WO2025137776A1 - Compositions, systèmes et procédés pour ciment d'asphalte à base de graphène turbostratique et modificateurs de béton - Google Patents

Compositions, systèmes et procédés pour ciment d'asphalte à base de graphène turbostratique et modificateurs de béton Download PDF

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Publication number
WO2025137776A1
WO2025137776A1 PCT/CA2024/051741 CA2024051741W WO2025137776A1 WO 2025137776 A1 WO2025137776 A1 WO 2025137776A1 CA 2024051741 W CA2024051741 W CA 2024051741W WO 2025137776 A1 WO2025137776 A1 WO 2025137776A1
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WIPO (PCT)
Prior art keywords
asphalt
graphene
modifier
asphalt cement
polymer
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Pending
Application number
PCT/CA2024/051741
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English (en)
Inventor
Eytan MAZOR
Yasamin KAZEMI
Zhiyong Zhang
Marco CHU
Nicholas Anthony GOODWIN II
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Universal Matter Inc
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Universal Matter Inc
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Publication of WO2025137776A1 publication Critical patent/WO2025137776A1/fr
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Classifications

    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/022—Carbon
    • C04B14/024—Graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/90—Other morphology not specified above
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the embodiments disclosed herein relate to asphalt cement and asphalt concrete mixtures, and, in particular, to compositions of graphene and graphene-based polymers composites and asphalt cement modifiers for asphalt cement and methods of manufacture of the same.
  • Asphalt cement is commonly used in the pavement, construction, and roofing industries.
  • asphalt cement is often used as a binder for mineral aggregates in asphalt concretes or pavements.
  • asphalt cement and compositions thereof become damaged due to factors such as temperature-induced deformation or rutting, thermal cracking caused by low temperatures, and fatigue from heavy loads. This can lead to costly repairs such as frequent road repaving.
  • mineral aggregates make up most of these mixtures the effect of the asphalt cement-containing binder on these properties is significant.
  • the prices of asphalt cement and polymer modifiers have increased based on, at least, the decline of crude oil reserves globally, the demand for petroleum products, and the increase in applications of asphalt cement. Therefore, is beneficial to optimize the asphalt cement’s rheology, and strength to minimize cost and improve longevity of the asphalt.
  • modifiers such as fibrous reinforcements, surfactants, adhesion promoters, nanofillers, or polymers are included in the asphalt concrete mixtures to improve performance, such as the durability and environmental resilience of pavement construction. Performance improvements depend substantially on the modifier selected and the dosage of each modifier. The compatibility of the modifier and incorporation method is also a factor effecting phase separation during storage, transportation, application, and service.
  • a wet method is used to mix a solid modifier with neat asphalt cement.
  • the solid modifier is mixed with asphalt cement at high temperatures resulting in a modified binder.
  • the modified binder is mixed with aggregates to obtain asphalt concrete or pavement. Mixing temperature and duration will depend on the type of modifier and neat asphalt.
  • the wet process may also change the rheological response of polymer-modified asphalt due to the aging and oxidation of asphalt components, yielding an increase in the linear viscoelastic functions and steady-state viscosity.
  • the wet method may require a high energy mixing process and/or the addition of a crosslinker to stabilize and disperse the modifier in the asphalt cement, particularly where the modifier is a high molecular weight polymer.
  • a dry method is used to mix polymer granules or chips of the modifier are first mixed with aggregates and then neat asphalt cement is added to the mix.
  • the dry method may be more difficult to implement due to lower mixing energy used to disperse the polymer phase in the asphalt concrete mixture compared to the wet method one.
  • the modifier is a polymer modifier, such as styrene-butadiene block copolymers (SBSs).
  • SBSs styrene-butadiene block copolymers
  • Polymer modifiers enhance the elasticity, strength, durability, cohesion, and adhesion of asphalt cement.
  • the polymer modifiers enable or improve the asphalt cement binder’s resistance to deformation, rutting, cracking, and fatigue, and distributes stresses more effectively.
  • Polymer-modified asphalt cement often exhibits improved performance in terms of temperature susceptibility, with increased stiffness at high temperatures and reduced brittleness at lower temperatures. They also demonstrate enhanced resistance to aging, oxidative degradation, and moisture damage.
