Covetic material

Abstract

To provide a microwave plasma torch reactor for manufacturing a covetic material.SOLUTION: A reactor has an energy source configured to provide microwave energy to the reactor, a first inlet through which a hydrocarbon gas flows into the reactor, an inner tube disposed in fluid communication with the first inlet, the inner tube configured to dissociate the hydrocarbon gas into a plasma based on the microwave energy, the plasma comprising carbon and carbon radicals, an annular region surrounding the inner tube, a second inlet disposed downstream of the first inlet and coupled to the annular region, the second inlet configured to receive metal particles entrained in a carrier gas, a heat source disposed in thermal communication with the reactor, the heat source configured to melt the metal particles, and an outlet configured to produce a carbon-metal composite based on at least a portion of the melted metal particles and the plasma.SELECTED DRAWING: Figure 18B

Description

Technical Field

[0001] Related Applications This application is a continuation-in-part of U.S. Patent Application No. 16 / 460,177, filed on July 2, 2019, with the title "PLASMA SPRAY SYSTEMS AND METHODS", which claims the priority of U.S. Provisional Application No. 62 / 720,677, filed on August 21, 2018, with the title "PLASMA SPRAY SYSTEMS AND METHODS", and U.S. Provisional Application No. 62 / 714,030, filed on August 2, 2018, with the title "PLASMA SPRAY DEPOSITION", and this application claims the priority of U.S. Provisional Application No. 62 / 903,649, filed on September 20, 2019, and this application claims the priority of U.S. Provisional Application No. 62 / 868,493, filed on June 28, 2019, and this application claims the priority of U.S. Provisional Application No. 62 / 839,995, filed on April 29, 2019, and this application claims the priority of U.S. Provisional Application No. 62 / 797,306, filed on January 27, 2019. All of these applications are hereby incorporated by reference in their entirety.

[0002] This disclosure generally relates to the production and use of covetic materials.

Background Art

[0003] The term "covetic material" refers to a metal fused with carbon particles of nanoscale dimensions. Covetic materials are desirable in various applications because they have many physical, chemical, and electrical properties that exceed the capabilities of conventional non-carbon-fused materials. However, covetic materials obtained from conventional covetic material manufacturing techniques are unable to achieve many of the above physical, chemical, and electrical properties.

[0004] Even in the face of a strong desire for materials exhibiting the above physical, chemical, and electrical properties, the technological development for the fabrication and use of cobic materials has been hampered by numerous technical difficulties. Such technical difficulties arise from multiple areas and include, as difficulties: (1) the difficulty of combining the analytical methods necessary to measure the carbon content for individual compounds with high specificity and the methods for characterizing the microstructure or nanostructure, (2) the relatively high variability of the carbon content distribution seen in samples manufactured to date, (3) the variability and potential unpredictability in property measurements, and (4) the uncertainty regarding the scientific mechanisms that are precisely the cause of the strong bonding observed between carbon particles and the matrix surrounding the particles.

[0005] Conventional metal melting methods used in the production of cobic carbon metal composite alloys have suffered from inconsistent conversion yields, and the lack of consistency has contributed to the wide variety observed in the properties of the resulting materials. For example, due to irregularities in carbon dispersion in the melt, undesirable agglomeration and undesirable clustering often occur. Such irregularities in carbon dispersion in the metal can lead to the formation of cracks and pores, and these cracks and pores ultimately cause early defects in the resulting materials. Furthermore, due to the high solubility of carbon in the metal, non-uniform carbon growth (e.g., becoming thicker) may occur on the metal surface as the metal cools and solidifies. Also, the solubility of carbon may be higher near the free surface than in the bulk of the metal, and the higher solubility, when combined with the interfacial energy at the melt-air interface, favors undesirable precipitation at the melt-air interface.

[0006] The production of cobetic carbon-metal composite alloys by conventional heat-utilizing metal melting methods has not, at present, been able to easily adjust the process conditions such that the resulting cobetic material exhibits a set of desirable or targeted properties. The inability to control the process conditions such that the resulting cobetic material exhibits a set of adjusted properties leads to the inability (correspondingly) to apply the cobetic material to specific applications that require such a specific set of properties. What is needed is a technology for manufacturing cobetic material products that exhibit properties adjustable within a certain range. Moreover, what is needed is a cobetic material product that can be used in a wide range of end-use areas and applications (e.g., ranging from material strengthening to improving long-life performance, such as for use between enterprises or between corporate consumers).

SUMMARY OF THE INVENTION

[0007] This summary is provided to introduce selected concepts in a simplified form and is further explained in the following detailed description. This summary is not intended to identify key features or essential features of the claimed invention nor is it intended to limit the scope of the claimed invention. Moreover, the systems, methods, and devices of the present disclosure each have a plurality of innovative aspects, and no single one of them alone bears the desirable attributes disclosed herein.

[0008] Various embodiments of the subject matter of the invention disclosed herein generally relate to apparatuses, methods, and various compositions of carbon-metal composite materials. Apparatuses related to the controlled utilization of a plasma spraying torch apparatus for generating various carbon-metal bond compositions are presented and considered. This carbon-metal bond composition is generally referred to in this disclosure and as the "cobetic material".

[0009] One configuration of a plasma spray torch is embodied as an apparatus comprising a reaction chamber configured to receive a hydrocarbon process gas that is mixed with a plurality of molten metal nanoparticles, a microwave energy source operably coupled to the reaction chamber to provide power to the reaction chamber, and a controller that adjusts the microwave energy source to create in the reaction chamber conditions such that the hydrocarbon process gas dissociates into its constituent carbon atoms and single layer graphene (SLG) or few layer graphene (FLG) grows from the carbon atoms on the molten metal nanoparticles to form a plurality of carbon-metal nanoparticles. In some configurations, the conditions in the reaction chamber result in: (i) a first temperature at which carbon atoms dissolve into the molten metal nanoparticles, and (ii) a second temperature at which at least some of the dissolved carbon atoms bond with the molten metal in a crystallographic arrangement. Depending on the configuration of the apparatus, a cooling zone is utilized to cool the plurality of carbon-metal nanoparticles into a powder, and the powdered particles are collected and stored in a storage container juxtaposed near the reaction chamber.

[0010] Details of one or more embodiments of the subject matter of the invention described in this disclosure are set forth in the following accompanying drawings and description. Other features, aspects, and advantages will be apparent from the description, drawings, and claims. Note that the relative dimensions in the following drawings may not be drawn to scale.

[0011] Embodiments of the subject matter of the invention disclosed in this specification are illustrated by way of example and are not intended to be limited by the figures of the accompanying drawings. Throughout the drawings and the specification, like numerals refer to like elements. Note that the relative dimensions in the following drawings may not be drawn to scale. A copy of this patent or patent application publication with color drawings can be obtained from the United States Patent and Trademark Office by request and payment of the necessary fee.

Brief Description of the Drawings

[0012]

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DETAILED DESCRIPTION OF THE INVENTION

[0013] Aspects of the present disclosure relate to an approach for manufacturing cobeitic materials using a thermal spraying technique, rather than by mixing carbonaceous materials into the bulk of a molten metal slurry. Some embodiments relate to techniques for reducing the dimensions of the inter-lattice carbon structure to the nanometer (nm) scale. The accompanying drawings and the discussion herein provide exemplary environments, exemplary systems, and exemplary methods for manufacturing “cobeitic” materials, by way of which it is implicitly shown that, as generally understood and as defined herein, high concentrations (>6 wt%) of carbon are included and incorporated into a metal (or metal-containing material) in a manner such that carbon does not segregate during melting or magnetron sputtering. The resulting materials have numerous unique and improved properties over the base metals from which the materials are derived. Carbon is dispersed in the metal matrix in multiple ways that contribute to the improvement of the material properties. Carbon binds very strongly to the cobeitic material and often withstands many standard methods of detecting and characterizing its shape. By including carbon on the nanoscale, the melting point and surface tension increase. Cobeitic bodies have higher hot working strength and cold working strength.

[0014] Identification and Significance of Problems and Opportunities A metal matrix composite can be composed of a matrix of (at least) a metal or metal alloy (especially a metal made by combining two or more metal elements to enhance strength or corrosion resistance), combined with a more highly elastic ceramic, a carbon-based reinforcing agent, or a micro filler in the form of continuous or discontinuous fibers, whiskers, or particles. The size of the reinforcing agent is important as micron-sized reinforcing metals can exhibit improved strength and stiffness up to an acceptable level over the base alloy. Nevertheless, such reinforcing agents can also be associated with undesirable poor ductility as well as undesirable low yield strength, machinability, and fracture toughness at the load limit due to unwanted agglomeration between particles during processing. To avoid early cracking and other drawbacks of metal matrix composites containing incompatible micron-sized reinforcing agents, it may be essential to reduce the size of the reinforcing phase to the nanometer scale. Furthermore, a method is needed such that the reinforcing phase is incorporated into the metal alloy matrix.

[0015] A significant increase in mechanical, thermal, electrical, and tribological properties (referring to the science and engineering of interacting surfaces in relative motion) has been observed corresponding to the addition of the above carbon-based reinforcing agents. Of note is that as the size of the reinforcing agent decreases from the micron scale to the nano scale (e.g., <100 nm), such properties may change and / or improve due to an increase in the cohesive force between the matrix and the particles. The improvement in properties may be due to the formation of a strong interface that promotes an efficient strengthening mechanism. Improvements in tensile strength and yield strength have been reported in the comparison of nano-sized particles (about 20 nm) and micron-sized particles (about 3.5 μm). However, when making the order of magnitude the same, the added volume of nano-sized particles is smaller compared to micron-sized particles. Therefore, past techniques may not be able to provide reinforcement at the nanometer scale. Thus, there is a current need to reduce the carbon structure containing interlattice vacancies to the nanometer scale.

[0016] Microwave (MW) plasma torch reactor Using a microwave (MW) plasma torch reactor, pristine 3D few-layer graphene (FLG) particles can be continuously nucleated, for example, in-flight, in an atmospheric pressure vapor stream of carbon-containing species such as methane gas, in which case such nucleation occurs from initially synthesized carbonaceous or carbon-containing "seed" particles. When densely highly structured adjustable 3D mesoporous carbonaceous particles composed of multiple layers of FLG (e.g., 5-15 layers) grow from carbon-containing species, simultaneous incorporation of a metal element or metal-based alloy also occurs, forming a carbon-metal composite in which the carbon and metal are at least partially covalently bonded (and at least partially, metallically or ionically bonded). This carbon-metal composite is also referred to herein as a "cobetic" particle structure. In some embodiments, "pristine" graphene (indicating graphene with few or no defects) is provided to or generated in the described MW torch reactor, which is either not oxidized or contains only a very small amount of oxygen (e.g., <1%). In some embodiments, the metals are fixed to each other by metallic bonds (in the resulting cobetic material), and the carbon is fixed to each other by (primarily) covalent bonds (extensively in graphene or some other organized carbonaceous 2D or 3D structure, e.g., a matrix or lattice). The composite carbon-metal structure may include covalent bonds between carbon atoms and metal atoms that occur at the metal-carbon interface.

[0017] The microwave plasma-assisted reactor process of the present disclosure provides a reaction and processing environment in which gas-solid reactions can be controlled under non-equilibrium conditions (non-equilibrium conditions refer to a physical system that is not in thermodynamic equilibrium but can be described in terms of variables that represent the extrapolation of the variables used to define a system in thermodynamic equilibrium. Non-equilibrium thermodynamics relates to transport processes and chemical reaction rates, and the initial melting of metal powders can be controlled independently by ionization potential and momentum in addition to thermal energy). After in-situ (indicating in the reactor or reaction chamber itself) nucleation, solid, substantially solid, or semi-solid carbon-based particles can emerge from the plasma torch and deposit on a temperature-controlled substrate (such as a drum) in a layer-by-layer addition manner. The emerging particles can be sprayed onto a specific substrate and bonded onto or into the substrate. In some cases, instead of using a substrate, the emerging semi-solid particles are assembled to form one or more self-supporting, self-standing structures with an organized orientation. Unlike standard plasma torches, which have limitations in terms of operating flow, power, and configuration, the microwave plasma torch of the present disclosure is equipped with control mechanisms (such as flow control, power control, temperature control, etc.) to independently control one or more constituent material temperatures and gas-solid reaction chemistry to create a unique, highly dense, highly organized covalently bonded carbon-metal structure with advantageous and surprisingly high levels of uniformity.

[0018] The cobetic materials produced by the techniques using the MW reactor of the present disclosure provide various competitive advantages that cannot be obtained in current materials or products outside the present disclosure. One such advantage relates to the unique, physically and chemically stable, inherent extensibility and versatility of being able to incorporate general-purpose metal-carbon composites, where the general-purpose metal-carbon composites incorporated exhibit predictable deformations (showing stress, strain, elasticity, or certain other identifiable physical characteristics) in various configurations and / or structures, and the configurations and / or structures include, for example, but are not limited to: (1) high-density thin-film implants, (2) coatings, (3) thick strip materials, and (4) powder particles that can undergo subsequent remelting and casting and / or are used to form industrial metal alloy components. Any of the above carbon-based metal composite implants, and / or coatings, and / or strip materials, and / or powder particles produced by the high-density thin-film MW reactor exhibit improved physical, chemical, and electrical properties when compared to existing base metal alloy formulations.

