WO2008000163A1 - Nanotubes de carbone sous forme d'aérogel et procédés de préparation de ces derniers, membrane et matériau composite contenant ces derniers - Google Patents

Nanotubes de carbone sous forme d'aérogel et procédés de préparation de ces derniers, membrane et matériau composite contenant ces derniers Download PDF

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WO2008000163A1
WO2008000163A1 PCT/CN2007/001957 CN2007001957W WO2008000163A1 WO 2008000163 A1 WO2008000163 A1 WO 2008000163A1 CN 2007001957 W CN2007001957 W CN 2007001957W WO 2008000163 A1 WO2008000163 A1 WO 2008000163A1
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carbon nanotubes
aerogel
membrane
bundles
arrays
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PCT/CN2007/001957
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English (en)
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Fei Wei
Qiang Zhang
Weiping Zhou
Guanghui Xu
Zhou Yang
Weizhong Qian
Guohua Luo
Yao Wang
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Tsinghua University
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Publication of WO2008000163A1 publication Critical patent/WO2008000163A1/fr

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B01D71/0212—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0046—Inorganic membrane manufacture by slurry techniques, e.g. die or slip-casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • 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
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/168—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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/04—Nanotubes with a specific amount of walls
    • C—CHEMISTRY; METALLURGY
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    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5284—Hollow fibers, e.g. nanotubes
    • C04B2235/5288—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • Carbon nanotubes have many unique properties stemming from the small size, cylindrical structure, and high aspect ratio of length to diameter.
  • Single- walled carbon nanotubes consist of a single graphite sheet wrapped around to form a cylindrical rube.
  • Multi-walled carbon nanotubes comprise an array of such nanotubes that are concentrically nested like the rings of a tree trunk.
  • CNTs have extremely high tensile strength ( ⁇ 150 GPa) 5 high modulus ( ⁇ 1 TPa), large aspect ratio, low density, good chemical and environmental stability, and high thermal and electrical conductivity.
  • Carbon nanotubes have found various applications, including the preparation of conductive, electromagnetic and microwave absorbing and high-strength composites, fibers, sensors, field emission displays, inks, energy storage and energy conversion devices, radiation sources and nanometer-sized semiconductor devices, probes, and interconnect.
  • the present invention is directed to methods for the facile preparation of solvent free and well-dispersed aerogel carbon nanotubes that are useful in the preparation of nanotube membranes and nanocomposite materials.
  • the present invention allows the synthesis of aerogel carbon nanotubes having predetermined and/or controlled density, aspect ratio and diameters with ease.
  • the present invention provides a method for preparing aerogel carbon nanotubes.
  • the method includes contacting a plurality of carbon nanotube aggregates with a shearing means under conditions sufficient to form a plurality of carbon nanotube agglomerates having a density from about 0.1 to about 100 g/L.
  • the method further includes dispersing the plurality of carbon nanotube agglomerates in a gas, and descending the plurality of carbon nanotubes agglomerates to form aerogel carbon nanotubes having a predetermined density.
  • the aggregates are bundles, arrays or a combination of bundles and arrays.
  • the present invention provides aerogel carbon nanotubes.
  • the aerogel carbon nanotubes include a plurality of dispersed carbon nanotube aggregates, wherein said aggregates include bundles, arrays or a combination thereof and wherein said aggregates have a diameter from about 1 nm to about 100 ⁇ m, an aspect ratio from about 10 to about 10 6 , and a density from about 0.1 to about 100g/L.
  • the present invention provides a method for preparing a carbon nanotube membrane.
  • the method includes depositing aerogel carbon nanotubes on a planar solid support under condition sufficient to form a carbon nanotubes membrane.
  • the present invention provides a method for preparing a polymer composite material.
  • the method includes admixing a polymer with aerogel carbon nanotubes under conditions sufficient to form a polymer composite material.
  • the method further includes thermal-pressing the composite to form a membrane.
  • the present invention provides a method for preparing an inorganic composite material.
  • the method includes admixing an inorganic compound with the aerogel carbon nanotubes to form a mixture, heating the mixture, and hot-pressing the mixture under conditions sufficient to form an inorganic composite material.
  • Fig. 1 illustrates a schematic diagram for the preparation of aerogel carbon nanotubes according to an embodiment of the present invention.
