or ion stream to remove the surface of the substrate.
  • Plasma etching produces energetic free radicals which are neutrally charged and react with and remove the surface of the substrate.
  • Sputter etching bombards the substrate with a stream of energetic ions, typically of noble gasses, which knock atoms from the substrate surface.
  • abrasive blasting techniques may be employed to abrade the surface by utilising compressed air and abrasive media.
  • a sensitizing and catalysing process In order to initiate electroless plating on an insulating substrate, it is necessary to activate the substrate surface. This can be done by a sensitizing and catalysing process.
  • palladium metal is employed as a catalyst.
  • the catalyst allows the metal plating to proceed as an autocatalytic reaction, without the requirement of an external electrical current source.
  • Palladium particles can be deposited on the insulator surface in a single, double or multi-step process. In the single-step process, the insulating substrate can be treated with a mixed acidic solution of SnCl 2 and PdCl 2 in the form of a hydrosol to deposit palladium in accordance with reaction (VI):
  • the metallic Pd is in colloidal form and is adsorbed onto the substrate surface.
  • the adsorbed colloidal Pd particles act as a catalyst for the metal deposition during subsequent metal plating.
  • the insulating substrate can be consecutively sensitized with an acidified SnCl 2 solution and then catalysed with a PdCl 2 solution in a double-step process, with an optional intervening rinsing step.
  • Substrate surface activation can be omitted if the substrate is a conducting substrate.
  • a further advantage of the method of the present invention is that the metal and particulate material can be co-deposited on insulating as well as conducting substrates, provided that any insulating substrate is activated as discussed above. It is preferred that the substrate is rinsed between one or more of the pre- treating steps, or between the pre-treating and plating steps. Rinsing removes any residual contaminants from the pre-treating steps, providing a clean surface for the plating step. Rinsing may be carried out with a suitable analytical reagent grade solvent, or high purity deionised water.
  • Electroless plating particularly with nickel, provides excellent corrosion, wear and abrasion resistance, ductility, lubricity, electrical properties, hardness and solderability.
  • the thickness of metal coating applied by electroless plating is dependent upon the time the substrate is immersed in the plating bath. A deposition rate of 16- 20 ⁇ per hour is typical for a nickel plating process.
  • two coated substrates were prepared. The first - the control - was subjected to electroless co-deposition of nickel and yttria stabilised zirconia particulate material onto an alumina tile substrate. No magnetic field was applied during the co-deposition. The second involved the co-deposition of nickel and cobalt-coated yttria stabilised zirconia particulate material onto an identical alumina tile substrate similar bath conditions. A magnetic field was applied during the second co- deposition. Comparative Example 1: Electroless co-deposition of nickel and yttria stabilised zirconia onto an alumina substrate without generation of a magnetic field
  • An alumina tile substrate (Unitec Ceramics Ltd) was suspended in 200ml of Cuprolite® solution (Alfachimici srl.), an alkaline cleaning agent, for 15 minutes at 60°C in order to clean the substrate. The tile was then removed from the cleaning solution and dried.
  • the cleaned alumina tile substrate was then placed in a pre-catalyst solution of anhydrous stannous chloride (obtained from Schloetter Company Limited and manufactured by Alfachimici srl.) for 15 minutes at room temperature to sensitise the surface of the substrate.
  • the sensitised substrate was then removed from the pre-catalyst solution.
  • the sensitised substrate was then suspended in a catalyst solution containing anhydrous palladium chloride (obtained from Schloetter Company Ltd and manufactured by Alfachimici srl.) for 15 minutes at 35°C.
  • the substrate containing catalyst was separated from the catalyst solution by filtration and dried in an oven for 10 minutes at 80°C.
  • the dry substrate containing catalyst was then suspended in an electroless cobalt plating solution comprising Cobalt Chloride (Sigma-Aldritch Ltd), Sodium Hypophosphite (Sigma-Aldritch Ltd), Sodium Citrate (Sigma-Aldritch Ltd), Ammonium Chloride (Sigma-Aldritch Ltd) and 1L De-ionised Water to which was added 2 micrometer diameter YSZ powder (Unitec Ceramics Ltd).
  • the resulting mixture had a pH of around 4.5.
  • the pH of the mixture was then raised to 9.5 by the addition of ammonium hydroxide (Sigma-Aldritch Ltd) in order to initiate the electroless plating under the conditions shown in Table 1.
  • the temperature was kept between 93 and 97°C for 45 minutes and the mixture was continuously agitated with a magnetic stirrer.
  • This plating showed a metal to ceramic ratio (by atomic %) of approximately 60:40, which is representative of the ceramic rate achievable without the generation of a magnetic field.
  • Example 2 Electroless co-deposition of nickel and cobalt/yttria stabilised zirconia onto an alumina substrate in a generated magnetic field