  • the asphalt modifier is added as an additive directly to an aggregate of the asphalt concrete.
  • adding the graphene-polymer composite into the asphalt concrete by dry mixing directly to one or more of a hot mix asphalt (HMA) and warm mix asphalt (WMA).
  • HMA hot mix asphalt
  • WMA warm mix asphalt
  • asphalt cement also known as and referred to herein as “asphalt binder”, “binder” or “pitch” is a mixture obtained by refining a complex mixture such as crude oil, tar, coal, or biomass, or a modified asphalt cement.
  • the asphalt cement may be for road pavement and road surface repair. It may also be for shingles or roof applications, and any other asphalt cement based composite.
  • the asphalt cement may be, without any limitation, a natural product. Asphalt cement examples include sticky, black, highly viscous liquid or semi-solid forms of hydrocarbons obtained naturally or synthetically as a residue from petroleum distillation. Asphalt cement may further contain various petrochemical components.
  • Asphalts may be classified by the SARA method into four fractions defined as saturates (S), aromatics (Ai), resins (R), and asphaltenes (A2) with the molecular weight (MW), aromaticity, polarity, and heteroatomic content increasing in the order S ⁇ A1 ⁇ R ⁇ A2. It will be appreciated may be used generally “asphalt cement” to describe neat asphalt cement or modified asphalt cement as defined below.
  • nitrogen asphalt cement refers to “asphalt cement” to be modified with a modifier as described below.
  • modified asphalt cement refers to asphalt cement including a modifier as described below.
  • asphalt concrete or “asphalt concrete mixture” as used herein refers to the mixture of asphalt cement and mineral aggregates.
  • Asphalt concrete is also known as “asphalt”, “asphalt concrete”, “blacktop”, “asphalt concrete conglomerates” or “pavement”.
  • the amount of asphalt cement may be between 4-10% of the asphalt concrete, preferably to be 4-5%.
  • mineral aggregates used herein is also known as “construction aggregates” or simply “aggregates” refers to a broad category of medium to coarsegrained mineral particles used in constructions.
  • Example mineral aggregates include, but are not limited to, sand, gravel, crushed stone, slag, recycled asphalt, recycled concrete, and geosynthetic aggregates.
  • the amount of aggregate may be between 90-96%, preferably to be 95-96%.”
  • asphalt plant refers to a site where asphalt concrete is handled.
  • graphene refers to any carbon-based structure comprising graphitic structural units present in various forms and morphologies. Existing forms and morphologies include 2D sheets, fiber-like structures, and polyhedral morphologies.
  • the term “graphene” further refers to a material which is a one-atom-thick planar sheet of sp2- bonded carbon atoms that are densely packed in a honeycomb crystal lattice, and, further, contains an intact ring structure of carbon atoms and aromatic bonds throughout at least a majority of the interior sheet and lacks significant oxidation modification of the carbon atoms.
  • Graphene has a predominately crystalline structure and its quality is measured by its degree of crystallinity. Graphene is distinguishable from graphene oxide in that it has a lower degree of oxygen-containing groups such as OH, COOH and epoxide.
  • a graphene monolayer refers to graphene that is a single layer of graphene.
  • very few-layer graphene refers to a graphene that is between 1 to 3 layers of graphene.
  • a few-layer graphene refers to graphene that is between 2 to 5 layers of graphene.
  • multilayer graphene refers to a graphene that is between 2 to 10 layers of graphene.
  • Flash Joule Heating refers to quickly and intensely heating a resistive carbon source, as defined below, by passing an electric current through the resistive carbon source.
  • flash joule heating examples are described in the flash joule heating synthesis method and compositions thereof of Patent Cooperation Treaty Application having International Publication Number WO 2020/051000 A1 to Tour et al., having an international publication date of March 12, 2020, which is herein incorporated by reference in its entirety and a system and methods for producing graphene by joule heating described in Patent Cooperation Treaty Application having International Application Number WO2023044569A1 to Mancevski et al., having an international publication date of March 03, 2023, which is herein incorporated by reference in its entirety and Device and method for continuous synthesis of graphene described in Patent Cooperation Treaty Application having International Application Number W02021092705A1 to Mancevski publication date of May 20, 2021 , which is herein incorporated by reference in its entirety.
  • the matrix polymer or polymeric additives 422 may be in pellet form, or flake form, or fine powder form, or wax form.
  • the joule heating flashed graphene used in the compounding may be in pellet form or fine powders, preferably to be fine powders for ease of combination with the matrix polymer.
