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WO2024049712A1 - Fil de nanofibres de carbone fonctionnalisé - Google Patents

Fil de nanofibres de carbone fonctionnalisé Download PDF

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Publication number
WO2024049712A1
WO2024049712A1 PCT/US2023/031152 US2023031152W WO2024049712A1 WO 2024049712 A1 WO2024049712 A1 WO 2024049712A1 US 2023031152 W US2023031152 W US 2023031152W WO 2024049712 A1 WO2024049712 A1 WO 2024049712A1
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WIPO (PCT)
Prior art keywords
yarn bundle
nanofiber
cnt
oxidizing agent
nanofiber yarn
Prior art date
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Ceased
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PCT/US2023/031152
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English (en)
Inventor
Takahiro Ueda
Marcio D. LIMA
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Lintec of America Inc
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Lintec of America Inc
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Priority to JP2025504316A priority Critical patent/JP2025530071A/ja
Priority to US18/996,101 priority patent/US20250347048A1/en
Publication of WO2024049712A1 publication Critical patent/WO2024049712A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/09—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with free halogens or interhalogen compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D10B2101/122—Nanocarbons
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/022—Moisture-responsive characteristics hydrophylic

Definitions

  • the present disclosure generally relates to carbon nanofibers. Specifically, the present disclosure relates to carbon nanofiber yam functionalization, fabrication, and applications of such modified carbon nanofiber yarns and yarn bundles.
  • Carbon nanofibers interchangeable with carbon nanotubes (CNTs), are long and thin cylinders made of carbon that are arranged in a remarkable hexagonal lattice structure.
  • Carbon nanofibers have a broad range of electronic, thermal, and structural superior properties, making them suitable for various applications, including, but not limited to, field emitters, conductors, transistors, energy storage, and fibers and fabrics with different strengths, biomedical applications, and industrial applications.
  • carbon nanofibers are generally hydrophobic in that their surface repels water making them liquid-unfriendly with a strong tendency to agglomerate for the carbon nanofibers themselves, mainly due to the Van der Waals forces. Accordingly, carbon nanofibers may not perform as well where liquid absorption properties are desired, and alternative materials may be sought for such applications.
  • treated nano fiber yarn bundles with higher water absorption rates with retained yam bundle structures are provided.
  • the treated nanofiber yarn bundles more than double or quadruple their water-absorption capacity than untreated or pristine nanofiber yarns or yarn bundles.
  • FIG. 1 is a schematic illustration of CNT synthesis by chemical vapor deposition (CVD) in accordance with an exemplary embodiment.
  • FIG. 2 is a schematic illustration of continuous CNT sheet production by a drawing method in accordance with an exemplary embodiment.
  • FIG. 3 is a schematic illustration of continuous CNT yarn production by drawing and spinning in accordance with an exemplary embodiment.
  • FIG. 4 is a flow chart illustrating a method of performing an acid treatment on a CNT yarn bundle in accordance with an exemplary embodiment.
  • FIG. 5 is a flow chart illustrating a method of performing an ozone treatment on a CNT yarn bundle in accordance with an exemplary embodiment.
  • FIG. 6 is a graph illustrating increases of water absorption in treated CNT yarn bundles in accordance with an exemplary embodiment.
  • Carbon nanofibers or CNTs are long tubes with small diameters typically measured in nanometers. They have a high aspect ratio of length vs. diameter in a range of generally above 1000:1 and are made up of one or more graphene sheets rolled up into a concentric structure. Each graphene sheet is regarded as a wall; a single- wall CNT (SWCNT) is made of a single graphene sheet; a double-wall CNT is made of two graphene sheets; a multi-wall CNT (MWCNT) has multiple graphene sheets.
  • SWCNT single- wall CNT
  • MWCNT multi-wall CNT
  • CNT synthesis methods have been developed depending on product types, precursors, heating source, reaction time, temperature, and atmosphere.
  • the most common methods include, but are not limited to, arc discharge, electrolysis, laser ablation, chemical vapor deposition (CVD), flame synthesis, mechano-thermal, etc.
  • the well-known CVD methods have been classified into plasma-enhanced PE-CVD, aerosol CVD (AACVD), water-assisted WA- CVD, oxygen- assisted CVD, catalytic CVD, etc.
