Method For Forming An Electrically Conductive Multilayer Coating With Anti-Corrosion Properties Onto A Metallic Substrate

Abstract

A method for forming an electrically conductive multi-layer coating with anti-corrosion properties and with a thickness comprised between 1 m and 10 m onto a substrate, comprising the following subsequent steps of (a) providing a suspension consisting of electrically conductive fillers into a matrix forming material; (b) depositing the suspension on at least a surface portion of a substrate; (c) exposing an atmospheric pressure plasma to the surface portion so as to form one electrically conductive layer with anti-corrosion properties; and (d) repeating the steps (a), (b) and (c). The method is remarkable in that the electrically conductive fillers are electrically conductive particles.

Claims

1.-19. (canceled)

20. A method for forming an electrically conductive multi-layer coating with anti-corrosion properties and with a thickness comprised between 1 m and 10 m onto a metallic substrate, said method comprising the following subsequent steps: (a) providing a solvent-free suspension with electrically conductive fillers into a liquid matrix-forming material; (b) depositing the suspension on at least a surface portion of a metallic substrate; (c) exposing an atmospheric pressure plasma to the surface portion so as to form one electrically conductive layer with anti-corrosion properties; and (d) repeating the steps (a), (b) and (c); wherein, the electrically conductive fillers are electrically conductive carbon-based particles, and the liquid matrix-forming material is based on a first organosilicon compound.

21. The method according to claim 20, wherein the electrically conductive carbon-based particles have dimensions between 0.1 m and 50 m.

22. The method according to claim 21, wherein the electrically conductive carbon-based particles with dimensions between 0.1 m and 50 m are one-dimensional carbon-based particles or two-dimensional carbon-based particles.

23. The method according to claim 21, wherein the electrically conductive carbon-based particles have dimensions between 0.1 m and 5 m.

24. The method according to claim 20, wherein the electrically conductive fillers further comprises electrically conductive carbon-based particles with dimensions between 1 nm and 99 nm, the carbon-based particles with dimensions between 1 nm and 99 nm being three-dimensional carbon-based particles.

25. The method according to claim 21, wherein the electrically conductive carbon-based particles with dimensions between 0.1 m and 50 m have a size superior to the thickness of each layer formed by steps (a), (b) and (c).

26. The method according to claim 25, wherein the thickness of a layer is comprised between 5 nm and 100 nm.

27. The method according to claim 20, wherein the electrically conductive multi-layer coating with anti-corrosion properties has a thickness comprised between 2 m and 5 m.

28. The method according to claim 21, wherein the volume fraction of electrically conductive carbon-based particles with dimensions between 0.1 m and 50 m in the electrically conductive coating with anti-corrosion properties is comprised between 50% and 85%.

29. The method according to claim 24, wherein the volume fraction of electrically conductive carbon-based particles with dimensions between 1 nm and 99 nm in the electrically conductive coating with anti-corrosion properties is equal to or less than 25%.

30. The method according to claim 21, wherein the electrically conductive carbon-based particles with dimensions between 0.1 m and 50 m and electrically conductive carbon-based particles with dimensions between 1 nm and 99 nm are based on at least one of graphene and graphite.

31. The method according to claim 20, wherein the liquid matrix-forming material based on the first organosilicon compound is a first siloxane compound.

32. The method according to claim 24, wherein the average diameter of the electrically conductive carbon-based particles with dimensions between 1 nm and 99 nm is comprised between 5 nm and 50 nm.

33. The method according to claim 20, wherein the atmospheric pressure plasma is composed of nitrogen gas and/or oxygen gas and/or a second organosilicon compound.

34. The method according to claim 20, wherein the suspension of step (a) is sonicated for one hour before step (b).

35. The method to claim 20, wherein the step (c) is performed at a temperature comprised between 5 C. and 90 C.

36. The method claim 20, wherein the metallic substrate is provided on a moving stage transporting the metallic substrate through a suspension deposition zone to deposit the suspension on at least a portion of the metallic substrate and a plasma zone in which the atmospheric pressure plasma is applied.

