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    • 专利摘要:
    A product comprising a substrate, the substrate comprising a coating of carbon and at least one metal, wherein carbon is in the form of carbon nanotubes, graphene, graphene oxide, fullerenes or a mixture thereof. The combination of the at least one metal of the coating and the carbon on the substrate results in a product comprising a hybrid coating on the substrate.
    公开号:BE1024791B1
    申请号:E2017/5158
    申请日:2017-03-14
    公开日:2018-07-03
    发明作者:Jan Janssen
    申请人:Aurubis Belgium Nv；
    IPC主号:
    专利说明:

    (73) Holder (s):
    AURUBIS BELGIUM NV 1000, BRUSSELS Belgium (72) Inventor (s):
    JANSSEN Jan 3001 HEVERLEE Belgium (54) Metal / carbon hybrid coating for metal conductors (57) A product comprising a substrate, the substrate comprising a coating of carbon and at least one metal, where carbon is in the form of carbon nanotubes, graphene, graphene oxide, fullerenes or a mixture thereof.
    The combination of the at least one metal of the coating and the carbon on the substrate results in a product that includes a hybrid coating on the substrate.
    FIG, 2
    BELGIAN INVENTION PATENT
    FPS Economy, K.M.O., Self-employed & Energy
    Publication number: 1024791 Filing number: BE2017 / 5158
    Intellectual Property Office International classification: C25D 5/48 C25D 5/50 C25D 7/06 C25D 15/00 C25D 5/54 Date of issue: 03/07/2018
    The Minister of Economy,
    Having regard to the Paris Convention of 20 March 1883 for the Protection of Industrial Property;
    Having regard to the Law of March 28, 1984 on inventive patents, Article 22, for patent applications filed before September 22, 2014;
    Having regard to Title 1 Invention Patents of Book XI of the Economic Law Code, Article XI.24, for patent applications filed from September 22, 2014;
    Having regard to the Royal Decree of 2 December 1986 on the filing, granting and maintenance of inventive patents, Article 28;
    Having regard to the application for an invention patent received by the Intellectual Property Office on 14/03/2017.
    Whereas for patent applications that fall within the scope of Title 1, Book XI, of the Code of Economic Law (hereinafter WER), in accordance with Article XI.19, § 4, second paragraph, of the WER, the granted patent will be limited. to the patent claims for which the novelty search report was prepared, when the patent application is the subject of a novelty search report indicating a lack of unity of invention as referred to in paragraph 1, and when the applicant does not limit his filing and does not file a divisional application in accordance with the search report.
    Decision:
    Article 1
    AURUBIS BELGIUM NV, Broekstraat 31, 1000 BRUSSELS Belgium;
    represented by
    HERTOGHE Kris, Hundeigemsesteenweg 1116, 9820, MERELBEKE;
    a Belgian invention patent with a term of 20 years, subject to payment of the annual fees as referred to in Article XI.48, § 1 of the Economic Law Code, for: Metal / carbon hybrid coating for metal conductors.
    INVENTOR (S):
    JANSSEN Jan, Groeneweg 5, 3001, HEVERLEE;
    PRIORITY:
    03/14/2016 GB 1604342.4;
    BREAKDOWN:
    Split from basic application: Filing date of the basic application:
    Article 2. - This patent is granted without prior investigation into the patentability of the invention, without warranty of the Merit of the invention, nor of the accuracy of its description and at the risk of the applicant (s).
    Brussels, 03/07/2018,
    With special authorization:
    BE2017 / 5158
    Metal / carbon hybrid coating for metal conductors
    Field of the invention
    The invention relates to a hybrid coating on a substrate. More specifically, the present invention relates to a metal / carbon hybrid coating on a substrate, e.g. a conductive substrate, a metal or semiconductor carrier, wherein carbon is provided in the form of carbon nanotubes, graphene, graphene oxide, fullerenes or mixtures thereof and a method of producing of a substrate, e.g. metal support, coated with carbon and a metal.
    Background of the invention
    The provision of a composite coating on metal strips or prepunched metal strips including carbon nanotubes and / or fullerenes and a metal are known. However, problems are still often experienced as a result of poor frictional value and / or contact resistance, low wear resistance and / or poor formability.
    Therefore, there is a need for improved methods and devices that overcome the above-mentioned drawbacks.
    Summary of the invention
    It is an object of embodiments of the present invention to provide a metal / carbon hybrid coating on metal supports which has at least one of improved frictional value, good contact resistance, good frictional corrosion resistance, good wear resistance and good formability, and preferably has more of or all these characteristics.
    The above object is achieved by a method and apparatus according to the present invention.
    In a first aspect, the present invention provides methods of producing a substrate coated with carbon and a metal, comprising the steps of:
    - at least partially coating the carrier substrate with carbon,
    BE2017 / 5158 wherein the carbon is provided in the form of carbon nanotubes, fullerenes, graphene, graphene oxide or mixtures thereof;
    - depositing at least one metal on the coated substrate coated with carbon, resulting in a hybrid coating on the substrate.
    It is an advantage of embodiments of the present invention that a hybrid coating on a substrate, e.g., a hybrid conductor, is provided with improved conductivity compared to prior art conductors.
    It is an advantage of embodiments of the present invention that a hybrid coating on a substrate, be. a hybrid conductor is provided which has an improved frictional value and / or good contact resistance and / or good wear resistance and / or good formability.
    It is an advantage that embodiments of the present invention can be used in electrical applications, for example, for conducting electricity. The combination of at least a metal and carbon coating, more specifically copper and carbon nanotubes, improves the properties of the metal support, at least the conductivity or ampacity, and preferably combines these properties. Conductivity and / or ampacity can be improved in that the temperature of the hybrid conductor according to embodiments of the present invention is lower than prior art conductors.