[0019] Summary The disclosure herein describes the integration of low-loading nanofiller carbon-based materials, such as graphene, with metals. Graphene is known for its unique structural features, for example, having a high aspect ratio and a "2D" planar structure. Graphene has surprisingly suitable mechanical, physical, thermal, and electrical properties due to its in-plane sp 2 C=C bonds (which result in a 2D planar shape). Thus, graphene is thought to function as an ideal reinforcing agent for metal matrix composites when compared to alternatives such as microfiller polyacrylonitrile (PAN)-based carbon fibers. Even when the graphene nanoplatelet content (addition amount) is low, an anisotropic (indicating that an object or material has physical properties that show different values when measured in different directions) 3D network is formed, resulting in significantly improved thermal and electrical conductivity as well as mechanical properties.

[0020] When using carbon nano-fillers in metal matrix composites, problems are encountered in that dispersion is difficult due to poor wetting (the ability of a liquid to maintain contact with a solid surface, which occurs from intermolecular interactions when the two come into contact, and the degree of wetting is referred to as wettability, which is determined by the balance of forces between adhesion and cohesion). The increase in surface area brought about by the nano-fillers causes the particles to agglomerate and cluster, and also causes twisting due to the van der Waals forces between carbon atoms. Agglomerates and clustering of nano-fillers in metal matrix composites can lead to the formation of undesirable cracks and pores, which can ultimately compromise the structural integrity of the resulting material and lead to premature failures under high loads or high usage conditions.

[0021] Although a number of processing approaches, such as conventional powder metallurgy, hot rolling, casting, and additive manufacturing, have been used (and may still be used) in the production of metal matrix composites, there are still problems associated with the uniform dispersion of nano-fillers. Damage to the nano-fillers due to the stresses applied during consolidation, as well as unwanted or uncontrollable chemical reactions with the matrix at high temperatures during sintering and casting, are some examples of the problems faced during attempts to achieve dispersion of the nano-fillers.

[0022] The defect-free basal plane of graphene exhibits unusually favorable chemical stability compared to the sides and edges of the graphene sheet. The sides and edges interact more readily with the metal than the basal plane, and as a result, there is a possibility of forming carbides (which is thermodynamically favorable according to Gibbs free energy). However, during processing, defects are easily formed on the basal plane, which can lead to carbide formation and adverse effects on the composite properties. Therefore, relatively severe processing conditions, such as high temperature and high pressure, can have an adverse effect on the quality of the interface between the carbon nano-fillers and the metal-based matrix surrounding them. Specifically, high temperature and high pressure can have an adverse effect on wettability and structural integrity, and can have an undesirable effect on carbide formation, and can also cause other harmful interfacial reactions.

[0023] By using an alternative process, referred to as the cobetic process (as introduced earlier), we have successfully incorporated carbon nanofillers into a metal matrix. In the cobetic-related process, it has been shown that by applying an electric field, a network of graphene "ribbons" and nanoparticles is formed within the liquid metal, and this network exhibits exceptional stability within the metal matrix even after remelting. Correspondingly, the composite structure conducts heat and electricity more efficiently than the base metal.

[0024] Uniform dispersion One of the problems in incorporating graphene into a metal matrix was achieving uniform dispersion. Thus, cobetic processing overcomes this problem through the accompanying exfoliation and wetting of graphene ribbons and / or particles (either from the carbon electrode or from the breakdown of carbonaceous adducts) within the applied electric field. Impurities such as oxygen and hydrogen can be managed through redox reactions on the particle surface, and assuming an appropriate surface induced voltage, it is possible to promote wetting / dispersion. The problem is one of controlling the structural integrity and uniformity of the graphene ribbons and / or particles (such as uniformity regarding dimensions, defects, etc.), as well as controlling the chemical reactivity with the metal at high temperatures, and controlling the distribution of particles within the bulk and at the melt surface.

[0025] Further complexity The basic mode of energy conduction (in both heat and electricity) in metals may be (at least in part) carried out by electrons, and although the crystallinity of fillers such as graphene and the degree of impurities control and improve the thermal conductivity of the metal matrix composite (when conduction is through phonons in graphene), there must be some way of connection (registry) and / or interference with the metal lattice (additionally or alternatively referred to as a scaffold, matrix, or structure), for example, integrally bonded nanoscale carbon, or a minimum platelet spacing that limits conduction between platelets (e.g., proximity or network). (For example, graphene would need to be a single layer or just a few layers and tens of nanometers in length). However, with respect to strengthening the metal matrix, graphene may need to chemically bond (or in some cases, also physically bond) with the matrix for proper load transfer. (Note that for maximum load transfer, the length of graphene can also exceed about 0.5 μm). Solid solution strengthening relies on adhesion and / or semi-adhesive elastic strain between the carbon (graphene) nanofiller and the metal lattice. Separately, discrete graphene nanoparticles can act as barriers to dislocation pile-up or pinning at grain boundaries (such as Hall-Petch grain refinement, which represents a method of strengthening materials by changing the average crystallite (grain) size. This method is also based on the finding that grain boundaries are boundaries that dislocations cannot cross, and the number of dislocations within a grain affects how stress builds up in adjacent grains, which ultimately activates dislocation sources and thus allows dislocations in adjacent grains. Therefore, by changing the grain size, it is possible to affect the number of dislocation deposits at grain boundaries and bring about strength), and both of these improve mechanical properties.

[0026] Once again, in addition to alignment along slip planes within the metallic structure, due to its 2D nature and large surface area, graphene can be oriented along regions at grain boundaries. Regardless of whether the property of interest is chemical, mechanical, thermal, or electrical, the more significant the alignment of the nanofiller and its registry (at the atomic level) with the surrounding metallic matrix crystal structure, the greater the stability and improvement of the properties of the metallic matrix composite structure.

[0027] Fundamentally, whether carbon grows (heterogeneously) on the metal surface or precipitates from the melt (homogeneously) depends on the solubility of carbon in the metal (as shown in the binary phase diagram on the right side of Figure 10). The solubility of carbon in pure transition metals (and generally many pure metals) is very low, for example, near the melting point of the metal, but increases as the temperature rises well above the melting point of the metal (e.g., above 2,000 °C). The solubility of carbon in nickel, for example, is around 2.5% near the hypereutectic point, which is one of the higher solubilities of carbon in pure metals. Additionally, adding interstitial impurities such as oxygen, boron, or nitrogen, or substitutional atoms to the metal can potentially affect (e.g., increase) the solubility of carbon. It has been shown that the higher the solubility of carbon in the metal or the higher the temperature of the molten metal, the thicker the carbon precipitate on the metal surface when the metal is cooled and solidified. An important point to note is that the solubility of carbon is higher closer to the free surface, which, combined with the interfacial energy of the liquid-air interface, favors the precipitation of solid carbon at the metal melt-air interface. The equipment and operating techniques for solving the problems associated with this phenomenon will be addressed in connection with the drawings and corresponding descriptions.

[0028] Definitions and Use of Drawings To make it easier to refer to, some of the terms used in this description are defined below. The presented terms and their individual definitions are not strictly limited to those definitions. A term may be further defined by the way it is used within this disclosure. The term "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" should not necessarily be construed as preferred or advantageous over other aspects or designs. Rather, the use of the term exemplary is intended to present concepts in a concrete manner. As used in this application and the appended claims, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless otherwise specified or clear from the context, "X uses A or B" is intended to mean any of the natural inclusive variations. That is, "X uses A or B" is satisfied in any of the above examples if X uses A, X uses B, or X uses both A and B. As used herein, at least one of A or B means at least one of A, or at least one of B, or at least one of both A and B. In other words, this phrase is disjunctive. The articles "a" and "an", as used in this application and the appended claims, should generally be construed to mean "one or more" unless otherwise specified or clearly intended to refer to the singular form from the context.

[0029] Various embodiments are described herein with reference to the drawings. The drawings are not necessarily to scale, and components of similar structure or similar function may sometimes be represented by like reference characters throughout the drawings. Also, the drawings are only intended to facilitate the description of the disclosed embodiments. The disclosed embodiments do not cover all possible embodiments and are not intended to ascribe any limitation with respect to the claims. Also, the illustrated embodiments do not necessarily depict all aspects or advantages of use in any particular environment.

[0030] Aspects or advantages described in conjunction with a particular embodiment are not necessarily limited to that embodiment and may be practicable in any other embodiment even if not so described. References throughout this specification to "some embodiments" or "other embodiments" indicate that a particular feature, structure, or characteristic described in connection with the embodiments is included in at least one embodiment. That is, the appearances of the phrases "in some embodiments" or "in other embodiments" in various places throughout this application do not necessarily refer to the same embodiment(s). The disclosed embodiments are not intended to limit the scope of the claims.

[0031] Description of Embodiment Examples FIG. 1A is a comparative view 1A00 showing two different cobetic material forming techniques 102 and respective exemplary materials obtained by utilizing each of them.

[0032] In the case of the conventional metal melting method 103 for generating cobeitic materials, solid carbon is added to the molten metal. This conventional metal melting technique is controlled by the kinetics of carbide formation under an applied electric current and interdiffusion across the solid-liquid (e.g., carbon-metal) interface, and the applied electric current provides additional energy to eliminate the stacking defect energy between carbon atoms and metal atoms. Therefore, the conventional metal melting technique for forming cobeitic processing is not significantly different from other composite processing methods such as powder metallurgy and / or hot rolling. Such composite processing involves consolidating second-phase particles into a metal matrix. Such conventional composite processing methods face many problems related to dispersion and / or distribution, reactivity, and variability of material properties. Moreover, conventional cobeitic processing relies on batch processing, often resulting in inconsistent conversion rates and a wide variability in the resulting properties.

[0033] As depicted in the agglomerate image 105, when the conventional metal melting method 103 is used, the resulting material is plagued by the problem of extreme carbon agglomeration, which results in (1) a limited role of carbon in reinforcing the lattice and (2) a limited ability to adjust the surface morphology for surface functionalization. In comparison, when the technique of the present disclosure is used, the resulting material exhibits substantially uniform homogeneity (e.g., no agglomerates), which results from the uniform dispersion of carbon in the lattice. This is shown in the homogeneous image 106.

[0034] Cobeitic materials such as those depicted in the homogeneous image 106 can be characterized by many desirable material properties 108, such as uniformity, a high carbon addition, and a low carbon content on the surface. Such properties are highly desirable and not exhibited by materials formed using the conventional metal melting method 103. Therefore, what is being pursued is an improved approach that overcomes the drawbacks of the conventional metal melting method 103.

[0035] One such improved approach includes the plasma spraying torch method 104. By utilizing the plasma spraying torch method, a consistent yield of cobic material is achieved, thereby overcoming the yield drawbacks of conventional metal melting methods. Moreover, the utilization of the plasma spraying torch method results in a cobic material that retains the improved mechanical properties, improved thermal properties, and improved electrical properties described above, thereby overcoming the drawbacks of materials obtained by conventional metal melting methods.

[0036] Improved approach As shown in the figure, the plasma spraying torch method 104 can be configured to use the input materials as introduced (indicating the provision of a gaseous carbon-containing raw material species such as methane and the addition of energy to the raw material species by applying MW energy towards methane gas, etc.). However, at high temperatures, the dissociation of carbon-containing gases (such as methane or other hydrocarbon sources) can cause carbon, and more specifically, self-limiting monolayers of pristine graphene, to grow on or within the metal (e.g., copper, gold, zinc, tin, and lead) lattice. The number of monolayers depends, at least in part, on the solubility of carbon in the metal. The growth kinetics, bonding, and final structure of the graphene film on the metal substrate depend on the valence electrons and symmetry (closest-packed plane) of the metal. Similarly, the metal can preferentially nucleate and grow at the defect sites of carbon or, alternatively, at the oxygen-terminated or hydrogen-terminated sites when growing on carbon. Subsequently, an alternating stack of monolayers of carbon and metal is formed, realizing the improved properties of the graphene-reinforced metal composite structure.

[0037] By using a microwave plasma reactor, the nucleation and growth of pristine 3D few-layer graphene particles can be continuously carried out from a hydrocarbon gas source. Also, by adding selected elements to the plasma gas stream, they can be incorporated into the 3D graphene particle scaffolds. The microwave plasma reactor process provides a unique reaction environment in which the gas-solid reaction can be controlled under non-equilibrium conditions (e.g., the ionization potential and momentum can be combined with thermal energy to independently control chemical reactions by them). Reactants can be introduced into the plasma reactor zone as solids, liquids, or gases to independently control the nucleation and growth dynamics of unique non-equilibrium structures (e.g., graphene on metal and metal on graphene).

[0038] For example, to fabricate an integrated graphene-metal composite on a nanometer scale, fine nanometer-scale metal particles can be introduced into a microwave plasma torch together with a hydrocarbon gas such as methane. Methane dissociates into hydrogen and carbon (e.g., using a microwave plasma with ideal energy to form C and C2), and then these can nucleate and grow regular graphene on the semi-molten surface of the metal particles. The non-equilibrium energy state can be created by adjusting the process conditions to independently control the metal temperature with respect to the reactivity and delivery of carbon to the metal surface. Ionized hydrogen (or other ions) in a controlled low-energy state can be used to act on / sputter the growing graphene surface and the metal surface without damaging the structure of the graphene-metal composition. This then promotes further growth of alternating graphene-metal layers. Also, depending on the residence time and energy within the plasma reaction zone, a metal-graphene structure with specific properties can be fabricated, and these specific properties are retained even when the metal-graphene structure is rapidly cooled when sprayed onto a substrate at a controlled temperature. The formation of the metal-graphene structure with controlled energy within the plasma and with the substrate temperature controlled results in independent control of the energy state throughout the entire progression of such cobaltic materials.