37. The method according to claim 36, wherein the moving stage is adapted to move the metallic substrate repeatedly through the zones.

38. The method according to claim 33, wherein the second organosilicon compound is a second siloxane compound.

40. The method to claim 35, wherein the step (c) is performed at a temperature comprised between 15 C. and 40 C.

Description

DRAWINGS

[0037] FIG. 1 shows a schematic perspective view of an apparatus for carrying out the method according to various embodiments of the present invention.

[0038] FIG. 2 shows a plot of the electrically conductivity in function of the carbon-based conductive filler volume fraction, according to various embodiments of the present invention.

[0039] FIG. 3 shows top-view secondary electron microscopy (SEM) images of electrically conductive composite coatings elaborated from different conditions and employing carbon-based conductive fillers, according to various embodiments of the present invention.

[0040] FIG. 4 shows side-view secondary electron microscopy (SEM) images of electrically conductive composite coatings elaborated from different conditions and employing carbon-based conductive fillers, according to various embodiments of the present invention.

[0041] FIG. 5 shows chronoamperometry curves in order to determine the anti-corrosion properties of the obtained multilayer coating, according to various embodiments of the present invention.

[0042] FIG. 6 shows the optical images of the electrically conductive composite coating elaborated from different deposition conditions prior and after 8 hours of chronoamperometry test, according to various embodiments of the present invention.

[0043] FIG. 7 illustrates one layer obtained according to the method of the invention, with large and small electrically conductive fillers, according to various embodiments of the present invention.

[0044] FIG. 8 shows the formation of the multi-layered coating on the metallic substrate, in accordance with various embodiments of the method of the invention.

DETAILED DESCRIPTION

[0045] FIG. 1 shows a schematic view of an exemplary system for carrying out the invention. According to FIG. 1, a suspension 2 consisting of electrically conductive fillers into a matrix forming material is deposited onto a portion of one substrate 4. No solvent whatsoever is present in the suspension 2. The liquid form of the suspension 2 is due to the matrix forming material. A stage 6 transports the substrate 4 into the direction x such that the portion of the substrate 4 is moved through a plasma zone 8 in which the coated substrate is exposed to an atmospheric pressure dielectric barrier discharge (AP-DBD) plasma 8. Both zones do not overlap, or are spatially distinct, respectively. The dielectric barrier discharge is provided via a system of two electrodes 10 arranged side by side and having a slot between them through which a gas G may pass to be directed in the direction of the coated substrate 4. Both electrodes 10 are coated with a dielectric layer 12. Being exposed to the dielectric barrier discharge plasma, the matrix forming material forms a solid layer embedding the electrically conductive fillers on the substrate 4. Having passed the plasma zone 8, the substrate 2 comprises a layer 14 including the electrically conductive fillers. Although not depicted, the above-mentioned steps should be carried out several times in order to obtain an effective multi-layered coating. Furthermore, the method is carried out at atmospheric pressure, i.e., at pressures of about 10.sup.5 Pa and at relatively low temperature, for example between 5 C. and 90 C., in various instances between 15 C. and 40 C.

[0046] In particular, it is possible that the moving stage 6 is arranged as a conveyor belt so that the metallic substrate 2 can in principle pass endlessly through the zones of the system.

[0047] Alternatively, the mentioned zones could be adapted to repeatedly pass over the substrate. A further variant consists in repeating sequences of depositing the suspension and/or applying the plasma to a production line.

[0048] Numerous electrically conductive fillers, including metallic or non-metallic core particles, have been investigated. Carbon-based electrically conductive fillers are of particular interest due to their physical and chemical properties. They can be indeed more robust than steel, lighter than aluminium, more conductive than copper and less prone to corrosion than most metals or metal alloys. Among the carbon-based electrically conductive fillers, the following can be used: carbon black, carbon fibres, synthetic or natural graphite, graphene, carbon nanotube including multi-walled carbon nanotubes (MWCNTs). Examples of commercially-available carbon-based conductive fillers are: Timrex SFG6, C-NERGY Super C65, Ketjenblack EC300J, Vulcan XC72R, Ketjenblack EC330JMA, Ketjenblack EC600JC, C-NERGY Super C45, Conductex 975 Ultra, Shewinigan Black, Timrex KS6, SUPER P Li, C-NERGY SFG6L, C-NERGY KS6L, Raven, Raven 1220 Ultra, Raven 1250, Raven 410, Pearls 2000, Pearls 3610, Micro 850, Micro 230U, Micro 5601, FC3243.

