GRAPHENE MATERIALS

CROSS REFERENCE TO RELATED APPLICATION(S)

[0001] This patent document claims the benefit of priority of U.S. Patent Application No. 14/215,945, entitled "CARBON-BASED MANUFACTURING OF FIBER AND GRAPHENE MATERIALS" and filed on March 17, 2014, which claims priority to U.S. Provisional Patent Application No. 61 /801 ,522, entitled "ADVANCED CARBON-BASED MANUFACTURING OF FIBER AND GRAPHENE FOR ANG STORAGE TANKS" and filed on March 15, 2013. The aforementioned patent applications are entirely incorporated by reference herein.

TECHNICAL FIELD

[0002] This patent document relates to systems, devices and processes that use nanoscale materials for improved fibers and composites.

BACKGROUND

[0003] Nanotechnology provides techniques or processes for fabricating structures, devices, and systems with features at a molecular or atomic scale, e.g., structures in a range of one to hundreds of nanometers in some applications. For example, nano-scale devices can be configured to sizes about one hundred to ten thousand times smaller than living cells, e.g., similar in size compared to some large biological molecules that make up such cells. Nanoscale materials are used to create a nanostructure, nanodevice, or a nanosystem, which can exhibit various unique properties which are not present in the same materials scaled at larger dimensions, and such unique characteristics can be exploited for a wide range of applications. SUMMARY

[0004] In one aspect, a method to fabricate an acryl-modified polymer includes obtaining a hydrocarbon substance or other substance containing hydrogen and carbon from one or both of a waste stream or natural gas, separating constituents from the hydrocarbon substance to form hydrogen gas and a carbonaceous fluid including one or more of methane, butane, or ethane, dehydrogenating the carbonaceous fluid by adding heat to form a dehydrogenated carbon material, and reacting the dehydrogenated carbon material with a nitrogen material including one of ammonia or urea to produce

polyacrylonitrile (PAN).

[0005] Another aspect produces inexpensive fibers from low-cost precursors compared to conventional carbon-fiber PAN, cultured pitch etc. Low-cost precursors include graphene-oxide, carpet and clothing grades of PAN, rayon, polyolefins and other commodity polymers, recycled polymers and glass along with melted rocks. Utilization of such inexpensive fibers to produce high strength fiber-reinforced composites is achieved by addition of fuzzy deposits on the inexpensive fibers by dissociation of substances such as carbon, boron, nitrogen, and/or silicon donors to provide depositions of tubes, rods, pods, strings, bulbs, flower-like petals, and/or other high surface to volume fuzzy forms on the surfaces of such inexpensive fibers made from such low cost precursors. Production of high strength fiber-reinforced composites can be achieved by utilizing thermoset or otherwise cross-linked epoxy, polystyrene, urethane, polyamide, polyimide, polyamide- imid, polyetherimide, Portland, phosphate, or sulfate cements, and/or other adhesive compositions that include tubes, rods, graphene particles, and/or other high surface to volume particle forms to interlock with the fuzzy deposits on fibers.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] FIG. 1 shows a diagram of an exemplary method to produce an intermediary substance as a precursor (e.g., such as a cellulosic or olefin derivative, pitch or

polyacrylonitrile (PAN)) for subsequent carbon fiber and/or graphene production.

[0007] Figure 2 shows an embodiment with multiple material selections to serve as precursor for fiber production. [0008] Figure 3 shows another embodiment for application of the principles of the invention.

[0009] Figures 4A, 4B, and 4C show other embodiments for application of the principles of the invention.

[0010] Figures 5, 5A, 6, and 7 show other embodiments for application of the principles of the invention.

