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EP-4238753-B1 - COMPOSITE LAMINATES WITH METAL LAYERS AND METHODS THEREOF

EP4238753B1EP 4238753 B1EP4238753 B1EP 4238753B1EP-4238753-B1

Inventors

  • BRUTON, ERIC ALAN
  • CHILDERS, Christopher H.
  • YOUNG, KENNETH W.

Dates

Publication Date
20260506
Application Date
20230302

Claims (15)

  1. A multilayered article (100, 200, 300, 316), comprising: a thermosetting polymer material (102, 202, 302) having at least one surface; a thermoplastic polymer layer (104, 204, 304) deposited on the at least one surface of the thermosetting polymer material (102, 202, 302); a cold sprayed metal layer (206, 306) present on at least a portion of a surface of the thermoplastic polymer layer (104, 204, 304); at least one additional layer (308, 314), the at least one additional layer (308, 314) sandwiching at least a portion of the cold sprayed metal layer (206, 306) between the additional layer (308, 314) and the thermoplastic polymer layer (104, 204, 304); and wherein the thermoplastic polymer layer (104, 204, 304) has a crystallinity of about 5% to about 60% and wherein the thermosetting polymer material (102, 202, 302) is cured after deposition of the thermoplastic polymer layer (104, 204, 304).
  2. The multilayered article (100, 200, 300, 316) of claim 1, wherein the thermosetting polymer material (102, 202, 302) comprises an epoxy resin.
  3. The multilayered article (100, 200, 300, 316) of claim 1 or 2, wherein the thermosetting polymer material (102, 202, 302) comprises multiple layers.
  4. The multilayered article (100, 200, 300, 316) of any of claims 1-3, wherein the thermosetting polymer material (102, 202, 302) further comprises one or more fillers or reinforcement materials comprising one or more of carbon, carbon nanotubes, graphite, carbon fibers, graphite fibers, fiberglass, glass fibers, metals, metal alloys, metalized fibers and metal coated glass fibers and/or wherein the thermoplastic polymer layer (104, 204, 304) comprises a carbon fiber or glass fiber reinforced poly-ether-ether-ketone (PEEK) or poly-ether-ketone-ketone (PEKK).
  5. The multilayered article (100, 200, 300, 316) of any of claims 1-4, wherein the cold sprayed metal layer (206, 306) is selected from silver, gold, aluminum, cobalt, chromium, copper, iron, nickel, molybdenum, palladium, platinum, rhodium, ruthenium, tin, titanium, tungsten, zinc, zirconium, or alloys thereof.
  6. The multilayered article (100, 200, 300, 316) of any of claims 1-5, wherein the multilayered article (100, 200, 300, 316) is a component or part of an aerospace vehicle (400).
  7. The multilayered article (100, 200, 300, 316) of claim 6, wherein the component or part of an aerospace vehicle (400) is an external surface (402) thereof.
  8. The multilayered article (100, 200, 300, 316) of any of claims 1-7, further comprising: a second thermoplastic polymer layer (310) deposited on the at least one surface of the thermosetting polymer material (102, 202, 302); a second cold sprayed metal layer (312) present on at least a portion of the second surface of the second thermoplastic polymer layer (310); and wherein the second thermoplastic polymer layer (310) has a crystallinity of about 5% to about 60%, optionally wherein the second thermoplastic polymer layer (310) comprises a carbon fiber or glass fiber reinforced poly-ether-ether-ketone (PEEK) or poly-ether-ketone-ketone (PEKK) and/or wherein the second cold sprayed metal layer (312) is selected from silver, gold, aluminum, cobalt, chromium, copper, iron, nickel, molybdenum, palladium, platinum, rhodium, ruthenium, tin, titanium, tungsten, zinc, zirconium, or alloys thereof.
  9. A method of providing a composite laminate structure, the method comprising: providing a multilaminate thermosetting polymer structure (102, 202, 302) prior to the thermosetting polymer structure (102, 202, 302) being in a fully cured state; depositing a thermoplastic polymer layer (104, 204, 304) onto a first surface of the multilaminate thermosetting polymer structure (102, 202, 302); introducing particles of a metal powder to a gas stream; directing the gas stream toward the thermoplastic polymer layer (104, 204, 304), wherein the gas stream has a temperature and pressure adjusted to prevent thermal softening or ablation of the surface of the thermoplastic polymer layer (104, 204, 304); forming a metallic coating (206, 306) on at least a portion of the thermoplastic polymer layer (104, 204, 304); and curing the multilaminate thermosetting polymer structure (102, 202, 302), wherein the thermoplastic polymer layer (104, 204, 304) has a crystallinity of about 5% to about 60% .
  10. The method of providing a composite laminate structure of claim 9, wherein the thermoplastic polymer layer (104, 204, 304) comprises poly-ether-ether-ketone (PEEK), poly-ether-ketone-ketone (PEKK), or a combination thereof.
  11. The method of providing a composite laminate structure of claim 9 or 10, wherein the thermoplastic polymer layer (104, 204, 304) has a crystallinity of about 15% to about 40%.
  12. The method of providing a composite laminate structure of any of claims 9-11, wherein the metal coating (206, 306) is selected from silver, gold, aluminum, cobalt, chromium, copper, iron, nickel, molybdenum, palladium, platinum, rhodium, ruthenium, tin, titanium, tungsten, zinc, zirconium, or alloys thereof.
  13. The method of providing a composite laminate structure of any of claims 9-12, wherein the temperature of the gas stream is between 100°C and 500°C and the pressure of the gas stream is between 100 psi and 400 psi.
  14. The method of providing a composite laminate structure of any of claims 9-13, wherein curing the multilaminate thermosetting polymer structure (102, 202, 302) comprises subjecting the composite laminate structure to an elevated temperature under pressure.
  15. The method of providing a composite laminate structure of any of claims 9-14, further comprising: depositing a second thermoplastic polymer layer (310) onto a second surface of the multilaminate thermosetting polymer structure (102, 202, 302); directing the gas stream toward the second thermoplastic polymer layer (310); and forming a metallic coating (312) on at least a portion of the second thermoplastic polymer layer (310).

