WO2016040612A1 - Entraînement d'oxyde de graphite dans un composite de ciment et d'asphalte - Google Patents

Entraînement d'oxyde de graphite dans un composite de ciment et d'asphalte Download PDF

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Publication number
WO2016040612A1
WO2016040612A1 PCT/US2015/049398 US2015049398W WO2016040612A1 WO 2016040612 A1 WO2016040612 A1 WO 2016040612A1 US 2015049398 W US2015049398 W US 2015049398W WO 2016040612 A1 WO2016040612 A1 WO 2016040612A1
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WIPO (PCT)
Prior art keywords
bitumen
graphene oxide
graphene
flakes
oxide flakes
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PCT/US2015/049398
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English (en)
Inventor
Sean CHRISTIANSEN
David RESTREPO
Richard Stoltz
Jeff Bullington
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Garmor, Inc.
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Publication date
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Publication of WO2016040612A1 publication Critical patent/WO2016040612A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/26—Bituminous materials, e.g. tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates in general to the field of graphite, and more particularly, to compositions and methods of graphite oxide entrainment in cement and asphalt composites.
  • Graphene is one of the strongest materials ever tested.
  • Various research institutes have loaded hosts with carbon allotropes such as carbon nanotubes (CNT), graphene flakes (GF), graphene oxide (GO), and graphite oxide and have seen up to a 200% increase in tensile strength in the loaded host, but with inconsistent results.
  • Measurements have shown that graphene has a breaking strength 200 times greater than steel, with a tensile modulus (stiffness) of 1 TPa (150,000,000 psi).
  • An atomic Force Microscope (AFM) has been used to measure the mechanical properties of a suspended graphene sheet. Graphene sheets held together by van der Waals forces were suspended over S1O 2 cavities where an AFM tip was probed to test its mechanical properties. Its spring constant was in the range 1-5 N/m and the Young's modulus was 0.5 TPa (500GPa) thereby demonstrating that graphene can be mechanically very strong and rigid.
  • Nano-silica's spherical shape, carbon nanotubes (CNTs) and Hummers' based GO that has both surface oxidation, epoxy groups and surface distortion have high-aspect-ratio.
  • CNTs and Hummers' based graphene/graphite oxide are suspended and dispersed in water then combined with Ordinary Portland Cement and or other materials reacted to form a cementitious composite.
  • CNTs Depending on whether they are single walled CNTs (SWCNTs) or multi-walled CNTs (MWCNTs), CNTs generally have the diameter of 1-3 nm or 5-50 nm, respectively.
  • the length of CNTs can be up to centimeters, which gives an aspect ratio exceeding 1000.
  • CNTs also exhibit extraordinary strength with moduli of elasticity on the order of TPa and tensile strength in the range of GPa, With the concurrent benefits of high aspect ratio and excellent mechanical performance, CNTs have been found to improve the toughness and strength of cementitious matrix materials. Incorporation of CNTs in cement composites has proven to be complex, yielding inconsistent results.
  • CNTs results in little change in strength or even deterioration of the composite in some cases. Poor dispersion of CNTs in the water based cement matrix is due to the weak bonding between the CNTs and the cement matrix. Owing to strong Van der Waal's attractive forces between particles, CNTs tend to form agglomerates or self -attraction/assembly similar to that seen in carbon black creating defect sites in the composites. CNTs without a dispersing agent had worse mechanical properties than the plain cement paste. Non-uniform distribution/dispersion of CNT bundles are responsible for the deterioration of the mechanical properties. Attempts have been made to incorporate CNTs into Bitumen. The Bitumen was either heated or modified the pH while being stirred in a vessel to incorporate the CNTs. The resulting suspension was then combined with the dry portions constituents of the asphalt. Although non- optimally dispersed the resulting composite had reasonable enhanced performance.
  • Hummers' based graphite/graphene oxide is produced by using concentrated acids and oxidants and often required significant purification of the HGGO product.
  • HGGO is more readily suspendable/dispersible in a polar solvent (ultra pure water) because the high level of oxidation making it hydrophilic.
  • the HGGO can also irreversibly precipitate from the suspension in the polar solvent as a function of pH or exposure to mobile ions in a short period of time. This forces the suspension/dispersion of the HGGO to be done on site using tap water, done at a remote facility using ultra pure (Dl) water or done at a remote facility and continuously mixed until it is used.