DETAILED DESCRI PTION

[0011] Conventional carbon-fiber reinforced manufacturing is too expensive to drive economic development in key industries such as transportation, energy storage, and renewable energy harvesting. The paradigm that dominates U.S. power generation, transportation, and manufacturing sectors and drives the U.S. economy is founded upon burning fossil hydrocarbons for energy. The concomitant problems of this paradigm are large, well-documented, and trending toward crisis: 1 ) Carbon wastes produced by hydrocarbon combustion pollute the air and contribute massively to the greenhouse gas (GHG) impact on climate; 2) Petroleum hydrocarbons are finite resources subject to depletion, international commodity price manipulations, and harmful trade deficits; 3) Carbon in suitable feedstocks for production of carbon fiber is too costly for greater applications in transportation products that would reduce fuel consumption. This paradigm also involves large shipping and processing costs and generates wastes that must be managed at high cost.

[0012] The disclosed methods, systems, and devices describe technology to establish a new paradigm for disruptive innovation in energy and materials production, e.g., including the separation of hydrocarbons into hydrogen and carbon resources first and, in doing so, convert waste into value (e.g., Hydrogen = fuel and energy storage;

Carbon = abundant material resource). This carbon resource will create new low-cost fiber (applicable to numerous uses) and graphene (a new form of carbon that is exceptionally thin, light weight, and very strong). [0013] The disclosed technology can be applied to cutting the cost of carbon fiber manufacturing in half or less by reducing the cost of the precursor such as selected pitches, polyolefins, polyacrylonitrile (PAN) and other intermediates. The disclosed technology includes an anaerobic electrolysis system (AES) that may convert at least twice the amount of carbon from organic feedstock into a precursor such as PAN, e.g., as compared to equal costs by conventional means. Also, for example, hydrogen is utilized for process energy requirements and to generate PAN without pollution.

[0014] The disclosed technology can also be applied to new manufacturing methods using graphene to produce storage tanks for gaseous and liquid fuels. For example, current tests indicate that the storage density of methane and hydrogen can be increased by more than four times in the same tank volume, dramatically extending the distance that can be traveled by vehicles using these fuels. Graphene includes carbon atoms jointed together in a flat lattice, e.g., similar to a honeycomb structure but only one atom thick for each graphene crystal layer. This lattice provides massive new surface area for

adsorption of the fuel. In chemistry, adsorption is the attraction and holding of molecules of a substance to a surface liquid or solid causing a high concentration of the substance to be achieved.

[0015] The disclosed technology can also be applied to methods using both (fossil fuel) natural gas and (renewable) biomethane feedstocks for environmentally friendly purposes. For example, natural gas is available in most urban settings and along natural gas pipeline corridors in rural settings. Exemplary environmentally friendly processes applying the disclosed technology include increasing the value of the natural gas

commodity when (1 ) hydrogen is separated and liberated for use as a clean fuel and (2) carbon is co-harvested for manufacturing precursor or fiber or another product while (3) avoiding the substantial amounts of cost for carbon footprint damages and clean-up.

Development of both carbon fiber, graphene, and other carbon enhanced products may interchangeably utilize petroleum such as white mineral oil, petrolatum and/or natural gas constituents such as flare gas and/or paraffinic fluids including thermoplastics, semi-solids, gels or liquids and/or gases and biomethane feedstocks. For example, in certain locations, renewable feedstock (e.g., biomethane) is a preferred resource because locally available and constantly replenished from sources such as biomass and biowaste materials that can be obtained at little to no cost, while avoiding handling costs and fuel consumption for shipping from distant sources. Exemplary anaerobic electrolysis systems can be used to maximize production of methane from the feedstock. Hydrogen and carbon can be co- produced in the biowaste electrolysis process. Such locally available natural gas and biowaste derivatives can be utilized with substances such as ubiquitous petrolatum including petrolatum preparations with dissolved, suspended or mixtures with other substances such as transition metal organics, urea, and other components to seed or serve as catalysts for particle developments on low cost fibers, graphene, graphite, boron nitride, glass and rock and other ceramic surfaces. After such catalytic initiation of such particles on the selected substrate surfaces, natural gas, methane, or other inexpensive carbon and hydrogen donor fluids can be dissociated to grow the particles to the extent desired for purposes of increasing the surface area, interlocking characteristics, and other enhanced chemical and/or physical performance characteristics.