[0049] Matrix-forming material can be polymer-forming material. Plethora of matrix or binder materials has been investigated for the formation of electrically conductive composite coatings. The careful selection of the matrix or binder materials may provide additional properties to the resulting conductive composite material. Various corrosion resistant matrices have been successfully investigated, including polytetrafluoroethylene (PTFE), polypropylene (PP), polyphenylene sulphide (PPS), phenolic resins, polyvinylidene fluoride (PVDF), siloxane, vinyl ester resins.

[0050] Substrates can be metallic substrates, for instance a plate of titanium, substrates in paper, in wood, in glass, in polymer, in cellulose, etc.

[0051] More particularly, a suspension composed of carbon black nanoparticles, e.g., Ketjenblack EC600JC, and a siloxane precursor as the matrix forming material, e.g., vinyltrimethoxysilane (VTMOS), is deposited as a thin liquid layer, ca. hundreds of nanometres, onto a metallic substrate, for instance, a plate of titanium. Subsequently, the coated substrate, placed on the grounded electrode of an atmospheric-pressure dielectric barrier discharge (AP-DBD) setup, is exposed to an AP-DBD ignited by a 10,000 Hz sinusoidal electrical excitation of 8,000 V. The plasma discharge gas is composed of nitrogen, oxygen and vapours of a second siloxane precursor, e.g., octamethylcyclotetrasiloxane (OMCTS). The suspension deposition step and the plasma curing step, (i.e., the deposition cycle), may be repeated multiple times to achieve electrically conductive composite coatings with the desired thickness. In the present example, fifty deposition cycles are performed. As a result of exposure to the AP-DBD, a solid and adherent electrically conductive composite coating is formed on top of the metallic substrate.

[0052] The carbon black nanoparticles concentration into the liquid matrix precursor, i.e., VTMOS, is varied between 0.5 to 10 g.Math.L.sup.1, allowing to investigate various carbon-based electrically conductive fillers volume fraction, i.e., 10% to 40%, in the resulting composite coating. Two different conductive fillers, with average diameter size below 50 nm and 25 nm, were also investigated. The resulting composite coatings are shown to follow the percolation theory. This theory consists in a sharp increase of the conductivity, from several orders of magnitude, when the volume fraction of conductive fillers exceeds a critical value, i.e., the percolation threshold (see FIG. 2). Following to this rapid increase of the conductivity, no significant changes in the electrical properties of the composite coatings are observed anymore.

[0053] It is to be noted that the volume fraction of the electrically conductive carbon-based particles is determined by energy-dispersive X-ray spectroscopy (EDX), since the liquid matrix-forming material is volatile and the concentration of the suspension can be different from the formed electrically conductive multi-layer coating.

[0054] Sample A, which is a sample with a low volume fraction, has a specific contact resistivity of 130,000 m.Math.cm.sup.2. In other words, sample A is poorly electrically conductive.

[0055] When the volume fraction increases, as shown in FIG. 2, the percolation threshold is reached and thus, samples B to E reaches the plateau with a minimum specific contact resistivity of 10 m.Math.cm.sup.2, therefore with an increased electrical conductivity.

[0056] However, an increase of the carbon-based electrically conductive fillers volume fraction above a certain value, i.e., 25%, results in the formation of powdery and non-adherent coatings. Corrosion problems start to appear above the plateau shown in FIG. 2.

[0057] That is the reason why the ratio of electrically conductive particles with dimensions between 1 nm and 99 nm in the coating is equal or less than 25%.