  • Dl ultra pure
  • HGGO suspension If the HGGO suspension is improperly handled it will result in aggregation of the HGGO resulting in defects and damaging the physical properties in the composite. Additionally, strongly oxidized HGGO has mechanical distortions on the surface of the flake and epoxy groups due to the oxidation process. The physical distortions prevent optimal improvement of the physical properties in a cementations material. In addition to the physical damage to the graphene/graphite oxide flake the creation of epoxy groups prevent the formation of chemical reaction in the cementitious material.
  • bitumen In order to mix bitumen with road-building aggregates, you first need to considerably reduce the viscosity of the cold hard binder. Traditionally, this was done by heating the bitumen and mixing it with heated aggregates to produce hot-mix asphalt. Other methods of reducing the bitumen viscosity include dissolving the bitumen in solvents and emulsification. Foamed asphalt was developed as a technology to uniformly incorporate Bitumen with the aggregates in asphalt.
  • FIG. 1 shows a foamed asphalt 10 of the prior art that is based on a process that heats Bitumen 12, the binder for asphalt, between 135°C to 180°C, and is injected with a small quantity of cold water 14 and compressed air 16.
  • the water achieves a sudden temperature increase and becomes steam.
  • the water expands on contact with the hot asphalt expanding (or foaming) the asphalt to 5-40 times its initial volume.
  • the three ingredients are combined in a small chamber optimized to create the foaming of the material.
  • the percentage of cool water to the Bitumen is 1% to 5% by mass. D. Csanyi at Iowa State University first demonstrated foam Bitumen/Asphalt.
  • the foamed asphalt, or asphalt bubbles can be dispersed into the mix fairly uniformly with a variety of solids to improve their properties and produce superior asphalt-based products. This can be compared to a traditional liquid asphalt binder at high temperature without foaming would immediately become globules when it contact cold aggregates and as such poorly dispersed. In general, if the ambient air temperature is greater than 10°C (50°F) or the road surface temperature is greater than 15°C (60°F) for uniform dispersion of the foamed asphalt in the aggregate.
  • the present invention can create foamed asphalt reinforced with graphene oxide (GO) by incorporated into the GO into the Bitumen foam.
  • the aggregate can comprise aggregate pieces of at least one of asphalt, concrete, and stone (e.g. rough stone or gravel).
  • foamed asphalt has often uses recycled road material in conjunction with 10% to 20% new limestone (mainly calcium carbonate and a small percent of quartz/silicon dioxide) and sand.
  • new limestone mainly calcium carbonate and a small percent of quartz/silicon dioxide
  • the specific composition of the aggregate changes based on the geographic region where the aggregate is mined.
  • the GO functionalization of COOH can react with calcium and silicon components found in limestone (mainly calcium carbonate and a small percent of quartz/silicon dioxide) sand to catalyze C-S-H (Calcium Silicate Hydrate) crystal formation and growth in the aggregate dramatically enhancing the strength of the final foamed bitumen product.
  • the aggregate can then be combined with the foamed Bitumen where the foamed bitumen is produced in the normal method.
  • the present inventors' flat- flake reduced-oxygen GO (r-GO) material can be suspended in water or suspended for a long period of time in hot bitumen.
  • r-GO reduced-oxygen GO
  • bitumen is a thermoplastic such that the r-GO will react chemically with it, to strengthen the final foamed asphalt product.
  • the present invention also includes a method of making a foamed-bitumen reinforced asphalt structure comprising: preparing an asphalt aggregate; mixing said asphalt aggregate with hot bitumen, graphene oxide and cool water; and forming said mixture into an expansion-confining volume within a structure, wherein the graphene oxide flakes strengthen the structure.
  • the graphene oxide flakes are mixed with the hot bitumen before the cool water is added.
  • compressed air is added along with the cool water.
  • the mixture of asphalt aggregates, hot bitumen, graphene oxide and cool water also contains at least one of calcium carbonate and sand.
  • the structure becomes at least part of a roadway.
  • the aggregates contain at least 50% recycled asphalt.
  • the graphene oxide flakes have less than 20 layers, and at least 50% graphene oxide flakes are substantially flat and are made by stirred ball milling and have an oxidization of from 0.1% to 30%.
  • the invention uses an aggregate containing pieces of at least one of asphalt, concrete, and stone. Mixing the aggregate, hot bitumen and graphene oxide, cool water and compressed air causes foaming of said hot bitumen and produces a graphene oxide-containing foam. Inserting the foaming mixture into a restraining volume forms a foamed bitumen structure, wherein the graphene oxide strengthens the structure.