[0016] Regardless of the feedstock source, for example, hydrogen can be co- produced in the generation of dimethylether, diethylether, ethylene, propylene from feed stocks such as underwater clathrates, decaying permafrost methane, flare gas, etc., including methane, ethane or propane. Such hydrogen can be combined with nitrogen from ambient air to produce ammonia for PAN synthesis. Hydrogen from these process steps provides clean energy for operation of the system, avoiding pollution and

greenhouse gas (GHG) emissions.

[0017] Such exemplary systems can change the materials cycle process at essential points, e.g., waste recycling, feedstock preparation, carbon sequestration, power generation, and materials fabrication. Such exemplary systems can cascade outputs of each stage into subsequent operations that synergistically incorporate previously wasted substances into values. In contrast to conventional steam reforming or sequestration techniques, for example, the disclosed systems can utilize captured carbon donors in the subsequent carbon fiber production process. This method uses feedstock as both fuel and source material and creates values from chemical by-products (e.g., sulfur and ash). The technology's economic impact can also provide a model for distributed energy and materials production from local feedstocks combined with advanced manufacturing methods to produce, e.g., 1 ) High quality carbon fiber and graphene at a cost that significantly energizes industry; 2) Non-polluting, off-or-on-the-grid manufacturing; 3) New high-quality local jobs in manufacturing; and 4) A model that can be used to establish regional carbon-based industrial parks that exploit and harness the value of local wastes. It is also noted that the disclosed technology (e.g., devices, systems, and methods) can be utilized to convert vast permafrost and oceanic methane hydrate deposits into large quantities of energy and carbon fiber. Harvesting a pollutant and converting the material into financial benefit also brings with it significant reduction in the threat of pervasive harmful greenhouse gas releases into the global atmosphere - from two of the most seriously threatening mass-scale drivers of climate change.

[0018] Inexpensive mass production of carbon fiber and graphene from renewable and/or fossil fuel feedstocks will make carbon fiber reinforcement cost-effective for manufacturing, e.g., including, but not limited to: 1 ) Storage tanks to enable international adoption of methane and hydrogen as fuels for transportation, power generation, and heavy equipment; 2) Renewable energy conversion equipment; 3) Safer automotive components that have lower curb weight and inertia (to increase fuel efficiency), increased strength and safety, corrosion resistance and higher durability; 4) Consumer durable goods; and 5) New nanoscale products. In addition, the disclosed technology provides a model for "minus-emissions manufacturing" to actually clean the air as a net outcome.

[0019] Risk factors associated with conventional carbon fiber manufacturing include eye and skin irritation from carbon dust and exposure to volatile organic outgassing for technicians in the process, along with pollution and greenhouse gas emissions for the environment. The disclosed methods can control and redirect the waste products at each step in the process.

[0020] In one aspect, the disclosed technology includes methods to fabricate precursors such as PAN intermediaries to carbon fiber and/or graphene fabrications. An exemplary representative method to fabricate an acryl-modified polymer is described. The method includes a process to obtain a hydrocarbon substance from one or both of a waste stream or fossil source such as natural gas. The method includes a process to separate gases from the hydrocarbon substance to form hydrogen gas and a carbonaceous gas, e.g., including one or more of methane, ethane, propane, butane, etc. The method includes a process to dehydrogenate the carbonaceous gas by adding heat to form an intermediate or dehydrogenated carbon material. The method includes a process to react the intermediate or dehydrogenated carbon material with a nitrogen material, e.g., including ammonia and/or urea, to produce polyacrylonitrile (PAN).