[0039] Graphene can be applied (and / or deposited) onto the metal or metal-containing layer of a material by "sputtering" (which refers to the phenomenon where microscopic particles of the material are ejected from its surface after the solid material itself is impacted by energy particles of plasma or gas. The fact that sputtering can be made to act on an extremely thin layer of the material is frequently utilized in science and industry, where sputtering is used to perform precise etching, execute analytical techniques, and deposit thin film layers in the manufacture of optical coatings, semiconductor devices, and nanotechnology products, etc.). When such sputtering is used with the MW plasma reactor of the present disclosure, the sputtering can be controlled by controlling the residence time and energy within the plasma reaction zone, as described, to promote the growth of alternating graphene metal layers. Such alternating graphene metal layers are organized at the coherent plane of atoms in a regular (e.g., crystallographic) arrangement. This crystallographic arrangement is maintained even when the graphene is rapidly quenched (in the field of materials science, quenching, or rapid / quick quenching, refers to rapidly cooling a workpiece while controlling it in water, oil, or air to obtain certain material properties. Quenching, a type of heat treatment, prevents or controls the occurrence of unwanted low-temperature processes, such as phase transformation, by narrowing the time frame in which unwanted reactions are thermodynamically favored and kinetically reachable. For example, quenching can reduce the grain size of both metal materials and plastic materials and increase their hardness). Rapid quenching, as described, functions to essentially "freeze" graphene (not in the conventional definition of a simple phase change from liquid to solid, but rather indicating that it is substantially maintained as a solid) with respect to the metal in the desired crystallographic arrangement formed within the plasma reactor. The homogeneity within and on the resulting material is extremely uniform. This extremely uniform homogeneity can be used to distinguish the material formed using the metal melting method 104. This is because the metal melting method 104 cannot control the ion energy independently of the thermal energy.More specifically, since the metal melting method 104 cannot increase the ion energy as desired independently of the thermal energy, the temperature of the metal melting reaction chamber may become too high for the graphene metal layer, and it may not be possible to organize the graphene metal layer on the coherent plane of atoms in the desired crystallographic arrangement.

[0040] Therefore, when using the metal melting method 104, the desired crystallographic arrangement of the graphene metal will never occur, and thus, even when the graphene metal layer is quenched on a lower temperature substrate, the desired crystallographic arrangement cannot be retained. Instead, when using the metal melting method 104, undesired carbon precipitation occurs (e.g., carbon precipitates from the melt), which then leads to undesired agglomerates, which in turn introduce non-uniformity into the product. This non-uniformity in the product can prevent the chemical and / or physical (mechanical) characteristics of the resulting material from reaching the ideal, and can lead to, for example, but not limited to, early mechanical failures.

[0041] Figure 1B presents a high-resolution transmission electron microscope image 114 and a high-resolution energy-dispersive X-ray analysis image 116. The homogeneous image 106 of Figure 1A is also shown here for convenience.

[0042] As depicted in this exemplary set of images, carbon is uniformly distributed throughout the metal lattice. This is emphasized in the high-resolution transmission electron microscope image 114. Moreover, the extremely high carbon addition in the metal lattice is clearly shown in the high-resolution energy-dispersive X-ray analysis image 116. In this example, the carbon addition accounts for approximately 60% of the entire copper-carbon lattice. This is shown in the high-resolution energy-dispersive X-ray analysis image 116. In this particular image, the dark regions are carbon, and the bright regions (appearing as dots) are copper.

[0043] As can be seen from the image, and in particular, as can be seen from the pattern of the high-resolution energy-dispersive X-ray analysis target 116, carbon and the base metal (e.g., copper in this case) are uniformly dispersed. This uniform dispersion at the lattice level exists on the surface as shown in the figure, and moreover, this uniform dispersion at the lattice level also exists deep within the base metal. Further images of the cobic material are shown in FIGS. 20A1, 20A2, and 20B, which are after consideration of (1) the material progress process, (2) the plasma spraying torch device, and (3) various configurations of the plasma spraying torch.

[0044] In one usage scenario, the cobic material of FIG. 1B can be manufactured using an adjustable microwave plasma torch that produces an integrated graphene-metal composite film at high speed and in large quantities. One specific manufacturing process in which graphene grows on small molten metal particles will be briefly described herein.

[0045] FIG. 2 depicts a manufacturing process 200 for growing graphene on small molten particles. Optionally, the manufacturing process 200 or one or more variants of any aspect thereof are practicable in the context of the constructs or functionality of the embodiments described herein. The manufacturing process 200 or any aspect thereof is practicable in any environment.

[0046] One possible approach is to use a “non-equilibrium energy” microwave plasma torch to non-equilibrium control the temperature of the metal independently of carbon formation. This plasma torch energy is then directed towards the surface of the molten and / or semi-molten metal particles. This technique allows for the time for growth to occur in the melt. Growth in the melt (or semi-molten or core-shell material) generated within the torch will flow out onto the metal surface through the main plasma plume and grow there, and then be rapidly quenched. This technique provides a means for growing thick coatings, which can be laminated to grow into a homogeneous thick ingot and / or grow on or in component parts that are later machined or remelted and utilized.

[0047] Also, FIG. 2 is presented to illustrate the effect of independently controlling the constituent material temperature and the gas-solid reaction chemistry when growing graphene on small molten particles. FIG. 2 shows the progress through multiple processes of coetic material manufacture and presents the process used in the formation of coetic materials utilizing a plasma torch.

[0048] As shown in the figure, the semi-solid particles emerging from the plasma torch can be deposited on a temperature-controlled substrate in a layer-by-layer addition manner. Unlike a standard plasma torch, where the control is limited to power and other arrangements and the operable flow is restricted, the microwave plasma torch being considered here can be operated to independently control the constituent material temperature as well as the gas-solid reaction chemistry.

[0049] As can be seen from the above disclosure, a microwave plasma source can result in the following (by way of example): (1) a higher plasma density, (2) an ion energy with a narrower ion energy distribution, and (3) improved coating properties. This is at least partially due to the improved power coupling and (electromagnetic energy) absorption at 2.45 GHz. Depending on the pressure, a typical electron temperature is on the order of 1 eV to 15 eV, >10 11 cm -3results in a plasma density. Such a low electron temperature is not only advantageous for controlling plasma chemical reactions, but also for ion energy with respect to the limitation of ion energy, combined with the ion energy for argon-based coaxial microwave plasma. The ion energy for argon-based coaxial microwave plasma is typically in the range of 5 eV to 80 eV. As a result of the narrow plasma sheath formed using such a high-density plasma, the collisional broadening of the ion energy distribution is blocked, and as a result, the ion energy distribution becomes sharp, which aids in the precise control of certain film deposition processes. Also, by applying pulsed power to the microwave plasma, non-equilibrium energy can be formed and controlled. During the application of microwave energy, the power is delivered to the entire volume where the plasma is expected to be formed, and thus, the energy is accumulated in a stepwise collisional energy type.

[0050] The above consideration in FIG. 2 includes techniques for applying microwave energy power, which will be disclosed in more detail below.

[0051] FIG. 3 shows a plasma energy state diagram 300 showing how a pulsed microwave energy source is used to grow graphene on small molten particles.

[0052] The microwave plasma source holds the potential to achieve higher plasma density, ion energy with a narrower ion energy distribution, and improved coating characteristics as a result of improved power coupling and absorption at 2.45 GHz. Depending on the pressure, the typical electron temperature is on the order of 1 eV to 15 eV, >10 11 cm -3This results in a plasma density. Such a low electron temperature is not only advantageous for controlling plasma chemical reactions but also for ion energy in the case of argon-based coaxial microwave plasmas, with respect to the limitation of ion energy. The ion energy for argon-based coaxial microwave plasmas is typically in the range of 5 eV to 80 eV. As a result of the narrow plasma sheath formed using such high-density plasmas, the collisional broadening of the ion energy distribution is inhibited. Consequently, the ion energy distribution becomes sharp, and this narrow ion energy distribution is necessary for the precise control of some film deposition processes. Also, by using pulsed power for the power delivered to the microwave reactor, the plasma non-equilibrium energy can be formed and controlled. During the application of microwave energy, the power is delivered throughout the volume where the plasma is intended to be formed. Thus, the energy is accumulated in a stepwise collisional energy type.

[0053] When the initial plasma is formed in most of the volume, the energy is maximized at the delivery antenna and continues to increase in a very localized manner. The nearby plasma density decreases slightly until the plasma contracts. Further details regarding the general approach for fabricating and using a pulsed microwave energy source are described in U.S. Patent Publication No. 10,332,726, issued June 25, 2019, which is hereby incorporated by reference in its entirety.

[0054] Figure 3 shows that the initial energy of the plasma is very high in a non-equilibrium state until it significantly decreases to a stable temperature. More specifically, the plasma energy state diagram depicts the transition from an initial high-energy non-equilibrium state to a lower-energy stable equilibrium state. When the initial plasma is formed, the energy is maximized at the delivery antenna and continues to increase in a very localized manner until the plasma contracts and is lost in the rest of the chamber due to energy shielding.

[0055] The pulsed microwave energy source can be controlled to optimize the electron temperature for growing graphene on small molten particles. This is particularly effective when the pressure is >> 20 Torr. The chamber environment must be controlled to ensure that the chemical dissociation by the plasma is homogeneous and that the coating of the material is also homogeneous.

[0056] As shown in FIG. 3, the energy profile shows that the initial energy is high, then it drops to a lower level and remains at that level until the power is removed. After the plasma extinguishes and then restarts, it follows this energy cycle again. By shortening the time between the initial plasma ignition and the point where the plasma stabilizes, the plasma can mainly stay in the bulk of the system and cause more homogeneous dissociation of the material in the bulk of the system. Shortening the time between the initial plasma ignition and the point where the plasma stabilizes can be achieved by controlling the pulse frequency and duty cycle.

[0057] One technique for controlling the electron temperature in a pulsed microwave reactor is presented and described in relation to FIG. 4.

[0058] FIG. 4 depicts an electron temperature control technique 400 used for growing graphene on small molten particles. Optionally, the electron temperature control technique 400 or one or more variants of any aspect thereof are practicable in the context of the constructs or functionality of the embodiments described herein. The electron temperature control technique 400 or any aspect thereof is practicable in any environment.

[0059] FIG. 4 illustrates aspects related to growing multiple layers of graphene on molten nano-scale dimension particles rather than mixing carbon into the bulk of the molten slurry. Specifically, this figure is presented in relation to the contribution of this technique to the control of plasma temperature through the control of microwave pulse frequency.

[0060] Control of Plasma Temperature via Pulse Frequency Control As depicted in FIG. 3 above, the energy profile shows that the initial energy is high and then suppressed to a lower level and remains at that level until power is removed. The plasma extinguishes and, after restarting, follows this energy cycle again. By shortening the time between initial plasma ignition and stabilization, the plasma can mainly stay in the bulk of the system and cause more homogeneous dissociation of materials in the bulk of the system.

[0061] As shown in FIG. 4, this effect substantially depends on the timing of the on / off cycle of the microwave energy source. By controlling the pulse frequency, optimal chemical dissociation and uniform coating can be achieved. Moreover, by setting the pulse frequency, the average temperature of the plasma can also be controlled accordingly.

[0062] Plasma Temperature Control in a Microwave Plasma Torch The integrated microwave plasma torch considered in this specification is used to handle the formation of an integrated, second-phase carbon-metal composite structure with improved mechanical, thermal, and electronic properties compared to existing metal alloys and conventional composite processing methods. Moreover, by using the microwave plasma torch, carbon-metal composite coatings and particles can be formed directly on high-value asset components. Furthermore, the above methods and equipment meet many clean energy goals regarding power distribution improvement, efficient transformation, and heat exchanger performance.

[0063] Practical Applications of Microwave Plasma Torches Using integrated microwave plasma torch technology, materials can be deposited and / or formed rapidly and economically (e.g., with high cost efficiency) and applied in a wide variety of configurations. Beneficiaries of this technology include various energy production industries, particularly those related to power transmission and storage, the transportation industry, the military equipment industry, and many other manufacturing industries. As one specific example of practical application, the metal surface of an airplane can be treated by plasma spraying to produce a cobetic material on the metal-air interface. This makes the metal surface less prone to corrosion. Also, carbon atoms near the surface enable other materials to chemically bond with the carbon atoms and / or adhere to the surface. The other materials capable of chemically bonding with the carbon atoms may be selected based on the requirements arising in various practical applications.

[0064] As another specific example of practical application, the metal surface of a flying vehicle (e.g., an airplane, helicopter, drone, projectile, missile, etc.) can be treated by plasma spraying to produce a cobetic material coating that acts as an infrared obscurant (e.g., as a means of countering detection).

[0065] FIG. 5 illustrates a dual plasma torch apparatus 500 used for growing graphene on small molten particles. Optionally, the dual plasma torch apparatus 500 or one or more variants of any aspect thereof are practicable in the context of the structures or functionality of the embodiments described herein. The dual plasma torch apparatus 500 or any aspect thereof is practicable in any environment.

[0066] As the equipment setup shown, the following are used: (1) a metal plasma spraying torch for spraying molten metal onto the surface of a heated substrate (Al, Cu, Ag, etc.), and (2) a microwave plasma torch for delivering ionized carbon and plasma radicals to the molten surface so as to cause the growth of a cobetic body on the molten metal.

[0067] Insert the system into an inert gas environment or an atmosphere-controlled chamber to provide better control of the oxidation of the material. In one embodiment, the torch settings and operations of Figure 5 are as shown in Table 1, the details of which will be discussed below. [Table 1]

[0068] Step D1: Identification and selection of reactant materials Any number of metals can be simultaneously plasma sprayed together with metastable carbon species to form a nanocarbon-metal composite structure. When forming 2D graphene at a concentration exceeding the thermodynamic solubility limit, different metals with high electrical and thermal conductivities can be used. In some cases, two different metals with different carbon solubility limits and / or different melting points and / or different densities and / or different crystal structures are selected.