  • graphene may be pre-mixed with the matrix polymer, polymeric additives 422, or both, before being fed into the extruder 418 or any other mixing tool. Alternatively, graphene may be fed directly into the extruder 418.
  • graphene asphalt cement composite there is a graphene asphalt cement composite.
  • the graphene asphalt cement composite includes an asphalt cement, also known as asphalt, asphalt binder, or asphalt cement.
  • the graphene serves as an additive, modifier, or performance promoter.
  • graphene may be a turbostratic flake graphene.
  • the turbostratic flake graphene can be made from a natural material, for example, coke or coal; or from a processed material, for example, petroleum-based coke, processed biomass, etc.
  • turbostratic fiber graphene and flake graphene may be made from biomass wastes or low-cost fibrous feedstocks.
  • graphene can be added directly as an additive at low concentrations to asphalt cement to adjust asphalt cement’s rheology and improve its mechanical performance and aging performance when used in asphalt concrete.
  • the temperature performance can be fatigue cracking resistance, thermal cracking resistance, rutting-resistant, higher grading temperatures, lower grading temperature, etc.
  • the aging performance can be a longer service life with improved mechanical durability, improved stability to oxidation, improved resistance to stripping by moisture damage, drain down, etc.
  • the modification can be achieved by a surfactant, dispersant, organic or inorganic ligand, coupling agent, etc.
  • graphene can be compounded into polymer at low concentrations or as a master batch to make a graphene-polymer composite as an additive to asphalt cement to improve the mechanical and aging performance.
  • polymer can be a neat polymer or blends of several types of polymers.
  • the polymer can be Polyethylene, Polypropylene, Poly Vinyl Butyral, Ethylene Vinyl Acetate, Ethylene Acrylate, Ethylene Alkyl Acrylate, EPDM rubber, GTR (Ground Tire Rubber), Polyethylene Terephthalate, or a resin, such as Escorez resin, or a blend of these polymers.
  • polymer can be functionalized, for example, with maleic anhydride, or Glycidyl Methacrylate, grafted with Polyethylene, Polypropylene, Ethylene Vinyl Acetate
  • the polymers could be linear, branched, homopolymers, copolymers, grafted polymers, block polymers, random polymers, or any possible polymer configuration with different crystallinity levels and density levels.
  • the polymer(s) can be non-used neat polymer or from recycled polymer material.
  • the polymer(s) can be crosslinked by compounding with a crosslinker.
  • a crosslink can be a sulfur or sulfur-based crosslinker, Isocyanate crosslinker, or a peroxide crosslinker
  • the graphene - polymer composite can be used in parallel to other asphalt modifiers and additives such as, other polymers, polyolefins, SBS, SBR, SB, GTR (ground tire rubber) PET, RET- Reactive elastomeric terpolymers, hybrids thereof, warm mix additives, foaming technologies, wax additives, chemical additives, adhesion promotions - amines, phosphate esters, silanes, recycling agents, rejuvenators, stiffening agents, crosslinkers- sulfur, polyphosphoric acid (PPA), Isocyanate based, sulfur less agents, antioxidants, functional fillers, gilsonite, hydrated lime, portland cement, fly ash, steel slag, fiber
  • the graphene-polymer composite is added into asphalt cement by wet mixing directly in the asphalt terminal using a typical wet mixing tool at temperatures above asphalt cement’s melting temperature.
  • the mixing tool can be a high-shear mixer, standard high shear mil such as commonly used in asphalt terminals or similar.
  • the graphene-polymer composite is added into asphalt cement by wet mixing to adjust asphalt cement’s rheology and improve its mechanical performance and aging performance when used in asphalt concrete.
  • the temperature performance can be fatigue cracking resistance, thermal cracking resistance, rutting-resistant, higher grading temperatures, lower grading temperature, etc.
  • the aging performance can be a longer service life with improved mechanical durability, improved stability to oxidation, improved resistance to stripping by moisture damage, drain down, etc.
  • the wet mixing is done with the addition of a crosslinker.
  • a crosslinker can be a sulfur, sulfur-based chemical, Polyphosphoric Acid (PPA) or a peroxide crosslinker.
  • PPA Polyphosphoric Acid
  • the crosslinker creates 3D polymer network to improve the asphalt cement’s stability.
  • the graphene-polymer composite is added into asphalt concrete by dry mixing directly to Hot Mix Asphalt (HMA) and Warm mix asphalt (WMA) in asphalt plant via aggregates drum heater, RAP feeder, aggregate and asphalt cement mixer, etc.
  • HMA Hot Mix Asphalt
  • WMA Warm mix asphalt
  • the graphene-polymer composite is added into asphalt concrete by dry mixing directly to Hot Mix Asphalt (HMA) and Warm mix asphalt (WMA) in field asphalt mobile mixer via aggregates drum heater, RAP feeder, aggregate and asphalt cement mixer, etc.
  • HMA Hot Mix Asphalt
  • WMA Warm mix asphalt