[0021] Implementations of the method can include one or more of the following exemplary features. In some implementations, for example, the process to react the dehydrogenated carbon material with the nitrogen material can further include producing other nitrile substances and paraffin substances. In some implementations, for example, adding the heat in the dehydrogenation process can include applying the carbonaceous gas across an array of heat sources in a controlled process atmosphere such as provided by a vacuum furnace. In some implementations, the method can further include a process to draw the produced PAN to produce carbon fibers, in which the drawing causes nitrogen and hydrogen releases. For example, the produced carbon fibers can be configured or further processed to include a flat, twisted or fuzzy fiber structure. In some

implementations, for example, the drawing process can include forming and/or orienting internal nanofiber 304 or microfiber 308 within the produced carbon or boron nitride fibers 302 as shown by embodiment 300 in Figure 3. In some implementations, the method can further include a process to form or promote surface texture and/or adhesive bonds 122 to the internal nano or microfiber 120 of the produced carbon or boron nitride fibers including process provisions such as by chemically or radiatively cross-linking.

[0022] FIG. 1 A shows a diagram of an exemplary method to produce a precursor substance such as thermoplastic PAN or other intermediary substances and subsequent carbon fiber and/or graphene production. In certain embodiments the method includes a process 101 to recover waste (e.g., polymer and/or hydrocarbon waste) from ordinarily wasted substances. For example, the waste streams can include, but are not limited to, petroleum production or recycling, industrial waste streams, agricultural waste streams, waste streams produced during electrolysis by an electrolysis system, etc. The method includes a process to collect polymers such as rug fibers, plastic wrapping and/or containment articles and to separate materials and/or fluid from the recovered waste (e.g., hydrocarbon waste), e.g., forming hydrogen gas and carbonaceous fluid (e.g., including one or more of methane, ethane, propane, butane, etc.) In some implementations of the method, for example, the method includes a process 1 13 to collect the separated substance such as gas (e.g., collect hydrogen as an output of the gas separation process). The method can include a processes 103 to separate and/or purify selected substances, 105 to dehydrogenize the separated constituents of the separation process (e.g., dehydrogenize the carbonaceous gas). The method can include a process 107 to chemically react the one or more of the separated gases (e.g., carbonaceous gas and/or hydrogen gas) and/or with a nitrogenous material (e.g., including activated nitrogen, ammonia and/or urea) to produce an intermediary such as various polyolefins or polyacrylonitrile (PAN) product. The method can include a process 109 to collect the produced intermediary product, e.g. PAN, which can be outputted to another system or process. In some implementations of the method, the method further includes a process 1 1 1 to use the produced intermediary product such as PAN to produce a carbon fiber and/or a graphene material.

[0023] In some implementations, for example, the process 101 to recover waste and/or other processes of the exemplary method can include various techniques and systems as described in: U.S. Patent No. 8,318,997 titled "CARBON-BASED DURABLE GOODS AND RENEWABLE FUEL FROM BIOMASS WASTE DISSOCIATION", U.S. Patent No. 8,916,735 titled "CARBON-BASED DURABLE GOODS AND RENEWABLE FUEL FROM BIOMASS WASTE DISSOCIATION FOR TRANSPORTATION AND STORAGE", U.S. Patent No. 8,912,239 titled "CARBON RECYCLING AND

REINVESTMENT USING THERMOCHEMICAL REGENERATION", U.S. Patent

Application No. 13/584,554 titled "RECYCLING AND REINVESTMENT OF CARBON FROM AGRICULTURAL PROCESSES FOR FUEL AND MATERIALS USING THERMOCHEMICAL REGENERATION", U.S. Patent No. 8,784,095 titled