    It is an advantage of embodiments of the present invention that a substrate coated with carbon and at least one metal is allowed, the substrate being from a few centimeters to meters or even endless in length.
    In preferred embodiments, coating the substrate includes coating the substrate with carbon nanotubes, fullerenes, graphene, graphene oxide, or mixtures thereof that are functionalized to exhibit good wetting properties.
    In preferred embodiments, deposition of the at least one metal on the substrate coated with carbon is performed by electroplating. In embodiments where deposition of the at least one metal on the carbon-coated substrate is performed by electroplating, said deposition may include deposition of said at least one metal from an electroplating bath comprising the at least one
    BE2017 / 5158 metal. In further preferred embodiments, deposition of the at least one metal deposition of said metal from a galvanizing bath comprising both the metal and a carbon may comprise.
    In preferred embodiments, deposition of the at least one metal on the coated substrate coated with carbon can be performed by melting. In embodiments where deposition of the at least one metal on the carbon-coated substrate is performed by melting, said at least one metal or said at least one metal and a carbon are melted on the carbon-coated substrate.
    It is an advantage of embodiments of the present invention that a hybrid metal / carbon coating can be provided on the substrate, the deposited metal layer comprising carbon with a density distribution, e.g., a carbon gradient.
    In preferred embodiments, at least partial coating of the substrate with the carbon includes any of the following; chemical vapor deposition, mechanical plating, spraying powder of solutions with the carbon, providing carbon nanotubes, graphene, graphene oxide and / or fullerenes in a solution for dipping or painting solutions with the carbon.
    In preferred embodiments, the carbon is applied directly to the substrate.
    In alternative preferred embodiments, the carbon is applied indirectly to the substrate.
    In embodiments where the carbon is applied indirectly to the substrate, at least one layer may be deposited before coating a substrate comprising carbon, said application of the at least one layer comprising one of the following: pre-plating the substrate with a metal, e.g., tin, or providing a polymeric binder such as, for example, PAA or providing a nucleation layer.
    In preferred embodiments, the carbon may be in the form of carbon nanotubes, the carbon nanotubes being applied to the substrate in any or one way.
    In preferred embodiments in which carbon nanotubes are used
    BE2017 / 5158 applied in one way, the carbon nanotubes can be applied in one way by pulling the substrate after deposition of the carbon nanotubes. Carbon nanotubes can also be applied in a unidirectional manner using other techniques, such as magnetic and electric fields.
    In preferred embodiments, the method may further comprise a post-treatment step, said post-treatment step comprising at least one or a combination of the following steps: rinsing, drawing, annealing, pressure rolling or induction heating.
    In preferred embodiments, a preheating or annealing step is provided.
    It is an advantage of embodiments of the present invention that a pre- or post-heating or annealing step can be provided in a controlled manner by electric heating or induction heating, e.g. by applying a potential to the rollers comprising a groove.
    It is an advantage of embodiments of the present invention that adhesion of the coating is enhanced by providing pre or post heating steps.
    In preferred embodiments, the substrate is treated for carbon deposition to improve adhesion with carbon nanotubes, fullerenes, graphene, graphene oxide, or mixtures thereof. Preferably, said treatment is to change the shape of the substrate and / or roughen the surface of the substrate and / or treat the surface of the substrate with an antioxidant medium, a flow medium and / or an acid medium.
    In preferred embodiments, the substrate is a wire, a flow tube, a yarn, a metal profile, a metal wire, or a metal strip.
    In preferred embodiments, the substrate is a conductive substrate.
    In preferred embodiments, the substrate can be a metal substrate or a semiconductor substrate.
    In preferred embodiments, the substrate may be a metal substrate and the metal of the metal substrate and the at least one metal of the coating
    BE2017 / 5158 selected from the group consisting of non-ferrous metals and their alloys.
    In preferred embodiments, the substrate can be a metal substrate and the metal of the metal substrate and the at least one metal of the coating are the same or different.
    In preferred embodiments, copper may be deposited on a CNT-coated copper support or chromium and / or copper may be deposited on a CNT-coated copper support.
    In preferred embodiments, the substrate may be a metal substrate and the metal of the metal substrate and / or the at least one metal of the coating is oxygen-free copper (OFC), i.e. copper with an oxygen content of less than 10 ppm, preferably less than 2 ppm.
    It is an advantage of embodiments of the present invention that reactions which would be present by preventing the presence of oxygen and its oxidation improve the properties, e.g. fire safety, of the hybrid conductor at high currents.
    In preferred embodiments, the substrate is a metal substrate and the metal of the metal substrate and / or the at least one metal of the coating is Electrolytic-Tough-Pitch Copper (ETP).
    In a second aspect, the present invention provides products to be obtained by a method according to embodiments of the present invention.
    In a third aspect, the present invention provides a product comprising a substrate, the substrate comprising a coating of carbon and at least one metal on said carbon coating, wherein carbon is in the form of carbon nanotubes, graphene, graphene oxide, fullerenes or a mixture thereof and wherein the combination of the at least one metal of the coating and the carbon on the substrate results in a product comprising a hybrid coating on the substrate.
    In preferred embodiments, the at least one metal of the coating is selected from the group consisting of nonferrous metals and their alloys.
    In preferred embodiments, the substrate is a metal substrate and the metal of the substrate and the at least one metal of the coating are the same or different.
    BE2017 / 5158
    In preferred embodiments, when the carbon is in the form of carbon nanotubes, said carbon nanotubes are arranged on the substrate in an arbitrary or unidirectional manner.
    In preferred embodiments, the substrate is a metal wire of at least 30 cm.
    In a fourth aspect, the present invention provides methods for the continuous production of a substrate coated with carbon, wherein carbon is in the form of carbon nanotubes, graphene, graphene oxide, fullerenes and / or mixtures thereof, comprising the steps of:
    - providing a substrate coated with carbon on its surface;
    - transporting said substrate coated with carbon on its surface between anodes through an electrolyte solution bath containing at least one metal salt, and
    making the surface of said substrate coated with carbon electrically conductive;
    - depositing the metal ions of the metal salt on the electrically conductive surface of said substrate coated with carbon.