  • the foamed bitumen also contains at least one of calcium carbonate and sand.
  • the graphene oxide flakes have less than 20 layers and at least 50% graphene oxide flakes are substantially flat and are made by stirred ball milling and have an oxidization of from 0.1% to 30%.
  • This can also be method of making foamed-bitumen comprising: mixing graphene oxide flakes with hot bitumen, and cool water, wherein said graphene oxide flakes are added to at least one of the hot bitumen and/or the cool water and wherein compressed air is added along with the cool water; and Inserting said mixture into an expansion-confining volume, wherein the graphene oxide flakes strengthen the structure.
  • the bitumen also contains at least one of calcium carbonate and sand.
  • the graphene oxide flakes have less than 20 layers, and at least 50% graphene oxide flakes are substantially flat and are made by stirred ball milling and have an oxidization of from 0.1% to 30%.
  • the graphite oxide flakes can be hydrophobic and be mixed with other hydrophobic powders.
  • the graphite oxide flakes generally have a surface area to thickness ratio greater than 300 Angstroms, and thickness of less than 160 Angstroms, wherein the graphene flakes have no significant physical surface distortions, having no significant epoxy functionalization and has an oxidation level less than 1.5% by mass. In one aspect, 95% of the graphene oxide flakes are from about 0.8 to 16 nanometers in thickness. In some embodiments the maximum dimension of the graphene/graphite oxide flakes between 220 Angstroms and 100 microns. In another aspect, the graphene/graphite oxide flake has primarily edge oxidation, the flakes have the same hydrophobicity as the aggregate pieces, and/or the stirred media mill is an Attrition mill or ball mill.
  • FIG. 1 shows the making of a foamed asphalt of the prior art
  • FIG 2 shows one embodiment of the modified foamed asphalt of the present invention.
  • FIG. 3 shows another embodiment of the modified foamed asphalt of the present invention
  • Obtaining consistent size and thickness can require controlled pre-processing (e.g., milling and separation) of the crystalline graphite mechanochemical process that use crystalline graphite with a mild oxidizing agent in conjunction with mechanical energy (milling) for synthesis of graphene/graphite oxide flakes.
  • controlled pre-processing e.g., milling and separation
  • the mechanical energy in conjunction with a mild oxidizing environment can produce edge oxidation of the graphene minimizing the strong surface oxidation, formation of epoxy groups and mechanical defects generated in a Hummers' based process.
  • Graphite (30g) can be used as the starting material for the graphene/graphite oxide flakes mechanochemical process.
  • the mechanochemical process can be done in what is generically referred to as a "stirred ball mill.” Milling in a closed chamber for 360 minutes at 2,000 RPM or less. When grinding in the ball mill, the balls (media) in their random movement are spinning in different rotation and therefore are exerting shearing forces on the crystalline graphite.
  • the resulting graphene/graphite oxide preferably has edge-only oxidization flakes with a pristine surface primarily free of distortions, epoxy groups or corrugations with low surface energies allowing for easier incorporation and entrainment in a host through powder mixing resulting in enhance physical properties.
  • the edge oxidized graphene/graphite flake can be chemically separated via acidic precipitation by titrating hydrochloric acid into the bath, which causes the larger (thicker/heavier) material comes out of suspension first creating a narrow graphene oxide flake distribution.
  • the particle size can be monitored during this process by a Dynamic Light Scattering (DLS) measurement tool.
  • Dynamic Light Scattering tools can resolve particle sizes down to 30A.
  • the surface area to thickness ratio should be greater than about 300 to have a positive impact on the host as a suspension.
  • the pH of the water containing the oxidized graphite/graphene oxide can range from 5 to 9 while maintaining the suspension of the media the pH of the resulting water/ graphene/graphite oxide mixture is typically is about 7.
  • a mechanochemical process can be controlled to process graphene/graphite with oxidization from 0.1% to 30%. Unless otherwise indicated or produced by the Hummers' process (which produces more-highly oxidized non-flat flakes), the term "graphene” as used herein means graphene oxide with oxidization of from 0.1% to 30%.
  • the functionalization can be COOH on the edge carbons preserving the graphene structure with substantially no epoxy groups.
  • Oxidized graphene/graphite produced by this milling method is typically hydrophilic and easily suspended in a neutral aqueous solution.
  • the oxidized graphite can be kept in suspension until varying the pH of the solution.
