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    • 专利摘要:
    The present invention relates to a composition that can be used for coating or other applications. The composition comprises carbon in the form of carbon nanotubes, fullerene, graphene, graphene oxide, carbon black or mixtures thereof in a solvent medium and / or aqueous medium. The aqueous medium comprises at least one surfactant. The solvent medium comprises one or more compounds selected from the group of polymers, celluloses or cellulose derivatives, amino silanes or silanes. A coated product, a method for producing the composition and for coating a product as well as the use of the composition has also been described.
    公开号:BE1024843B1
    申请号:E2017/5157
    申请日:2017-03-14
    公开日:2018-07-24
    发明作者:Krzysztof Koziol；Marek Burda
    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):
    KOZIOL Krzysztof CB1 3JL CAMBRIDGE United Kingdom
    BURDA Marek
    CB3 0HU CAMBRIDGE
    United Kingdom (54) Composition of a carbonaceous layer for metal conductors (57) The present invention relates to a composition that can be used for coating or other applications. The composition includes carbon in the form of carbon nanotubes, fullerene, graphene, graphene oxide, carbon black or mixtures thereof in a solvent medium and / or aqueous medium. The aqueous medium comprise at least one surfactant. The solvent medium includes one or more compounds selected from the group of polymers, celluloses or cellulose derivatives, aminosilanes or silanes. A coated product, a method for producing the composition and for coating a product as well as the use of the composition has also been described.
    BELGIAN INVENTION PATENT
    FPS Economy, K.M.O., Self-employed & Energy
    Publication number: 1024843 Filing number: BE2017 / 5157
    Intellectual Property Office
    International Classification: HOIB 1/02 C08K 3/04 C23C 24/08 Date of Issue: 24/07/2018
    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, Hundelgemsesteenweg 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 Code of Economic Law, for: Composition of a carbon-containing layer for metal conductors.
    INVENTOR (S):
    KOZIOL Krzysztof, Coldhams Lane 558, CB1 3JL, CAMBRIDGE;
    BURDA Marek, Grosvenor Court 4, Woodlark Road, CB3 OHU, CAMBRIDGE;
    PRIORITY :
    03/14/2016 GB 1604341.6;
    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, 24/07/2018,
    With special authorization:
    BE2017 / 5157
    Composition of a carbonaceous layer for metal conductors
    Field of the invention
    The invention relates to coating compositions. More specifically, the invention relates to coating compositions and materials including carbons, substrates coated therewith, methods of making coating compositions and uses of such compositions.
    Background of the invention
    It is known from the prior art that carbon nanotubes are mixed with conventional polymers. The mechanical properties of the polymers are thereby substantially improved. It is further possible to produce electrically conductive plastics with carbon materials. For example, nanotubes have already been used to make anti-static films conductive.
    Tin or tin alloys are commonly used for soldering electrical contacts, for example, to connect copper wires together. Tin or tin alloys are also often applied to plug-type connections to improve the coefficient of friction, protect them from
    0 corrosion and to contribute to improved conductivity. Problems in using tin and tin alloys include the tendency to frictional corrosion, the high coefficient of friction of these materials, and more specifically, the softness of the metal or alloy. The soft nature of the alloy causes tin-containing coatings to wear out, more specifically when plug-type connectors are often coupled on and off and in case of vibration. As a result, the advantages of tin-containing coating can disappear. Similar problems arise when using other metals or alloys, for example those containing Ag, Au, Ni or
    Zn contain.
    US20130004752 provides a method for coating a
    BE2017 / 5157 substrate with a coating composition containing carbon and a metal.
    Application of the coating described in US'752 to metal substrates, in the liquid state or as a paste or as a dispersion, has not been successfully performed due to the low adhesion qualities.
    Thus, there is a need for improved compositions and methods for their use, which are provided by the present disclosure.
    Summary of the invention
    It is an object of embodiments of the present invention to provide improved carbon based compositions in which the carbon is in the form of carbon nanostructures such as, for example, carbon nanotubes, carbon nanotubes, carbon nanofibers or herringbone carbon nanostructures, graphite, fullerene, graphene, graphene oxide magnetic carbon or mixtures thereof , substrates coated therewith, method of making carbon-based compositions and use of such carbon-based compositions.
    It is an advantage of some embodiments of the present invention that advantageous cooling of substrates, such as, for example, of flow tubes, can be achieved by the combination of
    High emissivity and good thermal conductivity of the coating comprising carbon in the form of carbon nanostructures such as, for example, carbon nanotubes, carbon nanotubes, carbon nanofibers or herringbone carbon nanostructures, graphite, fullerene, graphene, graphene oxide magnetic carbon or mixtures thereof.
    It is an advantage of embodiments of the present invention that a coating can be provided that allows at least one or preferably more of electrical insulation, corrosion inhibition, increased nominal current range, perfect appearance, etc.
    It is an advantage of at least some embodiments of
    BE2017 / 5157 that expensive conventional coatings can be avoided and replaced with a coating according to an embodiment of the present invention.