[0069] Step D2: Selection, modification, and verification of a microwave plasma torch and a "standard" plasma spraying torch The apparatus of Figure 5 can be substantially composed of an "off-the-shelf" standard plasma spraying torch and a microwave plasma torch (in certain embodiments). By having two torches, two different processing steps are made possible, namely: (1) initial melting of the metal, and (2) nucleation / growth of graphene platelets from a hydrocarbon source. The two torches can each be controlled independently of each other.

[0070] As shown in Fig. 5, the two torches are arranged for simultaneous or sequential operation. Specifically, microwave plasma with a low electron temperature and a high electron density can be used to optimize graphene formation (including the nucleation rate at the carbon supersaturation limit), while using a standard plasma spraying torch can heat metal powders / particles to a molten or semi-molten state and then accelerate the particles towards the substrate (together with the nucleated ionized carbon / graphene). The two independent flows can be coordinated to achieve fine-scale graphene growth on the semi-molten particle surface. In some cases, the dual torch configuration includes means for maintaining an inert atmosphere (e.g., cover gas) at or near the exit flow of the torch and in or around the collision region of the substrate surface. This is because contaminants from the surrounding air (e.g., oxygen, nitrogen, and moisture) can affect the bond between carbon atoms and metal atoms. Thus, in certain embodiments, the dual torch system is configured to be inserted into a fully controlled inert gas environment (e.g., a chamber) to provide effective control of material oxidation.

[0071] Process D3: Theoretical Basis and Definition of Plasma Processing Parameters Reactants (e.g., hydrocarbons) and inert gases and flows are selected to ensure plasma stability and to ensure control of the nucleation and growth processes within the plasma (e.g., the supersaturation limit and flow rate of a given gas mixture). The acceleration and temperature of metastable carbon are controlled during the movement from the plasma to the substrate. Accordingly, the process conditions of the standard plasma spraying torch are set to produce a densified thin film on which carbon can collide and react. The surface temperature and local gas phase environment are controlled to promote the interaction and growth of the metastable carbon phase.

[0072] Process D4: Operation of the Dual (Metal and Microwave) Plasma Torch The various parameters of the process frames of both the metal and the microwave plasma torch are configured to be controlled independently or, in some embodiments, in conjunction with each other. Before, during, or after the operation of one or more of the metal and the microwave plasma torch (referred to herein as the "dual plasma torch"), the process frame of integrated carbon metal formation is characterized. Moreover, one or more parameters or combinations of parameters are selected, the deposition of carbon metal is observed, and the as-deposited sample can be characterized for various differences using any technique known in the art, such differences including, but not limited to: morphology (e.g., using a scanning electron microscope (SEM)), structure (e.g., by X-ray diffraction (XRD) and by Raman spectroscopy), and / or physical and chemical composition.

[0073] FIG. 6 illustrates an adjustable pulsed microwave plasma spraying torch apparatus 600 for growing graphene on small molten particles. By way of example, one or more variants of the pulsed microwave plasma spraying torch apparatus 600 (or any aspect thereof) are practicable in the context of the constructs or functionality of the embodiments described herein. The pulsed microwave plasma spraying torch apparatus 600 (or any aspect thereof) is practicable in any environment.

[0074] In this configuration, transverse electric (TE) microwave power means are coupled on (or in some embodiments, may substantially penetrate through) a central dielectric tube to propagate microwave energy therein over the entire length of the central dielectric tube. The gas supplied to the central region (in this example) can be a hydrocarbon gas such as methane that absorbs microwave radiation. Metal powder is supplied (carried by a substantially inert carrier gas) and heated within the body (or main chamber) of the pulsed microwave plasma spraying torch apparatus 600 by a combination of plasma-derived energy and the supplied thermal energy. Upon exposure to such energy, the metal powder reaches its melting point and melts to form a viscous, flowing liquid material, or droplets (which may contain semi-solid material), or any other possible dispersion (highly dependent on the attendant melting conditions).

[0075] As the hydrocarbon gas decomposes into its constituent species, carbon radicals nucleate on the exposed surface of the molten metal droplets. A combination of microwave energy regulation settings and thermal plume temperature settings allows for different temperatures in the central region of the pulsed microwave plasma spraying torch apparatus 600 between the melting temperature and the plasma decomposition / ionization temperature. The non-equilibrium state (indicating temperature, heat, etc.) within the central chamber or region of the plasma spraying torch apparatus allows (or at least facilitates) the graphene / carbon to take a place within the lattice (indicating that the synthesized lattice structure of the carbon material can be positioned such that individual carbon atoms and metal atoms (if any) can be at least partially aligned), while rapid quenching creates a state that promotes the growth of the cobic material. Figures 8A - 8B, 12, 26C, and 26D present a diagram showing an internal lattice in which the carbon lattice and the metal lattice are oriented such that the carbon atoms and the metal atoms are at least partially aligned, and this is also presented in the corresponding text description below.

[0076] The single integrated microwave plasma torch of FIG. 6 can be set up and operated as depicted in Table 2 below. Its details are described below.

Table 2

[0077] Process S1: Deploy a single integrated microwave plasma torch Figure 6 depicts a single integrated microwave plasma torch. The torch has the ability to process solid, liquid, and vapor reactant feedstock species using, for example, a small amount of inert gas or differential exhaust vacuum for control of the gas flow. The torch can be deployed in any environment (such as a laboratory, research facility, or large industrial company).

[0078] Process S2: Operate a single integrated microwave plasma torch to form a graphene-added metal composite (「cobetic」) alloy Microwave energy is delivered in a coaxial waveguide configuration with a central focused gas supply system for efficient microwave energy absorption. Using a microwave energy source, the metal is heated to a semi-molten state. As CH4 (or other hydrocarbon source) is decomposed (into its constituent species) within the exhaust plume directed into the surface wave plasma gas dissociation tube, carbon radicals can nucleate (e.g., in an organized layer-by-layer fashion) on the surface of the metal droplets via excitation by the plasma radicals (which are directed towards the metal droplets). By adjusting the microwave thermal plume temperature and the energy of the plasma, independent control of the temperature between melting and plasma dissociation / ionization occurring within the central region of the pulsed microwave plasma spraying torch device 600 can be achieved

[0079] Measure and optimize the process conditions. The desired process conditions are controlled by or for the integrated microwave plasma torch, thereby forming a graphene-added metal composite material directly within a single or multi-stage plasma reaction torch. By modulating the plasma torch within different regions of the surface wave plasma, the resonance (modulation) time can be improved and the formation of the desired metal-carbon structure can be optimized

[0080] In addition to the process gas ports shown at the locations described (e.g., for introducing hydrocarbon process gas 605), additional ports 604 can be provided at different locations. Such additional ports can be used to control how process gas is introduced into the microwave field and to introduce other process gases. By way of example, the process gas can be SiH4 or NH3. In some embodiments, there may be multiple inlets for gases or multiple inlets for particles (e.g., one for carbon and one for metal), and the locations of the inlets can be positioned in different zones of the plasma torch.

[0081] By optimizing the above settings and conditions, as well as other conditions, a state is brought about in which the impact particles can be consolidated into a film on the substrate surface. The as-deposited film is analyzed and characterized according to the method outlined in the following step S3.

[0082] Step S3: Verify / characterize graphene (secondary phase) metal particles Characterization of the as-deposited integrated carbon-metal composite structure is achieved using multiple techniques. For example, X-ray photoelectron spectroscopy (XPS) and / or SEM-EDS can be used to identify chemical composition, binding energy (nanoscale carbon detection), and distribution. Similarly, energy-dispersive X-ray spectroscopy (EDS) and / or SEM, and / or Raman spectroscopy, and / or XRD can be used to identify morphology and / or measure particle size and structural aspects. The electrical and thermal properties of the composite material, as well as the tensile strength and elasticity, can be evaluated using any known technique.

[0083] Results The above technique continuously manufactures a metal matrix composite using a microwave plasma torch. This process involves nucleation and growth zone formation of materials within the plasma, followed by an acceleration and collision zone for consolidating the materials on a substrate. Each zone provides unique control over the synthesis / blending and integration of different materials. So-called selective and unique formation of alloy particles within the plasma, and then the particles enable a unique additional process for controlling consolidation parameters such as porosity, defect density, residual stress, chemical and thermal gradients, phase transformation, and anisotropy, etc., through control of the momentum (mainly velocity) and thermal energy during their collision with the substrate.

[0084] For use spanning a wide range of growth dynamics within the plasma operating environment, various materials are selected. Specifically, different hydrocarbon gas sources containing a specific ratio of carbon to oxygen and hydrogen, as well as solid metal (or metal alloy) particle sources with different carbon solubility, melting points, and crystal structures, can be processed through a pulsed energy plasma torch processing system. Therefore, specific plasma processing parameters can be identified in relation to the accompanying initial surface melting of the particles, nucleation / growth, and incorporation of 2D graphene, and the metal re-sputtered on the metal surface.

[0085] When graphene is incorporated from a microwave plasma torch into a metal, the as-deposited material / coating is characterized with respect to "cobetic-like" properties. By way of example, such cobetic-like properties can be characterized with respect to (for example): (1) chemical composition (e.g., for impurity detection or carbon morphology detection), (2) carbon distribution (e.g., interstices, which indicates that the position of carbon atoms or carbon species is within the metal matrix or lattice, either intragranularly or intergranularly), (3) electrical conductivity, and (4) mechanical strength of the material. Characterization may involve a comparison between the graphene-added and the non-alloy base metal. Further, and by way of strict example, using a microwave plasma torch, the as-deposited material may exhibit a carbon-to-metal ratio over a range of about 3% to 90% (including these values). Depending on the situation, the carbon-to-metal ratio may range over about 10% to about 40% (including these values). Depending on the situation, the carbon-to-metal ratio may range over about 40% to about 80% (including these values). Depending on the situation, the carbon-to-metal ratio may range over about 80% to about 90% (including these values). Depending on the situation, the carbon-to-metal ratio is greater than 90% (including this value). The carbon-to-metal ratio may be affected (or further affected) by parameters or specifications (e.g., temperature, thickness, homogeneity, etc.) that define the coating process.

[0086] Figure 7 is a diagram 700 depicting a coating process. This figure shows a metal substrate that is subjected to plasma torch spraying of a cobetic material, resulting in the synthesis of a composite carbon coating. The metal substrate may include any one or more of copper, aluminum, or other bulk metal materials. The cobetic material may include one or more of carbon, graphene, nanoanions, carbon nanotubes (CNTs), carbide-injected materials, etc.

[0087] Plasma torch spraying serves to coat the feedstock with the deposited material and can be operated using pulsed energy. As shown in the figure, the deposited material (e.g., by layer-by-layer sputtering) can be any one or more of carbon, metal (e.g., Al, Cu, Ti, Ta, etc.), and / or oxide or nitride.

[0088] Multiple advantages arise from using the above torch. Among them, there are the advantages of scalability and versatility of the process of incorporating unique stable metal-carbon composites into various structures / buildings. Such structures / buildings range from sufficiently dense thin film coatings to thick strip materials or particles that are then remelted and cast / molded into processed metal alloy components. Each of the chemical species across the above range exhibits unexpectedly favorable (and desirable) improved mechanical, thermal, and electrical properties when compared with existing base metal alloy formulations. Also, the adjustability of the concentration and distribution of covalently bonded 2D graphene in the metal alloy matrix beyond the thermodynamic solubility limit, as well as the formation of laminates in a non-equilibrium environment, enable a new class of composite materials that can be processed to meet specific applications and / or specific property requirements. Moreover, this can be done at significantly reduced manufacturing costs compared to other techniques.

[0089] The improved mechanical, thermal, and electrical properties can be applied to most applications using copper and aluminum alloys. Examples of such applications include (but are not limited to): wire and high-voltage power transmission cables, microelectronics temperature management and heat exchangers, and numerous applications using thin film conductors, such as batteries, fuel cells, and photovoltaics. Specifically, the combination of the microwave plasma torch process and the feasible carbon-metal alloy manufacturing will significantly reduce the energy during manufacturing and bring about an increase in thermal efficiency and a decrease in electrical losses in the end-use performance.

[0090] The above plasma spraying technique only describes a part of the manufacturing methods of cermet materials. Another part includes spraying carbon particles onto small particles of molten metal. Such parts and various chemical species included in such parts are shown and discussed with respect to FIGS. 8A-8B, FIGS. 9, 10, 11, 12, 13, and 14, as well as in the description of the drawings herein.

[0091] FIGS. 8A-8B are schematic diagrams depicting a plasma spraying process 800 used to spray carbon particles onto small molten particles. Optionally, one or more variants of the plasma spraying process 800 (or any aspect thereof) are practicable in the context of the implementation constructs or functionality described herein. The plasma spraying process 800 or any aspect thereof is practicable in any environment.

[0092] The plasma spraying technique in the figures is used in various coating processes for spraying heated materials onto surfaces. The raw materials (e.g., coating precursors) are heated by electrical means (e.g., plasma or arc) and / or chemical means (e.g., combustion flame). By using such a plasma spraying technique, coatings having a thickness in the range of about 20 μm to about 3 mm can be provided depending on the process and the raw materials. The coatings can be applied over a wide range at a high deposition rate. Using the above technique, the deposition rate is much faster than the rates achievable by conventional coating processes such as electroplating or physical and chemical vapor deposition.

[0093] In addition to (or instead of) the above-exemplified materials, types of coating materials available for plasma spraying include metals, alloys, ceramics, plastics, and composites. Such materials are supplied to the spray torch in powder form or wire form, then heated to a molten or semi-molten state, and then accelerated towards the substrate in the form of micrometer-sized particles. Combustion or an electric arc discharge can be utilized as the energy source for plasma spraying. The resulting coating is built up by the accumulation of multiple layers of sprayed particles. In many applications, the surface of the substrate is not heated so much, and thus the coating of many materials, including the most flammable substances, is facilitated.