    In preferred embodiments, the surface of the substrate is made conductive by guiding the substrate along the metal salt along a long path, such a long path being obtained by using a system comprising grooved guide rollers in which the elongated substrate is positioned, so that the elongated substrate passes over the grooved guide rolls multiple times, creating a plurality of parallel routes through the metal salt bath.
    It is an advantage of embodiments of the present invention that allows uninterrupted circulation of the electrolyte.
    It is an advantage of embodiments of the present invention that a method and apparatus are provided which allow high-efficiency continuous electrolytic treatment of Substrates coated with carbon, e.g. CNTs and / or fullerenes.
    It is an advantage of embodiments of the present invention
    BE2017 / 5158 that when a wire is used as a substrate, long wires up to 1 meter or even endless can be galvanized.
    It is an advantage of embodiments of the present invention that if the substrate coated with carbon, e.g., CNTs and / or fullerene wires, is repeatedly fed into and out of the plating bath, it provides multiple plating. As a result, the present invention is advantageous in that multiple layers of galvanization of desired thickness with better adhesive properties are provided.
    It is an advantage of embodiments of the present invention that a much easier quality control and better working efficiency is provided and thus many economic advantages as well as technical advantages are provided by the fact that better quality of galvanized carbon, e.g. CNT and / or fullerenes, coated substrate can be obtained in the present invention.
    It is an advantage of embodiments of the present invention that additional pre- or post-treatment steps can be easily integrated into this method. Such as, for example, application of carbon, e.g. carbon nanotubes and / or fullerenes, may be aligned with and prior to plating equipment. In specific embodiments, the CNT galvanized copper or low alloy copper wire is preferably spooled after galvanization, reeled and optionally ready for further drawing an annealing step.
    In preferred embodiments, providing a substrate coated with carbon on its surface includes applying carbon to the substrate and / or applying the carbon to the electrolyte solution.
    In preferred embodiments, the grooves have the same diameter.
    In alternative preferred embodiments, the grooves have different diameters.
    It is an advantage of embodiments of the present invention that grooves of different diameters combined with different or equal transport speeds of the rolls advantageously result in drawing or elongation of the substrate.
    In a fifth aspect, the present invention provides products obtained by the continuous process according to embodiments of the present invention.
    BE2017 / 5158
    In a sixth aspect, the present invention provides the use of drawing or performing other methods of applying deformation to the substrate coated with carbon nanotubes and / or coated with carbon nanotubes and metal to align the carbon nanotubes along a specific direction.
    Specific and preferred aspects of the invention are included in the accompanying independent and dependent claims. Features of the dependent claims may be combined with features of the independent claims and features of other dependent claims as appropriate and not merely as expressly included in the claims.
    These and other aspects of the invention are clearly explained and explained with reference to the embodiment (s) described below.
    Brief description of the drawings
    Fig. 1 illustrates a surface of a substrate, e.g. metal support, comprising a hybrid coating according to embodiments of the invention, in a specific embodiment where a copper wire with a layer diameter of 0.08 mm is coated with a layer of CNTs, the CNT layer comprising a thickness of 0.003 mm, and wherein the coated metal support is galvanized with copper at a current density of 1200 A / m2.
    Fig. 2 illustrates a cross section of the embodiment of FIG. 1.
    Fig. 3 illustrates a surface of a substrate, e.g. metal support, comprising a hybrid coating according to embodiments of the invention, in a specific embodiment in which a copper wire with a diameter of 0.08 mm is coated with a 0.003 mm layer of CNTs and galvanized with copper at a current density of 400 A / m2.
    Fig. 4 illustrates a cross section of the embodiment of FIG. 3.
    Fig. 5 illustrates a cross-mandrel section of a substrate, e.g., metal support, comprising a hybrid coating according to embodiments of the invention, in a specific embodiment in which a copper wire with a diameter of 5.8 mm is coated with a layer of CNTs, the CNT layer comprising a thickness of 0.003 mm, and wherein the coated metal support is galvanized with copper at a current density of 1100 A / m2.
    Figures 6a and 6b illustrate the effect of providing a hybrid coating on copper according to embodiments of the present invention, wherein
    BE2017 / 5158 includes the hybrid coating CNTs on which copper is deposited by electroplating on a wire with a diameter of 3.3 mm, according to embodiments of the present invention. The figures illustrate a three-fold plot of a current measurement (1), the implied calculated resistance (2) and measured temperature (3) over time.
    Fig. 7 schematically illustrates a system according to embodiments of the present invention.
    Fig. 8 illustrates a cross-section of a substrate comprising a hybrid coating according to embodiments of the invention, wherein the substrate is guessable and wire pulling was performed to align the carbon nanotubes.
    The drawings are purely schematic and are not limiting. In the drawings, the size of some of the elements can be exaggerated and not scaled for illustrative purposes.
    All reference marks in the claims should not be interpreted as limiting the objective.
    In the different drawings, like reference characters refer to like or analogous elements.
    Detailed description of illustrative embodiments
    The present invention is described with reference to specific embodiments and with references to certain drawings, but the invention is not limited thereto but solely to the claims. The drawings described are purely schematic and not limiting. In the drawings, the size of some of the elements can be exaggerated and not scaled for illustrative purposes. The dimensions and relative dimensions do not correspond to actual reductions for the practice of the invention.
    Furthermore, the terms first, second and the like are used in the description and in the claims to distinguish between similar elements and not necessary for describing a sequence, neither in time, nor in space, in sequence or otherwise . It should be noted that the terms thus used are interchangeable under appropriate conditions and that the embodiments of the invention described herein may operate in sequences other than those herein
    BE2017 / 5158 described or illustrated.