  • a ball mill operating with less than or equal to 2000 RPM can be generally sufficient to prevent agglomeration of the graphene adhering to the milling balls or tank.
  • the present invention can be a composite with a foamed asphalt reinforced with reduced graphene oxide (r-GO) by incorporating the r-GO into the aggregate or into the Bitumen foam.
  • the GO oxidation, of COOH can be from 2% to 30%.
  • the COOH functional group will react with calcium and silicon components in limestone and sand to catalyze C-S-H (Calcium Silicate Hydrate) crystal formation and growth in the aggregate dramatically enhancing the strength of the final foamed asphalt product.
  • C-S-H Calcium Silicate Hydrate
  • FIG. 2 shows the process of the present invention, in which GO is incorporated into the foamed GO-Bitumen 20 prior to combing the foamed Bitumen with the aggregate.
  • This can be accomplished by two different insertion points.
  • the first insertion point is relates to the GO suspended in the cool water 24 and injected into the hot Bitumen 22 and compressed air 26 in the foaming cavity 28.
  • the second approach is to suspend GO in the hot Bitumen 22 before injection into the cool water 24 and compressed air foaming cavity 28.
  • FIG. 3 shows another embodiment in which GO can be incorporated in to the foamed Bitumen directly prior to combing the foamed Bitumen with the aggregate. This can be accomplished by injecting the GO in two different insertion points.
  • the first insertion of GO into the foamed Bitumen 32 can be accomplished by suspending the r-GO or GO in the cool water 34 prior to injecting the water in the foaming chamber 38.
  • Garmor's reduced GO (r-GO) material can be suspended, for a short time in water.
  • the cool water is 1% to 5% by mass relative to the mass of Bitumen to achieve foaming.
  • GO can be suspended in water in concentration from 0.0001% to 30% by mass. As the maximum percentage of water in the foaming process is 5%.
  • the maximum mass GO that can be injected into the foamed Bitumen through this approach is 1.5% by mass relative to Bitumen.
  • the second approach is to suspend GO in the hot Bitumen 32 before being injected into the cool water 34 and compressed air 36 foaming cavity. Garmor's r-GO can be suspended up to 30% by mass in the Bitumen.
  • bitumen suspended GO 32 is injected into the foaming chamber 38 it becomes thoroughly mixed with the bitumen, and in addition the Bitumen becoming less viscous and easier to incorporate with the aggregate.
  • Bitumen is a thermoplastic such that the r-GO will react chemically with it, to strengthen the final foamed asphalt product.
  • compositions of the invention can be used to achieve methods of the invention.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises"), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • “comprising” may be replaced with “consisting essentially of or “consisting of.
  • the phrase “consisting essentially of requires the specified integer(s) or steps as well as those that do not materially affect the character or function of the claimed invention.
  • the term “consisting” is used to indicate the presence of the recited integer (e.g., a feature, an element, a characteristic, a property, a method/process step or a limitation) or group of integers (e.g., feature(s), element(s), characteristic(s), propertie(s), method/process steps or limitation(s)) only.
  • A, B, C, or combinations thereof refers to all permutations and combinations of the listed items preceding the term.
  • A, B, C, or combinations thereof is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
  • expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth.
  • BB BB
  • AAA AAA
  • AB BBC
  • AAABCCCCCC CBBAAA
  • CABABB CABABB
  • words of approximation such as, without limitation, "about”, “substantial” or “substantially” refers to a condition that when so modified is understood to not necessarily be absolute or perfect but would be considered close enough to those of ordinary skill in the art to warrant designating the condition as being present.
  • the extent to which the description may vary will depend on how great a change can be instituted and still have one of ordinary skilled in the art recognize the modified feature as still having the required characteristics and capabilities of the unmodified feature.
  • a numerical value herein that is modified by a word of approximation such as "about” may vary from the stated value by at least ⁇ 1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%.
  • compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

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Abstract

La présente invention concerne un procédé de fabrication d'une structure améliorée de bitume renforcé de mousse. Ce procédé utilise un agrégat contenant des morceaux d'au moins l'un parmi de l'asphalte, du béton et de la pierre. Le mélange de l'agrégat, du bitume et d'oxyde de graphène chaud, d'eau froide et d'air comprimé provoque le moussage dudit bitume chaud et produit une mousse contenant de l'oxyde de graphène. L'introduction du mélange mousseux dans un volume de retenue forme une structure de bitume alvéolée, dans laquelle l'oxyde de graphène renforce considérablement la structure.