  • Figs.2a-d show a scanning electron microphotography (SEM) image of the carbon nanotubes arrays before crushing and/or shearing;
  • Fig. 2b shows an SEM image of the dispersed carbon nanotubes arrays after mechanical crushing and/or shearing;
  • Fig. 2c shows an SEM image of the aerogel carbon nanotubes arrays collected after mechanical crushing and/or shearing, dispersing in gas phase, and descending for 30s;
  • Fig. 2d shows an SEM image of the aerogel carbon nanotubes arrays collected after mechanical crushing and/or shearing, dispersing in gas phase, and descending for 4 minutes.
  • Fig. 3 shows an SEM image of the aerogel carbon nanotubes arrays collected after high gas velocity shearing, dispersing in gas phase, and descending for 1 minute.
  • Fig. 4a-b shows an SEM image of the aerogel carbon nanotubes bundles collected after mechanical crushing and /or shearing, dispersing in gas phase, and descending for 30s;
  • Fig. 4b shows an SEM image of the areogel carbon nanotubes bundles collected after mechanical crushing, dispersing in gas phase, and descending for 3 minutes.
  • Fig. 5 shows an SEM image of the areogel carbon nanotubes arrays collected after mechanical crushing and/or shearing, dispersing in gas phase, and descending for 15 minutes.
  • Fig. 6 shows an SEM image of a carbon nanotube membrane or paper prepared from aerogel carbon nanotubes according to an embodiment of the present invention.
  • Fig. 7 shows an SEM image of a transparent conductive film prepared from aerogel carbon nanotubes according to an embodiment of the present invention.
  • the present invention relates to the methods for the synthesis of well-dispersed aerogel carbon nanotubes having predetermined or controlled physical characteristics and properties; methods for the synthesis of nanotube membranes having unique physical properties; and methods for the synthesis of nanocomposite materials having enhanced and/or improved physical properties.
  • the present invention provides aerogel carbon nanotubes.
  • the aerogel carbon nanotubes are composed of a plurality of well-dispersed carbon nanotubes aggregates.
  • the aggregates are in the form of bundles, arrays or a combination of arrays and bundles.
  • the carbon nanotubes bundles or arrays have a diameter from about 1 nm to about 100 ⁇ m, an aspect ratio from about 10 to about 10 6 , and a density from about 0.1 to about 100g/L.
  • the aerogel carbon nanotubes form a plurality of carbon nanotubes agglomerates.
  • the aerogel carbon nanotubes bundles, arrays or agglomerates can have a diameter ranging from about 0.4-0.6 nm, 0.5-1 nm, 5-6 nm, 1-10 nm, 1-20 nm, 1-30 nm, 1-40 nm, 10-50 nm, 40-100 nm, 1-200 nm, 1-500 nm, 100-700 nm, 100-900 nm, 800 nm -10 ⁇ m, l ⁇ m- 30 urn, 10 ⁇ m-50 ⁇ m, 10 ⁇ m-80 ⁇ m or 10 ⁇ m-100 ⁇ m.
  • the carbon nanotubes bundles, arrays or agglomerates have a diameter ranging from about 1 nm -500 nm, 1 nm -200 nm, 10 nm - 350 nm, 0.5 ⁇ m- 40 ⁇ m or 5 ⁇ m-50 ⁇ m. More preferably, the carbon nanotubes bundles, arrays or agglomerates have a diameter ranging from about 1 ⁇ m-25 ⁇ m, 15 ⁇ m-30 ⁇ m, 50 nm-250 nm, or 10 nm-100 nm.
  • the aerogel carbon nanotubes bundles, arrays or agglomerates have an aspect ratio ranging from about 10-100, 100-500, 10-1000, 100-1000, 100-10000, 1000-10000, 1000-50000, 1000-100000, 10000-100000, 10000-500000, 100000-10 6 .
  • the aerogel carbon nanotubes bundles can have various lengths ranging from about 0.3 ⁇ m to about 5000 ⁇ m, preferably, from about 0.8 ⁇ m- 1600 ⁇ m, more preferably, from about 1 ⁇ m-1500 ⁇ m, even more preferably, from about 100 ⁇ m-1400 ⁇ m, 10 ⁇ m-100 ⁇ m, 1 ⁇ m-10 ⁇ m, 10 ⁇ m-500 ⁇ m or 200 ⁇ m-3000 ⁇ m.
  • the aerogel carbon nanotubes can have various densities.
  • the aerogel carbon nanotubes have a density from about 0.01 to 150 g/L.
  • the aerogel carbon nanotubes have a density from about 0.01-0.05, 0.05-0.1, 0.1-0.5, 0.5-1, 1-1.5, 1.5-2.5, 2.5-10, 10-30, 30-50 or 50-100 g/L.