    In addition, the terms above, below, and the like in the description and claims are used for descriptive purposes and not necessarily for describing relative positions. It is understood that the terms thus used are interchangeable under appropriate conditions and that the embodiments of the invention described herein may operate in orientations other than those described or illustrated herein.
    It is to be noted that the term comprising used in the claims is not to be construed as being limited to the means listed thereafter; it does not exclude other elements or steps. It should therefore be interpreted as specifying the presence of the stated properties, integers, steps or components referred to, but excludes the presence or addition of one or more other properties, integers, steps or components, or groups thereof, not off. Thus, the meaning of the term a device comprising means A and B is not limited to devices consisting exclusively of components A and B. It means that, with respect to the present invention, the only relevant components of the device are A and B.
    Reference throughout this specification to one particular embodiment or an embodiment means that a specific property, structure or feature described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the expression in one specific embodiment or in an embodiment in various locations throughout this specification may not necessarily all refer to the same embodiment, but may. Furthermore, the specific properties, structures or features may be combined in any suitable manner, as is apparent to anyone skilled in the art of this disclosure, in one or more embodiments.
    Likewise, it is clear that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for streamlining the disclosure and assisting in understanding one or more of the various inventive aspects. However, this method of revelation should not be interpreted as if the claimed invention would require more features than explicit
    BE2017 / 5158 stated in any claim. Instead, as the following claims show, the inventive aspects lie in less than all of the features of a single previous disclosed embodiment. Thus, the claims that follow in the detailed description are expressly included in this detailed description, each claim standing alone as a separate embodiment of this invention.
    Furthermore, while some embodiments described herein include some but not other features incorporated in other embodiments, combinations of features of different embodiments are intended to be within the scope of the invention, and to form different embodiments, as is apparent to those skilled in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination.
    Various specific details are included in the description provided herein. It is clear, however, that embodiments of the invention can be practiced without these specific details. In other instances, known methods, structures and techniques have not been presented in detail in order not to compromise the clarity of this description.
    Where in embodiments of the present invention reference is made to a hybrid coating, reference is made to a coating comprising at least two components, wherein the hybrid coating or material has a property or combination of properties that does not exist in any of the at least two parent components.
    Where reference is made to drawing in embodiments of the present invention, reference is made to a process using tensile forces to make a material, e.g., a metal, longer. When a metal is pulled through a die, it becomes thinner, in a desired shape and thickness. In preferred embodiments, an increase in length of 10% can be obtained. In addition, pulling a substrate can result in a reduction in the diameter or cross-section of the substrate (e.g. wire). Although the process bears similarities, drawing differs from extrusion in that pulling is pulled on the wire rather than pushed through a die. Drawing is usually performed at room temperature and is thus classified as a cold process, but can be done for large threads
    BE2017 / 5158 can also be performed at elevated temperatures to reduce forces.
    In a first aspect, the present invention provides a product comprising a substrate, e.g. a metal support or semiconductor support. The substrate includes a coating of carbon and a coating of at least one metal, the combination of the carbon and the at least one metal forming a hybrid coating for the substrate. The coating preferably at least partially covers the substrate, but may also completely cover the substrate. The carbon exists in the form of carbon nanotubes, graphene, graphene oxide, fullerenes, or mixtures thereof.
    A substrate, e.g. a metal or semiconductor support, may for example be a metal wire, a strip, a flow tube or an electromechanical component, which is preferably made of copper and / or copper alloys, aluminum and / or aluminum alloys, or iron and / or iron alloys. In preferred embodiments, the substrate is made from the group of oxygen-free copper and / or copper alloys or oxygen-free highly thermally conductive copper and / or copper alloys and / or oxygen-free highly conductive copper and / or copper alloys. Notwithstanding, in some embodiments, the substrate may also be a semiconductor material.
    The substrate is preferably treated, such as, e.g., roughened and / or coated to improve adhesion of the carbon to the substrate. The applied layer can be a nucleating layer deposited on the substrate, which can support columnar growth of the carbon, e.g. carbon nanotubes and / or precipitation of fullerenes. The layer used in embodiments of the present invention can be a transition metal.
    Preferably, the substrate may further comprise or carry a diffusion barrier layer, for example a transition metal, or consist of a transition metal. Preferred transition metals are, for example, Mo, B, Co, Fe / Ni, Cr, Ti, W or Ce. In preferred embodiments, the nucleation layer is applied to the diffusion barrier layer.
    In embodiments in which carbon nanotubes are used as the carbon material, the carbon nanotubes are preferably arranged on the substrate with a columnar structure, which can be obtained by the method of the invention described below. The carbon nanotubes can be single-walled or multi-walled carbon nanotubes, which can also be controlled by a method
    BE2017 / 5158 according to embodiments of the invention.
    In embodiments using fullerenes, the fullerenes are preferably arranged on the substrate in the form of spheres.
    In some embodiments, the coating may include graphene, optionally in combination with other carbon-based particles. Graphene refers to monoatomic layers of sp 2 hybridized carbon atoms. Graphene has a high in-plane electrical and thermal conductivity. Graphene can be prepared by separating graphite into its separate sheets. Oxygen is initially added. The oxygen partially reacts with the carbon and causes mutual repulsion of the layers. The graphene flakes are then suspended and embedded depending on the application, for example in polymers, or as used in the present invention as a coating strip for a metal strip.
    In a preferred embodiment, when blend requirement is used as the carbon material, the graphene and / or graphene oxide and / or carbon nanotubes and / or fullerenes form a composite. In other words, the graphene with carbon nanotubes, the graphene with fullerenes, the fullerenes with carbon nanotubes, or all components together can form a composite. In a specific preferred embodiment, the graphene may be arranged orthogonally on the carbon nanotubes and / or fullerenes, representing, for example, the termination of a tube in the axial direction, or the graphene or fullerenes may be arranged orthogonally on the carbon nanotubes. An orthogonal arrangement of graphene on the fullerenes represents a quasi tangential arrangement of the graphene on the fullerenes. An orthogonal arrangement of the fullerenes on carbon nanotubes can be viewed as a scepter, with the fullerenes located at one end of the carbon nanotube.