    In one aspect, the present invention relates to a composition suitable for coating or other application, the composition comprising carbon in the form of carbon nanostructures such as, for example, carbon nanotubes, carbon nanotubes, carbon nanofibers or herringbone carbon nanostructures, graphite, fullerene graphene, graphene oxide, magnetic carbon, carbon black or mixtures thereof in a solvent medium, said solvent medium comprising one or more of polymers, celluloses or cellulose derivatives, aminosilanes or silanes and / or in an aqueous medium, said aqueous medium comprising a surfactant. The mass ratio of carbons to surfactant can have a lower limit of 10:90 or 20:80 or 30:70 or 40:60 and an upper limit of 90:10 or 80:20 or 70:30 or 60:40. The mass ratio of carbon to surfactant may, in one example, be 50:50. In some embodiments, the mass ratio of carbon to surfactants can range from 30:70 to 60:40.
    The mass ratio of carbon to
    0 surfactants can be 50:50. It is an advantage of the present invention that improved adhesion of the composition to substrates is obtained and polishing of the coating is allowed to align the carbon present in the composition.
    The surfactant can be anionic, cationic, nonionic, or a combination thereof.
    The surfactant can be an alkyl sulfonate or an alkaryl sulfonate.
    Carbon can exist in the form of carbon nanotubes and graphene, the mass ratio of carbon nanotubes to graphene in the
    BE2017 / 5157 area is from 70:30 to 30:70.
    Carbon can exist in the form of carbon nanotubes and graphene, the mass ratio of carbons to graphene being 50:50. It is an advantage of the present invention to provide a coating comprising carbon nanotubes and graphene, or CNTs or graphene, which is not rigid, although graphene itself is rigid. It allows the application of a multitude of layers of the coating material.
    Carbon can exist in the form of carbon nanotubes, alone or in a mixture, the concentration of the carbon nanotubes being from 0.1 to 5% by weight.
    The concentration of the carbon nanotubes can be 0.1 to 5% by weight.
    Carbon can exist in the form of carbon nanotubes, alone or in a mixture, the carbon nanotubes being single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled nanotubes, or a combination thereof.
    The carbon nanotubes can be functionalized carbon nanotubes.
    The carbon nanotubes can have an average outside diameter between 0.4 nm and 100 nm.
    The carbon nanotubes can have a length between 1 nm and cm.
    The composition may further comprise one or more additives selected from the group consisting of acetates, alkoxylates, alkylolamides, esters, amine oxides, alkyl polyglucosides, alkylphenols, arylalkylphenols, water-soluble or water-soluble homopolymers, water-soluble or water-soluble random copolymers, water-soluble or water-insoluble block copolymers, water-soluble or water-soluble graft polymers, polyvinyl alcohols, polyvinyl acetates, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinylpyrrolidones, cellulose, starch, gelatin,
    BE2017 / 5157 Gelatin derivatives, amino acid polymers, polylysine, polyaspartic acid, stearic acid, maleic acid, calcium carbonate, polyacrylates, polyethylene sulfonates, polystyrene sulfonates, polymethacrylates, condensation products of aromatic sulfonic acids, formaldehyde, naphthalene sulfonates, lignosymersulfonates, copolymersulfonates, lignosymersulfonates, copolymersulfonates, copolymersulfonates, lignosymersulfonates, copolymersulfonates vinyl pyridines), block copolyethers, block copolyethers with polystyrene blocks and / or polydiallyldimethylammonium chloride, amino silanes and / or silanes, silica, copper powder or copper nanopowder.
    The present invention also relates to a product comprising a substrate and at least a full or partial coating made from a composition as described above. It is an advantage of embodiments of the present invention that a coating according to embodiments of the present invention inhibits corrosion of the substrate.
    It is an advantage of embodiments of the present invention that a coating according to embodiments of the present invention serves as a heat transfer agent, which evenly releases and distributes heat contained in the substrate.
    It is an advantage of embodiments of the present invention that a coating according to embodiments of the present invention improves the flow capacity of the substrate.
    It is an advantage of the present invention that a coating of only limited thickness is required to achieve the intended heat benefits.
    The substrate can be made of a metal.
    The substrate can be made of copper or aluminum.
    The substrate can be an electrical conductor or a semiconductor.
    The coating can be applied directly to the substrate.
    An additional layer can be applied between the substrate and the coating.
    BE2017 / 5157
    The additional layer can be a layer comprising or consisting of tin.
    The coating can be applied in one or more applications. Intermediate processing steps can be performed.
    The substrate can be selected from the group consisting of non-ferrous metals and their alloys.
    Carbon can exist in the form of carbon nanotubes, alone or in a mixture, in the coating, and can be aligned. Carbon can also exist in the form of graphene, alone or in a mixture, in the coating.
    The present invention also relates to a method of preparing a composition suitable for coating or other applications, the method comprising the steps of:
    providing a mixture comprising: a carbon in the form of carbon nanostructures such as, for example, carbon nanotubes, carbon nanotubes, carbon nanofibers or herringbone carbon nanostructures, graphite, fullerene, graphene, graphene oxide magnetic carbon, carbon black or mixtures thereof in one or more of the solvent of polymers, celluloses, amino silanes or silanes, and / or in an aqueous medium comprising a surfactant; and
    obtaining disaggregation and / or preventing aggregation of the carbon in the medium such that a composition comprising a plurality of individually dispersed carbon particles such as carbon nanostructures such as, for example, carbon nanotubes, carbon nanotubes, carbon nanofibers or herringbone carbon nanostructures, graphite, fullerene, graphene, graphene oxide magnetic carbon or mixtures thereof is produced.
