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WO2025052135A1 - Procédés de formation d'une couche de surface métallique intégrée sur un composite à matrice polymère renforcée par des fibres - Google Patents

Procédés de formation d'une couche de surface métallique intégrée sur un composite à matrice polymère renforcée par des fibres Download PDF

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Publication number
WO2025052135A1
WO2025052135A1 PCT/GB2024/052322 GB2024052322W WO2025052135A1 WO 2025052135 A1 WO2025052135 A1 WO 2025052135A1 GB 2024052322 W GB2024052322 W GB 2024052322W WO 2025052135 A1 WO2025052135 A1 WO 2025052135A1
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Prior art keywords
fibre
metallised
polymer matrix
fibres
metal
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PCT/GB2024/052322
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English (en)
Inventor
Stella JOB
Anastasis SAVVA
Andrew Bushby
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Ultima Forma Ltd
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Ultima Forma Ltd
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Publication of WO2025052135A1 publication Critical patent/WO2025052135A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2013—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by mechanical pretreatment, e.g. grinding, sanding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • 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
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • 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
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • 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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • 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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions

Definitions

  • the present disclosure relates to a fibre-reinforced polymer matrix composite comprising an integrated metallic surface layer, and methods for forming the integrated metallic surface layer on a fibre-reinforced polymer matrix composite, in particular for forming a graded interface between a metallic layer and a fibre-reinforced polymer matrix composite.
  • FRPMCs Fibre-reinforced polymer matrix composites
  • FRPMCs such as carbon fibre polymer composites
  • aerodynamic structures for example for aerodynamic structures.
  • FRPMCs such as carbon fibre polymer composites
  • wind turbine construction Another example is in wind turbine construction.
  • materials for both applications need to withstand corrosion, abrasion, weather, UV radiation, erosion, and temperature variations in the most extreme conditions.
  • a method for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite comprises obtaining a fibre-reinforced polymer matrix composite (FRPMC), wherein the FRPMC comprises fibres embedded within a polymer matrix.
  • the method then comprises ablating a first surface of the polymer matrix to expose a portion of the fibres at the first surface, and depositing metal onto the ablated first surface to embed the exposed portion of the fibres within a metal matrix.
  • FRPMC fibre-reinforced polymer matrix composite
  • Depositing metal onto the ablated first surface may advantageously enhance the surface properties of the composite, for example wherein the metallic surface layer may improve erosion and/or corrosion performance of the composite.
  • this method may also advantageously obtain a graded interface between the deposited metal surface layer and the polymer matrix of the FRPMC.
  • the graded interface may advantageously provide enhanced adhesion between the metallic surface layer and FRPMC relative to conventional surface coatings with non-graded interfaces.
  • the integrated and/or graded interface may improve adhesion performance and reduce failure between the metallic surface layer and FRPMC by at least one of:
  • the graded interface therefore improves functionality of FRPMC materials by enhancing wear and erosion resistance, increasing durability, and extending the use conditions to more demanding environments, such as but not limited to higher and lower temperature environments, environments experiencing rapid temperature changes, and/or environments experiencing sand, water, and/or ice impact challenges.
  • the fibres of the FRPMC may be carbon (graphite), glass, aramid, metal, natural fibres, or any other fibre.
  • the polymer matrix may be a thermoset polymer or resin, thermoplastic polymer or resin, or any other polymer or resin.
  • Ablating the first surface of the polymer matrix may be achieved by, but is not limited to, at least one of thermal ablation, chemical ablation, laser ablation, plasma ablation, removal with solvents, or other forms of ablation.
  • Ablating the surface of the polymer matrix may comprise ablating the surface of the polymer matrix to a pre-determined depth.
  • the pre-determined depth of ablation may be, but is not limited to, between 10 and 100 microns. In some embodiments, the pre-determined depth of ablation may be approximately 25 microns.
  • the method may further comprise obtaining a fibre surfacing veil and embedding the fibre surfacing veil into a first surface of the polymer matrix prior to ablating the first surface. Ablating the first surface of the polymer matrix may then be configured to expose a portion of fibres from the fibre surfacing veil at the first surface.