    The substrate can be a metal strip, preferably having a thickness of 0.06 to 3 mm, particularly preferably of 0.08 to 2.7 mm. In other embodiments, the substrate may be a metal wire, preferably 0.05 to 25 mm in diameter. Notwithstanding, in some embodiments, the metal wire may have a diameter greater than 25mm or less than 0.05mm.
    According to the present invention, a hybrid coated substrate is provided with improved adhesion and wear resistance, as is evident from the following examples. In addition, as will be explained below, make embodiments
    BE2017 / 5158 of the present invention also allows improved electrical properties of the substrate.
    Example 1: a copper wire with a diameter of 80 micrometers and a length of 40 cm, coated with CNTs
    Copper wires with a diameter of 80 micrometers that are 40 cm long, coated with CNTs are provided. Preferably single-walled and / or multi-walled CNTs are used. Preferably no Fe traces are found, but may be present on the CNTs, but some S is present. The CNTs are preferably 5 micrometers long with a diameter of 100 nm. The copper wires coated with the CNTs are electrolytically deposited with copper, with applied current densities ranging between 10 A / m 2 and 700 A / m 2 , and more preferably between 33A / m 2 and 586 A / m 2 . The temperature of the electrolyte can vary between 50 ° C and 60 ° C, and more preferably between 53 ° C and 56 ° C, with a copper content between 40 g / l and 50 g / l, and more preferably between 47 g / l and 49 g / l, with a sulfuric acid content between 167 g / l and 183 g / l.
    Example 2: a copper wire with a diameter of 80 micrometers, coated with CNTs and variously deposited copper layers
    First, a copper wire with a diameter of 80 micrometers or 0.08 mm is coated with a CNT layer. Copper is then deposited by means of a redox reaction. The mass of the copper deposited can be expressed by m = (lxdxM / ZxF) xY, where I is the applied flow, F = 96485 C / mol, M = 63.54 g / mol, Z = 2, d the deposition time in seconds and Y is the part of the stream that participates in the metal deposition or process yield. The layer thickness of the deposited copper can be expressed by t = m / rxA, where r is the density (8.9 g / cm 3 ), m is the mass of the copper and A is the area of the deposition (cm 2 ) .
    Figure 1-11 illustrates a SEM image of the surface of a hybrid coating according to embodiments of the present invention, of which Figure 2 is a cross-sectional view. In FIG. 2, three zones can be distinguished, the core, which is representative of the copper wire with a diameter of 80 micrometers, a black coating which is representative of the layer of CNTs with a thickness of 0.003 mm, and copper deposition on the 0.08 micrometer CNT- coated wire, where the copper is applied, by galvanization, with a current density of 1200 A / m2.
    BE2017 / 5158
    Figure 3 illustrates the surface of a hybrid coating according to embodiments of the present invention, of which Figure 4 is a cross section. In Figure 3 the effect is illustrated of using a different current density, for example as illustrated in Figures 1 and 2, for depositing the copper. In FIG. 4 three zones can be distinguished, the core, which is representative of the copper wire with a diameter of 80 micrometers, a black coating which is representative of the layer of CNTs and copper deposition on the CNT-coated wire, where the copper is applied, by galvanization , with a current density of 400 A / m2. As can be seen in Fig. 4, compared to FIG. 2, the application of a high current results in the production of pure metal powder which is applied to the coated metal wire.
    The wire can be advantageously treated (e.g., roughened) and / or the CNTs can be functionalized, which can result in even better adhesion of the CNTs to the copper wire during galvanization.
    Alternatively, the carbon, e.g., CNTs and / or graphene, can be introduced into the electrolyte solution and further deposited on the copper wire during copper deposition. In embodiments in which carbon, e.g. CNTs and / or graphene, is provided in the electrolyte solution and in which galvanization is performed, the galvanization results in the moving species, e.g. copper and CNT and / or graphene, being ions (in comparison with solid particles for galvanization deposition) and charge transfer occurs during deposition. The result is that providing at least one metal to the coated substrate, according to embodiments of the present invention, can provide a metal coating having CNTs and / or graphene (e.g., a composite metal layer) embedded therein.
    It is an advantage of embodiments of the present invention that a process is provided that provides a low cost, simple procedures, fast deposition rates, good thickness control and film uniformity. Example 3: a copper wire with a diameter of 5.8 mm, coated with CNTs and variously deposited copper layers
    Fig. 5 illustrates a cross section of a copper wire with a hybrid coating according to the present invention. In FIG. 5 three zones can be distinguished, the core, which is representative of a copper wire with a diameter of
    5.8 mm, a black coating representative of the CNTs coated on the copper wire, and
    BE2017 / 5158 copper deposition on the 5.8 mm CNT-coated copper wire, where the copper is applied, by galvanization, with a current density of 1100 A / m2. Thus, this embodiment differs from the cross-section shown in FIG. 2 in the diameter of the copper wire and the slightly different current density employed.
    The effect of the copper wire diameter (0.08 vs 5.8 mm) and the current used for the copper deposition were evaluated. The results are shown in Table I, which shows the results of a copper plating test on various CNT-coated copper wire samples. In the swatches shown in Table I, the thickness of the CNT layer applied to the copper wire is constant (e.g., 0.003 mm). Nevertheless, the invention is not limited to this thickness and other thicknesses can also be used.
    It is clear from the figures that different types of deposition conditions are made possible by using different current densities. In addition, dendrite formation with many nuclei was observed at high current densities.