    The mass ratio of carbon to surfactant can have a lower limit of 10:90 or 20:80 or 30:70 or
    40:60 and an upper limit of 90:10 or 80:20 or 70:30 or 60:40. The mass ratio of carbon to surfactant can be 50:50 in one example
    BE2017 / 5157.
    Obtaining disaggregation and / or preventing aggregation is accomplished by ultrasonic treatment.
    The ultrasonic treatment can be performed over a period of several minutes to several hours or until no noticeable increase in nanotube dispersion is observed.
    Ultrasonic treatment can be performed as a single step or in multiple steps.
    Obtaining disaggregation and / or preventing aggregation can be performed at any temperature at which the aqueous medium is in liquid form.
    The present invention also relates to a method of providing a composition as described above on a substrate, the method comprising:
    - providing the substrate;
    - providing the composition in a liquid state on at least a portion of the substrate resulting in a solid state coating on the substrate.
    In the method, providing the composition can provide heating of the composition in a liquid state, which results in a solid state coating on the substrate.
    The composition can be applied in the form of a coating. The coatings can be formed in one or more applications, with or without intermediate treatments.
    The provision of the substrate may comprise the provision of a metal support or a semiconductor.
    The method may further include a pretreatment step in which the substrate is chemically treated.
    The method may further comprise a post-heating treatment.
    BE2017 / 5157
    The method may include polishing the coated substrate so that the carbon in the composition is aligned.
    The method may include brushing the coating, which results in a metal support in which the carbon material is dispersed in the substrate.
    The heat treatment can be performed at high temperature. In some embodiments, the heat treatment can be performed at a high temperature. In some embodiments, the heat treatment can be performed by burning the coating with a flame. It is an advantage of embodiments of the present invention that the binder can be removed from the coating. It is an advantage of some embodiments of the present invention that an oxide layer can be formed in and / or under the coating.
    The present invention also relates to the use of the composition as described above for inhibiting corrosion of a substrate.
    The present invention also relates to the use of a composition as described above for dissipating and distributing heat provided in a substrate.
    The present invention also relates to the use of a composition as described above for improving a flow capacity of a system.
    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 the features of the independent claims and features of other dependent claims as appropriate and not merely as expressly contained in the claims.
    These and other aspects of the invention are clearly explained and explained with reference to the embodiment (s) described below.
    BE2017 / 5157
    Brief description of the drawings
    FIG. 1 (a) to (c) schematically illustrate a method according to the present invention.
    The drawings are purely schematic and are not limiting. In the 5 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.
    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.
    Furthermore, the terms first, second and the like are used in the description and in the claims to distinguish between
    0 similar elements and not necessary for describing a sequence, neither in time nor in space, in sequence or in any other way. It is to 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 described or illustrated herein.
    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 clear that the terms thus used are interchangeable under appropriate conditions and
    BE2017 / 5157 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 disclosure should not be interpreted as if the claimed invention has more features
    BE2017 / 5157 would then require explicitly stated in each conclusion. 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.
    In a first aspect, the present invention provides a coating composition, the composition comprising carbon in the form of carbon nanostructures such as, for example, carbon nanotubes, carbon nanotubes, carbon nanofibers or herringbone carbon nanostructures, carbon black, graphite, fullerene, graphene, graphene oxide, magnetic carbon, or mixtures thereof in a solvent medium, said solvent medium comprising one or more of polymers, celluloses or cellulose derivatives, aminosilanes or silanes, and / or in an aqueous medium, said aqueous medium comprising a surfactant. Some examples thereof are described in more detail, but embodiments of the present invention are not limited to them.
    BE2017 / 5157
    Carbon nanotubes can be single-walled nanotubes (SWCNTs), double-walled nanotubes or multi-walled carbon nanotubes (MWCNTs). The term single wall as used herein in connection with carbon nanotubes refers to single carbon wall carbon nanotubes. The nanotubes can vary in diameter and length. In embodiments, the diameter of the nanotubes can range from 0.4 nm to 100 nm or even up to 200 nm, including all values down to the smallest diameter as can be produced. In embodiments, the length of the carbon nanotubes can range from one or a few nanometers to centimeters, limited only by the maximum length at which these nanotubes can be synthesized. It is understood that external impurities, such as catalyst metal particles, fullerene containing carbon, amorphous carbon, graphite containing carbon and carbon rings, may be present in various sizes in prepared carbon carbon nanotubes. SWCNT materials are usually a mixture of both semiconductor and metal types. In one embodiment, the metal form of carbon nanotubes can be removed from the plurality of carbon nanotubes. In one embodiment, purified SWCNTs can be used. Methods for purification of commercially available or laboratory prepared nanotubes are known in the art.
    The synthesis of the carbon nanotubes is preferably performed by depositing carbon from a gas phase or a plasma. These techniques are known to anyone skilled in the art.
    Fullerenes are typically known as spherical molecules comprising carbon atoms that have a high degree of symmetry and form the third element modification of carbon (in addition to diamond and graphite).