  • the CVD method utilizes acetylene (C2H2), ethylene (C2H4), or other hydrocarbons as a carbon source in a reaction chamber with a catalyst and a temperature ranging from 350 to l,000°C. Depending on the actual reaction temperature, reaction time, selection of catalyst, catalyst density, and carbon sources, the resulting CNTs vary.
  • a catalyst may be in a free-floating form within the reaction chamber during the synthesis (FC-CVD).
  • FC-CVD synthesis
  • the nanofibers are then collected and turned into yams involving dispersing of CNTs in a liquid with a dispersant or surfactant, followed by extrusion and continuous spinning of the dispersed mixture into a conventional solution.
  • a variation of the above yarn spinning methods includes, but is not limited to, the use of superacid in the spinning solution and the use of polymer ethylene glycol for CNT dispersion.
  • An alternative and commonly deployed CVD synthesis method starts with a catalyst deposition on a substrate, e.g., a silicon wafer, by electron-beam (E-beam) deposition.
  • the substrate may also comprise stainless steel or aluminum disposed on underlying silicon (Si) wafer or other ceramic substrates.
  • other catalyst deposition methods include, but are not limited to, sputtering, electrochemical methods, atomic layer deposition, laser-assisted CVD, and plasma-enhanced CVD.
  • Exemplary catalysts include iron on a buffer layer of silicon dioxide or aluminum oxide over a substrate.
  • the result is a collection of individual nanofibers aligned vertically to each other with one end of the nanofibers attached to the substrate, like a forest, frequently referred to as a CNT forest.
  • the van der Waals force and the entanglement among adjacent nanofibers are the main attributes that these CNTs are maintained in such a vertically aligned position, considering the small diameter of these individual CNTs from 0.3 nm up to 100 nm.
  • a CNT forest may eventually be spun into a CNT yam, as described in WO 2007/015710 and incorporated herein.
  • CNT yarns may be made by other methods well known in the literature. They may be commercially available from various suppliers. CNT G/D RATIO
  • carbon nanofibers incorporate carbon from various carbon source materials during the synthesis steps into one of the carbon allotropes, which include, but are not limited to, diamond, graphite, fullerenes, graphene, etc. From a molecular perspective, these materials are all entirely composed of carbon-carbon (C-C) bonds, with different orientations of these bonds in a specific material, indicating a drastically different material with distinguishable properties.
  • Ramen spectroscopy is a commonly applied non-destructive tool well suited to characterize molecular interactions and bonds of carbon material. Its measured vibrational frequency is very sensitive to the orientation of the C-C bond and weights of the atoms at either end of the bond, indicative of one or more carbon allotropes.
  • the nanofibers show the graphene characteristics on a Raman spectrum, the G band at 1590 cm' 1 plus a prominent 1340 cm' 1 D- band. The latter is a defect -induced feature attributed to dislocation defects. Amorphous graphite on the surface of nanofibers may also influence this D-band in the testing sample.
  • the intensity ratio of both D/G bands quantitively reflects the defect status of the nano fibers; it also indicates the crystallinity. A smaller ID/IG value, compared to a large one, indicates better crystallinity or fewer defects. Changes in the ID/IG value of a CNT material after a defined treatment correlate to structural or microstructural modification of CNT walls, which would appear as functional or property alterations of the CNT material.
  • Raman spectrometers are commercially available, from handheld to tabletop.
  • the i- Raman Plus from B&W Tek was an exemplary spectrometer selected to scan the samples at power 100, collection time of 60,000 ms, and measure the G and D peak values at 1590 cm' 1 and 1350 cm 1 , respectively.
  • the IG/ID ratios are calculated.
  • Carbon nanotubes are generally hydrophobic; their surface repels water making them liquid unfriendly with a strong tendency to agglomerate for CNTs themselves, mainly due to the Van der Waals forces.
  • Surfactants are frequently applied to disperse CNTs in solutions to make CNT suspensions.
  • CNT yarns appear to inherit the same hydrophobic property. Insufficient contacts and interactions between individual CNT fibers or bundles of CNT fibers (CNT yarns) and other materials or matrix materials limit the uses and applications of CNT yams.
  • Each nanofiber yarn bundle may have an equal length, e.g., 2 cm.
  • the treated nanofiber yarn bundles are transferred into a silicone tube, which has an inner diameter of one- sixteenth inch (1/16") or an inner diameter, in general, larger than the diameter of the nanofiber yarn bundle or a collection of the nanofiber yam bundles.
  • the initial weight was measured and recorded.
  • One end of the nanofiber yam bundles and the silicone tube were inserted into a water container with a constant one (1) cm deep water for three (3) consecutive days in a closed chamber to avoid water evaporation.