[0094] Figure 9 is a scanning electron microscope image 900 showing the effect of spraying carbon particles (e.g., those with a particle size of 20 nm to 40 microns) onto small molten metal particles. The carbon particles sprayed onto the small molten metal particles can be used in various specialized applications. For example, a plasma aluminum-graphite composite may be specifically designed to provide a coating for turbine engines. As an alternative, the use of aluminum and titanium alloys can be mentioned. The growth rate of this plasma-sprayed coating material is parabolic. The plasma-sprayed coating material is deposited in a short time, and this deposition is almost independent of temperature. For the preparation of the material surface, a certain specific process includes preheating the material. In some embodiments, grit blasting is also performed for the preparation of the material surface. In some embodiments, some of the particles sprayed onto the surface form cobetic bonds on the surface of the substrate while still being hot enough. In other cases, the small molten particles are at a temperature at which metal-metal bonds are formed.

[0095] The use of the microwave plasma torch technique of the present disclosure enables the production of materials that are improved compared to the use of conventional torches. Specifically, the power control limitations and other configurational constraints inherent in conventional plasma torches limit the ability of conventional plasma torches to independently control feedstock and other conditions, an ability that is necessary to produce carbon that is effective in the production of cobetic materials exhibiting significantly high quality and homogeneity.

[0096] FIG. 10 shows a graph depicting the graphene growth temperature profile 1000 and a binary phase diagram. Optionally, the graphene growth temperature profile 1000 or one or more variant forms of any aspect thereof are practicable in the context of the constructs or functionality of the embodiments described herein. The graphene growth temperature profile 1000 or any aspect thereof is practicable in any environment. The figure also shows a binary phase diagram, in which the X-axis represents the carbon concentration in the selected metal (e.g., copper as shown in the figure) in atomic percent. The temperature of the temperature profile in the figure is also shown in the phase diagram. Various metals can be used (e.g., silver, tin, etc.). In some cases, an alloy is formed.

[0097] The concept behind the growth of single-layer graphene (SLG) or few-layer graphene (FLG) on molten metal is to dissolve carbon atoms in a transition metal melt at a certain temperature and then precipitate the molten carbon at a lower temperature (indicating the creation of a solid from a solution).

[0098] The schematic depicts graphene growth from molten nickel, for example, by: (1) melting the nickel while contacting it with graphite (as a carbon source), (2) dissolving carbon in the melt at a high temperature, and (3) lowering the temperature to grow graphene.

[0099] As shown in the figure, by maintaining the melt in contact with the carbon source at a predetermined temperature, dissolution of carbon atoms into the melt and saturation of carbon atoms in the melt occur based on the metal-carbon binary phase transition. When the temperature is decreased, the solubility of carbon in the molten metal decreases, and an excess amount of carbon precipitates at the top of the melt.

[0100] Figure 11 is a cross-sectional view of a (conventional) plasma torch apparatus 1100. This figure is presented to distinguish the use of past plasma torch apparatuses as a comparison to the use of the microwave plasma torch of the present disclosure. Specifically, while the use of past plasma torch apparatuses can produce diamond or diamond-like materials on a metal surface, this process requires a significant amount of time to dissolve and diffuse the carbon material such that the final material deposits on the metal surface. While manufacturing the metal-carbon composite material as disclosed herein using embodiments of the present disclosure, it is desirable for graphene to grow and be fixed interstitially between (or within the lattice or matrix sites of) the layers of the metal or metal-containing composite material. However, to do so, the temperature must be adjusted rapidly. Unfortunately, past plasma torches do not provide the substantial control of temperature and other conditions (as desirable in relation to the achievement of the cobetic materials as desired herein) required to reduce the dimensions of the interstitial carbon structure to the nanometer scale.

[0101] In contrast, the pulsed microwave reactor (as related to embodiments of the present disclosure as introduced above) and the corresponding process are shown and described in FIG. 12 to provide sufficient detail regarding the control of temperature and other conditions required to reduce the dimensions of the interstitial carbon structure to the nanometer scale.

[0102] FIG. 12 depicts a pulsed microwave process flow 1200 used when "growing" graphene, where "growing" means depositing or applying graphene layer by layer in an orderly manner on a substantially flat exposed surface of molten metal particles. Optionally, the pulsed microwave process flow 1200 or one or more variants of any aspect thereof are practicable in the context of the structures or functionality of the embodiments described herein. The pulsed microwave process flow 1200 or any aspect thereof is practicable in any environment.

[0103] When using the pulsed microwave process flow 1200 shown, graphene grows on small molten particles. This is achieved by the interaction that occurs around the inlet 1204 in the pulsed microwave reactor (e.g., where the metal powder and carrier gas enter the reactor chamber). In addition to the inlet 1204, process gas ports 1202 and additional ports (e.g., additional port 12031 and additional port 12032) are provided at different heights on the side of the reactor device. The waveguide traverses at least the distance from the location of the process gas port 1202 on the side of the reactor to the location of the inlet 1204 on the side of the reactor. Details of how to create and use the ports for introducing and continuously supplying materials into such a reactor for growing graphene on small molten particles are further disclosed below. More specifically, certain components of the reactor of FIG. 12 are shown and described in connection with FIG. 13.

[0104] FIG. 13 is a perspective view of a conventional pulsed microwave plasma spraying waveguide device 1300 used for growing graphene on small molten particles. Optionally, the pulsed microwave plasma spraying waveguide device 1300 or one or more variants of any aspect thereof are practicable in the context of the structures or functionality of the embodiments described herein. The pulsed microwave plasma spraying waveguide device 1300 or any aspect thereof is practicable in any environment.

[0105] In this embodiment, the microwave delivery component and the pulsed power supply are integrated to form a "surfaguide" (or similar) gas reactor. As shown in the figure, the combination of these components is configured to promote the growth of graphene on small molten particles using a microwave plasma torch.

[0106] An alternative approach is to perform micro-welding using a tungsten inert gas (TIG) plasma source to partially or completely melt the metal. Such micro-welding techniques are shown and described in connection with FIG. 14.

[0107] FIG. 14 is a schematic diagram of a micro-welding technique 1400 used to grow graphene on small molten particles. Optionally, the micro-welding technique 1400 or one or more variants of any aspect thereof are practicable in the context of the structures or functionality of the embodiments described herein. The micro-welding technique 1400 or any aspect thereof is practicable in any environment.

[0108] All types of metal particles can be heated by effectively using a low-power, low-flow TIG welder power supply and a control device with a custom plasma storage unit. As shown in the figure, the exhaust plume, when introduced into the surface wave plasma gas dissociation tube, maintains the temperature at a level sufficient for graphene growth. This growth mode, including the control of plasma radicals composed of hydrocarbons and other additive gases formed under non-equilibrium conditions, offers numerous adjustment opportunities available with microwave plasma spraying devices of various configurations. FIGS. 15, 18A, 18B, 18C, and 18D, as well as other drawings and corresponding descriptions, disclose exemplary configurations of plasma spraying devices.

[0109] FIG. 15 is a schematic view of a plasma spraying apparatus of a coaxial configuration 1500. Optionally, one or more variants of the coaxial configuration 1500 or any aspect thereof are practicable in the context of the structures or functionality of the embodiments described herein. The coaxial configuration 1500 or any aspect thereof is practicable in any environment.

[0110] In an embodiment of the coaxial mode, microwave energy delivery is achieved via a TEM wave supplied to an antenna, the outer portion of the coaxial member of the antenna being a quartz tube, outside of which powdered metal particles flow. The gas supplied to the central region in this example is a hydrocarbon gas such as methane, and the gas absorbs microwave radiation. The powder is heated by the microwave energy leaking from the central region and by external inductive heating, and this heating causes melting of the metal powder (particle shape) near the inclined portion or the top of the reaction chamber shown. As CH4 decomposes (into its constituent species, carbon, hydrogen, and / or their derivatives), carbon radicals nucleate on the surface of the molten metal droplets via the energy of the plasma radicals. By adjusting the microwave duty cycle, as well as the inductive heating, and the plasma characteristics, the maintenance of the temperature difference between the melting and the plasma decomposition / ionization regions is facilitated. Moreover, the non-equilibrium temperature enables (facilitates) the in-lattice placement of graphene / carbon, and rapid quenching creates conditions that promote further growth of the cobetic material.

[0111] FIG. 16 is a schematic view of a plasma spraying apparatus 1600 showing the progression of a material by processing through a series of non-equilibrium energy states. Optionally, one or more variants of the plasma spraying apparatus 1600 (or any aspect thereof) are practicable in the context of the structures or functionality of the embodiments described herein. The plasma spraying apparatus 1600 or any aspect thereof is practicable in any environment.

[0112] This figure depicts the progression as the material passes through the apparatus. Specifically, this figure depicts regions where different changes in progression occur, such that in the region near the tip, graphene grows on small particles of molten metal. This material is deposited on a substrate.

[0113] Figure 17 depicts a surface wave plasma system 1700 for growing graphene on molten particles. Optionally, the surface wave plasma system 1700 or one or more variants of any aspect thereof are practicable in the context of the constructs or functionality of the embodiments described herein. The surface wave plasma system 1700 or any aspect thereof is practicable in any environment.

[0114] In the configuration shown, the feed gas is supplied to the central region of the apparatus. In this example, a hydrocarbon gas such as methane is used. The hydrocarbon gas absorbs microwave radiation, which provides a heat source for heating the metal powder. Thus, the metal powder is heated from both: (1) the microwave energy leaking from the central region, and (2) external inductive heating to melt it into a molten liquid near the tip. As the hydrocarbon gas decomposes, carbon radicals nucleate on the surface of the molten metal droplets via the energy of the plasma radicals.

[0115] Figure 18A1 depicts the axial electric field configuration 1810 of a plasma spraying torch. Regarding the formation of cobeitic materials, multiple different apparatuses and corresponding processes have been studied. Any of the above apparatuses and corresponding processes can be adjusted to achieve specific conditions for the formation of cobeitic materials. In the specific axial electric field configuration of the figure, the process includes forming an electric field 1804 between electrodes to create a current passing through the molten liquid of the metal material and the carbon material. Specifically, as shown in the figure, a specially configured plasma torch has an externally controlled electric field, where the molten particles form a plasma, and then this plasma becomes a meta electrode. The electrode on the opposite side of the electric field is formed by the shown growth plate 1803. The cobeitic material is accelerated through the acceleration zone 1821 and then deposited on the surface. The generated alloy and cobeitic materials continue to be deposited on the growth plate and / or on the previously deposited materials in the collision zone 1823. This deposition technique results in a material with homogeneous and high-concentration carbon addition.

[0116] The input materials can be selected and modified to achieve materials with specific properties. For example, as shown in the figure, the inputs to the plasma spraying torch can include various input gases 1812 as well as input metal and / or carbon particles 1818. The above inputs can be introduced into one or more input ports 1862. In some cases, the input metal and / or carbon particles are mixed into the flow of the input gas 1812. Moreover, the growth plate can be modified in terms of its own dimensions and composition during the progress of deposition. For example, as shown in the figure, the growth plate 1803 can initially be a substrate 1816, and the hot cobeitic material of the torch flow is deposited on its top, and this hot cobeitic material at least partially melts the substrate as it deposits. The deposited hot cobeitic material is cooled from the molten or partially molten state to form a quenched layer 1824.

[0117] In this manner, any number of layers can be formed. The temperature of the substrate and / or the top layer or near it can be controlled such that when the next layer of material lands on the molten metal of the immediately preceding deposited layer, the newly deposited layer grows laterally to produce monolayer graphene on the surface of this molten metal. This mechanism, in contrast to the conventional molten metal method 103 where carbon precipitates from the molten metal slurry, the application of the plasma spraying torch method 104 of the present disclosure results in a quench in a short time such that there is not enough carbon precipitating from the matrix, at least in that regard, distinguishing it from other techniques. For this reason, the covalent bond is maintained throughout the layer. Immediately after a solid consisting of metal and sufficiently dispersed carbon is formed by quenching, another layer is sprayed on top of that solid, thereby forming a stacked monolayer graphene, which grows, is fixed, and is rapidly quenched to produce a true covalent material with an extremely high carbon content in the matrix. As an example, when using the conventional molten metal method 103 (see Figure 1A), the carbon addition is thought to potentially reach 6% carbon metal. In contrast, when using the plasma spraying torch method 104 (see Figure 1A), a carbon addition of 60% is easily achieved. In some cases, strict control of the input and the process parameters of the plasma spraying torch and its environment enables the carbon addition to approach as much as 90% carbon in the resulting material.

[0118] Experimental results using a plasma spraying torch showed that covalent layers with high addition amounts and high uniformity can be formed by at least two types of rapid quench (e.g., "splat") methods. The first method is to cover metal particles with carbon particles (e.g., in plasma) and spray the resulting hot mixture onto a substrate that is significantly cooler than it. The second method is to generate graphene in plasma and then cover the graphene with molten metal. In both cases, a true covalent bond (indicating a combination of a covalent bond and a metal chemical bond) occurs while in the plasma plume, and the rapid quench of the sprayed material serves to fix the mixture in the organometallic lattice.

[0119] The depth or thickness of the quenched layer can be increased or decreased by controlling the distance between the plasma flame 1814 and the substrate, and / or by controlling the temperature of the substrate (e.g., making it either higher or lower than ambient), and / or by controlling the pressure in and around the reactor.

[0120] Figure 18B depicts the radial electric field configuration 1820 of the plasma spraying torch. In this configuration, the molten particles form a plasma within the torch, and this plasma serves as the meta - electrode. The other electrode is formed by the side portion of the inner wall.