    Graphene is typically known as monoatomic layers of sp 2 hybridized carbon atoms. Graphene is known to exhibit excellent in-plane electrical and thermal conductivity. Graphenes can be obtained, for example, by graphite exfoliation, CVD, epitaxial growth, total organic
    BE2017 / 5157 synthesis, plasma refraction of natural gas, etc.
    In a preferred embodiment, for preparing the composition, mixing the carbon in the solvent medium, said solvent medium comprising one or more of polymers, celluloses or cellulose derivatives, aminosilanes or silanes, and / or in the aqueous medium is carried out in the liquid state , using sufficient solvent (fluid dispersion medium) to produce a paste or dispersion (more specifically, a suspension). At least one surfactant, but optionally also one or more other additives / surfactants, may be added during the liquid mixing. The one or more additives / surfactants are preferably selected from further surfactants, antioxidant media, binders, solvents, flow media and / or acidic media.
    The surfactants can be of a non-ionic, anionic, cationic and / or amphoteric type, and more specifically contribute to obtaining a stable dispersion or suspension. Suitable surfactants in the context of the invention are, for example, an alkyl sulfonate or alkaryl sulfonate surfactant. For example, the surfactant may include SDBS, sodium dodecyl sulfate (SDS), sodium dodecyl sulfonate (SDSA), sodium n2 0 lauroyl sacrosinate (e.g., Sarkosyl®), sodium alkyl allylsulfosuccinate (e.g., TREM®), poly (styrene sulfonimethylethyl ammonium (PSStronium)) sodium salt (PSS). (DTAB), cetyltrimethylammonium bromide (CTAB), Brij (e.g., Brij 78, Brij 700), Triton 'X (e.g., Triton' X-100, Triton 'X-114, Triton' X-405), PVP (e.g. , PVP-10, PVP-40, PVP-1300, polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO triblock polymer) (Pluronic®) (e.g., Pluronic® P103, Pluronic® P104 Pluronic® P105
    Pluronic® P108, Pluronic® F98, Pluronic® F68, Pluronic® F127, Pluronic® F87,
    Pluronic® F77, Pluronic® F85), polyethylene oxide-polybutylene oxide polyethylene oxide (PEO-PBO-PEO triblock polymer) (eg, EBE), Tween® (eg Tween®
    20, Tween® 40, Tween® 60, Tween® 80, Tween® 85), and sodium cholate.
    BE2017 / 5157
    Surfactant combinations can also be used. Suitable surfactants are commercially available or can be prepared by methods known in the art.
    In preferred embodiments, at least one of the following 5 surfactants can be used: C16TMABr as cationic surfactant, SDBS as anionic surfactant and Pluronic®
    F127 as a non-ionic surfactant.
    The concentration of the surfactant may vary. In extremely low concentrations, surfactants are typically found primarily on the surface of the aqueous phase with their hydrophilic ends facing the water and its hydrophobic tails facing away. As the concentration increases, the surface of the aqueous environment eventually becomes saturated and molecules must begin to exist in the solution. This point is known as the critical micelle concentration (CMC) and immediately at this point surfactant molecules are in the form of atmospheric micelles. In the presence of CNTs, self-mounting of surfactants is activated by the latter's affinity for the CNT sidewalls. The dispersing ability of various surfactants is inherent due to their chemical organization. The quality of nanotube dispersion is possible
    0 are optimized in function of the ratio of CNT to surfactant.
    A solvent medium can be glycolforal, ethylene glycol, methylene ether, formal ethylene glycol formal, formaldehyde ethylene acetal, 1,3-dioxolane, formalglycol, glycoformal, glycolmethylene ether, methylene glycolmethylene ether, dihydro-1,3 dioxol, dioxolane, dioxolanne, tetrahydroxy oxane, furanyl oxane hydrofuran, oxacyclopentane, tetramethylene oxide, tetraidrofurano, 1,4-epoxybutane, tetrahydrofuran, tetrahydrofuran, cyclotetramethylene oxide, tetrahydrofuran, Agrisynth THF, cyclotetramethylene,
    THF, tetrahydrofuran, butane, 1,4-epoxy, polytetrahydrofuran, butane a, d-oxide
    BE2017 / 5157. The solvent medium can comprise one or more of polymers, celluloses or cellulose derivatives, aminosilanes or silanes.
    In some embodiments, the coating may also include other particles, such as, for example, microparticles. Such particles can be, for example, metal particles, such as metal particles.
    In one aspect, the disclosure provides a method of preparing a composition suitable for coating or other applications. Coating may advantageously provide a coating of a metal substrate or metal support. In one embodiment, the method comprises the steps of:
    - providing a mixture comprising: carbon in an aqueous medium comprising a surfactant or in a solvent medium comprising polymers, celluloses, amino silanes, silanes; and
    - obtaining the disaggregation and / or preventing aggregation of the carbon in the medium to produce a composition comprising a plurality of individually dispersed carbon particles of carbon nanotubes, fullerene, graphene, graphene oxide or mixtures thereof. The mass ratio of carbon to surfactant can have a lower limit of 10:90 or 20:80 or 30:70 or 40:60 and an upper limit of
    0 90:10 or 80:20 or 70:30 or 60:40. The mass ratio of carbon to surfactant can be 50:50 in one example.