  • the bottom of the container was at least ten times larger than the total cross-section of the silicon tubes to ensure a sufficient amount of water supply during the water (or liquid) absorption test.
  • Each silicon tube with the nanofiber yarn bundles was weighted and subtracted by its initial weight to calculate the water absorption.
  • Untreated CNT yams and CNT yarn bundles preserve their primitive surfaces and hydrophobic characteristics and are herein referred to as pristine yarns and yam bundles.
  • CNT pristine yam bundles may be treated with an agent or a group of agents with a strong oxidizing potential to alter the CNT material surface and structure or microstructure to endorse new properties and functions.
  • the agent may be substantially pure, close to 100% purity, or have a percentage between 0-100%, depending on the chemical nature of the agent.
  • an exemplary oxidizing agent may be a gas or at least two gases.
  • Exemplary strong oxidizing gases may include but are not limited to ozone and chlorine.
  • CNT yarn bundles may be placed in a sealed treatment chamber. Then the chamber may be filled with at least one selected oxidizing gas at a target flow rate for a predetermined period of time. Once the predetermined period is expired, the treatment chamber is purged with inert gas or gas mixture, such as argon and/or nitrogen.
  • CNT treatment may include applying strong oxidizing agents and removing such agents upon achieving desired results.
  • Exemplary oxidizing agents may include but are not limited to strong chemical liquids, such as one or more strong acids. Moreover, certain acids may be mixed together in a volumetric ratio, such as a two-to-one volumetric ratio. In chemistry, a strong acid is an acid which ionizes its target or substrate completely in a water solution.
  • Exemplary strong acids include but are not limited to nitric acid, sulfuric acid, perchloric acid, nitic acid, perchloric acid, and combinations of nitric acid and sulfuric acid, sulfuric acid and potassium dichromate, and sulfuric acid and potassium permanganate.
  • FIG. 4 is a flow chart illustrating a method of performing an acid treatment on a CNT yarn bundle in accordance with an exemplary embodiment.
  • CNT forests were synthesized by standard chemical vapor deposition method on a silicon wafer using iron catalysts and acetylene gas as a carbon source.
  • CNT forests were drawn into CNT sheets.
  • the CNT sheets were twisted into CNT yarns with a predetermined diameter. The predetermined diameter may be 15 pm with standard deviation of 1 pm.
  • the CNT yams are wounded into spools. In an example, a spool may have 100 loops of CNT yams.
  • a spool of CNT yarns is cut open to form a CNT yarn bundle or more than one bundles, which may be referred to as a nanofiber yarn bundle or bundles.
  • strong acids may include, without limitation, at least nitric acid (HNO3) and sulfuric acid (H2SO4).
  • the mixture of strong acids may be formed of a 70% nitric acid mixed with a 98% sulfuric acid.
  • the nitric acid and the sulfuric acid may be mixed in a two-to-one volumetric ratio, respectively (i.e., two parts nitric acid and 1 part sulfuric acid).
  • the mixture of strong acids may include, without limitation, a perchloric acid, a nitric acid, a sulfuric acid, a potassium dichromate, or a potassium permanganate.
  • a mixture of acids is disclosed herein, aspects of the present disclosure are not limited thereto, such that a single acid solution may be utilized.
  • the single acid solution may vary in its chemical concentration level.
  • the CNT yarn bundles were submerged in the mixture of strong acids for a predetermined period of time.
  • the predetermined period of time may be at least 30 minutes, 300 minutes, or less than 24 hours.
  • the predetermined period of time may be any amount of time that results in a target increase of hydrophilicity for as short as 10 minutes.
  • the target hydrophilicity may be at least double or quadruple of innate hydrophilicity of untreated or pristine CNT yam bundles while maintaining the structural integrity of the CNT yarn bundles.
  • the CNT yarn bundles may be submerged in the mixture of strong acids for the predetermined period of time with occasional stirring.
  • the treated CNT yarn bundles are removed from the acid mixture, soaked in a water bath and rinsed with distilled water thoroughly.
  • FIG. 5 is a flow chart illustrating a method of performing an ozone treatment on a CNT yarn bundle in accordance with an exemplary embodiment.
  • carbon nanotube forests were synthesized by standard chemical vapor deposition method on a silicon wafer using iron catalysts and acetylene gas as a carbon source.
  • CNT forests were drawn into CNT sheets.
  • the CNT sheets were twisted into CNT yarns with a predetermined diameter. The predetermined diameter may be 15 pm with standard deviation of 1 pm.
  • the CNT yams are wounded into spools. In an example, a spool may have 100 loops of CNT yams.