"OXYGENATED FUEL"; all of the aforementioned patent documents are incorporated by reference in their entirety as part of the disclosure of this patent document. [0024] Organic wastes contribute significant quantities of greenhouse gases and represent a large disposal cost to every segment of the economy. As shown in FIG. 1 A, recovered hydrocarbons from waste streams or a fossil resource such as natural gas can be used to create various intermediates or precursor materials such as dimethylether (DME), diethylether (DEE), ethylene, propylene, olefin copolymer compounds, and/or polyacrylonitrile (PAN). In certain instances the method includes separating gases that are emitted. For example, methane, ethane, propane, butane, can be separated and used to create olefin and/or PAN intermediaries. As shown by example in FIG. 1 A, the method includes dehydrogenizing the gas(es), e.g., by adding heat or other forms of energy. In some implementations, the method includes polymerization of the separated gas(es), e.g., such as polymerization of methane to form ethane, ethylene, propane, and/or propylene including modifying the intermediate process gases by adding or utilizing heat or other forms of energy. For example, this energy may be utilized or added across an array in a vacuum furnace. In exemplary instances where ethane is separated, a dehydrogenizing step would convert the hydrocarbon to ethane, ethylene, propane or propylene etc. As shown in FIG. 1 B, the precursor (such as dehydrogenized material) can be incorporated as a co-polymer or reacted with a substance (such as ammonia and/or urea) to create an intermediate (such as acryl-modified polymer, e.g., polyacrylonitrile or other PAN intermediaries, nitriles, and paraffins). The precursor (such as various pitch compositions, polyethylene, polypropylene, polybutylene, or copolymers of such formulations or PAN- characterized intermediaries) can then be drawn into fibers.

[0025] Methods to produce carbon fibers and/or graphene materials using the thermoplastic produced such as olefin copolymers, rayon, pitch, polyacrylonitrile (e.g.,

PAN intermediaries) etc., including composites with one or more layers 120, 122 (Fig. 2) can include producing particular fibers tailored to particular designs that depend on desired functional uses and characteristics. For example, such precursors including

thermoplastics such as polyolefins, rayon, PAN, etc., intermediaries can be drawn into branch fibers if more friction is desired. In some implementations, for example, fuzzy surface features or fibers 310 can be produced and configured to include nanofiber 304 or macro filament growths or deposits that increase bonding area or friction including Velcro- like, fuzzy surface features 310 (e.g., barbed, hook, and loop fasteners) and/or can have various chemical latches created or include adhesive bonding. In some implementations, for example, geometric arrays, flat fibers, or nanotape, e.g., for increasing packing efficiency, are produced. Such exemplary fibers can be drawn and modified to produce higher performance reinforcement components with desired shapes and reinforcement orientations as shown in Figure 1 B for casting, extruding, or pultruding precursor through a forming system 100 including a ram compactor or screw conveyer 1 10 within a

temperature regulated forming die assembly 106, 108, 1 12 to plasticize feed stock added through passageways 104 with provisions for one or more precipitates or additional substances (e.g., the nanofibers 304 and/or microfibers 308) to be incorporated together to form one or more fibers 300, 452, 454, 456, 458, 460, 462, 464, 466, 468, etc., in flat arrays or other arrays and/or multiple shapes to increase an ability of the fibers to be packed together (i.e., a packing factor) such as shown in the graphite fiber 450 of Figure 4B. Illustratively, this includes variations 122 and 300 such as shown in Figures 2 and 3 including fuzzy surface features 310 that are anchored by the process. The fuzzy surface features provide more stability, internal friction, and/or adhesive strength to the boron nitride fiber 302 or composite application 414. Strength improvements may be provided by adhesive bonds that include chemical or radiative cross linking. Optionally, for example, a method for producing the embodiments described herein can include adding an activated carbon such as a single or multilayered architectural construct (e.g., the boron nitride fiber 302) and/or graphene that adsorptively contains and presents one or more suitable reactants such as a peroxide (e.g., methyl, ethyl, ketones) as an exemplary method for creating adhesive or chemical compounding bonds.