    In various embodiments, where the carbon material is carbon nanotubes, which may be SWCNT, DWCNT, MWCNT or combinations thereof, disaggregation or prevention of aggregation is accomplished by ultrasonic treatment. Sonification can also be used for the other carbon-based particles that can be used in the composition of the present invention. Disaggregation or prevention of aggregation can be performed at any temperature at which the aqueous medium or solvent medium is in liquid form. For example, if ultrasonic treatment becomes
    BE2017 / 5157 can be performed at a temperature in a range from 0 ° C to 85 ° C. In one embodiment, the ultrasonic treatment can be performed at a temperature in a range from 7 ° C to 15 ° C. Ultrasonic treatment times may vary. Ultrasonic treatment can be performed in a time span ranging from a few minutes to several hours. For example, ultrasonic treatment can be performed for 1 hour, 2 hours, 3 hours, or until no significant increase in the nanotube dispersion is observed. Ultrasonic treatment can be performed in a single step or in multiple steps. For example, a two-stage ultrasonic treatment step can be performed: 3% amplitude for 30 min followed by 25% amplitude for 1 hour. This first, low-power ultrasonic treatment phase can replace traditional high shear mixing. A pulsed energy profile (10 s pulses with 2 s dead time) can be included for both phases to avoid heating. After ultrasonic treatment, the dispersions can be centrifuged to remove bundled nanotubes and metal particle impurities.
    In another embodiment, the method comprises preparing a solvent medium and / or aqueous medium by adding a surfactant to an aqueous liquid (such as water) or by adding polymers, celluloses, amino silanes or silanes to a solvent medium and then adding carbon, for example in the form of carbon nanotubes and graphene, to the solvent medium and / or the aqueous medium. It is clear that the various components of the present composition can be added in any order to obtain the same end result.
    By the method according to embodiments of the present disclosure, a composition can be obtained which comprises individually dispersed carbon nanotube particles and / or fullerene particles and / or graphene particles and / or graphene oxide particles and / or mixtures thereof. The individually dispersed
    BE2017 / 5157 nanotubes can be SWCNT, DWCNT, M WCNT or combinations thereof. Dispersion is a measure of the extent to which the nanotubes exist in individualized form.
    In one embodiment, the method further comprises the step of ultracentrifuging the sonicated mixture. It is believed that ultracentrifugation of the sonicated mixture can help to remove impurities such as catalyst particles (i.e., Fe impurities), amorphous carbon present in the initial raw carbon nanotube material, and also assist in removing bundled carbon nanotubes from the solution. Ultracentrifugation conditions can be chosen to obtain optimal results.
    While using the composition, the composition can be applied to the substrate in a liquid state, such as a paste, or as a dispersion. This can be done, for example, by injection, spraying, doctorblading, immersion, rolling and the like, or a combination of the methods mentioned. These techniques are known to anyone skilled in the art. The coating composition can further be applied to the entire surface of the substrate or only a portion thereof. For selective applications on only a few parts of the substrate, for example, methods are used which are conventionally used in printing technology such as, for example, rotogravure, screen printing or stamp printing. Furthermore, control can be performed accordingly via, for example, inkjet techniques to direct the spray flow only to a portion of the surface of the substrate during spray operation.
    A substrate such as, for example, a metal support in the context of embodiments of the present invention should preferably be interpreted as a metal wire, strip, flow tube or an electromechanical component which is preferably made of non-ferrous materials such as copper and / or copper alloys, aluminum and / or aluminum alloys, or
    BE2017 / 5157 ferrous materials such as iron and / or iron alloys. In preferred embodiments, the metal support is made from the group of oxygen-free copper and / or copper alloys or oxygen-free high-thermally conductive copper and / or copper alloys.
    In one embodiment, the presence of carbon-based particles, such as, for example, from SWCNT, MWCNT or graphene, can be detected after it has been deposited on a substrate by applying the composition. For example, NIR emission spectra of the substrate on which the composition was deposited can be obtained by standard methods. The spectra can be compared with a reference spectrum for comparison or tracking purposes.
    Aspects of the present disclosure facilitate counterfeit countermeasures allowing disclosure compositions to be printed on and / or impregnated in and / or coated on any item at any point in the manufacture or distribution of the item. Accordingly, the compositions can be detected on the article after production or distribution to verify a legitimate source of the article through detection of the near infrared signal from the composition, thereby authenticating the article. On the other hand, for any item expected to
    0 was printed and / or impregnated with a composition of the disclosure, absence of the near infrared signal from the composition indicating that the article is not authentic, such as in the case of a counterfeit article, or an article that was not properly distributed and / or imported.
    In another aspect, the present invention provides methods of applying a composition to a substrate such as, for example, a metal support or a semiconductor, the method comprising applying the substrate; applying the composition in a liquid state to at least a portion of the surface of the substrate; and optionally heating the composition in the liquid state to form a coating
    BE2017 / 5157 obtainable solid state on the substrate. The substrate to be coated can be applied to an automatic transport means, which may include rollers, and which can automatically pass the substrate through a coating and heating unit.