  • the aerogel carbon nanotubes have a density selected from the group consisting of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.24.5, 5.0, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 50, 60, 70, 80, 90 and 100 g/L.
  • the aerogel carbon nanotubes have a density selected from the group consisting of 0.1, 0.2, 0.5, 1.3, 1.4, 2, 2.2 and 42 g/L.
  • aerogel carbon nanotubes can be multi-walled carbon nanotube bundles, few-walled carbon nanotube bundles, single-walled carbon nanotube bundles, a multi-walled carbon nanotube arrays, few-walled carbon nanotube arrays, single-walled carbon nanotube arrays, or combinations thereof.
  • single-walled carbon nanotubes have a diameter ranging from less than 1 nm to a few nanometers.
  • Double-walled carbon nanotubes have a diameter of several nanometers.
  • Few- walled carbon nanotubes have a diameter ranging from a few nanometers to several tenths of nanometers.
  • Multi- walled carbon nanotubes have a diameter ranging from a few nanometers to 100 nm, such as from about 1 nm-100 nm.
  • the present invention provides a method for the preparation of aerogel carbon nanotubes.
  • the method includes contacting a plurality of carbon nanotube aggregates with a shearing means under conditions sufficient to form a plurality of carbon nanotube agglomerates having a density from about 0.1 to about 100 g/L.
  • the aggregates can be bundles, arrays or a combination of bundles and arrays.
  • the method further includes dispersing the plurality of carbon nanotube agglomerates in a gas; and descending said plurality of carbon nanotube agglomerates to form aerogel carbon nanotubes having a controlled or predetermined density.
  • Conventional device and methods can be used for crushing carbon nanotubes bundles and/or arrays or a mixture of bundles and arrays to form areogel carbon nanotubes.
  • the crushing or shearing can usually be conducted at an ambient temperature, such as at a temperature from about 10-40 0 C.
  • Shearing or crushing of the material can also be conducted at an elevated temperature, such as 50-200 0 C or a temperature less than 5 0 C, such as at a temperature from -197 - 0 0 C.
  • the shearing is conducted at room temperature from about 10-30 0 C. In general, longer crushing or shearing time results in aerogel carbon nanotubes bundles or arrays having smaller diameters.
  • a gaseous or fluidic cooling media can be applied to the shearing means.
  • Exemplary cooling media include, but are not limited to, water, organic solvents or lubricants.
  • a crushing or shearing time from about Is to about 0.5 hour can be used to obtain aerogel carbon nanotubes bundles or arrays having desirable diameters.
  • a shearing time of about 1-5 minutes is preferred.
  • the crushing or shearing means includes, but are not limited to mechanical shearing, high-velocity gas shearing, skives and explosion.
  • a mechanical shearing device contains a cutting means for shearing the carbon nanotubes bundles or arrays.
  • the cutting means can be made of a metal, such as steel; or ceramic, such as silicon carbide, tungsten carbide and the like, hi certain instances, the cutting means is capable of rotating at a certain speed from about 1000 rad/min to about 50000 rad/min, preferably from about 10000-30000 rad/min. In some embodiments, higher rotating speed is desirable since it results in carbon nanotube bundles or arrays having smaller diameters.
  • High velocity gas shearing can also be used for the preparing of aerogel carbon nanotubes bundles or arrays.
  • an inert gas such as nitrogen, air or a noble gas is used.
  • the line velocity of the gas is from about 1-50 m/s.
  • the line velocity is from about 1-20 m/s, more preferably, from about 1-10 m/s.
  • a gas having a line velocity of about 5m/s is used for shearing.
  • the aerogel carbon nanotubes having various densities can be prepared by dispersing the carbon nanotubes agglomerates in a gas, followed by descending and collecting the carbon nanotube agglomerates at various time intervals.
  • the carbon nanotubes agglomerates are dispersed into a housing using a gas.
  • the housing can have various shapes and sizes.
  • the housing can optionally be further connected to a container.
  • a tubular housing connected to a spherical container can be used for the dispersion process.
  • a gas is selected from air, nitrogen, oxygen, noble gas, carbon dioxide, carbon monoxide, C 1-S hydrocarbon gases or mixtures thereof. Cj.
  • hydrocarbon gases include methane, ethane, ethane, propane, propylene, butane, butene, pentane, pentene, hexane, hexene, heptane, heptene, octane, octane, benzene, mixtures and isomers thereof.