[0026] Embodiments 400 and 450 of Figures 4A, 4B, and 4C show how one or multiple fibers 300, 414 can be produced and further processed in reactor 402 with selected cross sections and substance combinations 452, 454, 456, 458, 460, 462, 464,

466, 468, etc., for compact reinforcement of structures such as 414 with fuzzy fiber 410 surfaces that are produced by anaerobic decomposition of a carbon donor on seeds or catalysts including hydrocarbons CxHy such as methane that can be delivered at adaptively regulated pressure and temperature according to controller 420 by regulator

409 and regulator 406 for produced hydrogen at adaptively controlled pressures in reactor

402 ranging from vacuum to ambient or above ambient pressures. In certain instances, the system 400 utilizes directed energy such as electron beams or monochromatic radiation such as provided by one or more CNC lasers is utilized in a process similar to 3- D printing to decompose a fluid carbon donor substance such as a gaseous ether, propane, ethane or methane to produce graphene, graphite, nanotubes or rods 504 (Fig. 5, 6, and 7) including one or more bulbous hollow, gas filled, or solid spheroids 505, or other nano, micro or macro-scale structures 502, 504, 506, and/or 508. Such operations can include anaerobic decomposition of paraffin, petrolatum, or pitch to provide seed deposits that can be epitaxially or randomly grown as crystalline or amorphous deposits by the hydrocarbon decomposition to form and/or grow single or multiple wall tubing, single and/or multiple layer graphene including scrolls and flower-like structures that form high surface areas of fuzzy surfaces for interlocking in composite assemblies.

[0027] In embodiment 450 various fibers 452-468 that can be processed into graphite fibers of the same or altered cross sections and can be further treated in system 400 including application in selected regions or more or less continually with thin deposits of wax or petrolatum from die treatment ports 472. Such hydrocarbon precursors can be dissociated and/or dehydrogenated to produce carbon seeds that can be crystalline or amorphous and that can be subsequently processed in reactor 402 to produce fiber reinforced assemblies of widely varying forms and shapes.

[0028] Embodiment 500 of Figure 5 shows low cost fiber 502 that has further fuzzy feature structures 504, 505 and 506. A fiber reinforced composite structure 600 shows interlocking of such feature structures 504, 505, and 506. A high composite strength component structure 700 shows interlocking fibers such as 502 by structures 504, 505, 506 along with interlocking by tubes, wires, flower petal-like structures or graphene platelets 508 that can be delivered by matrix adhesive 512. Figure 5A shows a cross- sectional view of the embodiment 500 (i.e., fiber 502).

[0029] In other exemplary embodiments of the disclosed methods, the method to produce carbon fibers and/or graphene materials can include adding iron to a carbon solution to allow for seeding of the carbon to catalytically initiate and produce the fiber or another form of architectural construct. Rejecting heat or process cooling may also be provided to produce graphene or graphitic forms or fibers that are precipitated from suitable organic or metal solutions. Management of thermal gradients allows control over the purification and orientation of the chemical bond structure of the fiber. Fibers can then be surface treated with a reactant such as a gaseous silicon contributor, e.g., such as silicon tetrafluoride, siloxane or silane to form silicon carbide.

[0030] In another exemplary embodiment of the disclosed methods, a nanotape or flat fiber can be produced using other precursor substances and forms, e.g., such as glass or glass-ceramic filaments as precursors. This fiber can be coated with carbon such as diamond like carbon (DLC), and the bonds may be strengthened or oriented by pulling in tension as such deposition occurs. An exemplary thermoplastic such as polyetherimide, polyimide, or another thermoset substance such as monomer styrene catalyzed by methyletherketone peroxide or epoxy that is typically utilized to form an inexpensive composite with the fiber can be reduced or eliminated due to the form factor, high strength, and linking or friction enhancing characteristics of the resulting fiber.