    The resistance of the copper and CNT-coated copper wire was measured and varied between 33.4 micro-Ohm / cm and 24.4 micro-Ohm / cm for the 0.08 mm diameter copper wire and between 0.0677 micro-Ohm / cm and 0.072 micro-ohms / cm for a copper wire with a diameter of 5.8 mm.
    Table I: Copper plating tests on various CNT coated
    0 copper wire steel
    Steel 1(mA) T(min) L(cm) J (A / m2) Cu-layer thickness(micron) R (micro-Ohm / cm) Figure 5.8 mmdiameterCNT coatedCu wire 200 30 5 220 10 0.0065 1000 30 5 1100 58 0.0062 Fig. 5 0.08 mmdiameterCNT coatedCu wire 10 30 10 400 19 16.9 Fig. 4 30 30 10 1200 50 7.53 Fig. 2
    BE2017 / 5158
    Figures 6a and 6b illustrate the effect of providing a hybrid coating on copper according to embodiments of the present invention, the hybrid coating comprising CNTs on which copper is deposited during electroplating on a 3.3 mm diameter wire. Fig. 6a illustrates a triple expansion over time of a current measurement (1), the implied calculated resistance (2) and measured temperature (3) for a copper wire of 3.3 mm diameter. When a current is applied between 180 A and 185 A (average 182.5 A), a temperature between 296 ° C and 318 ° C (average 307.8 ° C) is measured with a resistance between 4453 micro-Ohm and 4676 micro -Ohm (average 4560 micro-Ohm). Fig. 6b illustrates a triple expansion as a function of time of current measurement (1), the implied calculated resistance (2) and measured temperature (3) for a Cu / CNT hybrid coating on a copper wire of 3.3 mm diameter. It is clear that a rapid drop in resistance is observed of about 6.3% compared to Fig. 6a. When a current is applied between 180 A and 185 A (average 182.5 A), a temperature between 277.2 ° C and 297.2 ° C (average 284.4 ° C) is measured with a resistance between 4169 microOhm and 4442.2 micro-Ohms (average 4272 micro-Ohms).
    Another object of the invention is to provide a method of preparing a substrate coated with carbon and a metal, the carbon in the form of carbon nanotubes, graphene, graphene oxide, fullerenes or mixtures thereof comprising the steps of:
    - optionally, coating a substrate with a diffusion barrier layer,
    - optionally, treating the substrate by depositing a nucleation slave or roughening the substrate,
    - exposing the substrate to an atmosphere containing organic gaseous compounds,
    - forming the carbon, e.g. carbon nanotubes and / or fullerenes, on the substrate at a temperature of 200 ° C to 1500 ° C,
    - coating and / or penetrating the carbon nanotubes and / or fullerenes with at least one metal, by electroplating the metal on the carbon nanotubes.
    In alternative embodiments, instead of electroplating, other methods are known which can be used equally well for
    BE2017 / 5158 deposition of the metal on the carbon material applied to the substrate. Examples of such alternative methods may include electroless plating and solution spraying.
    In preferred embodiments, methods according to embodiments of the present invention can be performed in a stationary manner, e.g., where the substrate is held stationary while the steps of the method are performed.
    Carbon particles such as carbon nanotubes and / or fullerenes are typically found on the substrate at a temperature from 200 ° C to 1500 ° C. Preferably, multi-walled carbon nanotubes (MWCNTs) are formed at a temperature of 200 ° C to 900 ° C. Preferably, single wall carbon nanotubes (SWCNTs) are formed at a temperature above 900 ° C to about 1500 ° C. The quality of the carbon nanotubes can be improved when growth takes place in a humid atmosphere. The carbon nanotubes on the metal strip are formed with a columnar structure, which is supported by the nucleation layer. The fullerenes preferably deposit on the metal strip in the form of spheres.
    Graphene can also preferably be introduced into the coating. The carbon material, e.g. graphene and / or carbon nanotubes and / or fullerenes, preferably form a composite. In other words, the graphene with carbon nanotubes, the graphene with fullerenes, the fullerenes with carbon nanotubes, or all components together can form a composite. In a specific preferred embodiment, the graphene may be arranged orthogonally on the carbon nanotubes and / or fullerenes, representing, for example, the termination of a tube in the axial direction, or the graphene or fullerenes may be arranged orthogonally on the carbon nanotubes. An orthogonal arrangement of graphene on the fullerenes represents a quasi tangential arrangement of the graphene on the fullerenes. An orthogonal arrangement of the fullerenes on carbon nanotubes can be viewed as a scepter, with the fullerenes located at one end of the carbon nanotube.
    Then the carbon-coated substrate, e.g., coated with carbon nanotubes and / or the fullerenes, is coated and / or permeated with at least one metal. Suitable metals can be the metals Sn, Ni, Ag, Au Pd, Cu, Cr or W and their alloys. In further embodiments, the at least one metal can be a mixture
    BE2017 / 5158 of metals, e.g., metals doped with another metal or a combination of two metals in the hybrid coating by co-deposition. In still further embodiments, the carbon-coated substrate can be coated and / or impregnated with a metal and a carbon.
    Coating and / or penetration of the carbon nanotubes and / or fullerenes and / or graphene and / or graphene oxide with the at least one metal is preferably carried out by a vacuum process, for example CVD (chemical vapor deposition) or PVD (physical vapor deposition), electrolytic, electroless reductive, or by melting / infiltration.