  • Providing the fibre surfacing veil may be advantageous as it can be added to a surface of a prefabricated FRPMC, and thereby reduce ablation of the prefabricated FRPMC itself, rather only ablating the polymer matrix which at least partially embeds the fibre surfacing veil to adhere it to the prefabricated FRPMC.
  • a fibre surfacing veil may also be included in the surface of a FRPMC at the time of manufacture to create are more even surface.
  • the fibre surfacing veil is a metallised fibre surfacing veil.
  • the metallised fibre surfacing veil may assist in providing the graded interface to provide enhanced adhesion between the metallic surface layer and FRPMC.
  • Incorporation of a metallised veil may also improve the consistency of metal deposition onto the exposed fibres.
  • obtaining a metallised fibre surfacing veil comprises obtaining a fibre surfacing veil, and metallising the fibre surfacing veil by metal deposition. The metallised fibre surfacing veil may then be embedded into a first surface of the polymer matrix, as described above.
  • the fibre surfacing veil may be a carbon fibre surfacing veil.
  • the fibre surfacing veil is not limited to a carbon fibre surfacing veil and may, alternatively or in addition, comprise otherfibres such as glass, aramid, metal, natural fibres, or any other fibre.
  • Embedding the metallised fibre surfacing veil into the first surface of the polymer matrix may comprise curing the metallised fibre surfacing veil into a first surface of the polymer matrix.
  • the curing process parameters may be defined by the properties of the polymer matrix of the FRPMC.
  • the polymer matrix may comprise a thermoplastic polymer.
  • the polymer matrix may comprise a thermoset polymer.
  • Curing the metallised fibre surfacing veil into the first surface of the polymer matrix may additionally comprises applying pressure to the metallised fibre surfacing veil and the polymer matrix. This may advantageously improve adhesion between the polymer matrix and the metallised fibre surfacing veil, for example by promoting penetration of the polymer matrix, such as a resin, within the metallised fibre surfacing veil.
  • the skilled person will understand that this is not essential and may depend on the composite system and its normal curing process.
  • the metallised fibre surfacing veil may be partially exposed at the outer surface of the stack. As such, depositing metal onto the outer surface of the stack may be configured to embed the exposed portion of the metallised fibre surfacing veil within a metal matrix.
  • the volume fraction of metallised fibres within the metallised fibre surfacing veil may be defined as the volume fraction of fibres and metal. Purely for illustration, a 35 % volume fraction of metallised fibres may comprise a 20 % of volume fraction of fibres, such as carbon fibres, and a 15 % volume fraction of metal deposited onto the fibres.
  • the remaining volume fraction within the obtained metallised fibre surfacing veil may be empty space or air.
  • the empty volume fraction within the metallised fibre surfacing veil may then be saturated by (i) polymer matrix to at least partially embed the metallised fibre surfacing veil into the FRPMC, and/or (ii) metal matrix during metal deposition on the stack surface.
  • the volume fraction of metal may increase towards the outer surface of the stack, for example such that the volume fraction of metal is configured to be graded across the integrated metallic surface layer.
  • the second metal layer may comprise a volume fraction of metal of 100 %.
  • the volume fraction of metal is configured to provide a gradient of metal volume fraction from 100 % metal on the outer surface to the bulk polymer matrix on the inside of the FRPMC.
  • a fibre-reinforced polymer matrix composite comprising a metallic surface layer, obtained by the method of any of the preceding aspects of the invention.
  • a fibre-reinforced polymer matrix composite comprising a polymer matrix comprising a first portion of embedded fibres, and a second layer comprising a second portion of fibres, wherein the second portion of fibres are partially embedded within the polymer matrix and partially embedded within a metal matrix.
  • the second layer is configured to form an integrated metallic layer on a surface of the polymer matrix.
  • the second portion of fibres partially embedded within the polymer matrix and partially embedded within a metal matrix may advantageously provide an integrated interface between the metal matrix and the polymer matrix of the FRPMC.