[0031] High composite strength component structures 700 can be produced by utilizing filler adhesives 512 that initially lubricate the compaction process and then bind the reinforcement elements. Illustratively, various multi-part epoxies, polyimides, styrene catalyzed by methylethylkeytone peroxide, polyetherimide, etc., serve as interlocking matrix formulations with particles of graphene 508 that can be developed by inexpensive production of graphene by facile non-oxidative solution-phase exfoliation of graphite to avoid oxidative functionalization that interrupts the sp ² -hybridized or conjugated carbon atoms in the typical structure of graphene. Such graphene particle production may include intercalated types of graphite that are subdivided and exfoliated in di methyl formamide to yield suspensions of crystal Sine single- and/or few-layer graphene platelets with nano, micro, or macro dimensions. In some applications, such graphite can be prepared by ultra- sonificaiion in N-methylpyrroSidone (NMP) to produce such non-functionalized graphene platelets 508. High strength composites including types with elevated temperature capabilities can be produced by various combinations of materials and manufacturing technologies including suitable Prepreg Techniques (PT), Resin Transfer Moiding(RTM), and Vacuum Assisted Resins Transfer Molding (VARTM) in which the resin system such as RTM370 includes suspensions of nano, micro and/or macro dimensioned particles such as tubes, scrolls or such graphene platelets and/or other particles to interlock with fuzzy structures on surfaces of low cost fibers, graphite or graphene reinforcement selections. Preparations such as RTM compared to Vacuum Assisted Resin Transfer Molding (VARTM) as described by "Composite Properties of RTM370 Poiyimide Fabricated by Vacuum Assisted Resin Transfer Molding (VARTM)"

(http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.qov/201 20000732.pdf) which is incorporated by reference herein are illustrative of such materials including RTM and VARTM assemblies.

[0032] In other applications filler adhesive is prepared by polymerization of suspensions of such nano, micro and/or macro dimensioned platelets and/or particles in polyetherimide precursor such as poiyamec acid that is polymerized in place with macroscopic selections of low cost fibers, graphene, and graphite reinforcement, in other instances, such particles and/or platelets are delivered for interiocking of fuzzy surfaces of iow cost macroscopic reinforcement seiections by co-polymerization of a diamine and an anhydride. Selections of high strength adhesives such as in situ polymerization of poiyamec acid to form polyetherimide enable production of lower cost fiber reinforced structures with or without fuzzy surfaces on the macroscopic reinforcement selections for improved composite strength at temperatures up to 175°C (350°F) or higher. Further improvement can be provided with adhesives such as RTM370 on iow cost fuzzy surfaced fibers and other macroscopic reinforcement seiections for improved composite strengths at temperatures such as 325°C (817°F) or higher.

[0033] In some implementations, for example, the disclosed technology includes methods to produce ceramic characterized compositions by 1 ) Melting local rocks, gravel, or sand; 2) Adjusting melt chemistry by hot refining and additions; 3) Producing press molded, extruded profiles, and/or blowing one or more melt streams into fibers; and 4) Heat treating to ceramic-glass products to adjust optical, physical, and composite strength outcomes.

[0034] The glass crystal fibers can be woven, matted, or incorporated as cables or composites in the architectural products for applications ranging from vertical farms to clathrate harvesting systems from permafrost to ocean deposits. For example, filaments, fiber and thin ribbon can be made from heated and fused minerals or "rocks" by the following exemplary steps. In a first step, for example, calcining can be performed to release, oxidize or drive out sulfur compounds, C0 ₂ , and water vapor and other undesirable contaminates as may be provided by a heated oxidizing atmosphere. In a second step, for example, melt refinement to adjust the chemistry and viscosity by various suitable arrangements for radiant, resistance and/or induction heating can be performed. In a third step, for example, molten filaments are formed by pouring, expelling fused liquid through a spinner die, or by valve operation, such as opening the bottom bung out of the production apparatus (e.g., crucible) that has been refined to have a suitable molten rock formula in it. In a fourth step, for example, conditioning with a gas can be performed. For example, conditioning events can include blowing gas across, in some instances perpendicular, and in other instances not perpendicular, which depends on the desired outcome. For example, conditioning events can include monitoring and/or applying surface tension of the fiber as it is formed over a mandrel with flow forming features. For example, the low density and flexible filaments, fibers, and/or strip that are produced have properties and characteristics such as fire-resistance or fire-proof qualities, chemical inertness, and may have thermal and or electrical resistance that are enhanced or produced by coatings such as DLC or conductive carbon allotropes as may be needed. Exemplary desired outcomes can include variable pressure and impingement angles of conditioning gas blows to produce short, curly, or scrunched fibers that may be