    Figure 7 schematically illustrates a system for performing a method according to embodiments of the present invention. In the system of FIG. 7, a substrate, e.g. a metal wire, is placed in a steel holder. The sample container containing the substrate is positioned in a container or receptacle (E). The containers preferably have a cylindrical shape (e.g. containing a volume of 15 liters), which is preferably filled with a solution of sulfuric acid and the metal to be deposited on the substrate, which is a carbon-coated substrate, e.g. with CNT coated copper wire, placed in the steel holder. The sample holder preferably comprises an anode plate (e.g. a copper plate) and a wire as a substrate. However, the wire can be a plating substrate or cathode. In preferred embodiments, the plating fluid circulates constantly through the container and is maintained at an appropriate temperature. The plating liquid is introduced into the receptacle by an input means (A) and is removed from the receptacle by an output means (B). In further preferred embodiments, the plating fluid comprises a solution comprising at least one metal, sulfuric acids and optionally additives. Depending on the intended application, the sample holder can be adapted and configured to accommodate various shapes and types of Substrates. The resistance of the sample holder can be measured with a four-point measurement. In preferred embodiments, a constant current, preferably a constant DC current, can be applied and a voltage drop is accurately measured. The system of FIG. 7 may optionally also include a temperature sensor that can be used to compensate for the temperature differences. The system according to embodiments of the present invention may optionally include drawing means (not shown in Fig. 7) which pull the substrate for,
    BE2017 / 5158 for example, allow alignment of the carbon nanotubes when applied as a coating to the substrate. Figure 8 illustrates a cross section of a copper wire with an original diameter of 5.8 mm, coated with a hybrid CNT and copper coating according to embodiments of the present invention, the copper wire being drawn and reduced to a diameter of 5.2 mm.
    Optionally, a system according to embodiments of the present invention may further comprise imaging means to allow for metallographic observations. Examples of such imaging agents can be a Reichert metallographic microscope or a JEOL scan electron microscope providing SE images (e.g., a JEOL SEM). Another object of the invention is to provide a continuous process for preparing a substrate coated with carbon, carbon applied in the form of carbon nanotubes, graphene, fullerenes or mixtures thereof, comprising the steps of:
    - applying a substrate coated with the carbon to its surface;
    - transporting said carbon-coated substrate on its surface between anodes through a bath of an electrolyte solution containing a metal salt, and
    - depositing the metal ions of the metal salt on the electrically conductive surface of said carbon-coated substrate. The surface of the substrate can be made electrically conductive. The substrate can, for example, when it is an elongated substrate, be guided in the metal salt along a long route. Such a long route can be achieved, for example, by using a system comprising grooved guide rollers in which the elongated substrate is positioned so that the elongated substrate travels over the grooved guide rollers a number of times through a plurality of parallel routes through the metal salt bath is being created.
    A further object of the present invention is to provide an apparatus for continuously producing electrolytically treated wires comprising repeated immersion of a substrate, e.g. a metal support such as a wire, preferably coated with carbon, in an electrolyte contained in an electrolytic treatment tank positioned between guide rollers that move the wire back and forth continuously
    BE2017 / 5158 pass between the guide rollers by stepwise guiding of the wire onto the guide rollers, with the wire as the electrode, and placing another electrode in the electrolytic treatment tank to obtain electrolytic plating and / or polishing at high production efficiency.
    The device and method for the continuous production of electrolytically treated according to the present invention may also be suitable for both electrolytic polishing and electroplating of metal wires, and more specifically in the case of electroplating metal wires in which the wires are repeatedly fed into and out of the plating bath to provide plating layers. Therefore, the present invention offers advantages in that multiple layers of electroplating of desired thickness with better adhesion are obtained.
    In one particular embodiment of the present invention, the electrolytic treatment tank may be provided with slots and grooves at its inlet and outlet to pass the wires and prevent the electrolyte, and a forced electrolyte circulation system is used for the forced return from the electrolyte flowing from the inlet and outlet to the electrolytic treatment tank so that a constant amount of electrolyte is retained in the electrolytic treatment tank. As for the guide rollers, their rotary shafts may be horizontal or perpendicular, and the means for guiding
    The wires applied to the guide rollers are suitably a plurality of grooves arranged around the circumferential surfaces of the guide rollers. The wires to be treated in accordance with the present invention are pretreated in a pretreatment tank as necessary.
    BE2017 / 5158
    权利要求:
    Claims (39)
    [1]
    CONCLUSIONS
    A method for producing a substrate coated with carbon and a metal, comprising the steps of:
    - at least partially coating a carrier substrate with carbon, the carbon being provided in the form of carbon nanotubes, fullerenes, graphene, graphene oxide or mixtures thereof;
    - depositing at least one metal on the coated substrate coated with carbon, resulting in a hybrid coating on the substrate.
    [2]
    The method of claim 1, wherein coating the substrate comprises coating the substrate with carbon nanotubes, fullerenes, graphene, graphene oxide or mixtures thereof which are functionalized to exhibit good wetting properties.
    [3]
    The method of any one of the preceding claims, wherein the depositing of the at least one metal on the coated substrate coated with carbon is performed by electroplating.
    [4]
    The method of claim 3, wherein said depositing of at least one metal comprises depositing said at least one metal from a galvanizing bath comprising the metal.
    [5]
    The method of claim 3, wherein said depositing at least one metal comprises depositing said metal from a galvanizing bath comprising both the metal and a carbon.
    [6]
    The method of claim 3, wherein deposition of the at least one metal on the coated substrate coated with carbon is performed by melting.
    [7]
    The method of claim 6, wherein depositing the at least one metal comprises melting said at least one metal and a carbon.
    [8]
    A method according to any one of the preceding claims, wherein at least partial coating of the substrate with the carbon comprises one of the following; chemical vapor deposition, mechanical plating, spraying powder of solutions with the carbon, providing carbon nanotubes, graphene, graphene oxide and / or fullerenes in a solution to dip or dye the solutions with the carbon.
    [9]
    A method according to any preceding claim, wherein the carbon is applied directly to the substrate.
    [10]
    The method of any preceding claim, wherein the carbon is indirect
    BE2017 / 5158 is applied to the substrate.