[0121] The configurations of FIGS. 18A and 18B above are merely examples. Different configurations, including different input materials and different input port configurations, are possible without departing from the concept of the plasma spraying torch disclosed herein. Moreover, different configurations, including different input materials and different input port configurations, can achieve the same intended result. For example, two different configurations adjusted to obtain the same material product are shown and described in connection with FIGS. 18C and 18D. Specifically, the exemplary configurations of FIGS. 18C and 18D can be used to plasma spray a ceramic coating material onto carbon - containing particles (e.g., graphene - containing particles).

[0122] In fact, thin film deposition of carbon-containing materials (e.g., via atmospheric pressure chemical vapor deposition (APECVD) and / or other variants of chemical vapor deposition (CVD)) has been utilized in many fields of materials processing. Various composites and coatings containing such carbon-containing materials may exhibit improvements in physical properties (e.g., strength, corrosion impermeability, etc.). The various 2D and 3D morphological features of carbon, thanks to the molecular-level constitution within the carbon-containing materials, enable such improvements in physical properties to be demonstrated in the composites and coatings. In some cases, the use of 2D and 3D carbon in composites and coatings leads to a significant increase in the high-temperature impermeability of the resulting carbon-containing materials. However, in some cases, such high temperatures exceed about 2100 °C, and such temperatures are high enough for the 2D and 3D carbon themselves to burn. Unfortunately, when the 2D and 3D carbon is destroyed, the benefits originally obtained by the carbon in the composite or coating are then destroyed. Therefore, deposition techniques (e.g., plasma spray torch configurations) need to create composites or coatings that are not affected by temperature, even at temperatures higher than the combustion temperature of carbon.

[0123] FIG. 18C depicts such a configuration, which is strictly only a non-limiting illustration. By adjusting the input and various reactor conditions, the graphene-containing material can be coated with a heat-absorbing layer of organically modified silicon (ORMOSIL). Depositing the ORMOSIL ceramic material on the graphene-containing material can be achieved by a plurality of methods, such methods including those through an atmospheric pressure reactive plasma-assisted chemical vapor deposition process using a silicon-containing precursor 1841 (e.g., hexamethyldisiloxane) and a reactive gas such as oxygen. This specific mixture of the silicon-containing precursor and oxygen becomes reactive in the plasma. The molecular dissociation occurring in the plasma flame leads to the deposition of silicon oxide on surfaces such as the growth plate 1803 described above. To achieve this, as carbon-containing particles are formed in the reactor, the reactor conditions are controlled such that an organically modified silicon ceramic is deposited on their surfaces. The control of in-reactor growth and in-reactor deposition (e.g., by controlling the APECVD process) results in a thin quartz coating around the carbon-containing particles, which then deposit on the substrate. The thin quartz coating acts as a flame-retardant layer to protect the carbon-containing particles from combustion at high temperatures.

[0124] FIG. 18D depicts an alternative configuration, which is strictly only a non-limiting illustration. As shown in the figure, a metal and / or carbon-containing material is introduced into the reactor. The microwave energy 1822 is controlled to at least achieve the temperature at which the carbon-containing material dissociates (e.g., T(c-dissolution) in FIG. 10). A silicon-containing precursor 1841 (e.g., HMDSO, HMDSN, etc.) is introduced into the plasma flame, and the temperature decreases in the plasma afterglow. As the temperature decreases, carbon particles begin to form and are coated with silicon oxide. Then, the carbon particles coated with silicon oxide deposit on the substrate.

[0125] In one embodiment, a thin layer of such 3D material having a thickness of approximately 10 nm can be deposited on a substrate, and this thin layer does not burn or catch fire even at 1200 °C. This is because the pristine carbon (e.g., graphene) is crystallized, for example, it is not an amorphous material. Rather, the carbon has simply been fragmented to the state where it no longer burns further.

[0126] In one example of use, the above plasma spraying torch technique can be used to produce a new type of solder that is non-eutectic. Alternatively, as another example of use, the plasma spraying torch sprays a coating material directly onto a substrate to prevent the underlying material from oxidizing.

[0127] Placing quartz around the material often brings great advantages in application, in addition to forming a material that does not catch fire even at 1200 °C in atmospheric pressure.

[0128] Not only organically modified silicon, but also other organic substances can be used for coating carbon particles or carbon layers. The properties of the coating are controllable. As one example, the pores on the surface of the sprayed material can be adjusted to be hydraulically smooth.

[0129] Using a plasma spraying torch, a glass-coated thermally absorptive incombustible graphene composed of graphene and silicon can be formed. In this case, silicon coats the graphene so that the graphene can withstand high temperatures exceeding 1600 °C. Such glass-coated thermally absorptive incombustible graphene absorbs infrared energy.

[0130] One specific method of generating an organically modified silicon coating includes the following steps (for example): (1) introducing a silicon-containing precursor into a plasma spraying torch device; (2) mixing the silicon-containing precursor with a carrier gas containing carbon particles, where this carrier gas entrains the precursor gas; and (3) coating the carbon particles with silicon.

[0131] The properties of the flame retardant and infrared stealth materials obtained from the plasma spraying torch configurations of FIGS. 18C and / or 18D are, at least in part, adjustable by controlling the time-temperature profile through the reactor. More generally, the properties of the materials obtained from the plasma spraying torch configurations of FIGS. 18A, 18B, 18C, or 18D are, at least in part, adjustable by controlling (e.g., pulsing) the microwave energy within the reactor.

[0132] FIG. 19 is FIG. 1900 depicting energy versus time between pulse on and pulse off. More specifically, this figure shows one full time cycle, where from T = 0 to 50 microseconds, the microwaves are continuously on, and then the remainder of the cycle shown depicts the time when the microwaves are off. The plotted curve depicts (1) the change in density and (2) the change in temperature over the cycle. At the T = 0 point, the temperature is at a minimum (e.g., as depicted at the start of the figure). The temperature rises rapidly and then falls, but during that time, the plasma density has reached a relatively stable value. When the microwaves turn off at T = 50 microseconds, both the plasma density and the electron temperature over time drop rapidly. The pulse time and duty cycle can be controlled to achieve a specific density and time at any given point.

[0133] Figure 20A1 shows an image displaying an organometallic bond that occurs when carbon and copper are combined using a plasma spraying torch. As shown in the figure, carbon 2052 is deeply buried within copper 2054. As generally understood and as referred to herein, organometallic chemistry refers to the study of organometallic compounds, i.e., chemical substances having at least one chemical bond between a carbon atom of an organic molecule and a metal such as an alkali metal, an alkaline earth metal, and a transition metal, and is sometimes extended to include metalloids such as boron, silicon, and tin. Apart from the bond with an organyl fragment or molecule, the bond with "inorganic" carbon such as carbon monoxide (metal carbonyl), cyanide, or carbide is also generally regarded as organometallic. Related compounds, for example, transition metal hydrides and metal phosphine complexes, may be included in the study of organometallic compounds, but strictly speaking, these are not necessarily organometallic.

[0134] In the realm of organometallic chemistry, organocopper compounds have a chemical bond between carbon and copper and may have unique physical properties, synthesis, and reactivity. Organocopper compounds may have diversity in structure and reactivity, but there are still some limitations such as the oxidation state being copper(I), for example, represented by Cu + There is still some limitation that it is represented by Cu. d 10 As a metal center, copper(I) is related to Ni(0), but because this oxidation state is higher, it is less involved in π back-donation. Organic derivatives of Cu(II) and Cu(III) may appear as intermediates, but these are rarely even observed, let alone isolated. Regarding the geometric structure, copper(I) adopts a symmetric structure according to its spherical electron shell. Typically, it can adopt one of three coordination structures: linear two-coordination, trigonal three-coordination, and tetrahedral four-coordination. Organocopper compounds form complexes with various soft ligands such as alkylphosphine (R3P), thioether (R2S), and cyanide (CN - ).

[0135] By any one or more of the above techniques, the carbon depicted in FIGS. 20A1 and 20A2 chemically bonds to the copper. This is in contrast to merely adhering thereto by van der Waals forces (e.g., distance-dependent interactions between atoms or molecules) juxtaposed with the copper. Unlike ionic or covalent bonds, van der Waals attractive forces do not result from chemical electron bonding. Van der Waals forces are relatively weak and thus more susceptible to the influence of disturbances. Moreover, van der Waals forces disappear as soon as the distance between the interacting molecules becomes long. Instead, what is desirable is an organometallic bond between the metal and the carbon.

[0136] FIG. 20A2 shows an image of an inclined composition applied to a substrate material, and three material property bands are shown in the image. The bulk metal band 2066 is the first material property band among these three material property bands. As shown in the figure, the first material property band contains a metal in a first crystallographic arrangement, and the first crystallographic arrangement has a substantial metal bond between the metal atoms present in the first material property band. This first material property band is substantially adjacent to the second material property band, and this second material property band at least partially overlaps with the first material property band. The cobic material band 2064 contains at least some carbon atoms in a second crystallographic arrangement, and the second crystallographic arrangement has at least some covalent bonds between some of the carbon atoms present in the second material property band and some of the metal atoms present in the first material property band. The top surface band 2062 is the third material property band, and this third material property band at least partially overlaps with the second material property band. This top surface band contains additional carbon atoms oriented in a third crystallographic arrangement. The third crystallographic arrangement is characterized by having at least some covalent bonds between each of the additional carbon atoms present in the third material property band. In various embodiments, some metal atoms may be present in any of these material property bands, and some carbon atoms may be present in any of these material property bands, but this embodiment is characterized in that the band 2074 with a high metal content is adjacent to the bulk metal band 2066. In various embodiments, here, some carbon atoms may be present in any of these material property bands, and there, some metal atoms may be present in any of these material property bands, but this embodiment is characterized in that the band 2072 with a high carbon content is adjacent to the top surface band 2062.

[0137] Figure 20B is a material development diagram 20B00 depicting a stacked configuration that occurs when carbon is added to bulk aluminum. In these embodiments, the material is sprayed onto an existing rich-carbon cobetic substrate or carbide layer to create carbon-carbon bonds through carbon sintering and / or metal melt encapsulation, and this bonding then results in adhesion to form a composite coating. Material development diagram 20B00 is only an example of a combined material (silicon carbide) sprayed onto an aluminum bulk material. The process can be adjusted to produce a cobetic or cobetic-like coating deposited on the bulk material. The resulting material can then be coated to produce a functional top layer. One possible configuration of an apparatus for spraying a combined material onto a substrate is presented in Figure 21A.

[0138] Figure 21A depicts an apparatus for spraying a molten mixture of materials onto a substrate. This figure depicts a microwave reactor with multiple regions inside a storage container. Pulsed microwave energy is delivered into the storage container. Hydrocarbon process gas 605 is provided through an inlet. The microwave energy heats the process gas to a high temperature sufficient to form a plasma. As the material expands within the storage container, a plasma plume is generated. When the material is continuously added into the storage container, combined with the above expansion, a torch effect is brought about in and around the plume. As a result of the high temperature inside and around the plasma plume, carbon dissociates from hydrogen, thereby forming a plurality of different hydrocarbon species (e.g., CH3, CH2). As the temperature continues to rise (e.g., in the first region 2104 as shown in the figure), all or almost all carbon atoms dissociate from hydrogen. By using any known technique (e.g., the use of a gas-solid separation device), hydrogen-only chemical species are separated from the solid carbon species.

[0139] At the interface between the first region 2104 and the second region 2106 of the storage container, a molten metal or molten metal composite, or a molten ceramic metal, or a metal matrix, or any kind of metal mixture is introduced into the storage container through the second inlet (as shown in the figure). The location of the second inlet is selected based on the dimensions of the plasma plume and / or the temperature of the molten metal at the inlet point to the storage container. More specifically, the molten metal 2108 is introduced into the reactor where the molten metal mixes with the carbon species. As the mixture flows through the storage container (e.g., at high speed), the temperature of the mixture decreases. The flowing mixture exits the storage container at high speed such that the mixture of carbon and molten metal is sprayed from the outlet 2110. The mixture is deposited on the target substrate 2116 (e.g., via the spraying of the spraying material 2112). Various mechanisms for controlling the uniformity of the spraying material 2112 and / or the resulting deposited material 2114 are shown and discussed in relation to FIGS. 23A - 23D.

[0140] The temperature of the second region is low enough for at least a portion of the carbon to precipitate out of the mixture. However, most of the dissociated carbon remains in the mixture with the molten metal. The molten metal mixed with carbon cools and solidifies when it reaches the target substrate 2116. During the transition from the molten mixture to the solid deposit, carbon is trapped between the layers of metal and carbon. At a certain temperature, carbon forms a covalent bond with the metal, resulting in a cermet material. This cermet material exhibits a range of mechanical, thermal, electrical, and tribological properties due to the increased cohesive force (e.g., covalent bond) between the metal matrix and carbon.

[0141] Such cobetic materials are the result of utilizing pulsed microwave energy to control the energy distribution of the material composition in the first and second regions of the reactor. More specifically, the energy distribution of the material composition in the first and second regions of the reactor can be controlled, in part, by the use of pulsed microwaves and, in part, by pre-melting metal particles in the external environment of the reactor chamber (e.g., introducing fully melted or partially melted metal into the reactor chamber). Any known technique can be used, either alone or in combination with the melting of metal particles. Thus, the degree and / or mixing of whether the particles are fully melted or partially melted can be controlled.