    This is schematically illustrated in Figures 1 (a) - (c). Figure 1 (a) illustrates one example of how a composition is applied to a substrate by spraying by means of a spray coating unit. Suitable spray coating units can include an inkjet printing process, for example, thermal inkjet printing, piezoelectric inkjet printing or continuous and drop-on-demand inkjet printing (continuous inkjet printing, DOD inkjet printing) and aerosol printers. In inkjet printing, drop formation is preferably obtained in a piezoelectrically driven print head. A more practical approach can be to use a conventional spray gun system. An HVLP or LVLP air gun spraying technique can be used, as can an airless spraying technique. Spraying can be done manually, with automated spraying systems or in spray booths. Figure 1 (b) illustrates dip coating as a means of applying the coating and finally Figure 1 (c) illustrates brushing as a means of applying the coating to the substrate.
    After the substrate is coated, the coating is in a liquid
    0 state, the coated substrate is optionally heated and cured by a heat treatment unit. It should be noted that although a heating step is initiated in the present examples, this heating step is optional. Also, according to embodiments of the present invention, the method can be performed without a heating step. When heating is used, heating of the coated substrate can be performed by hot air heating at temperatures between 30 ° C and 800 ° C, which is an average oxidation temperature of carbon materials characterized by a high degree of graphitization, preferably up to 600 ° C, which is the average oxidation temperature of carbon materials characterized by low
    BE2017 / 5157 degree of graphitisation.
    A pre-treatment step can be performed before applying a coating, for example by rinsing the substrate with an acid. Examples of acids that can be used can be non-oxidizing acids, such as acetic acid, citric acid, tartaric acid, hydrochloric acid and also dilute oxidizing acids. For example, if the substrate is a copper substrate, non-oxidizing acids react with the oxidized copper to leave pure copper only. Concentrated oxidizing acids dissolve copper, but properly diluted can be used to remove oxides alone. Pretreatment can also include the application of solvents such as acetone. When the copper is immersed in acetone, oxidized particles are stripped away from the material to leave only pure copper. Other types of materials can be used when other substrates are used.
    In embodiments of the present invention, a substrate can be at least partially or completely coated with a composition of the present invention. This can be in function of the desired heat dissipation property of the obtained coated substrate.
    A post-treatment step can also be performed on the coated substrate, where the coating is in a dried or solid state. A post-treatment step may comprise heating, for example, a flame treatment step at a temperature between 300 and 800 ° C, e.g., between 300 ° C and 800 ° C, depending on the materials used, for example, for 1 s to 100 s or more, e.g. between 1 s and 10 s. Advantageously, after heating the coated substrate, the substrate being copper and the carbon material comprising carbon nanotubes and graphene, an oxide layer is formed on the coating. In this way, the coated substrate is passivated by the oxide layer, which improves the corrosion properties of the substrate. In some embodiments, after heating the coated substrate, where the substrate is a metal support, the coating may be brushed off, resulting in a metal support
    BE2017 / 5157 with carbon in the form of carbon nanotubes diffused on or embedded in the metal support. The heat treatment can also be used to remove surfactant and other impurities from the substrate, such as, for example, removal of amorphous carbon, etc.
    In further embodiments, the post-treatment step may comprise a polishing step, so that when carbon nanotubes are used as the carbon material, the carbon nanotubes can be aligned, preferably perpendicular to the surface of the substrate, so that more heat dissipation is obtained in the aligned parts of the surface.
    In still further embodiments, the post-treatment can be a homogenization step, wherein the coating is homogenized after application by pressure and / or temperature. For example, a punch or a roller can put pressure on the coating. This results in improved homogenization of the coating on the substrate.
    EXAMPLE: dispersed carbon nanotubes and graphenes in an aqueous medium comprising a surfactant
    This example discloses a paint composition comprising distilled water as the solvent, surfactant as the dispersant and a nano-structured carbon material alone.
    Surfactants used included cationic (C16 ™ ABr), anionic (SDBS) and non-ionic (Pluronic F 127), Pluronic P123, CTAB (hexadecyl trimethyl ammonium bromide) and T80 (Tween 80). The best dispersion grades were obtained for Pluronic F 127. Optimal results were obtained for the following water / surfactant / carbon ratios: 100 / 1.6 / 1.6 by weight (e.g. 400 ml water, 6.4 g CNT and 6, 4 g Pluronic F127 surfactant). Preferably, the ratio of surfactant to carbon is 50:50, but a surfactant surplus is also accepted. A low surfactant concentration affects dispersibility and is preferably avoided. The
    BE2017 / 5157 carbon concentration in the water can be fine-tuned from 0 to 2%. Above 2%, the viscosity is generally high and paint production can be very time consuming. The paint can be thinned, but an optimal coating is usually obtained for carbon concentrations in the range of 0.8-1.8 g / 100 ml. In further preferred embodiments, the composition can be thickened by, for example, carboxymethyl cellulose (CMC).
    The paints are made with a 400 W sonic device / cell disruptor Branson 450 CE with 19 mm disruptor horn. The sonication operates at a fundamental frequency of 20 kHz, but other frequencies (> 20 kHz) can also be used. The sonication is preferably provided with a temperature probe for monitoring the temperature of the dispersion. When the temperature limit is reached, ultrasonic treatment is preferably stopped to prevent overheating. The batch temperature is preferably kept below 40-45 ° C to reduce evaporation. Due to the significant heat generation during ultrasonic treatment, it is recommended to keep the cup (or any other container used for this purpose) in an ice bath. In order to minimize heat build-up during ultrasonic treatment, it is preferable to use a pulsed mode instead of continuous mode. A suggested program would be the following: pulse on: 2 s, pulse off: 0.5 s, ultrasonic power 40% or more (for a 400 W system). Alternative pulse on: 3 s, pulse off: 1 s. We work with volumes no larger than 1000 ml, but for smaller or larger volumes the input power has to be decreased or increased respectively.