  • the integrated interface may advantageously provide enhanced adhesion, not least by increasing the surface area for adhesion of the metallic matrix to the second portion of fibres.
  • encapsulating the fibres in the metal matrix may advantageously enable deposition of further metallic layers onto the metal matrix, having improved adhesion by virtue of the metal-metal interface.
  • the fibre-reinforced polymer matrix composite, FRPMC may further comprise a third metallic layer.
  • the third metallic layer may be arranged adjacent to the metal matrix of the second layer.
  • the third metallic layer may be configured to provide desired surface properties. Depositing a third metallic layer onto the metal matrix may advantageously provide enhanced adhesion of the third metallic layer due to a similar metallic interface of between the third metallic layer and metal matrix.
  • the second layer may comprise a fibre surfacing veil, such that the second portion of fibres are provided by the fibre surfacing veil.
  • the second layer may comprise a metallised fibre surfacing veil.
  • Metal may occupy up to approximately a 90 % volume fraction of the second layer.
  • the volume fraction of metal may increase towards the outer surface of the second layer, for example such that the volume fraction of metal is configured to be graded across the integrated metallic surface layer.
  • the third metal layer may comprise a volume fraction of metal of 100 %.
  • the volume fraction of metal in the second layer is configured to provide a gradient of metal volume fraction from up to 100 % metal in the third layer to the bulk polymer matrix of the FRPMC.
  • the portion of metallised fibres may occupy from a 35 % volume fraction of the second layer.
  • the volume fraction of metallised fibres may be defined as the volume fraction of the second portion of fibres and metal.
  • the volume fraction of metallised fibres may comprise the volume fraction of the second portion of fibres in the second layer and the volume fraction of the metal matrix deposited onto the fibres.
  • a 35 % volume fraction of metallised fibres may comprise a 20 % of volume fraction of fibres, such as carbon fibres, and a 15 % volume fraction of metal deposited onto the fibres.
  • the volume fraction of metallised fibres may comprise the volume fraction of the obtained metallised fibre surfacing veil exposed at the first surface, and optionally the volume fraction of the metal matrix embedding the metallised fibre surfacing veil.
  • the portion of metallised fibres may occupy at least a 50 % volume fraction of the second layer.
  • the portion of metallised fibres may occupy an average volume fraction of approximately 50 % of the integrated metallic surface layer.
  • the second portion fibres may occupy from a 12.5 % volume fraction of the second layer.
  • the fibres, such as carbon fibres may occupy at least a 20 % volume fraction of the fibre surfacing veil.
  • the second portion of fibres may occupy at least a 50 % volume fraction of the second layer.
  • the second portion of fibres may occupy approximately a 50 % volume fraction of the integrated metallic surface layer.
  • the volume fraction of the second portion of fibres may be constant across the integrated metallic surface layer.
  • the volume fraction of metal matrix may provide a gradient of metal volume fraction across the second layer, for example wherein the volume fraction of metal is greater towards the outer surface of the second layer, and the volume fraction of polymer matrix in the second layer increases towards the bulk polymer matrix of the FRPMC.
  • Fig. 1 shows a flow diagram of an example method for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite.
  • Fig. 2 shows a schematic illustrating an example method for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite, for example such as the method of Fig. 1.
  • Fig. 3 shows a flow diagram of another example method for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite.
  • Fig. 4 shows a schematic illustrating an example method for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite, for example such as the method of Fig. 3.
  • Fig. 5 shows a plan view of a metallised fibre veil, for example for use with the method of Figs. 3 and 4, and optionally Figs. 1 and 2.
  • Fig. 6 shows a cross-section through a metallised veil integrated with fibre-reinforced polymer matrix composite (FRPMC).
  • FRPMC fibre-reinforced polymer matrix composite
  • Embodiments of the claims relate to a fibre-reinforced polymer matrix composite comprising an integrated metallic surface layer, and methods for forming the integrated metallic surface layer on a fibre-reinforced polymer matrix composite, in particular for forming a graded interface between a metallic layer and a fibre-reinforced polymer matrix composite.
  • Fig. 1 shows a flow diagram 100 of an example method for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite.