accumulated into wool-like or cotton-like assemblies; or conditioning gas blows may be of suitable temperature, pressure and chemical characteristics to produce long straight fibers that may be combed and/or woven into tapes or fabrics; and other conditioning gas blows may be made in conjunction with tooling to produce profiles, such as one or more temperature regulated rollers including one or more textured pinch rolls to create flat or textured ribbon that is flexible and ductile. For example, gas supplies may provide a reactant to produce a conversion coating and may be accomplished on substrate that is in tension to produce high strength and flexibility along with chemical and fatigue resistance. For example, conditioning gases can be carbon donors such as methane, ethane, propane, acetylene nitrogen, ammonia, including temperature controlled process gases. In many instances, for example, the desired outcomes utilize phase diagrams for choosing reactants, substrate constituents, and process parameters.

[0035] In some aspects, the disclosed technology includes methods to produce fuzzy fibers. The method includes electrospinning and/or a process to spin, pull, or draw a polymer material (e.g., polyethylene) into fiber in a suitable process to dehydrogenate the tensioned fiber to produce a carbon graphite fiber. Subsequently a process to deposit architectural constructs such as silicon carbide, silicon nitride and/or boron nitride or carbon nanotubes (e.g., single walled or multi walled nanotubes) on the tensioned carbon fiber produces a fuzzy fiber composition. For example, heat from the drawing process can provide substantial amounts of energy to dissociate donor substances and grow suitable fuzzy forms on the drawn fiber. Illustratively, for example, hydrocarbons and/or other reactants, e.g., such as selections of various chemical vapor deposited poly(p-xylylene) polymers, are deposited and heat treated to form architectural constructs such as nanotube structures to produce the fuzzy carbon fiber configuration. Exemplary architectural constructs are described in the U.S. Patent documents: U.S. Patent No. 8,980,416, entitled "ARCHITECTURAL CONSTRUCT HAVING FOR EXAMPLE A PLURALITY ARCHITECTURAL CRYSTALS", and U.S. Patent Application No. 13/584,658, entitled "ARCHITECTURAL CONSTRUCT HAVING A PLURALITY OF IMPLEMENTATIONS", both of which are incorporated by reference in their entirety as part of the disclosure in this patent document. In some instances, for example, the produced fuzzy carbon fiber appears 'black' in the visible, UV, and infrared spectra, where the fuzzy carbon fiber absorbs radiation from these spectra (e.g., large frequency radiation absorption).

[0036] In some implementations, the method can use polyolefin polymers to produce long fibers, e.g., that may have reduced tensile strength compared to PAN sourced fibers, but such fiber production output can be two or more times (e.g., approximately 2X to 6X) that of conventional methods using PAN feedstock. In other instances lower strength PAN produced fibers may be utilized to produce fuzzy fibers. Subsequently the same or greater properties compared to high strength composites of PAN produced fibers may be provided by converting the lower strength fibers to fuzzy fibers. [0037] The method can include multiple preliminary processes to produce a polymer used in the production of the fuzzy fibers. A preliminary process of the method can include producing ethane or ethylene from methane that is polymerized. Such preliminary processes can include recovering the hydrogen produced by forming ethylene, and polymerizing the ethylene to form polyethylene. Such hydrogen may be utilized as an energy carrier or to produce other valuable products such as ammonia, urea, or other compounds including liquid fuels such as fuel alcohols or formic acid by producing liquids or suspended substances such as urea and other compounds with nitrogen and/or carbon dioxide from sources such as the atmosphere.

[0038] While this patent document contains many specifics, these should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features that may be specific to particular embodiments of particular inventions. Certain features that are described in this patent document in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable sub combination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a sub combination or variation of a sub combination.

[0039] Similarly, while operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be

performed, to achieve desirable results. Moreover, the separation of various system components in the embodiments described in this patent document should not be understood as requiring such separation in all embodiments.

[0040] Only a few implementations and examples are described and other

implementations, enhancements and variations can be made based on what is described and illustrated in this patent document.