  • a spool of CNT yarns is cut open to form a CNT yarn bundle or more than one bundles, which may be referred to as a nanofiber yarn bundle or bundles.
  • the CNT yarn bundles are placed in a treatment chamber, and then the treatment chamber is sealed.
  • the treatment chamber is filled with a selected oxidizing gas.
  • oxidizing gas may be formed of 20% ozone gas plus 80% nitrogen.
  • aspects of the present disclosure are not limited thereto, such that other ozone percentage makeup oxidizing gas may be utilized.
  • the CNT yarn bundle may be exposed to the oxidizing gas for a predetermined period of time.
  • the predetermined period of time may have a minimum value of 10 minutes, 30 minutes, 300 minutes, or a maximum value of 24 hours.
  • the predetermined period of time may be any amount of time that results in a target increase of hydrophilicity.
  • the target hydrophilicity may be at least double or quadruple of innate hydrophilicity of untreated or pristine CNT yarn bundles while maintaining the structural integrity of the CNT yam bundles.
  • the treatment chamber is purged with inert gas.
  • the inert gas may include, without limitation, nitrogen, argon and the like.
  • the treatment chamber is returned to the atmospheric environment, and the treated CNT yarn bundles are promptly removed from the treatment chamber and placed in storage, preferably in a sealed storage filled with inert gas.
  • One group of CNT yam bundles is treated with a strong acid mixture for 300 minutes, as detailed in the description of FIG. 4 provided above.
  • the CNT yarn water absorption capacity may be doubled or quadrupled with the most aggressive treatment, from a gain of 10 mg water per mg of CNT yarn bundles to 19 mg, 30 mg, and 47 mg for the pristine, 30-min ozone-treated, 300-min ozone-treated, acid-treated CNT yam groups, respectively.
  • Exemplary molecules include, but are not limited to, biomolecules, proteins, growth hormones, recombinant proteins, small molecules, therapeutic agents, chemicals, or gas molecules.
  • Nanofiber yarn bundles with improved hydrophilicity sidewall may support new applications in various technical fields and industries, including but not limited to lithium intercalation, gas storage, slow-release of large active agents, new composite material, and biotechnology and medical devices (implantable and ex- vivo).
  • Nanofiber yarns may be treated first for improved hydrophilicity. Then a bundle of treated yarns may be twisted together to form a twisted nanofiber yarn bundle. The twisted nanofiber yarn bundle may be further untwisted to produce a false -twisted nanofiber yam bundle as detailed above.
  • the Van der Waals forces between the nanofibers As the hydrophilicity of the nanofiber yam's surface changes, so are the Van der Waals forces between the nanofibers.
  • the reduced Van der Waals forces may leave with a loosely bundled twisted and false-twisted nanofiber yarn bundle, limiting such material's utilities and applications.
  • the loosely bundled nanofiber yarn bundles may present opportunities and/or advantages for migration or penetration of exogenous material crossing the nanofiber yarn bundles themselves.
  • inventions of the disclosure may be referred to herein, individually and/or collectively, by the term “invention” merely for convenience and without intending to voluntarily limit the scope of this application to any particular invention or inventive concept.
  • inventions merely for convenience and without intending to voluntarily limit the scope of this application to any particular invention or inventive concept.
  • specific embodiments have been illustrated and described herein, it should be appreciated that any subsequent arrangement designed to achieve the same or similar purpose may be substituted for the specific embodiments shown.
  • This disclosure is intended to cover any and all subsequent adaptations or variations of various embodiments. Combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the description.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne des fils de nanofibres fonctionnalisés présentant un caractère hydrophile accru avec une propriété d'absorption d'eau plus que doublée. L'invention concerne également des procédés de traitement destinés à produire de tels fils de nanofibres fonctionnalisés.
PCT/US2023/031152 2022-08-30 2023-08-25 Fil de nanofibres de carbone fonctionnalisé Ceased WO2024049712A1 (fr)

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JP2025504316A JP2025530071A (ja) 2022-08-30 2023-08-25 機能性カーボンナノファイバ糸
US18/996,101 US20250347048A1 (en) 2022-08-30 2023-08-25 Functionalized carbon nanofiber yarn

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US202263402185P 2022-08-30 2022-08-30
US63/402,185 2022-08-30

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US20080170982A1 (en) * 2004-11-09 2008-07-17 Board Of Regents, The University Of Texas System Fabrication and Application of Nanofiber Ribbons and Sheets and Twisted and Non-Twisted Nanofiber Yarns
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