[0058] Additional investigations have demonstrated that this maximum volume fraction is higher for composite coatings elaborated from the bigger carbon-based conductive fillers, e.g., Ketjenblack EC330JMA. In accordance with previous research works, the percolation threshold is reached with a lower fraction of carbon-based conductive fillers for the composite coatings elaborated from the highest specific surface area carbon-based conductive fillers.

[0059] Scanning electron microscopy (SEM) (see FIG. 3) shows that the electrically conductive composite coatings cover the whole surface of the metallic substrate. The electrically conductive composite coatings with the lowest carbon-based conductive fillers volume fraction, i.e., condition A, exhibit a dense morphology with carbon-based conductive fillers present at all over their surface.

[0060] Composite coatings prepared from a volume fraction above the conductivity percolation threshold (conditions B to E) show a large number of spherical carbon-based conductive fillers, seemingly laced together to form necklaces. The observed necklaces appear thinner as the volume fraction of carbon-based conductive fillers increase.

[0061] The thickness of the electrically conductive composite coatings grown from fifty deposition cycles, determined from Scanning Electron Microscopy (SEM) side-view observations (see FIG. 4), is shown to fluctuate from 1 to 10 m, or more often from 2 to 5 m, irrespective of the deposition conditions. This allows the use of such multilayer coating in order to make bipolar plates for fuel cell application. Interesting electrical properties can be demonstrated when such a low thickness is provided to a substrate.

[0062] Indeed, the low thickness of the multi-layer coating, i.e., comprised between 1 m and 10 m, allows for a material which is functionalized with such electrically conductive multi-layer coating with anti-corrosion properties to display a high electrically conductance G. This provides an increase of the electrical intensity I during electrical connection.

[0063] Chronoamperometry tests have been provided to determine the anti-corrosion properties of the multi-layered coating obtained according to the method of the invention.

[0064] The corrosion tests are carried out in a conventional corrosion cell (V=300 mL) coupled to a GAMRY 600 potentiostat. The corrosion test conditions are chosen to simulate a fuel cell operation conditions. The electrolyte composition is as following: pH=3 (H.sub.2SO.sub.4); Cl.sup. 10 ppm (NaCl) and F.sup. 30 ppm (NaF). The chronoamperometry parameters are the following: the voltage is set up to 0.9 V vs SHE; the electrolyte temperature 80 C. and the duration of the tests is 100 hours. These conditions are actually quite harsh conditions in order to obtain a relevant idea of the anti-corrosion properties of the coated substrates.

[0065] FIG. 5 shows that all the electrically conductive composite coatings ensure a reduction of the corrosion current.

[0066] The corrosion performances are shown to be inversely related with the volume fraction of conductive fillers. This result is consistent with the observations made by SEM as denser layers are expected to provide a far better protection. Samples A and B did allow to maintain the corrosion current to 0.25 A.Math.cm.sup.2 for several hours. However, delamination occurred on several places and led to a rapid increase of the corrosion current after three hours under the test conditions.

[0067] Interestingly, condition B, which is already above the percolation threshold, provides a significant corrosion protection to the metallic substrate.

[0068] This highlights the suitability of the proposed approach for the deposition of electrically conductive composite coatings for the preparation of fuel cell bipolar plates.

[0069] For conditions C to E, the numerous voids within the electrically conductive composite coatings induce lower corrosion properties of the films. Nevertheless, contact resistance measurements performed after the eight hours chronoamperometry test show an unaltered or barely altered contact resistance (i.e., tens of m.Math.cm.sup.2).

[0070] Therefore, these deposition conditions are also very interesting in the preparation of bipolar plates for fuel cell application.

[0071] Additionally, optical and SEM observations of the electrically conductive composite coatings after the corrosion test did not reveal any change of the morphology of the film in relation with sample E (see FIG. 6). These results indicate the excellent behavior of the electrically conductive composite coatings when exposed to the fuel cell operating conditions.