    [11]
    The method of claim 10, wherein at least one layer is deposited to apply a coating to a substrate comprising carbon, said providing at least one layer comprising any of the following: pre-plating the substrate with a metal or providing the polymeric binder such as, for example, PAA or providing a nucleation layer.
    [12]
    The method of any preceding claim, wherein the carbon is in the form of carbon nanotubes, the carbon nanotubes being applied to the substrate in an arbitrary or unidirectional manner.
    [13]
    The method of claim 13, wherein the carbon nanotubes are applied in a unidirectional manner by drawing the substrate after deposition of the carbon nanotubes.
    [14]
    The method of any one of the preceding claims, further comprising a post-treatment step wherein said post-treatment step comprises at least one or a combination of the following steps: rinsing, drawing, annealing, pressure rolling or induction heating.
    [15]
    A method according to any preceding claim, wherein a pretreatment or annealing step is provided.
    [16]
    A method according to any one of the preceding claims, wherein the substrate is treated for carbon deposition to enhance adhesion with carbon nanotubes, fullerenes, graphene, graphene oxide or mixtures thereof.
    [17]
    The method of claim 16, wherein said treatment comprises altering the shape of the substrate.
    [18]
    The method of claim 16, wherein said treatment comprises roughening the surface of the substrate or treating the surface of the substrate with an anti-oxidation medium, a flux medium and / or an acid medium or change the shape of the substrate.
    [19]
    A method according to any one of the preceding claims, wherein the substrate is a wire, a flow tube, a yarn, a metal profile or metal wire or a metal strip.
    [20]
    The method of any preceding claim, wherein the substrate is a conductive substrate.
    [21]
    The method of claim 20, wherein the substrate is a metal substrate or a
    BE2017 / 5158 is semiconductor substrate.
    [22]
    The method of any preceding claim, wherein the substrate is a metal substrate and the metal of the metal substrate and the at least one metal of the coating is selected from the group consisting of non-ferrous metals and their alloys.
    [23]
    The method of any preceding claim, wherein the substrate is a metal substrate and the metal of the metal substrate and the at least one metal of the coating are the same or different.
    [24]
    The method of claim 23, wherein the substrate is a metal substrate and the metal of the metal substrate and / or the at least one metal of the coating is oxygen-free copper (OFC).
    [25]
    The method of claim 23, wherein the substrate is a metal substrate and the metal of the metal substrate and / or the at least one metal of the coating is Electrolytic-Tough-Pitch (ETP) copper.
    [26]
    26. Product obtained by a method according to any one of the preceding claims.
    [27]
    A product comprising a substrate and a coating of carbon and at least one metal on said carbon coating on the substrate, wherein the carbon is in the form of carbon nanotubes, graphene, graphene oxide, fullerenes or a mixture thereof and wherein the combination of the at least one metal of the coating and the carbon on the substrate results in a product comprising a hybrid coating on the substrate.
    [28]
    The product of claim 27, wherein the at least one metal of the coating is selected from the group consisting of non-ferrous metals and their alloys.
    [29]
    The product of any one of claims 27 or 28, wherein the substrate is a metal substrate and the metal of the substrate and the at least one metal of the coating are the same or different.
    [30]
    A product according to any one of claims 27 to 29, wherein the carbon in the form of nanotubes on the substrate are arranged in an arbitrary or unidirectional manner.
    [31]
    The product of any one of claims 27 to 30, wherein the substrate is a metal wire of at least 30 cm.
    [32]
    A method of continuously producing a substrate coated with carbon, wherein carbon is in the form of carbon nanotubes, graphene, graphene oxide, fullerenes, or a mixture thereof, comprising the steps of:
    - providing a substrate coated with carbon on its surface;
    BE2017 / 5158
    - transporting said substrate coated with carbon on its surface between anodes through an electrolyte solution bath containing at least one metal salt, and
    making the surface of said substrate coated with carbon electrically conductive;
    - depositing the metal ions of a metal salt on the electrically conductive surface of said substrate coated with carbon.
    [33]
    The method of claim 32, wherein the surface of the substrate is made conductive by guiding the substrate into the metal salt along a long route, such a long salt being obtained by using a system comprising grooved guide rollers in which the elongated substrate is positioned so that the elongated substrate passes over the grooved guide rolls a number of times, creating a plurality of parallel routes through the metal salt bath.
    [34]
    The method of any one of claims 32 or 33, wherein providing a substrate coated with carbon on its surface comprises a pretreatment step for applying carbon to the substrate and / or applying the carbon in the electrolyte solution.
    [35]
    A method according to any of claims 33 or 34, wherein the grooves have the same diameter.
    [36]
    A method according to any of claims 33 or 34, wherein the grooves have different diameters.
    [37]
    A product obtained by the method according to any one of claims 32 to 35.
    [38]
    38. Use of deformation of a substrate coated with carbon nanotubes and / or with carbon nanotubes and metal to align the carbon nanotubes along a specific direction.
    [39]
    The use of claim 38, wherein deformation of a substrate comprises drawing the substrate.
    BE2017 / 5158
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    同族专利:
    公开号 | 公开日
    GB201604342D0|2016-04-27|
    BE1024791A1|2018-06-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20120121986A1|2009-07-06|2012-05-17|Zeptor Corporation|Carbon nanotube composite structures and methods of manufacturing the same|
    US20140339092A1|2011-12-02|2014-11-20|Byk-Chemie Gmbh|Method for producing electrically conductive structures on non-conductive substrates and structures made in this matter|
    US20140348450A1|2011-12-08|2014-11-27|Mahle International Gmbh|Sliding bearing|
    法律状态:
    2018-08-29| FG| Patent granted|Effective date: 20180703 |
    优先权:
    申请号 | 申请日 | 专利标题
    GBGB1604342.4A|GB201604342D0|2016-03-14|2016-03-14|Substrate|
    GB1604342.4|2016-03-14|
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