[0142] Figure 21B depicts a method of spraying a cobetic material onto a substrate. This method can be used in conjunction with the apparatus of Figure 21A. As shown in the figure, this method is performed using a microwave reactor equipped with an inlet for process gas, an inlet for molten metal, and an outlet. Prior to operation, the microwave reactor is positioned (operation 21B02). In operation 21B10, the inlet serves to introduce a hydrocarbon process gas into the first region of the reactor. Using microwave energy, the temperature of the first region of the reactor is increased such that the hydrocarbon process gas dissociates into carbon and hydrogen species before reaching the molten metal. A different inlet serves to introduce the molten metal into the second region of the reactor (operation 21B20). The high temperature of the second region is maintained until the dissociated carbon mixes with the molten metal (operation 21B30). The effect of the plume serves to move the mixture into the third region of the reactor (operation 21B40). The movement away from the microwave energy source has the effect of reducing the temperature of the mixture until at least a portion of the carbon exits the mixture by concentration (operation 21B50). However, even though the temperature has decreased, the plasma torch effect serves to move the mixture at high speed through the outlet (operation 21B60). Thus, the molten mixture is sprayed onto the substrate (operation 21B70).

[0143] Figure 21C is a schematic diagram depicting a plasma spraying process used to spray a film. As shown in the figure, carbon radicals, polycyclic aromatics, graphene sheets, and metal particles are mixed at high temperature in a plasma reactor (see, for example, the first region 2104 in the figure). Nucleation occurs at such high temperatures, and as the temperature in the reactor decreases (see, for example, the second region 2106 in the figure), growth and assembly begin. One possible growth mechanism is depicted by submicron-sized aluminum particles being coated with several layers of graphene. The submicron-sized aluminum particles are grouped together by a combination of metallic, covalent, and covalent bonds. More specifically, and as shown on the 2nm scale, carbon atoms are bonded to aluminum atoms. The carbon atoms are organized within the coherent graphene plane located in the aluminum matrix. The above consideration involving aluminum is merely an example. Other metals can also be used. In fact, the coherent graphene plane can be located not only in the face-centered cubic (FCC) metal lattice, but also in the body-centered cubic (BCC) metal lattice or the hexagonal close-packed (HCP) metal lattice.

[0144] Next, the above-coated particles are sintered to form particles having a diameter on the order of 100 microns. These semi-molten particles are then accelerated through the reactor and collided with a substrate (e.g., in the first path), or collided with a previously deposited layer of collided particles (e.g., in the second path or the Nth path).

[0145] Figure 22A is a device for encapsulating carbon particles with molten metal. The configuration of the device in Figure 22A is different from that of the device in Figure 21A at least in that the introduction of the molten metal is controlled using a melting device 2209. The molten metal is controlled to produce a molten metal that encapsulates the carbon particles when introduced into the reactor.

[0146] Figure 22B depicts a method of encapsulating carbon particles with molten metal. This method is different from the method of Figure 21B at least in that, in operation 22B30, the temperature in different regions of the reactor is maintained such that a portion of the carbon particle species is formed from dissociated carbon. In operation 22B50, at least a portion of the carbon particles are encapsulated with molten metal. Some bonds are formed between the constituent atoms of the carbon particles and the atoms of the molten metal. In operation 21B60, the carbon particles encapsulated in the metal move through the outlet and further decrease in temperature. When the carbon particles encapsulated in the metal are deposited on the substrate (operation 21B70), additional bonds are formed between the carbon particles encapsulated in the metal and the metal of the substrate.

[0147] Figures 23A, 23B, 23C, and 23D depict examples of deposition techniques according to some embodiments.

[0148] As shown in Figure 23A, the deposited material has a curved surface shape characterized by a raised intermediate region and a lower end region. In some cases, this is the desired shape for the spot-deposited material. In other cases, it may be desirable to spray the deposited material over a larger area. This can be achieved by moving the substrate relative to the spray or by moving the spray relative to the substrate. Figure 23B shows a movable substrate 2310 disposed on a supply reel. The movable substrate can be lifted onto or wound onto a take-up reel. Thus, in the configuration of Figure 23B, by spraying, the cobic material is uniformly deposited on the moving substrate. When the relative movement between the material 2112 being sprayed and the substrate is controlled, the resulting deposited material will have a uniform thickness.

[0149] Depending on the situation, although not flat, it is desirable to have a uniform pattern on the surface of the deposited material. In such cases, the movement of the substrate can be stepped through a series of discrete positions, resulting in the pattern of FIG. 23C. In addition or alternatively, a slotted antenna can be placed between the material 2112 to be sprayed and the substrate. The slotted antenna functions by evenly distributing the sprayed material across the lateral distance of the slotted antenna. By using such a slotted antenna, a single sprayed material 2112 can have a thickness and surface uniformity substantially as shown in FIG. 23D.

[0150] FIGS. 24A and 24B depict conventional techniques for depositing materials onto a substrate. As shown in FIG. 24A, the carbon aggregates are grouped together through the use of a binder (e.g., a polymeric additive). As a result, the bond is weakened at the interface between the carbon aggregates and the substrate. FIG. 24B depicts the coating of a carbon material on a substrate using a binder. The conventional deposition methods using a binder are plagued with problems of delamination. Moreover, even when the surface of the substrate is mechanically pretreated and / or pretreated with the deposition of the binder material, the interaction between the substrate and the carbon aggregates is weak.

[0151] As described thus far, coatings based on depositing materials onto a substrate using a binder and / or coating techniques (such as those shown and described in relation to FIGS. 24A and 24B) are plagued with problems of delamination, low strength characteristics, and other undesirable mechanical properties. Improvements based on plasma spraying techniques are shown and considered in relation to FIGS. 25A and 25B.

[0152] Figures 25A and 25B depict, in accordance with some embodiments, exemplary deposition techniques that result in covalent bonds on the surface of a substrate. Specifically, as shown in the figures, when the techniques of the present disclosure are used, a covalent bond between carbon and the substrate forms a covalent material. Therefore, a binder is not necessary, i.e., not used. Moreover, many of the bonds formed at the interface between the substrate and the covalent material are strong covalent bonds. In one specific example, the substrate is aluminum, and the covalent bond is formed between atoms in the face-centered cubic structure of aluminum and carbon atoms in the hexagonal structure. A schematic diagram of the interfacial bond is shown in Figure 25B.

[0153] Figures 26A, 26B, 26C, and 26D present schematic diagrams depicting how covalent bonds are formed between sites in a square of the face-centered cubic structure of aluminum and sites in a hexagon resulting from a certain crystallographic structure of carbon.

[0154] Figure 26A is an orthogonal view showing a square of the face-centered cubic structure of aluminum. Figure 26B is an orthogonal view showing a hexagon resulting from a certain crystallographic structure of aluminum.

[0155] Figure 26C depicts one of the possible ways of overlapping a hexagon resulting from a certain crystallographic structure of carbon on top of a square of the face-centered cubic structure of aluminum. Figure 26D shows the covalent bonds formed at a specific site. The example of the face-centered cubic structure of aluminum is just one example. Other materials with other crystallographic structures are also possible.

[0156] Figure 26E is an example of a laminated cobetic material 26E00, where a graphene-like structure is sandwiched between layers of a metallic material. The lower metallic material layer is a substrate layer. The upper metallic material layer is formed of a quenched material that was molten while previously in a reactor. The graphene-like structure sandwiched between the layers of metallic material is trapped between the two metallic layers by the formation of metal-metal bonds between the two metallic layers. In addition to the metal bonds, other bonds are formed that serve to confine the graphene-like material between the metallic layers. At multiple locations, there are defects in the carbon lattice. Between or near such defects, various types of bonds are formed.

[0157] Any or all of the above techniques for forming cobetic materials can be used in many applications including a wide variety of substrates. Moreover, the relative movement between the sprayed material and the substrate can be controlled to result in deposits of any thickness. The relative movement can be controlled using any known technique. For example, the outlet can be moved relative to a fixed substrate. This can be accomplished using a hand-held device or a mechanically controlled device that moves relative to a fixed substrate. In some cases, a bias voltage can be applied to the substrate so that at least a portion of the material sprayed out of the outlet is electrically attracted to the substrate surface. This can be applied to applications where the substrate does not have uniform flatness. Examples of applications where the substrate does not have uniform flatness include: (1) formed components used in machines subjected to severe corrosion conditions, (2) turbine blades, (3) heat exchanger components, etc. Many of these applications will be further considered below.

[0158] In other situations, the properties of the deposit (e.g., thickness, lateral uniformity, etc.) can be improved through the use of various chemical vapor deposition techniques and / or combinations thereof. As a specific example, aspects or parameters related to plasma-assisted chemical vapor deposition techniques known in the art can be controlled such that the properties of the deposited cobic material layer are optimized. As another example, instead of depositing the cobic material on a surface to form a film or coating, the cobic material can be formed into particles (e.g., by spraying in a low-temperature environment), and the particles can be collected as a powder. Various techniques including the manufacture and use of powder cobic materials are briefly considered below.

[0159] Powder cobic material Depending on the situation, instead of forming the cobic material as a film or coating on or in a substrate, the cobic material can be delivered as a powder. Such powder cobic materials can be collected by cooling the cobic material to a temperature below its melting point where the cobic material exits the reactor and collecting it as a powder. Then, this powder becomes handleable at room temperature (e.g., storing, transporting, pouring, mixing, etc.). Subsequently, the powder can be remelted and compression molded or remelted and re-sprayed. As an example, components used in highly corrosive environments can be formed from such powder cobic materials using injection molding or extrusion molding. The formation and transport of powder cobic materials are possible by using many devices, either alone or in combination. Example devices are shown and described in connection with FIGS. 27A and 27B.

[0160] Figure 27A depicts an example apparatus 27A00 for manufacturing a powder cosmetic material 2710, which uses a cooling region 2702 to cool the sprayed material 2112 as the sprayed material is extruded through the outlet 2110 of the microwave reactor. Any one or more cooling techniques can be used in any combination to lower the temperature of the cosmetic material in the cooling region 2702 to a temperature lower than the melting point of the cosmetic material. The cooling region 2702 can accommodate one or more devices capable of causing cooling. For example, as shown in the figure, one or more devices can be attached to the collection container 2704 to cause a cyclone effect in the collection container, thereby extending the time for lowering the temperature of the cosmetic material. In some cases, the cooling time of the cosmetic material is controlled such that the cosmetic material is annealed with a very regular bond (e.g., by extending or shortening the time). In some cases, by controlling the time during which the cosmetic material is cooled, it is possible for the cosmetic material to remain in powder form and crystallize into a very regular crystal structure. In some embodiments, a mechanical tumbler agitator can be attached between the outlet 2110 of the microwave reactor and the collection container 2704. The tumbler agitator can be periodically cleaned or replaced.

[0161] Alternatively or additionally, and in situations where it is convenient and / or necessary to contain and / or transport the powder cosmetic material in a fluid, a fluidized bed apparatus can be used. For example, to avoid agglomeration of powder particles, the powder cosmetic material can be held in a liquid. In some embodiments, a fluidized bed apparatus can be attached between the outlet 2110 of the microwave reactor and the collection container 2704. One embodiment of such a fluidized bed apparatus is shown and described in relation to Figure 27B.

[0162] Figure 27B depicts an example fluidized bed apparatus 27B00 for cooling and handling a powder cosmetic material in a fluid.

[0163] As shown in the figure, the mixture of molten metal and carbon is pushed out through the reactor outlet and pushed into the top of the fluidized bed 2750. As the mixture of molten metal and carbon is pushed out through the outlet, it is cooled in a manner that forms particles. Downward gravity acts on the particles (e.g., in the downward direction as shown in the figure), while at the same time, the process fluid 2754 is pushed in from the bottom of the fluidized bed, creating an upward force. Therefore, the particles accelerate towards the bottom of the fluidized bed, but the acceleration is slower than the acceleration of local gravity. The dynamics of the flow can be partially regulated by the geometry of the fluidized bed. For example, as shown in the figure, a certain length of the fluidized bed can be made into a tapered body 2762. The first end of the tapered body has a first dimension D1, and the second end of the tapered body has a second dimension D2, provided that D1 > D2. The temperature within each part of the fluidized bed can be controlled, in part, by the power supply 2752 that supplies power to the coil (as shown in the figure) and / or by the heat source 2760 that heats the process fluid 2754, before the process fluid enters the bottom of the fluidized bed.

[0164] The pressure, flow rate, and other conditions within the fluidized bed and at the environmental interface of the fluidized bed function such that the mixture of powder and fluid behaves as a fluid together. The mixture exhibits properties and characteristics as a fluid, such as the ability to flow freely under gravity and / or the ability to be sent using fluid handling techniques.

[0165] In the embodiment of FIG. 27B, the fluidized bed has a plurality of ports at various heights of the tapered body. Thus, the fluid 27561 containing the first powder flows out at a specific temperature / pressure, while the fluid 27562 containing the second powder flows out at a second different specific temperature / pressure. The flow through the plurality of ports can be controlled such that the collection container can receive the fluid 27561 containing the first powder and the fluid 27562 containing the second powder in any ratio or amount.

[0166] Method for forming cobetic material Table 3 shows some, but not limited to, examples of the method for forming the powdered cobetic material.

Table 3

[0167] Method Example 1 In some embodiments of Method 1, structured carbon (e.g., a carbon allotrope) is formed in a first region of a microwave reactor (e.g., through dissociation of a hydrocarbon process gas). In a second region that is at a lower temperature than the first region, the structured carbon is modified with a metal such that a metalized carbon material (e.g., an organometallic material) is formed. The metalized carbon material is further cooled to a temperature lower than the melting point of the metal. In some embodiments, the metalized carbon material initially has the shape of carbon particles modified with a metal. The particles are further cooled such that a powder is formed. The powder can be collected and transported to a utilization facility. The powder containing the metalized carbon material having covalent bonds can be remelted and used in combination with any known technique for forming components from the powder. As a specific example, the components can be formed from the powder by using, for example, remelting following die pressing, remelting following isostatic pressing, hot forging, metal injection molding, laser sintering, etc.