[0072] Several literature works have reported an increase of the in-plane and through-plane conductivities with increasing size of the electrically conductive fillers (typically in the micrometre to tens of micrometres range). Indeed, the use of small conductive fillers is assumed to unproductively multiplicate the conductive pathway disruptions, increasing the contact resistance, and the structure defects, which gut the corrosion properties of the electrically conductive composite coatings. In addition, the shape of large conductive fillers is an important parameter. 1D (e.g., fibres, nanotubes) or 2D conductive materials (e.g., flakes) have notably been reported to confer better properties to the conductive and corrosion-resistant composite coatings than 3D conductive materials. Graphite flakes (2D) and carbon fibres (1D) effectively stacked to form effective conductive pathways. On the other hand, large 3D conductive fillers form large voids, which are detrimental to both the contact resistance and corrosion resistance.

[0073] A further improvement of the electrical conductivity and corrosion performances of the electrically conductive composite coatings is the use of smaller conductive fillers in complement to the large conductive fillers. The small fillers, filling the voids formed by the large fillers, can significantly improve the electrical conductivity of the composite coatings. One should be aware that the small conductive fillers size should be well below the large conductive fillers size to adequately fill the voids and form proper conductive pathways.

[0074] In general, it has been experimented that the large conductive fillers are particles with dimensions comprised between 0.1 m and 100 m while the smaller conductive fillers are particles with dimensions comprised between 1 nm and 99 nm.

[0075] The particles may be of one-dimensional shape, two-dimensional shape and/or three-dimensional shape, the particles with dimensions comprised between 1 nm and 99 nm being in various instances three-dimensional particles.

[0076] The particles with dimensions comprised between 0.1 m and 100 m, advantageously with dimensions comprised between 0.1 m and 50 m, have a size which is superior to the thickness of each layer which is comprised between 5 nm and 100 nm, in various instances between 5 nm and 25 nm. As the particles within one layer overtake the surface of the layer, the electrical conductivity between two adjacent layers is considerably enhanced.

[0077] It is to be noted that the dimensions of the carbon-based particles have been determined by Scanning Electron Microscopy (SEM) and are in fact the expression of D50 (medium value of the particle size distribution).

[0078] Both electrical conductivity and corrosion performances of the electrically conductive composite coatings are improved by simultaneously employing large 1D or 2D electrically conductive fillers and small 3D electrically conductive fillers. FIG. 7 shows such how such coating can be illustrated, while FIG. 8 shows the formation of the multi-layered coating on a substrate 4.

[0079] On one hand, the large electrically conductive fillers, made of natural graphite flakes with a 2D shape and a size in the micrometer range (for instance, Micro850 from Asbury Carbons), have been selected as the major electrically conductive filler with loading content from 50% to 85%. In various instances, the large conductive fillers are thus in excess in comparison to the smaller conductive fillers.

[0080] On the other hand, the smaller electrically conductive fillers, with a 3D shape and a 6 nm size (for instance, Ketjenblack EC600JC), have been selected as minor conductive filler with loading content from 0% to 25%.

[0081] The two types of electrically conductive fillers have been dispersed in the matrix precursor, e.g., a monomer with free-radical polymerisable bonds, and sonicated for one hour.

[0082] A thin layer of the polydisperse suspension is subsequently applied on the surface of the metallic substrate to be coated and briefly exposed to an atmospheric-pressure plasma discharge. The thickness of the deposited liquid and polydisperse suspension layer is in the range of several tens to several hundreds of nanometers, which is lower than the longest dimension of the major filler.

[0083] A total of ten deposition cycles is performed in order to mitigate the defects of each deposition cycle. As a result to this sequence, a plurality of stacked electrically conductive composite layers constituting an electrically conductive composite coatings coating are formed.

[0084] The resulting electrically conductive composite coating exhibits both a high electrical conductivity and corrosion-protection properties.

[0085] It is worth to note that the multi-layer coating obtained according to the present invention can be coated on other substrate 4 than the metallic substrate on which the exemplary embodiment has been described. For instance, substrate 4 such as paper, wood, cellulose, polymer or glass could be used.