  • the dispersion process is typically conducted at a temperature above the boiling point of the gas used. The process can be performed at a temperature from about -100 to 200 0 C, preferably from 0-100 0 C, more preferably at a temperature from about 0-40 0 C.
  • the descending of carbon nanotubes agglomerates in the gas phase and grading the carbon nanotubes agglomerates with different densities can be conducted for about 1 s to about 10 hours.
  • the descending and collecting processes are carried out for about 0.1 min to about 20 minutes, more preferably from about 0.5 min to about 15 min.
  • the process of shearing, dispersing and grading is repeatable until aerogel carbon nanotubes of having desired parameters are obtained. For example, if the product has not reached the desired density, then the CNT can be crushed or sheared again until aerogel nanotubes having a desired density, aspect ratio and diameter are obtained.
  • the present invention provides aerogel carbon nanotubes that can be used as heat conductive, electrical conductive materials itself, or in combination with other materials, such as polymers, ceramic, metals to form structural composite, electrical conductive composite, electromagnetic interference shielding, transparent conductive materials, thermal conductive, mechanical strength enhanced materials, thermal insulating materials or catalyst carriers.
  • the present invention provides a method for the preparation of an aerogel carbon nanotube membrane.
  • the method includes depositing aerogel carbon nanotubes on a planar solid support under conditions sufficient to form a carbon nanotubes membrane.
  • a binder is added to the carbon nanotube membrane together with the carbon nanotubes layer to form a paper like material that exhibits enhanced and/or improved mechanical properties.
  • the membrane is formed by depositing a gas dispersed aerogel carbon nanotubes onto to a solid support.
  • the carbon nanotube membrane is formed by spin coating of a solution of aerogel carbon nanotubes.
  • the solvent can be water or organic solvents, which include pentane, hexanes, petroleum ether, benzene, chlorinated solvent, such as dichloromethane, chloroform and dichloroethylene; ether, tetrahydrofuran (THF), ethanol, methanol and the like.
  • concentration of the aerogel carbon nanotubes can be from about 1 ppm to 100 ppm, for example, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, 80 or 90 ppm.
  • the thickness of the membrane can be from 1 nm to about 10 nm.
  • the membrane prepared can be transparent, semi transparent or opaque.
  • the membrane has high thermal and electrical conductivity. For instance, the membrane has a volume resistance less than 10 "2 ⁇ cm, a surface electrical resistance less than 1000 ⁇ /D; and a thermal conductivity greater than 1000W/mK.
  • the membrane also exhibits better mechanical properties than conventional paper. For example, the membrane prepared has a tensile strength greater than 20.2 Mpa and a Young modulation greater than 436 MPa higher than ordinary paper.
  • the solid support used in the present invention can be silica gels, derivatized plastic films, metal film, metal mesh, glass beads, cotton, plastic beads, alumina gels, polymer resins, a zeolite, a carbon, ceramic, an inorganic oxide, an inorganic hydroxide, a mixed inorganic hydroxides or mixed inorganic oxides.
  • Plastic films include polymer films derived from polyalkenes, such as polyethylene and polypropylenes.
  • the metals are typically groups 10-14 metals.
  • Non-limiting examples of polymer resins includes polystyrene resin and epoxy resin.
  • the binders used in the present invention include polymers, ceramic, oxide, glass, metals or semiconductors.
  • Non-limiting exemplary polymers include, but are not limited to, poly(vinylidene fluoride), poly(dicyclopentadiene), poly(tetrafluoroethylene), poly(ether-ether ketone), poly(ether sulfone),' silicones, dimethylsiloxane polymers, poly(pyrrole) 5j epoxy resins, polyacrylates, adhesives and polyaniline.
  • Non-limiting ceramic/oxide or glass includes SiO2, A12O3, MgO and cordierite.
  • Non-limiting metals or semiconductors include, but are not limited to, Ag, Au, Cu, Al, Ni, Fe, Zn, graphite, Ga/As and silicon.
  • the present invention provides a method for the preparation of polymer composite materials.
  • the method includes admixing a polymer composite material with aerogel carbon nanotubes under conditions sufficient to form a polymer composite.
  • Various polymers are suitable for preparing the composite materials.
  • the polymers can be synthetic polymers, such as plastics, rubbers and fibers; or naturally occurring macromolecules, such as proteins, polypeptides, poly(amino acids) and polysaccharides.
  • the synthetic polymers include • those prepared by both addition polymerization and condensation polymerization processes.