  • Fig. 2 shows a schematic illustrating an embodiment of the example method of Fig. 1 for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite.
  • the method comprises obtaining a fibre-reinforced polymer matrix composite 200 (FRPMC) (102).
  • FRPMC fibre-reinforced polymer matrix composite 200
  • the FRPMC 200 comprises a plurality of fibres 202 embedded within a polymer matrix 204.
  • the fibres 202 are carbon fibres, however the skilled person will understand that any other suitable reinforcing fibre may be used.
  • the FRPMC 200 may further comprise a fibre surfacing veil 206 arranged at a first surface 208 of the FRPMC 200 and at least partially embedded in the polymer matrix 204.
  • a veil 206 may be included in the surface 208 of the FRPMC 200 to create are more even surface finish.
  • the fibres within the fibre surfacing veil may occupy approximately a 50 % volume fraction of the fibre surfacing veil, however the skilled person will understand that other volume fractions may be used.
  • the method 100 then comprises ablating the polymer matrix 204 at the first surface 208 of the FRPMC 200 (104).
  • Ablating the polymer matrix 204 at the first surface 208 is configured to expose a portion of FRPMC fibres to a certain depth (known as the depth of ablation).
  • the FRPMC 200 comprises a fibre surfacing veil 206 arranged at the first surface 208
  • ablating the polymer matrix 204 at the first surface 208 is configured to expose a portion of fibres from the fibre surfacing veil 206.
  • the skilled person will understand that in embodiments wherein the FRPMC 200 does not comprise a fibre surfacing veil 206, ablating the polymer matrix 204 at the first surface 208 is configured to expose a portion of the fibres 202 arranged at the first surface 208.
  • the ablation step 104 is configured to selectively remove the polymer matrix 204, whilst preserving the fibres 206 (and/or fibres 202). This may be achieved by thermal or chemical ablation of the polymer matrix, including but not limited to laser treatment, plasma ablation, removal with solvents, or other forms of ablation.
  • thermal or chemical ablation of the polymer matrix including but not limited to laser treatment, plasma ablation, removal with solvents, or other forms of ablation.
  • international patent application WO2019091873A1 “SURFACE PREPARATION” discloses an example method of plasma ablation to remove a surface portion of matrix by plasma ablation so as to reveal a new surface with at least a portion of a plurality of the fibres exposed thereon.
  • the depth of ablation is approximately 25 pm, however the skilled person will understand that other ablation depths may be used, for example but not limited to between 10 and 100 pm.
  • the method 100 then comprises depositing metal onto the ablated first surface 208B to embed the exposed portion of the fibres within a metal matrix 210 (104).
  • metal is deposited by electroless deposition, electrodeposition, or both, to create a metal matrix 210 around the revealed fibres 206.
  • Surface processing steps such as but not limited to at least one of surface roughening, grit blasting, laser ablation, chemical etching (for example using permanganates), and plasma ablation, may also be carried out to improve adhesion of the metal between both the fibres 206 (or 202) and the polymer matrix 204, depending on the substrate materials.
  • the amount of metal deposited on the exposed fibres 206 (or 202) at the ablated first surface 208B of the FRPMC 200 influences the properties of the resulting graded interface that forms.
  • the limit on the volume occupied by metal is up to 90 % volume fraction of the integrated metallic surface layer 212.
  • the metal matrix may occupy approximately a 50 % volume fraction of the newly formed surface layer 212.
  • the method 100 comprises further deposition of metal layer 214 onto the metal matrix 210.
  • This may be advantageous to provide desired surface properties.
  • the method may comprise depositing a nickel layer onto the metal matrix 210 for a hard, erosion resistant surface.
  • the skilled person will understand that other metal layers may be used.
  • the metal of metal layer 214 may be the same or different to the metal of the metal matrix 210.
  • Fig. 3 shows a flow diagram 300 of another example method for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite.
  • Fig. 4 shows a schematic illustrating an embodiment of the example method of Fig. 3 for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite.
  • the method 300 comprises obtaining a metallised fibre surfacing veil 404 (302).