[0168] Method Example 2 In this method 2, one or more hydrocarbon gases (or in some cases gases and liquids) are introduced into the system. As a strict example, gases and / or liquids that can be introduced into the system include methane, ethane, methylacetylene-propadiene propane (MAPP), and hexane. In the first region 2104 at the first temperature, carbon atoms dissociate from other atoms (e.g., dissociate from hydrogen). The molten metal 2108 is introduced into the reactor as metal particles. Then, in the second region 2106, the carbon generated in the first region binds to the metal particles. Carbon grows on the surface of the metal particles and / or grows inside the metal particles. In some situations and under some conditions, the growth of carbon includes the growth of 2D carbon on or in the metal particles. In other situations and / or under other conditions, the growth of carbon includes the growth of 3D carbon on or in the metal particles. In any of the above growth situations, the growth can proceed to the maximum extent allowed by the lattice. For example, the molten metal can be aluminum with a face-centered cubic (FCC) crystal structure, and carbon can form a solid solution with aluminum up to a specific concentration. In some embodiments, carbon forms a solution with the metal up to a concentration determined by the properties of the metal (e.g., crystal structure), and then precipitates from the metal-carbon solution to form 2D or 3D carbon on and / or within the metal particles.

[0169] The growth in this method 2 is carried out under non-equilibrium temperature conditions. Specifically, various different temperature conditions control the following (for example): (1) the first temperature of the first region (e.g., the high-temperature side) required to control the above dissociation, and (2) the second temperature of the second region (e.g., the low-temperature side) for controlling the initial melting of the metal powder and / or the formation and properties of the metal-carbon particles in the second region. The temperatures in these two zones can be independently controlled. Using this method, the sprayed material is a true cobetic material that exhibits true cobetic behavior.

[0170] Method Example 3 Nor is it limiting. In yet further examples, materials and / or coatings can be generated or deposited onto the input particles from a mixture of materials such as trimethylamine (TMA), trimethylglycine (TMG), and methylacetylene-propadiene propane. The particles can be cooled and collected as a powder. Some examples of particles that can be generated from the target material in the first zone include carbon carbide, silicon carbide, metal oxides, metal nitrides, or metals. In some cases, the input particles are metals and a compound coating (e.g., a metal oxide or metal nitride) coats the input metal particles, while in other cases, the input particles contain a compound material and a metal coating is deposited onto the input particles. Some examples of particles that can be generated from the input gas in the first zone include carbon allotropes (e.g., elemental carbon), silicon, ZnO, AlOx, and NiO.

[0171] In some embodiments, the gas is introduced into the first zone, including various non-hydrocarbon gases or alcohols, and the first zone includes a sputtering device and a power source. The sputtering device is configured to generate a plurality of ion species from a selected target material. The target material and the ion species combine to form a plurality of particles. The power source can be an AC, DC, RF, high-power impulse magnetron sputtering (HIPIMS) power source, and can be configured to generate a plurality of ion species from the target material by adjusting the power, voltage, frequency, repetition rate, and / or other characteristics of the power source.

[0172] FIG. 27C is a schematic diagram depicting a plasma spraying process used to manufacture a powder cermet material.

[0173] Sequence of powder material processing FIG. 27C visually shows an example of the order of powder material processing from hydrocarbon decomposition and particle nucleation (e.g., the first region 2104 in the figure), to graphene growth (e.g., the second region 2106 in the figure), cooling the semi-molten particles (e.g., the cooling region in the figure), and collecting the powder cobetic material (e.g., in the collection region and placing it in the collection container 2104). The mechanism underlying the effectiveness of the example of the powder material processing order will be briefly considered here.

[0174] In the absence of a metal precursor (regardless of whether it is in an organometallic form or a particulate form), the microwave plasma dissociates methane to form carbon radicals (as well as polycyclic aromatics / acetylene), and then these carbon radicals will each form a few-layer (FL) graphene (or stacked lamella) structure. However, when a metal precursor is present in the plasma zone (e.g., as shown in the reactors of FIGS. 21A and 22A), the metal (derived from either an organometallic nucleus or a particle) can function as a seed for heterogeneous carbon growth (e.g., carbon in the form of ionized radicals, graphene nuclei, or polycyclic aromatics (acetylene)).

[0175] When using a metal with low solubility, such as Al or Cu, the graphene sheet may grow on the metal surface (e.g., through either adsorbed atoms / monomers or as clusters). The growth characteristics depend at least in part on the symmetry at the metal surface and the minimization of the interfacial free energy. Therefore, carbon growth occurs in parallel with surface metal atom re-sputtering events in the metal particles, generating a mixed and / or laminated metal / carbon structure. As is known in the art, the radius of the metal particles (e.g., surface curvature) can affect the solubility of carbon in the metal particles. As an example, the smaller the radius (e.g., corresponding to a higher curvature), the higher the solubility towards equilibrium (on a flat surface), and this increase in solubility can then affect the thickness of the graphene layer.

[0176] If the powdered cobetic material 2710 is collected in a collection container, the powdered cobetic material can be further processed using conventional techniques (e.g., injection molding techniques, other techniques using powder metals).

[0177] Manufacturing techniques using powdered cobetic materials Figure 28 depicts a method of fabricating a component from a powdered cobetic material using an injection molding technique. As shown in the figure, the method begins by gathering a set of properties of the component to be used in a particular application and / or environment (operation 2810), and then selecting a particular powdered cobetic material based on at least one of the properties for that application or environment (operation 2820). The selection can be made based on the mechanical properties desired for the component, and / or based on the corrosion resistance desired for the component in an environment corresponding to the intended use, and / or based on other desired properties. The selection can be made based on a plurality of desired properties, and in some cases it is thought that a selection tool may be able to solve an optimization problem based on the set of properties and an objective function.

[0178] Once the cobetic material has been selected (operation 2820), the selected powdered cobetic material 2825 is melted (operation 2830) and introduced into a mold (operation 2840). Inside the mold, a predetermined temperature and pressure are maintained for a predetermined period (operation 2850), and then the temperature and pressure inside the mold are brought to about 30°C and about atmospheric pressure (operation 2860). The component is removed from the mold (operation 2870) and deployed for the intended use (operation 2880).

[0179] As described so far, the selection of a particular cobetic material can be based on multiple desired characteristics, and some of such characteristics may be used as variables in the objective function. In some cases, the selection of a particular cobetic material may be based on a particular dominant characteristic (e.g., mechanical strength, weight, corrosion resistance, etc.). In some cases, the characteristic of interest is a ratio to other characteristics (e.g., strength to weight, specific heat to weight, etc.). In some cases, the dominant characteristic is the subject of maximization (or minimization) with respect to one or more constraints imposed on other characteristics.

[0180] Therefore, the powder cobetic material can be deployed for a wide range of applications. In many cases, the resulting components made of the powder cobetic material are superior to those made of other materials. Some examples of uses correlated with certain dominant characteristics are presented and examined in relation to Figure 29 below.

[0181] Figure 29 depicts various characteristics of the cobetic material. The characteristics in the figure include mechanical attributes, thermal conductivity, oxidation resistance, durability, resistance to softening at high temperatures, fatigue resistance, and electrical conductivity. Individual parameters and / or combinations of these parameters become dominant when selecting a particular cobetic material for a specific application.

[0182] Strictly as an example, oxidation resistance may be a dominant parameter when selecting a cobetic material for use in the manufacture of corrosion-resistant valves. As another example, when selecting a particular cobetic material used in the manufacture of the turbine blades of an aircraft engine, mechanical attributes, such as the strength-to-weight ratio and the subject of the minimum strength constraint, may be the dominant mechanical attributes. This blade may also need to exhibit very high fatigue resistance.

[0183] Typically, cobaltic materials not only exhibit the above properties but also exhibit a lower density than the metal or alloy used in the production of cobaltic powder. The lower the density, the lighter the weight of the formed component is likely to be, as compared to the case where the same component is made from a metal or alloy in the absence of carbon addition. Therefore, track parts (e.g., cab components as shown in the figure), automotive parts (e.g., doors, fenders, roof panels, etc.), motorcycle parts, bicycle parts, and various components (e.g., structural members) of aircraft, and / or ships, and / or space vehicles or platforms can utilize the lower weight-to-strength ratio of cobaltic materials when compared to the base metal or alloy used in the production of cobaltic materials.

[0184] As another example, cobaltic materials often exhibit extraordinary thermal conductivity such that components formed of cobaltic materials can be used in high-temperature applications (e.g., heat sinks for electronic devices, industrial heat exchangers, etc.).

[0185] Still another example is that cobaltic materials often exhibit extraordinary corrosion resistance. More specifically, cobaltic laminates produced using the above techniques exhibit extraordinarily high corrosion resistance even at the top layer (e.g., the interface between the component and the environment). This property is of particular interest when components made of cobaltic materials are exposed to harsh environments.

[0186] As yet another example, the cobetic material can have its surface smoothness adjusted. More specifically, the cobetic laminate fabricated using the above-described techniques exhibits unusually high surface smoothness. This surface smoothness can be of particular interest when the cobetic material functions as a thermal shield, for example, in applications where friction at the surface (such as friction that occurs when a fluid flows over the surface at high speed) results in undesirable heat generation at the surface. By using the techniques of the present disclosure, a hydraulically smooth surface can be obtained by using a specific composition of the cobetic material and / or by using the specific techniques of the present disclosure for depositing the cobetic material, and as a result, it can be made usable in aerospace and / or space vehicles.

[0187] In certain embodiments, one set of properties may be dominant over other properties. For example, the surface of a space vehicle (such as a satellite) may be required to be substantially non-reflective of a range of electromagnetic radiation (such as substantially non-reflective of visible light), while at the same time, the surface of the space vehicle may be required to be thermally insulating (such as thermally non-conductive). The above-described adjustment techniques address situations where a particular desired property (such as non-reflectivity) dictates the adjustment of the plasma spray torch such that a substantially non-reflective surface is produced even at the expense of other properties.

[0188] The properties shown and described in connection with FIG. 29 are merely exemplary. Additional properties and / or combinations of properties may be required or desirable for various applications, and such additional properties are exhibited by the resulting material based on the adjustment of the inputs and the control of the plasma spray torch. Specifically, as examples of such additional properties, such properties and / or combinations of properties may include or be related to strength-to-weight ratio, and / or specific gravity, and / or mechanical toughness, and / or shear strength, and / or flexural strength, etc.

[0189] In the above specification, although the present disclosure has been described with reference to its specific embodiments, it will be apparent that various modifications and changes can be made without departing from the broad spirit and scope of the present disclosure. For example, the above process flow has been described with reference to process actions in a specific order. However, the order of many of the described process actions can be changed without affecting the scope or practice of the present disclosure. The specification and drawings are to be received in an illustrative sense, and not in a limiting sense.

Claims

1. A reactor comprising: an energy source configured to provide microwave energy to the reactor; a first inlet through which a hydrocarbon gas flows into the reactor; an inner tube disposed in fluid communication with the first inlet and configured to dissociate the hydrocarbon gas into plasma based on the microwave energy, the plasma including carbon and carbon radicals; an annular region surrounding the inner tube and bounded by a reactor wall; a second inlet disposed downstream of the first inlet and coupled to the annular region, the second inlet configured to receive metal particles entrained in a carrier gas; a heat source disposed in thermal communication with the reactor and configured to melt the metal particles; an outlet configured to produce a carbon-metal composite based on at least a portion of the melted metal particles and the plasma; and a reactor having the same.

2. Furthermore, it has a contact region disposed near the outlet of the reactor, wherein the formation of the carbon-metal composite is based on contact between the contact region and the melted metal particles and the plasma, the reactor according to claim 1.

3. The carbon-metal composite includes alternating graphene-metal layers organized according to the crystal structure of the metal particles, the reactor according to claim 1.

4. The carbon filling amount in the carbon-metal composite is about 60%, the reactor according to claim 1.

5. The carbon filling amount in the carbon-metal composite is between about 60% and 90%, the reactor according to claim 1.

6. Furthermore, it has an acceleration zone configured to accelerate the flow of the carbon-metal composite through the outlet, the reactor according to claim 1.

7. The acceleration zone is further configured to quench the carbon-metal composite, the reactor according to claim 6.

8. Furthermore, it has a substrate, wherein the carbon-metal composite is cooled on the substrate, the reactor according to claim 1.

9. Furthermore, it has a mechanical tumbler agitator disposed downstream of the outlet, the reactor according to claim 1.

10. Furthermore, it has a fluidized bed reactor disposed downstream of the outlet, the reactor according to claim 1.

11. The microwave energy includes pulsed microwave energy, the reactor according to claim 1.

12. The pulsed microwave energy is related to transverse electromagnetic wave propagation, the reactor according to claim 11.

13. The pulsed microwave energy is related to transverse radio wave (TE) propagation, the reactor according to claim 11.

14. The reactor is configured to adjust one or more of the duty cycle of the pulsed microwave energy, or the power level or duty cycle of the heat source, the reactor according to claim 11.

15. The inner tube has a dielectric tube, the reactor according to claim 1.

16. The dielectric tube includes a quartz tube, the reactor according to claim 15.

17. The temperature of the metal particles is independent of the temperature of the plasma, the reactor according to claim 1.

18. The metal particles include one or more of aluminum, copper, nickel, copper, gold, zinc, tin, lead, or silver, the reactor according to claim 1.

19. The metal melt includes one or more of a fully molten metal or a partially molten metal, the reactor according to claim 1.

20. The metal melt includes metal molten droplets, the reactor according to claim 1.

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