    In some experimental tests, paints with a higher carbon concentration were produced, the carbon being graphene. A dye with a carbon concentration of up to 10% by weight was produced. The dye has a better coating capacity than a dye characterized by a low graphene concentration.
    BE2017 / 5157
    Other examples showed that carbon coating can increase load capacity by about 30%. All carbon coatings lower the temperature of the substrate, in the present example, a flow tube, for the same flow, although short circuit tests provide superior performance of graphene and
    CNT / graphene (50/50) coatings. In some embodiments, compositions comprising mixed carbon-based particles, e.g., graphene together with other carbon-based particles, are an advantage.
    BE2017 / 5157
    权利要求:
    Claims (5)
    [1]
    1,4-epoxybutane, tetrahydrofuran, tetrahydrofuran, cyclotetramethylene oxide, tetrahydrofuran, Agrisynth THF, cyclotetramethylene, THF, tetrahydrofuran, butane, 1,4-epoxy, polytetrahydrofuran, butane a, d-oxide.
    Product comprising a substrate and at least a full or partial coating made from a composition according to any one of claims 1 to 16.
    The product of claim 17, wherein the substrate is made of a metal.
    The product of claim 18, wherein the substrate is made of copper or aluminum.
    The product of any one of claims 17 to 19, wherein the substrate is a flow tube.
    A product according to any one of claims 17 to 20, wherein the substrate is an electrical conductor or semiconductor.
    A product according to any one of claims 17 to 21, wherein the coating is applied directly to the substrate.
    The product of any one of claims 17 to 22, wherein the substrate is selected from the group consisting of non-ferrous metals and their alloys.
    A product according to any one of claims 17 to 23, wherein carbon is in the form of carbon nanotubes, alone or in a mixture, in the
    BE2017 / 5157 coating, and is aligned.
    A product according to any one of claims 17 to 24, wherein an additional layer is provided between the substrate and the coating.
    The product of claim 25, wherein the additional layer is a layer comprising or consisting of tin.
    27. Method for preparing a composition that can be used for coating or other applications, the method comprising the steps of:
    providing a mixture comprising: a carbon in the form of carbon nanotubes, fullerene, graphene, graphene oxide or mixtures thereof in a solvent medium comprising one or more of polymers, celluloses or cellulose derivatives, aminosilanes or silanes, or in an aqueous medium comprising a surfactant dust; and
    obtaining disaggregation of the carbon or preventing aggregation of the carbon in the medium to produce a composition comprising a plurality of individually dispersed carbon particles of carbon nanostructures, graphite, fullerene, graphene, graphene oxide, carbon black or mixtures thereof.
    The method of claim 27, wherein the mass ratio of carbon to surfactants is in the range from 30:70 to 60:40.
    The method of claim 28, wherein the mass ratio of carbon to surfactants is 50:50.
    A method according to any one of claims 27 to 29, wherein the disaggregation is obtained by ultrasonic treatment.
    The method of claim 30, wherein the ultrasonic treatment can be performed over a period of from a few minutes to several hours or until no significant increase in the nanotube dispersion is observed.
    BE2017 / 5157
    A method according to any one of claims 27 to 31, wherein ultrasonic treatment can be performed in a single step or in multiple steps.
    A method according to any one of claims 17 to 32, wherein disaggregation is performed at any temperature at which the aqueous medium exists in liquid form.
    A method for providing a composition according to any one of claims 1 to 16 on a substrate, the method comprising:
    - providing the substrate;
    - providing the composition in a liquid state on at least a portion of the substrate, resulting in a solid state coating on the substrate.
    The method of claim 34, wherein providing the composition also includes heating the composition in a liquid state, which results in a solid state coating on the substrate.
    The method of any of claims 34 or 35, wherein providing the substrate comprises providing a metal support or a semiconductor.
    A method according to any one of claims 34 to 36, further comprising a pretreatment step, wherein the substrate is chemically treated.
    A method according to claims 34 to 37, wherein the method further comprises a post-heating treatment.
    The method of claim 38, wherein the method comprises polishing the coated substrate so that the carbon in the composition is aligned in a direction along the substrate surface or perpendicular thereto.
    The method of claim 38, wherein the method comprises brushing the coating resulting in a metal support wherein the carbon material is diffused into the substrate.
    BE2017 / 5157
    The use of a composition according to any one of claims 1 to 16 for preventing corrosion of a substrate.
    The use of a composition according to any one of claims 1 to 16 for the dissipation and distribution of heat provided in a substrate.
    1. A composition that can be used for coating or other application, comprising carbon in the form of carbon nanostructures, graphite, fullerene, graphene, graphene oxide, carbon black or mixtures thereof in a solvent medium comprising one or more of polymers, celluloses or cellulose derivatives, aminosilanes, silanes or in an aqueous medium comprising one or more surfactants.