  • Exemplary synthetic polymers include, but are not limited to, polyalkenes, such as poly(Cl-8alkylenes) and poly(substituted Cl-8alkylenes); polyethers; polyesters; polyamides; polyacrylates; polynitriles; polysulfones and polyketones.
  • the substituents can attach either to the sp2 or sp3 carbon of the alkylene.
  • Suitable substituents for Cl-8alkylene include, but are not limited to, -F, -Cl 5 -Br, I, aryl, arylalkyl, alkyl aryl, -ORa, -OSi(Ra)3, -OC(O)O-Ra, -OC(O)Ra, -OC(O)NHRa, -OC(O)N(Ra)2, -SH 5 -SRa, -S(O)Ra 5 -S(O)2Ra, -SO2NH2, -S(O)2NHRa,
  • the polymers used in the present invention can be linear, branched or cross-linked.
  • the cross-linked polymers can be polymer resins.
  • aerogel carbon nanotubes are added to a polymer solution.
  • mechanical blending techniques known to a person skilled in the art are used.
  • the aerogel carbon nanotubes can be admixed to the polymers in a ratio from about 0.001 wt% to about 99 wt %.
  • the aerogel carbon nanotubes have a concentration from about 0.003 to about 10%, more preferable from about 0.003 to about 5%.
  • the polymer composite, wherein the aerogel carbon nanotubes can have a weight percentage of about 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • the method further includes pressing the polymer composite to form a membrane.
  • the polymer composite can be mechanically and/or thermally pressed using the device known in the art.
  • thermal pressing is conducted at a temperature above the Tg of the polymer.
  • Composite films having a thickness from about 0.001 mm to about 1 mm can be obtained.
  • the film has a thickness of 0.1 mm.
  • the polymer composite films have a much higher tensile strength compared to the polymers. For example, a polyvinyl alcohol composite film has a tensile strength of at least 27 MPa and a Young modulation of at least about 1956 MPa.
  • the polymer composite materials are electrically and thermally conductive and have a low volume resistance.
  • the polymer composite has a conductivity of at least 10-3S/m, a thermal conductivity of at least 1000W/mK 5 and a volume resistance of l ⁇ cm or less.
  • the present invention provides a method for the preparation of inorganic composite materials.
  • the method includes admixing an inorganic compound or material with aerogel carbon nanotubes to form a mixture, heating the mixture, and hot-pressing the mixture under conditions sufficient to form inorganic composite.
  • the admixing includes, for example, mixing an inorganic compound, such as a metal oxide resin with aerogel carbon nanotubes to obtain a mixture.
  • the mixture can be heated or baked for a desirable amount of time, from about 1 minute to 5 hours.
  • the mixture can be heated at a temperature from about 80 0 C to about 500 0 C for about 2-72 hours.
  • the mixture is heated at about 100-200 0 C for about 24-48 hours.
  • the mixture is heated at 110 °C for about 24 hours.
  • Hot-pressing can be conducted at a temperature from about 700 0 C to about 2000 0 C and a pressure from about 10-60 MPa, preferably, a temperature from 1000-2000 0 C and a pressure from 15-30 MPa.
  • an AI 2 O 3 powder resin is hot pressed at about 1500 0 C, 20 MPa for about 60 minutes.
  • Suitable inorganic materials include, but are not limited to, metal oxides, metal sulfides, metal carbides, metal powders, alloys, semiconductors and combinations of the mixtures.
  • the metals can be either main group metals or transition metals.
  • Non-limiting semiconductors include silicon and gallium arsenide.
  • This example illustrates effect of mechanic shearing on carbon nanotube arrays and the effects of dispersing and descending on aerogel carbon nanotubes.
  • the length of the CNT array was 1.4mm, and the nanotubes have a surface area about several tenths square millimeters.
  • the rotation rate was about 10000 rad/min. After 2min shearing, the CNT array has been destroyed and dispersed well. Due to the week connection on the axis direction, when shearing happened, the CNT array has been tore into small bundles. Due to the flexible of CNT, it can be kept as the primitive length.
  • the SEM image of after crushing CNTs was shown in Fig 2b.
  • the CNT agglomerate has been into the CNT bundles with diameter of l-25 ⁇ m and a length of 100 ⁇ 1400 ⁇ m.
  • the density of CNT bundles were about 2g/L. It can be seen that the CNT array has been into aerogel CNT in big cluster from.
  • the length of the CNT array was 1.Omm, and the nanotubes have a surface area about several tenths square millimeters.
  • the density of aerogel CNTs were about 4g/L.