Description

Technical Field The present disclosure relates to a process for providing a metal layer for composite laminate structures, as well as multilayered composite structures having cold sprayed metallic layers integrated therein. Background Aerospace vehicles such as commercial aircraft and their integrated components undergo various fluctuations in mechanical, temperature, and other environmental conditions during manufacture, operation, and service. To address such fluctuations and undesirable impacts to the components, metallization of multilayered composites has been employed in the fabrication of components in such aerospace vehicles in various approaches but can be challenging. Metallization of composite materials may further provide advantageous properties such as electromagnetic interference (EMI) or direct lightning strike protection to the surface of a composite material. Many of the composites used in aerospace and automotive applications are based on thermoset materials. In particular, thermoset epoxies tend to more easily erode when using certain metallization techniques. While techniques exist to deposit conductive materials directly onto thermoset composites, thermoset composites tend to erode more easily when cold sprayed due to their inherent physical properties. Cold spray processing may lead to erosion and surface degradation under certain conditions. Other materials or layers may be available that can accept the cold spray layer metal layer without the same issues noted in cold spraying of thermoset materials. Thus, it is desirable to provide a simpler, more robust material and process for the fabrication of multilayered composite materials. There is further a need for the improvement in the fabrication methods and design of multilayered composite panels within aircraft and other vehicle components. US 2017/165906 describes a method of making a composite article that involves first forming an intermediate substrate. The intermediate substrate can be formed from fibers and an uncured thermoset polymer composition followed by partial cure, or from fibers and an uncured thermoset polymer composition followed by cure of the thermoset polymer composition and deposition of a thermoplastic on the surface of the substrate, or from fibers and an uncured thermoset polymer composition followed by cure and exposure of the substrate to organic solvent, a plasticizer, moisture, and/or heat. The intermediate substrate prepared according to any of the above techniques is then subjected to cold gas spray deposition to deposit a metal layer onto the intermediate substrate. In the case where the substrate was formed by partially curing a thermoset polymer composition, the metal-coated partially-cured thermoset polymer substrate is then fully cured. US 2020/399763 describes a method of molding a metalized composite part. The method comprises: introducing particles comprising at least one metal into a gas stream; directing the gas stream toward a surface of a thermoplastic composite part, thereby depositing a metal layer on the composite part to form a metallized composite part; and molding the metallized composite part to introduce a bend without delamination of the metal layer from the metallized composite part. Summary The following presents a simplified summary in order to provide a basic understanding of some aspects of the present teachings. This summary is not an extensive overview, nor is it intended to identify key or critical elements of the present teachings, nor to delineate the scope of the disclosure. Rather, its primary purpose is merely to present one or more concepts in simplified form as a prelude to the detailed description presented later. According to an aspect, there is provided a multilayered article. The multilayered article includes a thermosetting polymer material having at least one surface, a thermoplastic polymer layer deposited on the at least one surface of the thermosetting polymer material, a cold sprayed metal layer present on at least a portion of a surface of the thermoplastic polymer layer, at least one additional layer, the at least one additional layer sandwiching at least a portion of the cold sprayed metal layer between the additional layer and the thermoplastic polymer layer, and where the thermoplastic polymer layer has a crystallinity of about 5% to about 60% and wherein the thermosetting polymer material is cured after deposition of the thermoplastic polymer layer. Implementations of the multilayered article may include where the thermosetting polymer material includes an epoxy resin. The thermosetting polymer material may include multiple layers. The thermosetting polymer material further may include one or more fillers or reinforcement materials such as carbon, carbon nanotubes, graphite, carbon fibers, graphite fibers, fiberglass, glass fibers, metals, metal alloys, metalized fibers and metal coated glass fibers. The thermoplastic polymer layer may include a carbon f