  • the metallised fibres within the metallised fibre surfacing veil 404 may occupy from a 35 % volume fraction up to a 90 % volume fraction within the metallised fibre surfacing veil 404.
  • the metallised fibres within the metallised fibre surfacing veil 404 occupy approximately a 50 % volume fraction within the metallised fibre surfacing veil 404.
  • obtaining the metallised fibre surfacing veil 404 may comprise first obtaining a fibre surfacing veil 402, and then metallising the fibre surfacing veil 402 by metal deposition.
  • an obtained carbon fibre surfacing veil 402 may comprise carbon fibres approximately 6 micrometres in diameter, wherein the carbon fibres occupy approximately a 20 % volume fraction of the metallised fibre surfacing veil 404.
  • Metallising the carbon fibre surfacing veil may comprise depositing 2 to 3 micrometres of metal to this to give each metallised fibre an approximate diameter of 10 to12 micrometres.
  • this is merely one example and other fibre surfacing veils, and metallisation processing parameters may be used.
  • FIG. 5 A plan view of an example metallised fibre surfacing veil 404 is shown in Fig. 5.
  • Fig. 5 shows metallised carbon fibres with metal penetrating through the veil structure.
  • the veil 404 has a sheet-like structure, similar to paper, comprising a random orientation of fibres in a first direction, as shown in Fig. 5, and a more ordered orientation of fibres on a second perpendicular direction.
  • Fibre surfacing veils may be specified by their mass per area, for example in grams per square metre (gsm).
  • gsm grams per square metre
  • a 20 gsm carbon fibre veil may be used and metallised to achieve a 50 % volume fraction of metallised fibres.
  • other metallised fibre surfacing veils may also be used, such as but not limited to Kevlar, glass, aramid fibres etc, and/or fibre surfacing veils having a different mass per area.
  • the fibre of the fibre surfacing veil may be the as the same fibres within the underlying composite, FRPMC. This may be advantageous for property matching between the veil and the composite, such as but not limited to matched thermal expansion coefficients, however the skilled person will understand that this is not essential.
  • the metallised fibre surfacing veil 404 is about 40 micrometres in thickness.
  • the method 300 then comprises at least partially embedding the metallised fibre surfacing veil 404 into a first surface of a fibre-reinforced polymer matrix composite (FRPMC) 200 (304).
  • FRPMC fibre-reinforced polymer matrix composite
  • a polymer composite structure comprising a plurality of fibres 202 and a polymer matrix, is cured onto, and hence into, the metallised fibre surfacing veil 404 by curing the polymer matrix 204.
  • the curing process is determined by the normal curing process of the composite system, for example based on the polymer matrix.
  • the polymer matrix may comprise, but is not limited to, a thermoplastic polymer, or thermoset polymer.
  • the polymer matrix may be, but is not limited to, a resin.
  • pressure may be applied during curing and/or curing may be undertaken in a vacuum or low-pressure environment. This may be advantageous to ensure penetration of the polymer matrix, such as a resin, within the composite and into the metallised fibre surfacing veil 404.
  • the skilled person will understand that this is not essential and may depend on the composite system and its normal curing process.
  • the method may further comprise ablating the first surface of the FRPMC stack 200 comprising the metallised veil 404 to remove polymer matrix from the outer surface and expose a portion of the metallised veil 404 to a defined ablation depth, for example as described in relation to step 104 of the method of Figs. 1 and 2.
  • the ablation step may not be necessary in embodiments wherein the metallised fibre surfacing veil 404 is only partially embedded into the first surface of the FRPMC 200, i.e. wherein the metallised fibre surfacing veil 404 is already partially exposed at the outer surface of the FRPMC stack 200.
  • Fig. 6 shows an example cross-section of a fibre-reinforced polymer matrix composite (FRPMC) comprising an integrated metallised veil and metallic surface layer, for example resulting from any of the method described herein.
  • Fig 6 shows a first layer 602 comprising a polymer matrix 204 and a first portion of fibres 202 embedded in the polymer matrix 204.
  • a second layer 604, adjacent to the first layer 602, comprises a second portion of fibres from a metallised veil 404.