PCT/US2015/049398 2014-09-11 2015-09-10 Entraînement d'oxyde de graphite dans un composite de ciment et d'asphalte WO2016040612A1 (fr)

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US201462048819P 2014-09-11 2014-09-11
US62/048,819 2014-09-11

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CN106189297A (zh) * 2016-08-17 2016-12-07 河南师范大学 一种导电沥青及其制备方法
CN106433160A (zh) * 2016-07-31 2017-02-22 包头稀土研究院 抗紫外纳米稀土复合氧化石墨烯改性乳化沥青及制备方法
US9758379B2 (en) 2013-03-08 2017-09-12 University Of Central Florida Research Foundation, Inc. Large scale oxidized graphene production for industrial applications
CN107245247A (zh) * 2017-05-19 2017-10-13 同济大学 基于羧基改性氧化石墨烯的聚乙烯改性沥青及其制备方法
US9828290B2 (en) 2014-08-18 2017-11-28 Garmor Inc. Graphite oxide entrainment in cement and asphalt composite
US9951436B2 (en) 2011-10-27 2018-04-24 Garmor Inc. Composite graphene structures
CN108559289A (zh) * 2018-05-14 2018-09-21 重庆路维康交通科技有限公司 一种纳米改性乳化沥青及其制备和使用方法
CN108793792A (zh) * 2017-04-27 2018-11-13 江苏苏博特新材料股份有限公司 增韧增强水泥及其制备方法
CN109401349A (zh) * 2018-11-26 2019-03-01 长沙理工大学 一种氧化石墨烯改性沥青及其制备方法
CN109970405A (zh) * 2019-05-08 2019-07-05 温州市三箭混凝土有限公司 一种混凝土及其制备方法
US10351711B2 (en) 2015-03-23 2019-07-16 Garmor Inc. Engineered composite structure using graphene oxide
CN110144128A (zh) * 2019-06-13 2019-08-20 安徽省高等级公路工程监理有限公司 一种超高耐久高速公路路面用改性沥青混合材料
CN110272230A (zh) * 2019-06-24 2019-09-24 中南林业科技大学 一种高性能稀浆封层沥青混合料及其制备方法
CN110424217A (zh) * 2019-08-10 2019-11-08 深圳市市政工程总公司 泡沫沥青的发泡设备
US10535443B2 (en) 2013-03-08 2020-01-14 Garmor Inc. Graphene entrainment in a host
WO2020034822A1 (fr) * 2018-08-17 2020-02-20 广西大学 Matériau de graphène pour la modification d'asphalte ainsi que procédé de préparation et application
CN111154279A (zh) * 2020-01-09 2020-05-15 新疆宏宇志祥工程咨询有限公司 石墨烯/碳纳米管改性环氧树脂沥青材料及其制备方法
CN112341108A (zh) * 2020-11-26 2021-02-09 中国矿业大学 一种氧化石墨烯纳米改性水泥基注浆材料及其制备方法
WO2021034620A1 (fr) * 2019-08-16 2021-02-25 S3 Concrete Technologies, Inc. (A Georgia Corporation) Produit de béton et ses procédés de préparation
CN112480695A (zh) * 2020-11-06 2021-03-12 安徽工业大学 一种石墨烯改性沥青的制备方法及其产品
US10981791B2 (en) 2015-04-13 2021-04-20 Garmor Inc. Graphite oxide reinforced fiber in hosts such as concrete or asphalt
US11038182B2 (en) 2015-09-21 2021-06-15 Garmor Inc. Low-cost, high-performance composite bipolar plate
CN113337136A (zh) * 2021-06-15 2021-09-03 长沙理工大学 改性沥青及其制备方法
US11214658B2 (en) 2016-10-26 2022-01-04 Garmor Inc. Additive coated particles for low cost high performance materials
US11414347B2 (en) 2019-08-27 2022-08-16 S3 Concrete Technologies, Inc. Concrete product and methods of preparing the same
RU2781584C2 (ru) * 2020-05-15 2022-10-14 Общество с ограниченной ответственностью "НАУЧНО-ПРОИЗВОДСТВЕННОЕ ПРЕДПРИЯТИЕ "ИННОХИМ" Способ когезионного упрочнения битума
US11482348B2 (en) 2015-06-09 2022-10-25 Asbury Graphite Of North Carolina, Inc. Graphite oxide and polyacrylonitrile based composite

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