  • the above aerogel was put into a silica tube with a diameter of 75mm, the inlet air with a flow rate of 0.2m/s on the cross-section of the tube.
  • the CNT volume can be increased and dispersed in air.
  • the CNT aerogel can descend. Collect the sample after lmin.
  • the density of aerogel CNTs were about 1.4g/L.
  • the aerogel CNT product after 5min collection was with a density of 0.2g/L.
  • the length of the CNT bundles was about a few hundreds micrometers. Take 100mg CNT array in the mechanical shearing, and control the rotation rate at 10000 rad/min. After 2min shearing, the CNT array has been destroyed and dispersed well. Take the product out and the SEM image of after crushing CNTs was shown in Fig 4a. It can be seen that the CNT agglomerate has been into the CNT bundles with diameter of 50-250 nm and a length of 100 ⁇ 100 ⁇ m. The density of aerogel CNTs were about 42g/L.
  • the above aerogel was put into a silica tube with a diameter of 75mm, the inlet air with a flow rate of 0.2m/s on the cross-section of the tube.
  • the CNT volume can be increased and dispersed in air.
  • the CNT aerogel can descend. Collect the sample after 3min as shown in Fig. 4b.
  • the density of aerogel CNTs were about 2.2g/L.
  • This example illustrates the effect of mechanical shearing and descending on the dispersion of carbon nanotubes bundles in gas.
  • the length of the CNT bundles was about a few hundreds micrometers. Take 500mg CNT array in the mechanical shearing, and control the rotation rate at 30000 rad/min. After 20 min shearing, the CNT array has been destroyed and dispersed well. Take the product out and the SEM image of after crushing CNTs was shown in Fig 5.
  • the above aerogel was put into a silica tube with a diameter of 75mm, the inlet air with a flow rate of 0.05m/s on the cross-section of the tube. The CNT volume can be increased and dispersed in air. When the inlet air stopped, the CNT aerogel can descend. Collect the sample after 15min. It can be seen that the CNT agglomerate has been into the CNT bundles with diameter of 10-100 nm and a length of 10 ⁇ 500 ⁇ m as shown in Fig.5. The density of aerogel CNTs were about 0.1g/L.
  • This example illustrates the preparation of a carbon nanotube paper from aerogel carbon nanotubes.
  • Example 6 This example illustrates the preparation of polymer-carbon nanotubes composite.
  • Example 7 This Example illustrates the preparation of a carbon nanotube film.
  • This example illustrates the preparation of an electrically conductive polymer carbon-nanotube composite.
  • This example illustrates the preparation of an inorganic carbon-nanotube composite.
  • the aerogel CNT from embodiment 2 with Al 2 O 3 powder resin and mix them well. Bake the mixture at 110 0 C for 24 hr. Then the mixture hot-pressed at 1500 0 C, 20 MPa for 60min to get the Al 2 O 3 /CNT composite.
  • the Al 2 O 3 powder was a density of 3.80 g/cm 3 , tensile strength of 362 MPa; After 1% aerogel CNT adding, the density was 3.76 g/cm 3 , while tensile strength is 420MPa. Therefore, the aerogel CNT enhanced the ceramic powder with better performance.

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Abstract

La présente invention concerne des nanotubes de carbone sous forme d'aérogel et un procédé de préparation de ces derniers. Les nanotubes de carbone sous forme d'aérogel comprennent une pluralité d'agrégats de nanotubes de carbone dispersés présentant un diamètre compris entre environ 1 nm et environ 100 microns et une densité comprise entre environ 0,1 et 100 g/L. Le procédé de préparation correspondant consiste à mettre en contact une pluralité d'agrégats de nanotubes de carbone avec un moyen de cisaillement dans des conditions suffisantes pour former une pluralité d'agglomérats de nanotubes de carbone d'une densité comprise entre environ 0,1 et environ 100 g/L. Cette invention concerne également des procédés de préparation d'une membrane, d'un matériau composite polymère et d'un matériau composite inorganique dans lesquels on utilise lesdits nanotubes de carbone sous forme d'aérogel en tant que matière première.
PCT/CN2007/001957 2006-06-23 2007-06-22 Nanotubes de carbone sous forme d'aérogel et procédés de préparation de ces derniers, membrane et matériau composite contenant ces derniers WO2008000163A1 (fr)

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US20100189883A1 (en) * 2007-04-28 2010-07-29 Martin Pick Continuous process for preparing and collecting nanotube films that are supported by a substrate
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