  • the composite of the first layer 602 has been cured in situ onto the metallised veil 404, as discussed in relation to the method 300 of Figs. 3 and 4.
  • the second portion of fibres 404 are partially embedded within the polymer matrix 204 of the first layer 602 and partially embedded within a metal matrix 210.
  • the second layer 604 is configured to form an integrated metallic layer within a surface of the polymer matrix 204.
  • the second layer 604 is configured to provide a graded interface between a metallic surface layer and the polymer matrix 204.
  • the adhesion test data was obtained by conforming to testing standard ASTM D4541 for testing the pull-off strength of coatings.
  • the adhesion test data shows a normalised improvement in adhesive strength of 3.5 times for an embedded metallised veil in the surface of a carbon fibre composite, compared to electroformed metal layer on a carbon fibre composite with no surface integration.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
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Abstract

L'invention concerne un procédé de formation d'une couche de surface métallique intégrée sur un composite à matrice polymère renforcée par des fibres, le procédé consistant à obtenir un composite à matrice polymère renforcée par des fibres, FRPMC, contenant des fibres incorporées dans une matrice polymère, et à réaliser une ablation au niveau d'une première surface de la matrice polymère afin de découvrir une partie des fibres au niveau de la première surface. Le procédé consiste ensuite à déposer du métal sur la première surface ayant fait l'objet de l'ablation pour incorporer une matrice métallique à l'intérieur d'une partie découverte des fibres afin de former une couche de surface métallique intégrée. L'invention concerne également un second procédé de formation d'une couche de surface métallique intégrée sur un composite à matrice polymère renforcée par des fibres, le procédé consistant à obtenir un voile de surface de fibres métallisé et à incorporer au moins partiellement le voile de surface de fibres métallisé à une première surface d'un FRPMC comprenant des fibres incorporées dans une matrice polymère.
PCT/GB2024/052322 2023-09-06 2024-09-06 Procédés de formation d'une couche de surface métallique intégrée sur un composite à matrice polymère renforcée par des fibres Pending WO2025052135A1 (fr)

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GB2313565.0A GB2633338A (en) 2023-09-06 2023-09-06 Methods for forming an integrated metallic surface layer on a fibre-reinforced polymer matrix composite
GB2313565.0 2023-09-06

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999031944A1 (fr) * 1997-12-17 1999-06-24 Laude Lucien Diego Supports de circuit electrique
US8741392B2 (en) * 2009-06-02 2014-06-03 Integran Technologies, Inc. Anodically assisted chemical etching of conductive polymers and polymer composites
WO2019091873A1 (fr) 2017-11-07 2019-05-16 University College Dublin, National University Of Ireland Préparation de surface
US20200029430A1 (en) * 2018-07-23 2020-01-23 Seiko Epson Corporation Wiring substrate and method of manufacturing the wiring substrate
US10883177B2 (en) * 2016-03-25 2021-01-05 Mitsubishi Heavy Industries Engine & Turbocharger, Ltd. Plated fiber-reinforced member and plating method for fiber-reinforced member

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11634820B2 (en) * 2019-06-18 2023-04-25 The Boeing Company Molding composite part with metal layer
US12065742B2 (en) * 2022-03-03 2024-08-20 The Boeing Company Composite laminates with metal layers and methods thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999031944A1 (fr) * 1997-12-17 1999-06-24 Laude Lucien Diego Supports de circuit electrique
US8741392B2 (en) * 2009-06-02 2014-06-03 Integran Technologies, Inc. Anodically assisted chemical etching of conductive polymers and polymer composites
US10883177B2 (en) * 2016-03-25 2021-01-05 Mitsubishi Heavy Industries Engine & Turbocharger, Ltd. Plated fiber-reinforced member and plating method for fiber-reinforced member
WO2019091873A1 (fr) 2017-11-07 2019-05-16 University College Dublin, National University Of Ireland Préparation de surface
US20200029430A1 (en) * 2018-07-23 2020-01-23 Seiko Epson Corporation Wiring substrate and method of manufacturing the wiring substrate

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