    [2]
    The composition of claim 1, wherein the mass ratio of carbon to surfactants is in the range from 30:70 to 60:40.
    [3]
    A composition according to any one of the preceding claims, wherein the concentration of the mass ratio of carbon to surfactants is 50:50.
    [4]
    The composition of any preceding claim, wherein the surfactant is anionic, cationic, nonionic, or a combination thereof.
    The composition of claim 4, wherein the surfactant is an alkyl sulfonate or alkaryl sulfonate.
    The composition of any one of the preceding claims, wherein carbon is in the form of carbon nanotubes and graphene, the concentration of the mass ratio of carbon nanotubes to graphene ranging from 30:70 to 70:30.
    The composition of claim 6, wherein carbon is in the form of carbon nanotubes and graphene, the concentration of the mass ratio of carbon to graphene being 50:50.
    The composition of any preceding claim, wherein carbon is in the form of carbon nanotubes, alone or in a mixture, and the concentration of the carbon nanotubes is 0.1 to 5% by weight.
    The composition of claim 8, wherein the concentration of the
    BE2017 / 5157 carbon nanotubes is 0.1 to 2% by weight.
    The composition of any preceding claim, wherein carbon is in the form of carbon nanotubes, alone or in a mixture, and the carbon nanotubes are single-walled carbon nanotubes, multi-walled nanotubes, or a combination thereof.
    The composition of claim 10, wherein the carbon nanotubes are functionalized carbon nanotubes.
    The composition of any one of claims 10 to 11, wherein the carbon nanotubes have an average outer diameter between 0.4 nm and 100 nm.
    The composition according to any one of claims 10 to 12, wherein the carbon nanotubes have a length between 1 nm and 50 cm.
    A composition according to any one of the preceding claims, further comprising one or more additives selected from the group consisting of acetates, alkoxylates, alkylolamides, esters, amine oxides, alkyl polyglucosides, alkyl phenols, arylalkyl phenols, water-soluble or water-soluble homopolymers, water soluble or water-insoluble random copolymers, water-soluble or water-soluble block copolymers, water-soluble or water-insoluble graft polymers, polyvinyl alcohols, polyvinyl acetates, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinylpyrrolidones, cellulose, starch derivative , amino acid polymers, polylysine, polyaspartic acid, stearic acid, maleic acid, calcium carbonate, polyacrylates, polyethylene sulfonates, polystyrene sulfonates, polymethacrylates, condensation products of aromatic sulfonic acids with formaldehyde, naphthalene sulfonates, lignosulfonates, copolymers of acrylic monomers ines, polyvinylamines, polyallylamines, poly (2-vinylpyridines), block copolyethers, block copolyethers with polystyrene blocks and / or polydiallyldimethyl ammonium chloride, amino silanes and / or silanes, silica, copper powder or copper nanopowder.
    BE2017 / 5157
    The composition of any preceding claim, wherein the cellulose derivative or polymer or a combination thereof is water resistant.
    A composition according to any one of the preceding claims, wherein the solvent is organic, glycololforal, ethylene glycol, methylene ether, formal ethylene glycol formal, formaldehyde ethylene acetal, 1,3-dioxolane, formalglycol, glycoformal, glycol methylene ether, methylene glycol methylene ether, dihydro-1,3 dioxol, dioxolane, dioxolanne, tetrahydrofuran, oxolane, dioxilane, butylene oxide, furanidine, hydrofuran, oxacyclopentane, tetramethylene oxide, tetraidrofurano,
    [5]
    43. The use of a composition according to any one of claims 1 to 16 for improving a flow capacity of a system.
    BE2017 / 5157
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    BE2017 / 5157
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    同族专利:
    公开号 | 公开日
    BE1024843A1|2018-07-16|
    GB201604341D0|2016-04-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20080292887A1|2006-09-22|2008-11-27|Hyonny Kim|Conductive Multiwalled Carbon Nanotube/Polyethylene Oxide Composite Films and Methods of Use|
    DE102008053027A1|2008-10-24|2010-04-29|Kme Germany Ag & Co. Kg|Method for producing a coating comprising carbon nanotubes, fullerenes and / or graphene|
    JP2012056788A|2010-09-08|2012-03-22|Toray Ind Inc|Carbon nanotube water dispersion|
    EP2675004A1|2011-02-10|2013-12-18|Showa Denko K.K.|Current collector|
    WO2015178801A1|2014-05-22|2015-11-26|Мсд Текнолоджис Частная Компания С Ограниченной Ответственностью|Metal foil with conductive layer and method for manufacturing same|
    EP3147919A1|2014-05-22|2017-03-29|MCD Technologies S.a.r.l|Metal foil with conductive layer and method for manufacturing same|
    CN105070888A|2015-07-09|2015-11-18|山东玉皇新能源科技有限公司|Coupled carbon nano tube-graphene composite three-dimensional network structure-coated ternary material and preparation method thereof|
    法律状态:
    2018-10-03| FG| Patent granted|Effective date: 20180724 |
    优先权:
    申请号 | 申请日 | 专利标题
    GB1604341.6|2016-03-14|
    GBGB1604341.6A|GB201604341D0|2016-03-14|2016-03-14|Composition|
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