  • the YSZ particulate material was first electrolessly deposited with ferromagnetic cobalt to provide a cobalt/YSZ particulate material which is attracted to a magnetic field.
  • the cobalt deposition was carried out using the same electroless deposition method as described in Comparative Example 1. Preparation of cobalt/YSZ particulate material
  • YSZ powder (Unitec Ceramics Ltd) was cleaned in a solution of Cuprolite® solution (Alfachimici srl.) for 15 minutes at 60°C as described for Comparative Example 1. The powder and solution were then filtered through a Buchner funnel under vacuum to separate the cleaned YSZ powder. The cleaned YSZ powder was then placed in a pre-catalyst solution of anhydrous stannous chloride (obtained from Schloetter Company Limited and manufactured by Alfachimici srl.) for 15 minutes at room temperature to sensitise the surface of the particulates. The sensitised particulates were then separated from the pre- catalyst solution by filtration with a Buchner funnel under vacuum.
  • the white sensitised particulates were then mixed into a catalyst solution containing anhydrous palladium chloride - obtained from Schloetter Company Ltd and manufactured by Alfachimici srl. - for 15 minutes at 35°C.
  • the particulate containing catalyst was separated from the catalyst solution by filtration to reveal a brown powder which was then dried in an oven for 10 minutes at 80°C.
  • the plated YSZ particulate material was black in colour and evidently magnetic because it was attracted to the magnetic stirrer and had to be rinsed off with de- ionised water prior to separation from the solution by filtration.
  • the particulate material was then dried in an oven for 1 hour at 80°C and analysed using a Cambridge S-90 scanning electron microscope (SEM) and Oxford Instruments INCA Energy Dispersive X-Ray (EDX) analysis.
  • Figure 2 shows a scanning electron micrograph of the surface of the cobalt- deposited YSZ particulate material. The area highlighted in the micrograph is that selected for the SEM analysis.
  • Figure 3 shows the EDX spectrum from the highlighted area of the micrograph of Figure 2, in which the presence of cobalt on the surface of the YSZ particulate material can be seen.
  • the cobalt-deposited particulate material (2 g) was then used as a co-deposit with nickel onto an alumina tile substrate.
  • the substrate was pre-treated as described in Comparative Example 1 and then suspended by a steel support wire in a 100 ml electroless nickel plating bath comprising the Co-deposited YSZ particulate material.
  • the nickel plating bath was prepared and treated as described in Comparative Example 1.
  • a magnetic field having a magnetic field strength of 65 millitesla was generated around the substrate.
  • the process was similar to the non-magnetic co-deposition of Comparative Example 1 with the main difference being the addition of the magnetic field and the use of cobalt- deposited particulate material.
  • the experimental set-up is shown in Figure 6.
  • Figure 4 shows an image of the coated substrate and steel support wire.
  • the darker areas of the tile indicate increased deposition of the Co-deposited YSZ particulate material and correspond to those areas of the tile substrate nearest the steel support wire. This implies that the wire itself had become magnetised and that there had been increased attraction of the cobalt-coated powder to those locations.
  • EDX analysis on non-wire contacting areas near to the wire was carried out and the results are shown in Table 3.
  • Table 3 confirms that electroless plating in a generated magnetic field was successful in reducing the relative proportion of Nickel with respect to the co- deposited particulate material (the co-deposited YSZ).
  • the generation of a magnetic field around the substrate during electroless plating changed the Ni to particulate material ratio from approximately 60:40 to approximately 50:50 atomic%.
  • the presence of a magnetic field increased the particulate material to metal ratio (atomic%) of electrolessly co-deposited coatings.

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Abstract

L'invention concerne un procédé de fabrication d'un substrat revêtu et le substrat pouvant être obtenu de cette façon, le procédé comprenant au moins les étapes consistant à : . - fournir un substrat ; . - mettre en contact au moins une partie du substrat avec une solution de placage anélectrolytique comprenant un agent réducteur, un précurseur métallique et une suspension de matière sous forme de particules, dans laquelle ladite matière particulaire est attirée par un champ magnétique ; . - créer un champ magnétique autour du substrat ; et . - plaquer sans électrolyse du métal provenant du précurseur métallique sur la partie en contact du substrat, en co-déposant de ce fait la matière particulaire sur la partie en contact du substrat pour produire un substrat revêtu.
EP13709507.1A 2012-02-28 2013-02-28 Procédé de fabrication d'un substrat revêtu et substrat obtenu de cette façon Withdrawn EP2820171A1 (fr)

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GBGB1203425.2A GB201203425D0 (en) 2012-02-28 2012-02-28 Method for the manufacture of a coated substrate
PCT/GB2013/050496 WO2013128191A1 (fr) 2012-02-28 2013-02-28 Procédé de fabrication d'un substrat revêtu et substrat obtenu de cette façon

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