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Road Paving Structures (AREA)

Abstract

Sont proposés des compositions, des systèmes et des procédés pour ciment d'asphalte à base de graphène turbostratique et modificateurs de béton. Est proposé un modificateur d'asphalte pour modifier le ciment d'asphalte. Le modificateur est conçu pour être ajouté au béton ou au ciment d'asphalte et est composé de graphène obtenu par chauffage par effet Joule flash d'une source de carbone. Est proposé un procédé de modification d'asphalte. Le procédé comprend l'ajout au béton ou au ciment d'asphalte d'un modificateur d'asphalte composé de graphène obtenu par chauffage par effet Joule flash d'une source de carbone. Sont proposés un ciment d'asphalte modifié et du béton. L'asphalte modifié est composé d'un modificateur d'asphalte, le modificateur d'asphalte étant composé de graphène obtenu par chauffage par effet Joule flash d'une source de carbone.
PCT/CA2024/051741 2023-12-28 2024-12-30 Compositions, systèmes et procédés pour ciment d'asphalte à base de graphène turbostratique et modificateurs de béton Pending WO2025137776A1 (fr)

Applications Claiming Priority (2)

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US202363615329P 2023-12-28 2023-12-28
US63/615,329 2023-12-28

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WO2025137776A1 true WO2025137776A1 (fr) 2025-07-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120748541A (zh) * 2025-08-27 2025-10-03 内蒙古工业大学 基于响应面法的RAP-钢渣再生沥青混合料最优配比及Gr-TiO2掺杂方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020051000A1 (fr) * 2018-09-05 2020-03-12 William Marsh Rice University Procédé de synthèse par chauffage ohmique instantané et compositions associées
WO2022123499A1 (fr) * 2020-12-09 2022-06-16 Universal Matter Inc. Composites de graphène et leurs procédés de production
WO2023044569A1 (fr) * 2021-09-21 2023-03-30 Universal Matter Inc. Systèmes et procédés de production de graphène
CN116874224A (zh) * 2023-05-26 2023-10-13 中路交建(北京)工程材料技术有限公司 一种超高性能沥青混凝土改性剂及其制备和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020051000A1 (fr) * 2018-09-05 2020-03-12 William Marsh Rice University Procédé de synthèse par chauffage ohmique instantané et compositions associées
WO2022123499A1 (fr) * 2020-12-09 2022-06-16 Universal Matter Inc. Composites de graphène et leurs procédés de production
WO2023044569A1 (fr) * 2021-09-21 2023-03-30 Universal Matter Inc. Systèmes et procédés de production de graphène
CN116874224A (zh) * 2023-05-26 2023-10-13 中路交建(北京)工程材料技术有限公司 一种超高性能沥青混凝土改性剂及其制备和应用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120748541A (zh) * 2025-08-27 2025-10-03 内蒙古工业大学 基于响应面法的RAP-钢渣再生沥青混合料最优配比及Gr-TiO2掺杂方法

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